WO2018052006A1 - 有機エレクトロルミネッセンス表示素子用封止剤 - Google Patents

有機エレクトロルミネッセンス表示素子用封止剤 Download PDF

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Publication number
WO2018052006A1
WO2018052006A1 PCT/JP2017/032993 JP2017032993W WO2018052006A1 WO 2018052006 A1 WO2018052006 A1 WO 2018052006A1 JP 2017032993 W JP2017032993 W JP 2017032993W WO 2018052006 A1 WO2018052006 A1 WO 2018052006A1
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organic
water
sealing agent
display elements
absorbing filler
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PCT/JP2017/032993
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English (en)
French (fr)
Japanese (ja)
Inventor
康雄 渡邊
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積水化学工業株式会社
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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 KR1020217040934A priority Critical patent/KR102497896B1/ko
Priority to KR1020187022464A priority patent/KR102340967B1/ko
Priority to CN201780018770.0A priority patent/CN108781491B/zh
Priority to JP2017550263A priority patent/JP6933580B2/ja
Publication of WO2018052006A1 publication Critical patent/WO2018052006A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations

Definitions

  • the present invention relates to a sealing agent for organic electroluminescence display elements that has excellent barrier properties and can suppress panel peeling.
  • 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.
  • 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.
  • a sealant for example, Patent Document 1.
  • an inorganic film called a passivation film is usually provided on a laminate having an organic light emitting material layer in order to sufficiently suppress the transmission of moisture, oxygen, and the like. A method of sealing the top with a sealant is used.
  • a top emission type organic element that extracts light from the upper surface side of the organic light emitting layer is used.
  • EL display elements have attracted attention. This method has an advantage that it has a high aperture ratio and is driven at a low voltage, which is advantageous for extending the life.
  • a transparent moisture-proof substrate such as glass is interposed on the upper surface side of the light emitting element via a transparent sealing resin.
  • An object of this invention is to provide the sealing agent for organic electroluminescent display elements which is excellent in barrier property and can suppress panel peeling.
  • the present invention contains a curable resin, a polymerization initiator, and a water-absorbing filler, and the water-absorbing filler has an average primary particle diameter of 5 ⁇ m or less and a specific gravity of 3.3 g / cm 3 or less. It is a sealing agent for display elements.
  • the present invention is described in detail below.
  • a water-absorbing filler such as calcium oxide
  • the barrier property can be improved, but because of its high expansion coefficient, it absorbs moisture and causes defects such as panel peeling.
  • the present inventor has an excellent barrier property and can suppress panel peeling by using a water-absorbing filler whose average primary particle diameter and specific gravity are in specific ranges, respectively.
  • the present inventors have found that a sealant can be obtained and have completed the present invention.
  • the sealing agent for organic EL display elements of the present invention has a water absorbing filler having an average primary particle diameter of 5 ⁇ m or less and a specific gravity of 3.3 g / cm 3 or less (hereinafter referred to as “water absorbing filler according to the present invention”). Contain).
  • water absorbing filler according to the present invention a water absorbing filler having an average primary particle diameter of 5 ⁇ m or less and a specific gravity of 3.3 g / cm 3 or less. Contain).
  • the water-absorbent filler according to the present invention has the average primary particle diameter and specific gravity in the above-mentioned ranges, and has a small specific gravity and a high porosity compared to a general water-absorbent filler having the same average primary particle diameter. It is thought to have. Therefore, when water is absorbed, expansion of the outside is suppressed by filling the internal gap, and as a result, it is considered that panel peeling can be suppressed while exhibiting excellent barrier properties due to high water absorption performance.
  • the upper limit of the average primary particle diameter of the water-absorbing filler according to the present invention is 5 ⁇ m.
  • the preferable upper limit of the average primary particle diameter of the water-absorbing filler according to the present invention is 3.5 ⁇ m, and the more preferable upper limit is 3 ⁇ m.
  • a substantial minimum is 0.05 micrometer and a thing more than 0.5 micrometer is easier to obtain.
  • the “average primary particle size” can be measured by a dynamic light scattering type particle size measuring device (“ELSZ-1000S” manufactured by Otsuka Electronics Co., Ltd.) or the like.
  • the upper limit of the specific gravity of the water-absorbing filler according to the present invention is 3.3 g / cm 3 .
  • the specific gravity of the water-absorbing filler according to the present invention is 3.3 g / cm 3 or less, the obtained sealing agent for organic EL display elements is excellent in the effect of achieving both excellent barrier properties and suppression of panel peeling. It becomes.
