WO2015064410A1 - Sealing agent for organic el display elements - Google Patents

Sealing agent for organic el display elements Download PDF

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Publication number
WO2015064410A1
WO2015064410A1 PCT/JP2014/077821 JP2014077821W WO2015064410A1 WO 2015064410 A1 WO2015064410 A1 WO 2015064410A1 JP 2014077821 W JP2014077821 W JP 2014077821W WO 2015064410 A1 WO2015064410 A1 WO 2015064410A1
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Prior art keywords
organic
display elements
sealing agent
compound represented
formula
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PCT/JP2014/077821
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French (fr)
Japanese (ja)
Inventor
祐美子 寺口
康雄 渡邊
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2014556281A priority Critical patent/JP5703429B1/en
Priority to KR1020157026903A priority patent/KR102226349B1/en
Priority to CN201480034096.1A priority patent/CN105308092B/en
Publication of WO2015064410A1 publication Critical patent/WO2015064410A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/06—Triglycidylisocyanurates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to a sealant for organic EL display elements that can suppress the generation of outgas and is excellent in applicability.
  • organic electroluminescence (organic EL) display elements and organic thin film solar cell elements have been advanced.
  • the organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and thus has excellent productivity.
  • the organic EL display element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. When electrons are injected from one electrode into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-light emission. Compared with a liquid crystal display element or the like that requires a backlight, the visibility is better, the thickness can be reduced, and direct current low voltage driving is possible.
  • an organic EL display element has a problem that when the organic light emitting material layer and the electrode are exposed to the outside air, the light emission characteristics thereof are rapidly deteriorated and the life is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display element, in the organic EL display element, a sealing technique for shielding the organic light emitting material layer and the electrode from moisture and oxygen in the atmosphere is indispensable. Yes.
  • Patent Document 1 discloses a method of sealing a top emission organic EL display element by filling a curable adhesive between organic EL display element substrates and irradiating light.
  • a display element such as an organic EL display element is sealed using a curable adhesive in this way, outgas is generated during light irradiation or heating and fills the element, accelerating deterioration of the element. There was a problem that sometimes.
  • An object of this invention is to provide the sealing agent for organic EL display elements which can suppress generation
  • the present invention is an organic EL display element sealing agent containing a cationic curable resin and a cationic polymerization initiator, wherein the cationic curable resin has an epoxy group or an oxetanyl group, and an epoxy group.
  • an organic EL display element sealing agent that does not have an ether bond and an ester bond other than those contained in the oxetanyl group, and was measured using an E-type viscometer at 25 ° C. and 1 to 100 rpm.
  • This is a sealing agent for organic EL display elements having an overall viscosity of 80 to 5000 mPa ⁇ s.
  • the present invention is described in detail below.
  • the present inventors considered that the cause of outgas generation when a curable adhesive is used for sealing an organic EL display element is an ether bond or an ester bond contained in the curable resin used. That is, it was considered that the outgas was generated by the decomposition of the ether bond or the ester bond contained in the curable resin with an acid derived from an initiator or the like. For this reason, the use of a curable resin that does not contain an ether bond or an ester bond that causes outgassing was studied. Depending on the type of curable resin to be used, the obtained sealing agent for organic EL display elements was applied. It may become inferior.
  • the present inventors have specified a cationic curable resin having an epoxy group or an oxetanyl group as the curable resin and not having an ether bond and an ester bond other than those contained in the epoxy group or oxetanyl group. As a result, it was found that outgassing can be suppressed and a sealing agent for organic EL display elements having excellent coating properties can be obtained, and the present invention has been completed.
  • the sealing agent for organic EL display elements of the present invention contains a cationic curable resin.
  • the cationic curable resin has an epoxy group or an oxetanyl group and does not have an ether bond and an ester bond other than those contained in the epoxy group or the oxetanyl group (hereinafter referred to as “cationic curing according to the present invention”). Also referred to as “resin”.
  • the cation curable resin preferably contains a compound represented by the following formula (1) and / or a compound represented by the following formula (2), since generation of outgas can be effectively suppressed. From the viewpoint of curability and curing, it is more preferable to contain a compound represented by the following 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.
  • 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.
  • the said cationic curable resin shows favorable cationic curability, it is preferable to contain the compound represented by following formula (4) as a compound represented by the said Formula (1).
