WO2018052006A1 - Sealing agent for organic electroluminescent display element - Google Patents

Sealing agent for organic electroluminescent display element Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
organic
water
sealing agent
display elements
absorbing filler
Prior art date
Application number
PCT/JP2017/032993
Other languages
French (fr)
Japanese (ja)
Inventor
康雄 渡邊
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 KR1020217040934A priority Critical patent/KR102497896B1/en
Priority to KR1020187022464A priority patent/KR102340967B1/en
Priority to JP2017550263A priority patent/JP6933580B2/en
Priority to CN201780018770.0A priority patent/CN108781491B/en
Publication of WO2018052006A1 publication Critical patent/WO2018052006A1/en

Links

Images

Classifications

    • 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
    • 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
    • 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.

Abstract

The purpose of the invention is to provide a sealing agent for organic electroluminescent display elements that has excellent barrier properties and is capable of suppressing the peeling of a panel. This invention is a sealing agent for organic electroluminescent display elements, the sealing agent comprising a curable resin, a polymerization initiator, and a water-absorbent filler, wherein the water-absorbent filler has an average primary particle diameter of 5 µm or less and a specific gravity of 3.3 g/cm3 or less.

Description

有機エレクトロルミネッセンス表示素子用封止剤Sealant for organic electroluminescence display element
本発明は、バリア性に優れ、かつ、パネル剥がれを抑制できる有機エレクトロルミネッセンス表示素子用封止剤に関する。 The present invention relates to a sealing agent for organic electroluminescence display elements that has excellent barrier properties and can suppress panel peeling.
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。有機発光材料層や電極を大気と遮断する方法としては、封止剤を用いて有機ＥＬ表示素子を封止することが行われている（例えば、特許文献１）。有機ＥＬ表示素子を封止剤で封止する場合、通常、水分や酸素等の透過を充分に抑えるため、有機発光材料層を有する積層体上にパッシベーション膜と呼ばれる無機膜を設け、該無機膜上を封止剤で封止する方法が用いられている。 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. As a method for blocking the organic light emitting material layer and the electrode from the atmosphere, an organic EL display element is sealed with a sealant (for example, Patent Document 1). When sealing an organic EL display element with a sealant, 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.
近年、有機発光材料層から発せられた光を、発光素子を形成した基板面側から取り出すボトムエミッション方式の有機ＥＬ表示素子に代わって、有機発光層の上面側から光を取り出すトップエミッション方式の有機ＥＬ表示素子が注目されている。この方式は、開口率が高く、低電圧駆動となることから、長寿命化に有利であるという利点がある。このようなトップエミッション方式の有機ＥＬ表示素子では、発光層の上面側が透明であることが必要であることから、発光素子の上面側に透明な封止樹脂を介してガラス等の透明防湿性基材を積層することにより封止している（例えば、特許文献２参照）。
しかしながら、このようなトップエミッション方式の有機ＥＬ表示素子では、光の取り出し方向を遮蔽してしまわないようにするために乾燥剤を配置するスペースがなく、充分な防湿効果が得られにくく寿命が短くなるという問題があった。 In recent years, instead of a bottom emission type organic EL display element that extracts light emitted from an organic light emitting material layer from the side of the substrate surface on which the light emitting element is formed, 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. In such a top emission type organic EL display element, since the upper surface side of the light emitting layer needs to be transparent, 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. It seals by laminating | stacking a material (for example, refer patent document 2).
However, in such a top emission type organic EL display element, there is no space for disposing a desiccant so as not to shield the light extraction direction, and it is difficult to obtain a sufficient moisture-proofing effect and the life is short. There was a problem of becoming.
特開２００７－１１５６９２号公報JP 2007-115692 A 特開２００９－０５１９８０号公報JP 2009-051980 A
本発明は、バリア性に優れ、かつ、パネル剥がれを抑制できる有機エレクトロルミネッセンス表示素子用封止剤を提供することを目的とする。 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.
本発明は、硬化性樹脂と重合開始剤と吸水性フィラーとを含有し、上記吸水性フィラーは、平均一次粒子径が５μｍ以下であり、比重が３．３ｇ／ｃｍ３以下である有機エレクトロルミネッセンス表示素子用封止剤である。
以下に本発明を詳述する。 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 μm 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.
本発明者は、有機ＥＬ表示素子用封止剤のバリア性（透湿防止性）を向上させるため、酸化カルシウム等の吸水性フィラーを添加することを試みた。しかしながら、市販の吸水性フィラーを有機ＥＬ表示素子用封止剤に多く添加した場合、バリア性を向上させることはできるものの、膨張率が高いため水分を吸収することでパネル剥がれ等の不良を引き起こすという問題があった。
そこで、本発明者は更に鋭意検討した結果、平均一次粒子径及び比重がそれぞれ特定の範囲である吸水性フィラーを用いることで、バリア性に優れ、かつ、パネル剥がれを抑制できる有機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 inventor tried to add a water-absorbing filler such as calcium oxide in order to improve the barrier property (moisture permeability prevention property) of the sealing agent for organic EL display elements. However, when a large amount of commercially available water-absorbing filler is added to the sealant for organic EL display elements, the barrier property can be improved, but because of its high expansion coefficient, it absorbs moisture and causes defects such as panel peeling. There was a problem.
Therefore, as a result of further intensive studies, 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.
本発明の有機ＥＬ表示素子用封止剤は、平均一次粒子径が５μｍ以下であり、比重が３．３ｇ／ｃｍ３以下である吸水性フィラー（以下、「本発明にかかる吸水性フィラー」ともいう）を含有する。本発明にかかる吸水性フィラーを含有することにより、本発明の有機ＥＬ表示素子用封止剤は、バリア性に優れ、かつ、パネル剥がれを抑制できるものとなる。 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 μm 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). By containing the water-absorbing filler according to the present invention, the encapsulant for organic EL display elements of the present invention has excellent barrier properties and can suppress panel peeling.
本発明にかかる吸水性フィラーを含有することにより、パネル剥がれを抑制できる理由としては以下のことが考えられる。