  • a preferable upper limit of the specific gravity of the water-absorbing filler according to the present invention is 3.0 g / cm 3 .
  • a substantial minimum is 1.5 g / cm ⁇ 3 >.
  • the “specific gravity” means a value measured by a method according to JIS Z8807.
  • the minimum with a preferable average specific surface area of the water absorptive filler concerning this invention is 5 m ⁇ 2 > / g, and a preferable upper limit is 20 m ⁇ 2 > / g.
  • the average specific surface area of the water-absorbing filler according to the present invention is within this range, the obtained sealing agent for organic EL display elements is excellent due to the effect of achieving both excellent barrier properties and suppression of panel peeling.
  • the more preferable lower limit of the average specific surface area of the total surface area of the water-absorbing filler according to the present invention is 10 m 2 / g, and the more preferable upper limit is 18 m 2 / g.
  • the “average specific surface area” can be measured by a BET method using nitrogen gas with a specific surface area measurement apparatus (for example, “ASAP-2000” manufactured by Shimadzu Corporation).
  • the preferable lower limit of the water absorption rate of the water-absorbing filler according to the present invention is 10% by weight.
  • the more preferable lower limit of the water absorption rate of the water-absorbing filler according to the present invention is 20% by weight.
  • the “water absorption rate” means the rate of change in weight when a high temperature and high humidity test is performed for 24 hours in an atmosphere at a temperature of 85 ° C. and a humidity of 85%.
  • Examples of the material constituting the water-absorbing filler according to the present invention include oxides of alkaline earth metals such as calcium oxide, strontium oxide, and barium oxide, magnesium oxide, and molecular sieve. Among these, from the viewpoint of water absorption, an alkaline earth metal oxide is preferable, and calcium oxide is more preferable.
  • the content of the water-absorbing filler according to the present invention is preferably 5 parts by weight and preferably 60 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the water-absorbing filler according to the present invention is within this range, the obtained sealing agent for organic EL display elements is more excellent in the effect of achieving both improvement in barrier properties and suppression of panel peeling.
  • the minimum with more preferable content of the water absorbing filler concerning this invention is 10 weight part, and a more preferable upper limit is 40 weight part.
  • the sealing agent for organic EL display elements of the present invention contains other fillers in addition to the water-absorbing filler according to the present invention within the range not impairing the object of the present invention for the purpose of improving adhesiveness and the like. May be.
  • the other fillers include inorganic fillers such as silica, talc, and alumina, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. Of these, talc is preferable.
  • the sealing agent for organic EL display elements of this invention contains curable resin.
  • the curable resin include a cationic polymerizable compound having a cationic polymerizable group such as an epoxy group, an oxetanyl group, and a vinyl ether group, and a radical polymerizable compound having a radical polymerizable group such as a (meth) acryloyl group.
  • a cationic polymerizable compound is preferable, and a cationic polymerizable compound having an epoxy group is more preferable.
  • an epoxy resin having a bisphenol skeleton an epoxy resin having a novolac skeleton, an epoxy resin having a naphthalene skeleton, and an epoxy resin having a dicyclopentadiene skeleton
  • at least one epoxy resin selected from the group consisting of: an epoxy resin having a bisphenol skeleton is more preferable, and a bisphenol F-type epoxy resin is still more preferable.
  • the sealing agent for organic EL display elements of this invention is a compound represented by following formula (1) and / or following formula (2) as said cation polymeric compound from a viewpoint of suppressing generation
  • R 1 to R 18 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.
  • X is a bond, an oxygen atom, an alkylene group having 1 to 5 carbon atoms, an oxycarbonyl group, an alkyleneoxycarbonyl group having 2 to 5 carbon atoms, or a secondary amino group.
  • R 19 to R 21 are linear or branched alkylene groups having 2 to 10 carbon atoms, which may be the same or different.
  • E 1 to E 3 each independently represents an organic group represented by the following formula (3-1) or the following formula (3-2).
  • R 22 represents a hydrogen atom or a methyl group.
  • a compound represented by the following formula (4-1), a compound represented by the following formula (4-2), and a compound represented by the following formula (4-3) It is preferable to contain at least one selected from the group consisting of
  • a (meth) acryl compound is preferably used as the radical polymerizable compound.
  • the (meth) acrylic compound include epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound, and (meth) acrylic acid obtained by reacting a compound having a hydroxyl group.