  • the cationic curable resin contains a compound represented by the following formula (5) as a compound represented by the above formula (2) because it exhibits good cationic curability and the cured product exhibits a high glass transition temperature. It is preferable to do.
  • the cationic curable resin can easily adjust the curing retardation and viscosity of the obtained sealing agent for organic EL display elements, it is represented by the compound represented by the above formula (1) and the above formula (2). It is preferred to contain both compounds. Further, by containing the compound represented by the above formula (2) in addition to the compound represented by the above formula (1), it is possible to suppress the volatilization of the raw material until the curing reaction occurs, and to obtain the organic Application shape stability of the sealing agent for EL display elements is improved.
  • the cationic curable resin contains both the compound represented by the formula (1) and the compound represented by the formula (2), it is represented by the compound represented by the formula (1) and the formula (2).
  • cationic curable resin examples include dicyclopentadiene diepoxide and 1,2,5,6-diepoxycyclooctane.
  • the sealing agent for organic EL display elements of the present invention increases the dispersibility of the filler described later and moderately adjusts the viscosity of the resulting sealing agent for organic EL display elements within a range that does not impair the object of the present invention.
  • other cationic curable resins having an ether bond or an ester bond other than those contained in the epoxy group or oxetanyl group may be contained.
  • the other cationic curable resin is at least one selected from the group consisting of 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.
  • a kind of epoxy resin is preferable, an epoxy resin having a bisphenol skeleton is more preferable, and a bisphenol F-type epoxy resin is more preferable.
  • the content of the cation curable resin according to the present invention is preferably 10 parts by weight and preferably 80 parts by weight with respect to 100 parts by weight of the whole cation curable resin. It is.
  • the content of the cationic curable resin according to the present invention is less than 10 parts by weight or more than 80 parts by weight, the obtained sealing agent for organic EL display elements may be inferior in applicability.
  • the more preferable lower limit of the content of the cationic curable resin according to the present invention is 20 parts by weight, and the more preferable upper limit is 70 parts by weight.
  • the sealing agent for organic EL display elements of the present invention contains a cationic polymerization initiator.
  • the cationic polymerization initiator include a photocationic polymerization initiator that generates a protonic acid or a Lewis acid by light irradiation, and a thermal cationic polymerization initiator that generates a protonic acid or a Lewis acid by heating. These are not particularly limited as long as they are ionic acid generating types or nonionic acid generating types.
  • 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.
  • Examples of the ionic photoacid-generating photocationic polymerization initiator include those having a cation moiety of aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadien-1-yl). ) ((1-methylethyl) benzene) -Fe cation, and the anion portion is BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is at least two or more fluorine atoms) Or an onium salt composed of a phenyl group substituted with a trifluoromethyl group).
  • aromatic sulfonium salt examples include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetraflu
  • aromatic iodonium salt examples include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethy
  • aromatic diazonium salt examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
  • aromatic ammonium salt examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl)
  • Examples include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
  • Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene.
  • nonionic photoacid-generating photocationic polymerization initiator examples include nitrobenzyl ester, sulfonic acid derivative, phosphoric ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate and the like.
  • 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), IRGACURE 261, IRGACURE 290 (all from BASF Japan), PI 2074 (from Rhodia), and the like.
  • thermal cationic polymerization initiator examples include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (wherein X is substituted with at least two fluorine or trifluoromethyl groups.
  • a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, an iodonium salt, and the like are preferred.
  • 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 hexafluorohexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) ) Borate, methylphenyldibenzylammonium, methylphenyldibenzylammonium hexaf Oroantimonate hexafluorophosphate, methylphenyldibenzylammonium trakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) Borate
  • thermal cationic polymerization initiators examples include, for example, Adeka Opton CP-66, Adeka Opton CP-77 (both manufactured by ADEKA), and thermal cations having not only thermal activity but also photoactivity.
  • Polymerization initiators such as Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-100, Sun-Aid SI-110, Sun-Aid SI-180 (all manufactured by Sanshin Chemical Industry Co., Ltd.), CXC-1612, CXC-1738, CXC -1821 (all manufactured by King Industries).
  • the content of the cationic polymerization initiator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic curable resin. If the content of the cationic polymerization initiator is less than 0.1 parts by weight, the cationic polymerization may not proceed sufficiently, or the curing reaction may become too slow. When the content of the cationic polymerization initiator exceeds 10 parts by weight, the curing reaction of the resulting organic EL display element sealant becomes too fast, resulting in a decrease in workability or the resulting organic EL display element seal. The cured product of the stopper may become uneven.