即ち、本発明にかかる吸水性フィラーは、平均一次粒子径及び比重が上述した範囲であり、同程度の平均一次粒子径を有する一般的な吸水性フィラーに比べて比重が小さく、高い空隙率を有するものと考えられる。従って、吸水した際、内部の空隙が埋められることで外側への膨張が抑えられ、その結果、高い吸水性能による優れたバリア性を発揮しつつ、パネル剥がれを抑制できるものと考えられる。 The following can be considered as reasons why the panel peeling can be suppressed by containing the water-absorbing filler according to the present invention.
That is, 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.
本発明にかかる吸水性フィラーの平均一次粒子径の上限は５μｍである。本発明にかかる吸水性フィラーの平均一次粒子径が５μｍ以下であることにより、得られる有機ＥＬ表示素子用封止剤が優れたバリア性とパネル剥がれの抑制とを両立する効果に優れるものとなる。本発明にかかる吸水性フィラーの平均一次粒子径の好ましい上限は３．５μｍ、より好ましい上限は３μｍである。
また、本発明にかかる吸水性フィラーの平均一次粒子径の下限に特に制限はないが、実質的な下限は０．０５μｍであり、０．５μｍ以上のものが入手がより容易である。
なお、上記「平均一次粒子径」は、動的光散乱式粒子径測定装置（大塚電子社製、「ＥＬＳＺ－１０００Ｓ」）等により測定することができる。 The upper limit of the average primary particle diameter of the water-absorbing filler according to the present invention is 5 μm. When the average primary particle diameter of the water-absorbing filler according to the present invention is 5 μm 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. . The preferable upper limit of the average primary particle diameter of the water-absorbing filler according to the present invention is 3.5 μm, and the more preferable upper limit is 3 μm.
Moreover, although there is no restriction | limiting in particular in the minimum of the average primary particle diameter of the water absorbing filler concerning this invention, 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.
本発明にかかる吸水性フィラーの比重の上限は３．３ｇ／ｃｍ３である。本発明にかかる吸水性フィラーの比重が３．３ｇ／ｃｍ３以下であることにより、得られる有機ＥＬ表示素子用封止剤が優れたバリア性とパネル剥がれの抑制とを両立する効果に優れるものとなる。本発明にかかる吸水性フィラーの比重の好ましい上限は３．０ｇ／ｃｍ３である。
また、本発明にかかる吸水性フィラーの比重の下限に特に制限はないが、実質的な下限は１．５ｇ／ｃｍ３である。
なお、上記「比重」は、ＪＩＳ　Ｚ８８０７に準じた方法により測定される値を意味する。 The upper limit of the specific gravity of the water-absorbing filler according to the present invention is 3.3 g / cm 3 . When 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 .
Moreover, although there is no restriction | limiting in particular in the minimum of the specific gravity of the water absorbing filler concerning this invention, a substantial minimum is 1.5 g / cm < 3 >.
The “specific gravity” means a value measured by a method according to JIS Z8807.
本発明にかかる吸水性フィラーの平均比表面積の好ましい下限は５ｍ２／ｇ、好ましい上限は２０ｍ２／ｇである。本発明にかかる吸水性フィラーの平均比表面積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優れたバリア性とパネル剥がれの抑制とを両立する効果により優れるものとなる。本発明にかかる吸水性フィラーの総表面積の平均比表面積のより好ましい下限は１０ｍ２／ｇ、より好ましい上限は１８ｍ２／ｇである。
なお、上記「平均比表面積」は、比表面積測定装置（例えば、島津製作所社製、「ＡＳＡＰ－２０００」等）で窒素ガスを用いたＢＥＴ法により測定することができる。 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. When 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).
本発明にかかる吸水性フィラーの吸水率の好ましい下限は１０重量％である。本発明にかかる吸水性フィラーの吸水率が１０重量％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バリア性により優れるものとなる。本発明にかかる吸水性フィラーの吸水率のより好ましい下限は２０重量％である。
また、本発明にかかる吸水性フィラーの吸水率の好ましい上限は特にないが、実質的な上限は５０重量％である。
なお、上記「吸水率」は、温度８５℃、湿度８５％の雰囲気下で２４時間放置する高温高湿試験を行った場合における重量の変化率を意味する。具体的には、高温高湿試験（８５℃－８５％、２４時間）前の重量をＷ１、高温高湿試験後の重量をＷ２とした場合、下記式（Ｉ）により算出される。
　吸水率（重量％）＝（（Ｗ２－Ｗ１）／Ｗ１）×１００　　（Ｉ） The preferable lower limit of the water absorption rate of the water-absorbing filler according to the present invention is 10% by weight. When the water absorption rate of the water-absorbing filler according to the present invention is 10% by weight or more, the resulting organic EL display element sealant has better barrier properties. The more preferable lower limit of the water absorption rate of the water-absorbing filler according to the present invention is 20% by weight.
In addition, there is no particular upper limit for the water absorption rate of the water-absorbing filler according to the present invention, but the substantial upper limit is 50% 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%. Specifically, when the weight before the high-temperature and high-humidity test (85 ° C.-85%, 24 hours) is W 1 and the weight after the high-temperature and high-humidity test is W 2 , it is calculated by the following formula (I).
Water absorption rate (% by weight) = ((W 2 −W 1 ) / W 1 ) × 100 (I)
本発明にかかる吸水性フィラーを構成する材料としては、例えば、酸化カルシウム、酸化ストロンチウム、酸化バリウム等のアルカリ土類金属の酸化物、酸化マグネシウム、モレキュラーシーブ等が挙げられる。なかでも、吸水性の観点から、アルカリ土類金属の酸化物が好ましく、酸化カルシウムがより好ましい。 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.
本発明にかかる吸水性フィラーの含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が５重量部、好ましい上限が６０重量部である。本発明にかかる吸水性フィラー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バリア性の向上とパネル剥がれの抑制とを両立する効果により優れるものとなる。本発明にかかる吸水性フィラー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４０重量部である。 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. When 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.
本発明の有機ＥＬ表示素子用封止剤は、接着性を向上させること等を目的として、本発明の目的を阻害しない範囲において、本発明にかかる吸水性フィラーに加えて、その他のフィラーを含有してもよい。
上記その他のフィラーとしては、例えば、シリカ、タルク、アルミナ等の無機フィラーや、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機フィラー等が挙げられる。なかでも、タルクが好ましい。 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.
Examples of 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.
本発明の有機ＥＬ表示素子用封止剤は、硬化性樹脂を含有する。
上記硬化性樹脂としては、エポキシ基、オキセタニル基、ビニルエーテル基等のカチオン重合性基を有するカチオン重合性化合物や、（メタ）アクリロイル基等のラジカル重合性基を有するラジカル重合性化合物が挙げられる。なかでも、カチオン重合性化合物が好ましく、エポキシ基を有するカチオン重合性化合物がより好ましい。 The sealing agent for organic EL display elements of this invention contains curable resin.
Examples of 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. Among these, a cationic polymerizable compound is preferable, and a cationic polymerizable compound having an epoxy group is more preferable.
上記カチオン重合性化合物としては、粘度調整が容易である等の観点から、ビスフェノール骨格を有するエポキシ樹脂、ノボラック骨格を有するエポキシ樹脂、ナフタレン骨格を有するエポキシ樹脂、及び、ジシクロペンタジエン骨格を有するエポキシ樹脂からなる群より選択される少なくとも１種のエポキシ樹脂が好ましく、ビスフェノール骨格を有するエポキシ樹脂がより好ましく、ビスフェノールＦ型エポキシ樹脂が更に好ましい。 As the cationically polymerizable compound, from the viewpoint of easy viscosity adjustment, 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 Preferably, 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.