  • examples thereof include urethane (meth) acrylates obtained by reacting (meth) acrylic acid ester compounds and isocyanate compounds with (meth) acrylic acid derivatives having a hydroxyl group.
  • epoxy (meth) acrylate is preferable.
  • the “(meth) acryl” indicates acryl or methacryl
  • the “(meth) acrylate” indicates acrylate or methacrylate
  • the “epoxy (meth) acrylate” It represents a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid.
  • Examples of commercially available epoxy (meth) acrylates include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRY3603 EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy Ester 200PA, epoxy ester 80MFA Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Den
  • the sealing agent for organic EL display elements of the present invention contains a polymerization initiator.
  • the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Of these, a photopolymerization initiator is preferable.
  • the photopolymerization initiator examples include a photocationic polymerization initiator that generates a protonic acid or a Lewis acid by light irradiation, a photoradical polymerization initiator that generates a radical by light irradiation, and the like. Of these, a photocationic polymerization initiator is preferred.
  • 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.
  • ionic photoacid generating types include, for example, that the anion moiety is BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is at least An aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, an aromatic ammonium salt, or (2,4, which represents a phenyl group substituted with two or more fluorine or trifluoromethyl groups) -Cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt and the like.
  • 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 generators include, for example, nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, N-hydroxyimide sulfonates, and the like. Can be mentioned.
  • photocationic polymerization initiators examples include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all ADEKA), FC-508, FC-512 (all from 3M), IRGACURE290 (from BASF), PI 2074 (from Rhodia), and the like.
  • photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone, and the like.
  • Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucin TPO (both benzoin methyl ether, benzoin methyl ether) Examples include ethyl ether and benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.).
  • thermal polymerization initiator examples include a thermal cationic polymerization initiator that generates a protonic acid or a Lewis acid by heating, a thermal radical polymerization initiator that generates a radical by heating, and the like.
  • thermal cationic polymerization initiator examples include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is phenyl substituted with at least two fluorine or trifluoromethyl groups.
  • a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, or an iodonium salt, and a sulfonium salt is more preferable.
  • sulfonium salts include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium hexafluoride arsenic, tri (4-methoxyphenyl) sulfonium hexafluoride arsenic, and diphenyl (4-phenylthiophenyl). ) Sulfonium arsenic hexafluoride and the like.
  • the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.
  • Examples of the quaternary ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (penta).
  • Fluorophenyl) borate dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate , Methylphenyldibenzylammonium, methylphenyldibenzylammonium hexafluoroantimony Hexafluorophosphate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-
  • thermal cationic polymerization initiators include, for example, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, Sun-Aid SI-B4 (all of which are Sanshin Chemical Industry Co., Ltd.). CXC-1612, CXC-1738, CXC-1821 (all manufactured by King Industries), and the like.
  • thermal radical polymerization initiator examples include peroxides and azo compounds.
  • thermal radical polymerization initiator examples include peroxides and azo compounds.
  • commercially available products include perbutyl O, perhexyl O, perbutyl PV (all manufactured by NOF Corporation), V-30, V-65, V-501, V-601, VPE-0201 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
  • the content of the polymerization initiator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the polymerization initiator is within this range, the obtained sealing agent for organic EL display elements is more excellent in curability, storage stability, and barrier properties.
  • the minimum with more preferable content of the said polymerization initiator 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 contain a thermosetting agent.
  • the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like.
  • the hydrazide compound include 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
  • imidazole derivatives examples include 1-cyanoethyl-2-phenylimidazole, N- (2- (2-methyl-1-imidazolyl) ethyl) urea, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
  • acid anhydride examples include tetrahydrophthalic anhydride, ethylene glycol bis (anhydro trimellitate), and the like.
  • thermosetting agents examples include SDH (manufactured by Nippon Finechem Co., Ltd.), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.). ) And the like.
  • the content of the thermosetting agent is preferably 0.5 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the thermosetting agent is 0.5 parts by weight or more, the obtained sealing agent for organic EL display elements is more excellent in thermosetting.
  • the content of the thermosetting agent is 30 parts by weight or less, the obtained sealing agent for organic EL display elements is more excellent in storage stability and barrier properties.
  • the minimum with more preferable content of the said thermosetting agent is 1 weight part, and a more preferable upper limit is 15 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 photopolymerization initiator and further promoting the curing reaction of the sealant for organic EL display elements of the present invention.
  • the sensitizer examples include anthracene compounds such as 9,10-dibutoxyanthracene, thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1, and the like.