  • the minimum with more preferable content of the said cationic 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 sensitizer.
  • the sensitizer has a role of further improving the polymerization initiation efficiency of the cationic polymerization initiator and further promoting the curing reaction of the sealant for organic EL display elements of the present invention.
  • sensitizer examples include thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o- Examples include methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4-benzoyl-4′methyldiphenyl sulfide, and the like.
  • thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o- Examples include methyl 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 cationic curable resin.
  • the sensitizing effect may not be sufficiently obtained.
  • the content of the sensitizer exceeds 3 parts by weight, absorption may be excessively increased and light may not be transmitted to the deep part.
  • the minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
  • the sealing agent for organic EL display elements of the present invention preferably contains a filler for the purpose of improving the moisture resistance of the cured product.
  • a filler for the purpose of improving the moisture resistance of the cured product.
  • the compound represented by the above formula (1) having a low viscosity is used as the cationic curable resin according to the present invention, a large amount of filler can be blended without deteriorating the coating property.
  • the filler examples include talc, asbestos, silica, mica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, and magnesium hydroxide.
  • Inorganic fillers such as aluminum hydroxide, silicon nitride, barium sulfate, gypsum, calcium silicate, glass beads, sericite activated clay, bentonite, aluminum nitride, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, etc.
  • the preferred lower limit of the content of the filler is 10 parts by weight and the preferred upper limit is 80 parts by weight with respect to 100 parts by weight of the cationic curable resin. If the content of the filler is less than 10 parts by weight, the effect of improving moisture resistance may not be sufficiently exhibited. When content of the said filler exceeds 80 weight part, the viscosity of the sealing agent for organic EL display elements obtained will become high too much, and applicability
  • the minimum with more preferable content of the said filler is 15 weight part, and a more preferable upper limit is 70 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 cation curable resin.
  • the content of the silane coupling agent is less than 0.1 parts by weight, the effect of improving the adhesiveness of the obtained sealing agent for organic EL display elements may not be sufficiently exhibited.
  • content of the said silane coupling agent exceeds 10 weight part, an excess silane coupling agent may bleed out.
  • the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
  • the sealing agent for organic EL display elements of the present invention may further contain a thermosetting agent as long as the object of the present invention is not impaired. By containing the said thermosetting agent, thermosetting property can be provided to the sealing agent for organic EL display elements of this invention.
  • thermosetting agent is not particularly limited, and examples thereof include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like.
  • hydrazide compound include 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin] and the like.
  • imidazole derivative 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. These thermosetting agents may be used alone or in combination of two or more.
  • 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 cationic curable resin.
  • the content of the thermosetting agent is less than 0.5 parts by weight, sufficient thermosetting property may not be imparted to the obtained sealing agent for organic EL display elements.
  • the content of the thermosetting agent exceeds 30 parts by weight, the storage stability of the obtained sealant for organic EL display elements becomes insufficient, or the cured product of the obtained sealant for organic EL display elements. Moisture resistance may deteriorate.
  • 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 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.
  • surfactant and the leveling agent examples include silicon-based, acrylic-based, and fluorine-based ones.
  • examples of commercially available surfactants and leveling agents include BYK-345 (manufactured by BYK Japan), BYK-340 (manufactured by BYK Japan), Surflon S-611 (AGC Seimi Chemical). Etc.).
  • the encapsulant for organic EL display elements of the present invention reacts with the acid generated in the encapsulant for organic EL display elements in order to improve the durability of the element electrode within a range not impairing the object of the present invention.
  • a compound or an ion exchange resin may be contained.
  • Examples of the compound that reacts with the generated acid include substances that neutralize the acid, for example, alkali metal carbonates or bicarbonates, or alkaline earth metal carbonates or bicarbonates.
  • alkali metal carbonates or bicarbonates or alkaline earth metal carbonates or bicarbonates.
  • calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like are used.
  • 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 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.
  • Examples of the method for producing the sealing agent for organic EL display elements of the present invention include a cation curable resin using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll. And a method of mixing a cationic polymerization initiator and an additive to be added as necessary.