また、本発明の有機ＥＬ表示素子用封止剤は、アウトガスの発生を抑制する観点から、上記カチオン重合性化合物として、下記式（１）で表される化合物及び／又は下記式（２）で表される化合物を含有することが好ましい。 Moreover, 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 | occurrence | production of outgas. It is preferable to contain the represented compound.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
式（１）中、Ｒ１～Ｒ１８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。Ｘは、結合手、酸素原子、炭素数１～５のアルキレン基、オキシカルボニル基、炭素数２～５のアルキレンオキシカルボニル基、又は、第二級アミノ基である。 In the formula (1), 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.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
式（２）中、Ｒ１９～Ｒ２１は、直鎖状又は分岐鎖状の炭素数２～１０のアルキレン基であり、それぞれ同一であってもよいし、異なっていてもよい。Ｅ１～Ｅ３は、それぞれ独立して下記式（３－１）又は下記式（３－２）で表される有機基を表す。 In the formula (2), 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).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
式（３－１）中、Ｒ２２は、水素原子又はメチル基である。 In formula (3-1), R 22 represents a hydrogen atom or a methyl group.
なかでも、上記カチオン重合性化合物として、下記式（４－１）で表される化合物、下記式（４－２）で表される化合物、及び、下記式（４－３）で表される化合物からなる群より選択される少なくとも１種を含有することが好ましい。 Among them, as the cationically polymerizable compound, 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
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
上記式（１）で表される化合物のうち市販されているものとしては、例えば、セロキサイド８０００、セロキサイド２０２１Ｐ（いずれもダイセル社製）等が挙げられ、上記式（２）で表される化合物のうち市販されているものとしては、例えば、ＴＥＰＩＣ－ＶＬ（日産化学社製）等が挙げられる。 As what is marketed among the compounds represented by the above formula (1), for example, Celoxide 8000, Celoxide 2021P (both manufactured by Daicel Corporation) and the like can be mentioned, and the compounds represented by the above formula (2) Of these, commercially available products include, for example, TEPIC-VL (manufactured by Nissan Chemical Co., Ltd.).
上記ラジカル重合性化合物としては、（メタ）アクリル化合物が好適に用いられる。
上記（メタ）アクリル化合物としては、例えば、（メタ）アクリル酸とエポキシ化合物とを反応させることにより得られるエポキシ（メタ）アクリレート、（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られる（メタ）アクリル酸エステル化合物、イソシアネート化合物に水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレート等が挙げられる。なかでも、エポキシ（メタ）アクリレートが好ましい。
なお、本明細書において、上記「（メタ）アクリル」とは、アクリル又はメタクリルを示し、上記「（メタ）アクリレート」とは、アクリレート又はメタクリレートを示し、上記「エポキシ（メタ）アクリレート」とは、エポキシ樹脂中の全てのエポキシ基を（メタ）アクリル酸と反応させた化合物のことを表す。 As the radical polymerizable compound, a (meth) acryl compound is preferably used.
Examples of 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. Of these, epoxy (meth) acrylate is preferable.
In the present specification, the “(meth) acryl” indicates acryl or methacryl, the “(meth) acrylate” indicates acrylate or methacrylate, and the “epoxy (meth) acrylate” It represents a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid.
上記エポキシ（メタ）アクリレートのうち市販されているものとしては、例えば、ＥＢＥＣＲＹＬ８６０、ＥＢＥＣＲＹＬ３２００、ＥＢＥＣＲＹＬ３２０１、ＥＢＥＣＲＹＬ３４１２、ＥＢＥＣＲＹＬ３６００、ＥＢＥＣＲＹＬ３７００、ＥＢＥＣＲＹＬ３７０１、ＥＢＥＣＲＹＬ３７０２、ＥＢＥＣＲＹＬ３７０３、ＥＢＥＣＲＹＬ３８００、ＥＢＥＣＲＹＬ６０４０、ＥＢＥＣＲＹＬＲＤＸ６３１８２（いずれもダイセル・オルネクス社製）、ＥＡ－１０１０、ＥＡ－１０２０、ＥＡ－５３２３、ＥＡ－５５２０、ＥＡ－ＣＨＤ、ＥＭＡ－１０２０（いずれも新中村化学工業社製）、エポキシエステルＭ－６００Ａ、エポキシエステル４０ＥＭ、エポキシエステル７０ＰＡ、エポキシエステル２００ＰＡ、エポキシエステル８０ＭＦＡ、エポキシエステル３００２Ｍ、エポキシエステル３００２Ａ、エポキシエステル１６００Ａ、エポキシエステル３０００Ｍ、エポキシエステル３０００Ａ、エポキシエステル２００ＥＡ、エポキシエステル４００ＥＡ（いずれも共栄社化学社製）、デナコールアクリレートＤＡ－１４１、デナコールアクリレートＤＡ－３１４、デナコールアクリレートＤＡ－９１１（いずれもナガセケムテックス社製）等が挙げられる。 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, Denacol acrylate DA-314, Denacol acrylate DA-911 (all manufactured by Nagase ChemteX Corporation).
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、光重合開始剤や熱重合開始剤等が挙げられる。なかでも、光重合開始剤が好ましい。 The sealing agent for organic EL display elements of the present invention contains a polymerization initiator.
Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Of these, a photopolymerization initiator is preferable.
上記光重合開始剤としては、光照射によりプロトン酸又はルイス酸を発生する光カチオン重合開始剤や、光照射によりラジカルを発生する光ラジカル重合開始剤等が挙げられる。なかでも、光カチオン重合開始剤が好ましい。 Examples of the photopolymerization initiator 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.
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.
上記光カチオン重合開始剤のうちイオン性光酸発生型のものとしては、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）で構成される、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、又は、（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。 Among the above-mentioned photocationic polymerization initiators, 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.
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、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, bis (4- (di ( 4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, Bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di ( - (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide 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.
上記光カチオン重合開始剤のうち非イオン性光酸発生型のものとしては、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ナート等が挙げられる。 Among the above-mentioned photocationic polymerization initiators, 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.
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、ＤＴＳ－２００（みどり化学社製）、ＵＶＩ６９９０、ＵＶＩ６９７４（いずれもユニオンカーバイド社製）、ＳＰ－１５０、ＳＰ－１７０（いずれもＡＤＥＫＡ社製）、ＦＣ－５０８、ＦＣ－５１２（いずれも３Ｍ社製）、ＩＲＧＡＣＵＲＥ２９０（ＢＡＳＦ社製）、ＰＩ２０７４（ローディア社製）等が挙げられる。 Examples of commercially available photocationic polymerization initiators 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.
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、ベンジル、チオキサントン等が挙げられる。 Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone, and the like.
上記光ラジカル重合開始剤のうち市販されているものとしては、例えば、ＩＲＧＡＣＵＲＥ１８４、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ３７９、ＩＲＧＡＣＵＲＥ６５１、ＩＲＧＡＣＵＲＥ８１９、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ２９５９、ＩＲＧＡＣＵＲＥ　ＯＸＥ０１、ルシリンＴＰＯ（いずれもＢＡＳＦ社製）、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル（いずれも東京化成工業社製）等が挙げられる。 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.).