  • anthracene compounds such as 9,10-dibutoxyanthracene
  • thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1, and the like.
  • -One benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4-benzoyl-4'methyldiphenyl sulfide, and the like.
  • the content of the sensitizer is preferably 0.05 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the sensitizer is 0.05 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 this invention contains a stabilizer. By containing the said stabilizer, the sealing agent for organic EL display elements of this invention becomes a thing excellent in storage stability more.
  • the stabilizer examples include amine compounds such as benzylamine and aminophenol type epoxy resins.
  • the preferable lower limit of the content of the stabilizer is 0.001 part by weight and the preferable upper limit is 2 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the stabilizer is within this range, the obtained sealing agent for organic EL display elements is more excellent in storage stability while maintaining excellent curability.
  • the minimum with more preferable content of the said stabilizer is 0.005 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 curable resin.
  • 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 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, acrylic-based, and fluorine-based ones.
  • Examples of commercially available surface modifiers include BYK-300, BYK-302, BYK-331 (all manufactured by Big Chemie Japan), UVX-272 (manufactured by Enomoto Kasei), Surflon. S-611 (manufactured by AGC Seimi Chemical Co., Ltd.) and the like.
  • the encapsulant for organic EL display elements of the present invention may contain an ion exchange resin in order to improve the durability of the element electrode as long as the object of the present invention is not impaired.
  • any of a cation exchange type, an anion exchange type, and a both ion exchange type can be used, and in particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ions. Is preferred.
  • the sealing agent for organic EL display elements of this invention does not contain a solvent from a viewpoint of suppressing generation
  • the sealing agent for organic EL display elements of this invention is a range which does not inhibit the objective of this invention, and is a hardening retarder, a reinforcing agent, a softener, a plasticizer, a viscosity modifier, and an ultraviolet absorber as needed. Further, various known additives such as antioxidants may be contained.
  • the sealing agent for organic EL display elements of the present invention for example, using a mixer such as a homodisper, homomixer, universal mixer, planetary mixer, kneader, three rolls, And a method of mixing a polymerization initiator, a water-absorbing filler according to the present invention, and an additive such as a silane coupling agent added as necessary.
  • a mixer such as a homodisper, homomixer, universal mixer, planetary mixer, kneader, three rolls, and a method of mixing a polymerization initiator, a water-absorbing filler according to the present invention, and an additive such as a silane coupling agent added as necessary.
  • the sealing agent for organic EL display elements of the present invention is preferably a paste having a viscosity of 100 to 500 Pa ⁇ s at 25 ° C. using an E-type viscometer.
  • the viscosity is in this range, the organic EL display element sealant of the present invention is superior in both applicability and dispersibility of the water-absorbing filler.
  • a more preferable lower limit of the viscosity is 150 Pa ⁇ s, and a more preferable upper limit is 450 Pa ⁇ s.
  • a solvent is used to adjust the viscosity, it is difficult to suppress generation of outgas.
  • the viscosity is, for example, a VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer, and a rotational speed of 1 to 100 rpm as appropriate from the optimum torque number in each viscosity region using a CP1 cone plate. Can be measured by selecting.
  • the shape of the sealing portion formed by the organic EL display element sealant of the present invention 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, and the laminate is not limited.
  • the shape may be completely covered, a closed pattern may be formed in the periphery of the laminate, or a pattern having a shape in which a part of the opening is provided in the periphery of the laminate is formed. May be.
  • the sealing agent for organic EL display elements of this invention can be used suitably for sealing of the peripheral part of this laminated body.
  • the sealing agent for organic electroluminescent display elements which is excellent in barrier property and can suppress panel peeling can be provided.
  • (A) is a SEM image of the surface of the water-absorbing filler A according to the present invention
  • (b) is a SEM image of a cross section of the water-absorbing filler A according to the present invention.
  • (A) is a SEM image of the surface of a commercially available water-absorbing filler (Yoshizawa Lime Industry, “Quicklime J1P”)
  • (b) is a commercially available water-absorbing filler (Yoshizawa Lime Industry, “Quicklime J1P”). It is a SEM image of a cross section of “)”.
  • Examples 1 to 6, Comparative Example 1 In accordance with the blending ratio described in Table 1, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (“Primix Corporation,“ Homodisper L type ”). To 6 and a sealing agent for organic EL display elements of Comparative Example 1 were prepared.