  • the sealant for organic EL display elements of the present invention has an overall viscosity lower limit of 80 mPa ⁇ s and an upper limit of 5000 mPa ⁇ s measured using an E-type viscometer at 25 ° C. and 1 to 100 rpm.
  • the viscosity is less than 80 mPa ⁇ s
  • the obtained sealing agent for organic EL display elements is inferior in applicability and shape stability after application, composition unevenness occurs, and the cured product becomes transparent. It becomes inferior.
  • the sealing agent for organic EL display elements obtained will be inferior to applicability
  • the preferable lower limit of the viscosity is 150 mPa ⁇ s
  • the preferable upper limit is 3000 mPa ⁇ s
  • the more preferable lower limit is 200 mPa ⁇ s
  • the more preferable upper limit is 1000 mPa ⁇ s.
  • the viscosity can be measured, for example, with a CP1 type cone plate using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E type viscometer.
  • the viscosity when measuring using an E-type viscometer, when the viscosity is 1000 mPa ⁇ s or more and less than 5000 mPa ⁇ s, it is measured under the condition of 1 rpm, and when the viscosity is 500 mPa ⁇ s or more and less than 1000 mPa ⁇ s, it is 5 rpm. When the viscosity is 200 mPa ⁇ s or more and less than 500 mPa ⁇ s, the measurement is performed under the condition of 10 rpm.
  • the measurement is performed under the condition of 20 rpm, and the viscosity is 50 mPa ⁇ s. -When it becomes less than s, it is preferable to measure on the conditions of 100 rpm.
  • Example 1 As the cationic curable resin, 50 parts by weight of a compound represented by the above formula (4) (manufactured by Daicel, “Celoxide 8000”) and a compound represented by the above formula (5) (manufactured by Nissan Chemical Co., Ltd., “TEPIC-VL”). ”) 50 parts by weight and 1 part by weight of an aromatic sulfonium salt (manufactured by Midori Chemical Co.,“ DTS-200 ”) as a photocationic polymerization initiator are mixed and heated to 80 ° C., and then stirred and mixed (Sinky Corporation). Manufactured by “AR-250”) and uniformly mixed at a stirring speed of 3000 rpm to prepare an organic EL display element sealing agent.
  • a compound represented by the above formula (4) manufactured by Daicel, “Celoxide 8000”
  • a compound represented by the above formula (5) manufactured by Nissan Chemical Co., Ltd., “TEPIC-VL”.
  • Examples 2 to 7, Comparative Examples 1 to 6 Each material described in Table 1 was stirred and mixed in the same manner as in Example 1 in accordance with the blending ratio described in Table 1 to prepare an organic EL display element sealant.
  • the organic EL display element sealants obtained in Examples 4 to 6 and Comparative Examples 2 and 5 were cured by heating at 100 ° C. for 30 minutes without irradiation with ultraviolet rays.
  • the change in weight from the application of the sealant to the occurrence of the curing reaction was confirmed using a thermogravimetric apparatus (TA-INSTRUMENTS, “TGA”).
  • the organic EL display element sealants obtained in Examples 4 to 6 and Comparative Examples 2 and 5 were cured by heating at 100 ° C. for 30 minutes without irradiation with ultraviolet rays.
  • the outgassing prevention property was evaluated as “ ⁇ ” when the vaporized component amount was less than 20 ppm, “ ⁇ ” when it was 20 ppm or more and less than 100 ppm, and “X” when it was 100 ppm or more.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Epoxy Resins (AREA)
  • Sealing Material Composition (AREA)

Abstract

The purpose of the present invention is to provide a sealing agent for organic EL display elements, which can prevent the generation of an out gas and has excellent coatability. The present invention is a sealing agent for organic EL display elements, which comprises a cation-curable resin and a cation polymerization initiator, wherein the cation-curable resin has an epoxy group or an oxetanyl group, does not contain an ether bond other than an ether bond contained in the epoxy group or the oxetanyl group or an ester bond, and has a viscosity of 80 to 5000 mPa·s as a whole as measured using an E-type viscometer under the conditions of 25ºC and 1 to 100 rpm.

Description

有機ＥＬ表示素子用封止剤Sealant for organic EL display element
本発明は、アウトガスの発生を抑制することができ、かつ、塗布性に優れる有機ＥＬ表示素子用封止剤に関する。 The present invention relates to a sealant for organic EL display elements that can suppress the generation of outgas and is excellent in applicability.