上記熱重合開始剤としては、加熱によりプロトン酸又はルイス酸を発生する熱カチオン重合開始剤や、加熱によりラジカルを発生する熱ラジカル重合開始剤等が挙げられる。 Examples of the thermal polymerization initiator 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.
上記熱カチオン重合開始剤としては、ＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－（ただし、Ｘは、少なくとも２つ以上のフッ素若しく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）を対アニオンとする、スルホニウム塩、ホスホニウム塩、第４級アンモニウム塩、ジアゾニウム塩、又は、ヨードニウム塩が好ましく、スルホニウム塩がより好ましい。 Examples of the thermal cationic polymerization initiator 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.
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四フッ化ホウ素、トリフェニルスルホニウム六フッ化アンチモン、トリフェニルスルホニウム六フッ化ヒ素、トリ（４－メトキシフェニル）スルホニウム六フッ化ヒ素、ジフェニル（４－フェニルチオフェニル）スルホニウム六フッ化ヒ素等が挙げられる。
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六フッ化アンチモン、テトラブチルホスホニウム六フッ化アンチモン等が挙げられる。
上記第４級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、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六フッ化アンチモン、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルアニリニウム四フッ化ホウ素、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルピリジニウム六フッ化アンチモン、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 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.
Examples of 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-dimethyl-N-benzylanilinium hexafluoride antimony, N, N-diethyl-N-benzylanilinium boron tetrafluoride, N, N-dimethyl-N-benzylpyridinium antimony hexafluoride, 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、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（いずれも三新化学工業社製）、ＣＸＣ－１６１２、ＣＸＣ－１７３８、ＣＸＣ－１８２１（いずれもＫｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製）等が挙げられる。 Commercially available 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.
上記熱ラジカル重合開始剤としては、過酸化物やアゾ化合物が挙げられ、市販されているものとしては、例えば、パーブチルＯ、パーヘキシルＯ、パーブチルＰＶ（いずれも日油社製）、Ｖ－３０、Ｖ－６５、Ｖ－５０１、Ｖ－６０１、ＶＰＥ－０２０１（いずれも和光純薬工業社製）等が挙げられる。 Examples of the thermal radical polymerization initiator include peroxides and azo compounds. Examples of 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.
上記重合開始剤の含有量は、上記硬化性樹脂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。上記重合開始剤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硬化性、保存安定性、及び、バリア性により優れるものとなる。上記重合開始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 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.
本発明の有機ＥＬ表示素子用封止剤は、熱硬化剤を含有してもよい。熱硬化剤としては、例えば、ヒドラジド化合物、イミダゾール誘導体、酸無水物、ジシアンジアミド、グアニジン誘導体、変性脂肪族ポリアミン、各種アミンとエポキシ樹脂との付加生成物等が挙げられる。
上記ヒドラジド化合物としては、例えば、１，３－ビス（ヒドラジノカルボノエチル）－５－イソプロピルヒダントイン、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、マロン酸ジヒドラジド等が挙げられる。
上記イミダゾール誘導体としては、例えば、１－シアノエチル－２－フェニルイミダゾール、Ｎ－（２－（２－メチル－１－イミダゾリル）エチル）尿素、２，４－ジアミノ－６－（２’－メチルイミダゾリル－（１’））－エチル－ｓ－トリアジン、Ｎ，Ｎ’－ビス（２－メチル－１－イミダゾリルエチル）尿素、Ｎ，Ｎ’－（２－メチル－１－イミダゾリルエチル）－アジポアミド、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール等が挙げられる。
上記酸無水物としては、例えば、テトラヒドロ無水フタル酸、エチレングリコールービス（アンヒドロトリメリテート）等が挙げられる。 The sealing agent for organic EL display elements of the present invention may contain a thermosetting agent. Examples of 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.
Examples of 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.
Examples of the imidazole derivatives 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.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydro trimellitate), and the like.
上記熱硬化剤のうち市販されているものとしては、例えば、ＳＤＨ（日本ファインケム社製）、ＡＤＨ（大塚化学社製）、アミキュアＶＤＨ、アミキュアＶＤＨ－Ｊ、アミキュアＵＤＨ（いずれも味の素ファインテクノ社製）等が挙げられる。 Examples of commercially available thermosetting agents 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.
上記熱硬化剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．５重量部、好ましい上限が３０重量部である。上記熱硬化剤の含有量が０．５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熱硬化性により優れるものとなる。上記熱硬化剤の含有量が３０重量部以下であることにより、得られる有機ＥＬ表示素子用封止剤が保存安定性及びバリア性により優れるものとなる。上記熱硬化剤の含有量のより好ましい下限は１重量部、より好ましい上限は１５重量部である。 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. When 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. When 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.
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、上記光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 photopolymerization initiator and further promoting the curing reaction of the sealant for organic EL display elements of the present invention.
上記増感剤としては、例えば、９，１０－ジブトキシアントラセン等のアントラセン系化合物や、２，４－ジエチルチオキサントン等のチオキサントン系化合物や、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。 Examples of the sensitizer 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. -One, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4-benzoyl-4'methyldiphenyl sulfide, and the like.
上記増感剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限は０．０５重量部、好ましい上限は３重量部である。上記増感剤の含有量が０．０５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 0.05 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the sensitizer is 0.05 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、安定剤を含有することが好ましい。上記安定剤を含有することにより、本発明の有機ＥＬ表示素子用封止剤は、より保存安定性に優れるものとなる。 It is preferable that 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.
上記安定剤としては、例えば、ベンジルアミン等のアミン系化合物やアミノフェノール型エポキシ樹脂等が挙げられる。 Examples of the stabilizer include amine compounds such as benzylamine and aminophenol type epoxy resins.
上記安定剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．００１重量部、好ましい上限が２重量部である。上記安定剤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優れた硬化性を維持したまま保存安定性により優れるものとなる。上記安定剤の含有量のより好ましい下限は０．００５重量部、より好ましい上限は１重量部である。 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. When 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.