  • the water-absorbing filler A according to the present invention has an average primary particle size of 3.5 ⁇ m measured using a dynamic light scattering particle size measuring device, and a specific gravity measured by a method according to JIS Z8807.
  • Is 3.0 g / cm 3 calcium oxide having an average specific surface area of 11 m 2 / g and a water absorption of 25% by weight measured by the BET method using nitrogen gas with a specific surface area measuring device.
  • ELSZ-1000S manufactured by Otsuka Electronics Co., Ltd.
  • ASAP-2000 manufactured by Shimadzu Corporation
  • the “water-absorbing filler B according to the present invention” in the table was measured in the same manner as the water-absorbing filler A, and the average primary particle diameter was 1.0 ⁇ m, the specific gravity was 2.8 g / cm 3 , and the average specific surface area was This is calcium oxide having a weight of 18 m 2 / g and a water absorption of 30% by weight. Furthermore, “quick lime J1P (manufactured by Yoshizawa Lime Industry Co., Ltd.)” in the table was measured in the same manner as the water-absorbing filler A, and the average primary particle size was 3.0 ⁇ m, the specific gravity was 3.4 g / cm 3 , and the average specific surface area.
  • FIG. 1 The SEM image of the surface and the cross section of the water-absorbing filler A according to the present invention is shown in FIG. As shown in FIG. 1, it was confirmed that the water-absorbing filler A according to the present invention has a concavo-convex shape on the surface and a large number of voids inside. Moreover, the SEM image of the surface and cross section of the commercially available water absorbing filler (Yoshizawa lime industry company make, "quick lime J1P") used by the comparative example was shown in FIG. As shown in FIG. 2, it was confirmed that the commercially available water-absorbing filler used in the comparative example was flat in both surface and cross section.
  • a sealing agent for each organic EL display element obtained in the examples and comparative examples is applied to the surface. Were pasted together. At this time, bonding was performed so that the deposited Ca exists at positions of 2 mm, 4 mm, and 6 mm from the end face of the glass substrate.
  • the sealing agent was cured by irradiating an ultraviolet ray of 365 nm at 3000 mJ / cm 2 and further heating at 80 ° C. for 30 minutes, thereby producing a Ca-TEST substrate.
  • the organic EL display element sealant obtained in Example 5 was cured by heating at 100 ° C. for 30 minutes to prepare a Ca-TEST substrate.
  • the obtained Ca-TEST substrate was exposed to high-temperature and high-humidity conditions of 85 ° C. and 85% RH, and the moisture penetration distance per hour was observed from the disappearance of Ca. As a result, the moisture penetration distance reached 6 mm.
  • the barrier property was evaluated as “ ⁇ ” when the time was 1000 hours or more, “ ⁇ ” when the time was 500 hours or more and less than 1000 hours, and “X” when the time was less than 500 hours.
  • Adhesion state of the panel production of a substrate on which a laminate having an organic light emitting material layer is disposed
  • a glass substrate (length 45 mm, width 45 mm, thickness 0.7 mm) on which an ITO electrode was formed to a thickness of 1000 mm was used as the 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”).
  • this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -NPD) is put into an unglazed crucible and other different types.
  • 200 mg of tris (8-quinolinolato) aluminum (Alq 3 ) was put in an unglazed crucible, and the inside of the vacuum chamber was depressurized 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. 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, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire 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 was placed so as to cover the entire laminated body of the substrate on which the obtained laminated body was arranged, and an inorganic material film A was formed by a plasma CVD method.
  • SiH 4 gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, RF power is 10 W (frequency: 2.45 GHz), chamber temperature is 100 ° C., and chamber pressure is 0.
  • the test was performed at 9 Torr.
  • the formed inorganic material film A had a thickness of about 1 ⁇ m.
  • 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 film B is formed by plasma CVD to form an organic EL display element. Obtained.
  • 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 B had a thickness of about 1 ⁇ m.
  • the obtained organic EL display device was visually observed for the adhesion state of the panel after being exposed to an environment of 85 ° C. and 85% RH for 2000 hours.
  • the panel adhesion state was evaluated as “ ⁇ ” when there was no panel peeling, “ ⁇ ” when panel peeling was partially confirmed, and “X” when panel peeling was confirmed from the majority.
  • the sealing agent for organic electroluminescent display elements which is excellent in barrier property and can suppress panel peeling can be provided.

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PCT/JP2017/032993 2016-09-16 2017-09-13 有機エレクトロルミネッセンス表示素子用封止剤 WO2018052006A1 (ja)

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