近年、有機エレクトロルミネッセンス（有機ＥＬ）表示素子や有機薄膜太陽電池素子等の有機薄膜素子を用いた有機光デバイスの研究が進められている。有機薄膜素子は真空蒸着や溶液塗布等により簡便に作製できるため、生産性にも優れる。 In recent years, research on organic optical devices using organic thin film elements such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements has been advanced. The organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and thus has excellent productivity.
有機ＥＬ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薄膜構造体を有する。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自己発光を行う。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、より薄型化が可能であり、かつ、直流低電圧駆動が可能であるという利点を有する。 The organic EL display element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. When electrons are injected from one electrode into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-light emission. Compared with a liquid crystal display element or the like that requires a backlight, the visibility is better, the thickness can be reduced, and direct current low voltage driving is possible.
ところが、このような有機ＥＬ表示素子は、有機発光材料層や電極が外気に曝されるとその発光特性が急激に劣化し寿命が短くなるという問題があった。従って、有機ＥＬ表示素子の安定性及び耐久性を高めることを目的として、有機ＥＬ表示素子においては、有機発光材料層や電極を大気中の水分や酸素から遮断する封止技術が不可欠となっている。 However, such an organic EL display element has a problem that when the organic light emitting material layer and the electrode are exposed to the outside air, the light emission characteristics thereof are rapidly deteriorated and the life is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display element, in the organic EL display element, a sealing technique for shielding the organic light emitting material layer and the electrode from moisture and oxygen in the atmosphere is indispensable. Yes.
特許文献１には、上面発光型有機ＥＬ表示素子において、有機ＥＬ表示素子基板の間に硬化性接着剤を満たし、光を照射して封止する方法が開示されている。しかしながら、このように硬化性接着剤を用いて有機ＥＬ表示素子等の表示素子を封止した場合には、光照射時や加熱時にアウトガスが発生して素子内に充満し、素子の劣化が促進することがあるという問題があった。 Patent Document 1 discloses a method of sealing a top emission organic EL display element by filling a curable adhesive between organic EL display element substrates and irradiating light. However, when a display element such as an organic EL display element is sealed using a curable adhesive in this way, outgas is generated during light irradiation or heating and fills the element, accelerating deterioration of the element. There was a problem that sometimes.
特開２００１－３５７９７３号公報JP 2001-357773 A
本発明は、アウトガスの発生を抑制することができ、かつ、塗布性に優れる有機ＥＬ表示素子用封止剤を提供することを目的とする。 An object of this invention is to provide the sealing agent for organic EL display elements which can suppress generation | occurrence | production of outgas and is excellent in applicability | paintability.
本発明は、カチオン硬化性樹脂と、カチオン重合開始剤とを含有する有機ＥＬ表示素子用封止剤であって、上記カチオン硬化性樹脂は、エポキシ基又はオキセタニル基を有し、かつ、エポキシ基又はオキセタニル基に含まれる以外のエーテル結合、及び、エステル結合を有さないものであり、Ｅ型粘度計を用いて、２５℃、１～１００ｒｐｍの条件で測定した有機ＥＬ表示素子用封止剤全体の粘度が８０～５０００ｍＰａ・ｓである有機ＥＬ表示素子用封止剤である。
以下に本発明を詳述する。 The present invention is an organic EL display element sealing agent containing a cationic curable resin and a cationic polymerization initiator, wherein the cationic curable resin has an epoxy group or an oxetanyl group, and an epoxy group. Or an organic EL display element sealing agent that does not have an ether bond and an ester bond other than those contained in the oxetanyl group, and was measured using an E-type viscometer at 25 ° C. and 1 to 100 rpm. This is a sealing agent for organic EL display elements having an overall viscosity of 80 to 5000 mPa · s.
The present invention is described in detail below.