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、上記硬化性樹脂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のブリードアウトを防止しつつ、得られる有機ＥＬ表示素子用封止剤の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 curable resin. When the content of the silane coupling agent is within this range, it is more excellent in the effect of improving the adhesiveness of the obtained sealing agent for organic EL display elements while preventing bleed-out of excess silane coupling agent. It becomes. 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、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 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、アクリル系、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－３００、ＢＹＫ－３０２、ＢＹＫ－３３１（いずれも、ビックケミー・ジャパン社製）、ＵＶＸ－２７２（楠本化成社製）、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, 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.
本発明の有機ＥＬ表示素子用封止剤は、本発明の目的を阻害しない範囲で、素子電極の耐久性を向上させるために、イオン交換樹脂を含有してもよい。 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.
上記イオン交換樹脂としては、陽イオン交換型、陰イオン交換型、両イオン交換型のいずれも使用することができるが、特に塩化物イオンを吸着することのできる陽イオン交換型又は両イオン交換型が好適である。 As the ion exchange resin, 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.
本発明の有機ＥＬ表示素子用封止剤は、アウトガスの発生をより抑制する観点から、溶剤を含有しないことが好ましい。本発明の有機ＥＬ表示素子用封止剤は、該溶剤を含有しなくても、塗布性に優れるものとすることができる。 It is preferable that the sealing agent for organic EL display elements of this invention does not contain a solvent from a viewpoint of suppressing generation | occurrence | production of outgas more. Even if the sealing agent for organic EL display elements of this invention does not contain this solvent, it can be made excellent in applicability | paintability.
また、本発明の有機ＥＬ表示素子用封止剤は、本発明の目的を阻害しない範囲で、必要に応じて、硬化遅延剤、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 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.
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、硬化性樹脂と、重合開始剤と、本発明にかかる吸水性フィラーと、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。 As a method for producing 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.
本発明の有機ＥＬ表示素子用封止剤は、Ｅ型粘度計を用いて、２５℃における粘度が１００～５００Ｐａ・ｓのペーストであることが好ましい。上記粘度がこの範囲であるペーストであることにより、本発明の有機ＥＬ表示素子用封止剤が塗布性と吸水性フィラーの分散性との両方により優れるものとなる。上記粘度のより好ましい下限は１５０Ｐａ・ｓ、より好ましい上限は４５０Ｐａ・ｓである。なお、上記粘度を調整するために溶剤を用いた場合、アウトガスの発生を抑制することが困難となる。
なお、上記粘度は、例えば、Ｅ型粘度計としてＶＩＳＣＯＭＥＴＥＲ　ＴＶ－２２（東機産業社製）を用い、ＣＰ１のコーンプレートにて、各粘度領域における最適なトルク数から適宜１～１００ｒｐｍの回転数を選択すること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 is preferably a paste having a viscosity of 100 to 500 Pa · s at 25 ° C. using an E-type viscometer. When 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. In addition, when 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.
本発明の有機ＥＬ表示素子用封止剤により形成される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。なかでも、本発明の有機ＥＬ表示素子用封止剤は、該積層体の周辺部の封止に好適に用いることができる。 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. Especially, 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.
本発明によれば、バリア性に優れ、かつ、パネル剥がれを抑制できる有機エレクトロルミネッセンス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 electroluminescent display elements which is excellent in barrier property and can suppress panel peeling can be provided.
（ａ）は、本発明にかかる吸水性フィラーＡの表面のＳＥＭ像であり、（ｂ）は、本発明にかかる吸水性フィラーＡの断面のＳＥＭ像である。(A) is a SEM image of the surface of the water-absorbing filler A according to the present invention, and (b) is a SEM image of a cross section of the water-absorbing filler A according to the present invention. （ａ）は、市販の吸水性フィラー（吉沢石灰工業社製、「生石灰Ｊ１Ｐ」）の表面のＳＥＭ像であり、（ｂ）は、市販の吸水性フィラー（吉沢石灰工業社製、「生石灰Ｊ１Ｐ」）の断面のＳＥＭ像である。(A) is a SEM image of the surface of a commercially available water-absorbing filler (Yoshizawa Lime Industry, “Quicklime J1P”), and (b) is a commercially available water-absorbing filler (Yoshizawa Lime Industry, “Quicklime J1P”). It is a SEM image of a cross section of “)”.
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１～６、比較例１）
表１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１～６、比較例１の有機ＥＬ表示素子用封止剤を作製した。
なお、表中における「本発明にかかる吸水性フィラーＡ」は、動的光散乱式粒子径測定装置を用いて測定した平均一次粒子径が３．５μｍ、ＪＩＳ　Ｚ８８０７に準じた方法により測定した比重が３．０ｇ／ｃｍ３、比表面積測定装置で窒素ガスを用いてＢＥＴ法により測定した平均比表面積が１１ｍ２／ｇ、吸水率が２５重量％の酸化カルシウムである。上記動的光散乱式粒子径測定装置としてはＥＬＳＺ－１０００Ｓ（大塚電子社製）を用い、上記比表面積測定装置としてはＡＳＡＰ－２０００（島津製作所社製）を用いた。
また、表中における「本発明にかかる吸水性フィラーＢ」は、吸水性フィラーＡと同様にして測定した、平均一次粒子径が１．０μｍ、比重が２．８ｇ／ｃｍ３、平均比表面積が１８ｍ２／ｇ、吸水率が３０重量％の酸化カルシウムである。
更に、表中における「生石灰Ｊ１Ｐ（吉沢石灰工業社製）」は、吸水性フィラーＡと同様にして測定した、平均一次粒子径が３．０μｍ、比重が３．４ｇ／ｃｍ３、平均比表面積が２．５ｍ２／ｇ、吸水率が３０重量％の酸化カルシウムである。
本発明にかかる吸水性フィラーＡの表面及び断面のＳＥＭ像を図１に示した。図１に示したように、本発明にかかる吸水性フィラーＡは、表面に凹凸形状を有し、内部に多数の空隙を有することが確認された。また、比較例で用いた市販の吸水性フィラー（吉沢石灰工業社製、「生石灰Ｊ１Ｐ」）の表面及び断面のＳＥＭ像を図２に示した。図２に示したように、比較例で用いた市販の吸水性フィラーは、表面も断面も平坦なものであることが確認された。 (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.
In the table, “the water-absorbing filler A according to the present invention” has an average primary particle size of 3.5 μm 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.) was used as the dynamic light scattering particle size measuring apparatus, and ASAP-2000 (manufactured by Shimadzu Corporation) was used as the specific surface area measuring apparatus.
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 μm, 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 μm, the specific gravity was 3.4 g / cm 3 , and the average specific surface area. There 2.5 m 2 / g, water absorption is calcium oxide 30 wt%.
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.
＜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 Table 1.
（１）粘度
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℃における粘度を測定した。 (1) Viscosity About each sealing agent for organic EL display elements obtained in Examples and Comparative Examples, the viscosity at 25 ° C. was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”). Was measured.
（２）バリア性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤について、以下のＣａ－ＴＥＳＴを行った。
まず、３０ｍｍ×３０ｍｍのガラス基板に２ｍｍ×２ｍｍの開口部を複数有するマスクを被せ、Ｃａを真空蒸着機により蒸着させた。蒸着の条件は、真空蒸着装置の蒸着器内を２×１０－３Ｐａまで減圧してＣａを５．０Å／ｓの蒸着速度で２０００Å成膜するものとした。Ｃａを蒸着したガラス基板を露点（－６０℃以上）に管理されたグローボックス内に移動させ、表面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塗布したガラス基板を貼り合わせた。この時、ガラス基板端面から２ｍｍ、４ｍｍ、６ｍｍの位置に蒸着したＣａが存在するように貼り合わせた。次いで、３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射し、更に、８０℃で３０分加熱することで封止剤を硬化させ、Ｃａ－ＴＥＳＴ基板を作製した。なお、実施例５で得られた有機ＥＬ表示素子用封止剤については、１００℃にて３０分加熱することにより硬化させ、Ｃａ－ＴＥＳＴ基板を作製した。
得られたＣａ－ＴＥＳＴ基板を、８５℃、８５％ＲＨの高温高湿条件に暴露し、時間毎の水分の浸入距離をＣａの消失から観測した結果、水分の浸入距離が６ｍｍに達するまでの時間が１０００時間以上であった場合を「○」、５００時間以上１０００時間未満であった場合を「△」、５００時間未満であった場合を「×」としてバリア性を評価した。 (2) Barrier property The following Ca-TEST was performed on each sealing agent for organic EL display elements obtained in the Examples and Comparative Examples.
First, a mask having a plurality of openings of 2 mm × 2 mm was put on a 30 mm × 30 mm glass substrate, and Ca was vapor-deposited by a vacuum vapor deposition machine. The conditions for the vapor deposition were that the inside of the vapor deposition unit of the vacuum vapor deposition apparatus was depressurized to 2 × 10 −3 Pa and a film of 2000 mm of Ca was formed at a vapor deposition rate of 5.0 kg / s. A glass substrate on which a glass substrate on which Ca is deposited is moved into a glow box controlled at a dew point (−60 ° C. or higher), and 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. Next, 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. Note that 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, “Δ” when the time was 500 hours or more and less than 1000 hours, and “X” when the time was less than 500 hours.
（３）パネルの接着状態
（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４５ｍｍ、幅４５ｍｍ、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、他の異なる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を、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。 (3) 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”).
Next, 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 (α-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 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, 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. 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.
（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１０ｓｃｃｍ及び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。 (Coating with inorganic material film A)
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.
In the 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 μm.
（樹脂保護膜の形成）
無機材料膜Ａで被覆された基板に、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外周に線幅が６ｍｍとなるよう塗布し、その内部に充填剤を入れた。その後高圧水銀灯を用いて波長３６５ｎｍの紫外線を照射量が３０００ｍＪ／ｃｍ２となるように照射し、更に８０℃で３０分加熱することで有機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。なお、実施例５で得られた有機ＥＬ表示素子用封止剤については、紫外線の照射に代えて１００℃にて３０分加熱することにより硬化させて樹脂保護膜を形成した。 (Formation of resin protective film)
Each organic EL display element sealant obtained in Examples and Comparative Examples was applied to the substrate coated with the inorganic material film A so that the line width was 6 mm on the outer periphery, and a filler was put in the inside. . Thereafter, ultraviolet rays having a wavelength of 365 nm are irradiated using a high pressure mercury lamp so that the irradiation amount is 3000 mJ / cm 2, and further heated at 80 ° C. for 30 minutes to cure the sealing agent for organic EL display elements to form a resin protective film. Formed. In addition, about the sealing agent for organic EL display elements obtained in Example 5, it hardened by heating at 100 degreeC for 30 minutes instead of ultraviolet irradiation, and formed the resin protective film.
（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、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Ｂの厚さは、約１μｍであった。 (Coating with inorganic material film B)
After forming the resin protective film, 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.
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 B had a thickness of about 1 μm.
（パネルの接着状態の観察）
得られた有機ＥＬ表示素子を、８５℃、８５％ＲＨの環境下に２０００時間暴露した後のパネルの接着状態を目視にて観察した。パネル剥がれがなかった場合を「○」、パネル剥がれが一部確認された場合を「△」、パネル剥がれが大部分から確認された場合を「×」としてパネルの接着状態を評価した。 (Observation of panel adhesion)
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, “Δ” when panel peeling was partially confirmed, and “X” when panel peeling was confirmed from the majority.
（４）有機ＥＬ表示素子の信頼性
上記「（３）パネルの接着状態」と同様にして得られた有機ＥＬ表示素子を、８５℃、８５％ＲＨの環境下に２０００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「○」、僅かに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表示素子の信頼性を評価した。 (4) Reliability of organic EL display element An organic EL display element obtained in the same manner as in “(3) Panel adhesion state” above was exposed to an environment of 85 ° C. and 85% RH for 2000 hours, and then 3V The light emission state (the presence or absence of dark spots and pixel periphery quenching) of the organic EL display element was visually observed. Organic light-emitting diode display with “○” when there is no dark spot or peripheral quenching, “△” when dark spot or peripheral quenching is observed slightly, and “×” when non-light emitting part is significantly enlarged The reliability of the device was evaluated.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
本発明によれば、バリア性に優れ、かつ、パネル剥がれを抑制できる有機エレクトロルミネッセンス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 electroluminescent display elements which is excellent in barrier property and can suppress panel peeling can be provided.

Claims (6)

  1. 硬化性樹脂と重合開始剤と吸水性フィラーとを含有し、
    前記吸水性フィラーは、平均一次粒子径が５μｍ以下であり、比重が３．３ｇ／ｃｍ３以下である
    ことを特徴とする有機エレクトロルミネッセンス表示素子用封止剤。     Containing a curable resin, a polymerization initiator and a water-absorbing filler,
    The water-absorbing filler has an average primary particle diameter of 5 μm or less and a specific gravity of 3.3 g / cm 3 or less, and is a sealing agent for organic electroluminescence display elements.
  2. 吸水性フィラーは、アルカリ土類金属の酸化物であることを特徴とする請求項１記載の有機エレクトロルミネッセンス表示素子用封止剤。 The encapsulant for organic electroluminescence display elements according to claim 1, wherein the water-absorbing filler is an oxide of an alkaline earth metal.
  3. 吸水性フィラーは、酸化カルシウムであることを特徴とする請求項２記載の有機エレクトロルミネッセンス表示素子用封止剤。 The sealing agent for organic electroluminescence display elements according to claim 2, wherein the water-absorbing filler is calcium oxide.
  4. 吸水性フィラーは、平均比表面積が５ｍ２／ｇ以上２０ｍ２／ｇ以下であることを特徴とする請求項１、２又は３記載の有機エレクトロルミネッセンス表示素子用封止剤。 Water-absorptive filler is an organic electroluminescent display encapsulant element according to claim 1, 2 or 3, wherein the average specific surface area is less than 5 m 2 / g or more 20 m 2 / g.
  5. 吸水性フィラーの含有量は、硬化性樹脂１００重量部に対して、５重量部以上６０重量部以下であることを特徴とする請求項１、２、３又は４記載の有機エレクトロルミネッセンス表示素子用封止剤。 5. The organic electroluminescence display element according to claim 1, wherein the content of the water-absorbing filler is 5 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the curable resin. Sealant.
  6. 重合開始剤は、光重合開始剤であることを特徴とする請求項１、２、３、４又は５記載の有機エレクトロルミネッセンス表示素子用封止剤。 6. The encapsulant for organic electroluminescence display elements according to claim 1, wherein the polymerization initiator is a photopolymerization initiator.
PCT/JP2017/032993 2016-09-16 2017-09-13 Sealing agent for organic electroluminescent display element WO2018052006A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020217040934A KR102497896B1 (en) 2016-09-16 2017-09-13 Sealing agent for organic electroluminescent display element
KR1020187022464A KR102340967B1 (en) 2016-09-16 2017-09-13 Encapsulant for organic electroluminescent display elements
JP2017550263A JP6933580B2 (en) 2016-09-16 2017-09-13 Encapsulant for organic electroluminescence display elements
CN201780018770.0A CN108781491B (en) 2016-09-16 2017-09-13 Sealing agent for organic electroluminescent display element

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016181692 2016-09-16
JP2016-181692 2016-09-16

Publications (1)

Publication Number Publication Date
WO2018052006A1 true WO2018052006A1 (en) 2018-03-22

Family

ID=61618811

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/032993 WO2018052006A1 (en) 2016-09-16 2017-09-13 Sealing agent for organic electroluminescent display element

Country Status (5)

Country Link
JP (1) JP6933580B2 (en)
KR (2) KR102497896B1 (en)
CN (1) CN108781491B (en)
TW (1) TW201818782A (en)
WO (1) WO2018052006A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111837457A (en) * 2018-04-20 2020-10-27 积水化学工业株式会社 Sealing agent for organic EL display element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015129288A (en) * 2007-04-17 2015-07-16 株式会社カネカ Polyhedron structure polysiloxane modification body and composition using the modification body
WO2015147600A1 (en) * 2014-03-27 2015-10-01 주식회사 엘지화학 Sealing film and organic electronic device including same
WO2015152053A1 (en) * 2014-03-31 2015-10-08 古河電気工業株式会社 Resin composition for organic electronic device element encapsulation, resin sheet for organic electronic device element encapsulation, organic electroluminescent element and image display device
JP2015181135A (en) * 2001-02-01 2015-10-15 株式会社半導体エネルギー研究所 light-emitting device
WO2016136715A1 (en) * 2015-02-24 2016-09-01 積水化学工業株式会社 Sealing agent for organic electroluminescence display element

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100685845B1 (en) 2005-10-21 2007-02-22 삼성에스디아이 주식회사 Organic eletroluminescence display device and method for fabricating of the same
JP5044326B2 (en) 2007-08-28 2012-10-10 パナソニック株式会社 Epoxy resin composition and resin sealing device
KR101220047B1 (en) * 2009-10-12 2013-01-08 금호석유화학 주식회사 Sealant composition for liquid crystal display device
CN110951410B (en) * 2010-11-02 2022-05-31 Lg化学株式会社 Adhesive film and method for encapsulating organic electronic device using the same
JP5252327B2 (en) * 2011-07-14 2013-07-31 宇部マテリアルズ株式会社 Moisture adsorbent for organic EL device and method for producing the same
EP2875070B1 (en) * 2012-07-19 2020-09-09 BASF Coatings GmbH Radiation curable composition for water scavenging layer, and method of manufacturing the same
KR20140026257A (en) * 2012-08-23 2014-03-05 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Display device
US9777207B2 (en) * 2013-01-29 2017-10-03 Halliburton Energy Services, Inc. Wellbore fluids comprising mineral particles and methods relating thereto
WO2015037612A1 (en) * 2013-09-10 2015-03-19 共同印刷株式会社 Absorbent laminate provided with absorbent film, electronic device containing same, and method for producing same
KR102084586B1 (en) * 2013-11-29 2020-03-04 엘지디스플레이 주식회사 Organic light emitting diode display device
CN106415875B (en) * 2014-03-27 2018-12-25 株式会社Lg化学 Encapsulating film and organic electronic device including the encapsulating film
JP2016038509A (en) * 2014-08-08 2016-03-22 日本化薬株式会社 Liquid crystal sealing agent and liquid crystal display cell having the same
CN106459374B (en) * 2015-02-13 2020-10-13 积水化学工业株式会社 Sealing agent for organic electroluminescent display element

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015181135A (en) * 2001-02-01 2015-10-15 株式会社半導体エネルギー研究所 light-emitting device
JP2015129288A (en) * 2007-04-17 2015-07-16 株式会社カネカ Polyhedron structure polysiloxane modification body and composition using the modification body
WO2015147600A1 (en) * 2014-03-27 2015-10-01 주식회사 엘지화학 Sealing film and organic electronic device including same
WO2015152053A1 (en) * 2014-03-31 2015-10-08 古河電気工業株式会社 Resin composition for organic electronic device element encapsulation, resin sheet for organic electronic device element encapsulation, organic electroluminescent element and image display device
WO2016136715A1 (en) * 2015-02-24 2016-09-01 積水化学工業株式会社 Sealing agent for organic electroluminescence display element

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111837457A (en) * 2018-04-20 2020-10-27 积水化学工业株式会社 Sealing agent for organic EL display element

Also Published As

Publication number Publication date
CN108781491A (en) 2018-11-09
JPWO2018052006A1 (en) 2019-06-27
CN108781491B (en) 2021-12-14
JP6933580B2 (en) 2021-09-08
KR102497896B1 (en) 2023-02-08
TW201818782A (en) 2018-05-16
KR102340967B1 (en) 2021-12-17
KR20190049617A (en) 2019-05-09
KR20210155820A (en) 2021-12-23

Similar Documents

Publication Publication Date Title
JP5966113B1 (en) Sealant for organic electroluminescence display element
JP7377295B2 (en) Encapsulant for organic electroluminescent display elements
JP2020024938A (en) Curable composition and sealant for organic electroluminescent display element
JP6062107B1 (en) Sealant for organic electroluminescence display element
JP6527390B2 (en) Sealant for organic electroluminescent display device
WO2018052006A1 (en) Sealing agent for organic electroluminescent display element
JP2019147963A (en) Sealing agent for organic electroluminescence display element
JPWO2020149359A1 (en) Encapsulant set for organic EL display element and organic EL display element
WO2021002379A1 (en) Sealing agent set for organic el display element and organic el display element
JP6966454B2 (en) In-plane encapsulant for organic EL display element and encapsulant set for organic EL display element
WO2021002375A1 (en) Sealant for organic el display element
JPWO2020149363A1 (en) Organic EL display element Encapsulating resin composition, cured product, and organic EL display element
WO2020149360A1 (en) Cured product and organic el display element
WO2021059420A1 (en) Photocurable resin composition for electronic devices

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2017550263

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20187022464

Country of ref document: KR

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: 17850907

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17850907

Country of ref document: EP

Kind code of ref document: A1