本発明者らは、有機ＥＬ表示素子の封止に硬化性接着剤を用いた場合にアウトガスが発生する原因が、用いられる硬化性樹脂中に含まれるエーテル結合やエステル結合にあると考えた。即ち、硬化性樹脂中に含まれるエーテル結合やエステル結合が、開始剤等に由来する酸によって分解することにより、アウトガスが発生していると考えた。そのため、このようなアウトガス発生の原因となるエーテル結合やエステル結合を含まない硬化性樹脂を用いることを検討したが、用いる硬化性樹脂の種類によっては得られる有機ＥＬ表示素子用封止剤が塗布性に劣るものとなることがあった。
そこで本発明者らは、硬化性樹脂として、エポキシ基又はオキセタニル基を有し、かつ、エポキシ基又はオキセタニル基に含まれる以外のエーテル結合、及び、エステル結合を有さない特定のカチオン硬化性樹脂を用いることにより、アウトガスの発生を抑制することができ、かつ、塗布性に優れる有機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 present inventors considered that the cause of outgas generation when a curable adhesive is used for sealing an organic EL display element is an ether bond or an ester bond contained in the curable resin used. That is, it was considered that the outgas was generated by the decomposition of the ether bond or the ester bond contained in the curable resin with an acid derived from an initiator or the like. For this reason, the use of a curable resin that does not contain an ether bond or an ester bond that causes outgassing was studied. Depending on the type of curable resin to be used, the obtained sealing agent for organic EL display elements was applied. It may become inferior.
Therefore, the present inventors have specified a cationic curable resin having an epoxy group or an oxetanyl group as the curable resin and not having an ether bond and an ester bond other than those contained in the epoxy group or oxetanyl group. As a result, it was found that outgassing can be suppressed and a sealing agent for organic EL display elements having excellent coating properties can be obtained, and the present invention has been completed.
本発明の有機ＥＬ表示素子用封止剤は、カチオン硬化性樹脂を含有する。
上記カチオン硬化性樹脂は、エポキシ基又はオキセタニル基を有し、かつ、エポキシ基又はオキセタニル基に含まれる以外のエーテル結合、及び、エステル結合を有さないもの（以下、「本発明にかかるカチオン硬化性樹脂」ともいう）である。 The sealing agent for organic EL display elements of the present invention contains a cationic curable resin.
The cationic curable resin has an epoxy group or an oxetanyl group and does not have an ether bond and an ester bond other than those contained in the epoxy group or the oxetanyl group (hereinafter referred to as “cationic curing according to the present invention”). Also referred to as “resin”.
上記カチオン硬化性樹脂は、アウトガスの発生を効果的に抑制できることから、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く、耐湿性や硬化性の観点から、下記式（１）で表される化合物を含有することがより好ましい。 The cation curable resin preferably contains a compound represented by the following formula (1) and / or a compound represented by the following formula (2), since generation of outgas can be effectively suppressed. From the viewpoint of curability and curing, it is more preferable to contain a compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
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。 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.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
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-C000008
Figure JPOXMLDOC01-appb-C000008
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.
上記カチオン硬化性樹脂は、良好なカチオン硬化性を示すことから、上記式（１）で表される化合物として下記式（４）で表される化合物を含有することが好ましい。 Since the said cationic curable resin shows favorable cationic curability, it is preferable to contain the compound represented by following formula (4) as a compound represented by the said Formula (1).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
上記カチオン硬化性樹脂は、良好なカチオン硬化性を示し、硬化物が高いガラス転移温度を示すことから、上記式（２）で表される化合物として下記式（５）で表される化合物を含有することが好ましい。 The cationic curable resin contains a compound represented by the following formula (5) as a compound represented by the above formula (2) because it exhibits good cationic curability and the cured product exhibits a high glass transition temperature. It is preferable to do.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
上記カチオン硬化性樹脂は、得られる有機ＥＬ表示素子用封止剤の硬化遅延性や粘度を容易に調整できることから、上記式（１）で表される化合物及び上記式（２）で表される化合物の両方を含有することが好ましい。また、上記式（１）で表される化合物に加えて上記式（２）で表される化合物を含有することにより、硬化反応が起こるまでの原料の揮発を抑制することができ、得られる有機ＥＬ表示素子用封止剤の塗布形状安定性が向上する。 Since the cationic curable resin can easily adjust the curing retardation and viscosity of the obtained sealing agent for organic EL display elements, it is represented by the compound represented by the above formula (1) and the above formula (2). It is preferred to contain both compounds. Further, by containing the compound represented by the above formula (2) in addition to the compound represented by the above formula (1), it is possible to suppress the volatilization of the raw material until the curing reaction occurs, and to obtain the organic Application shape stability of the sealing agent for EL display elements is improved.
上記カチオン硬化性樹脂が式（１）で表される化合物及び式（２）で表される化合物の両方を含有する場合、式（１）で表される化合物と式（２）で表される化合物との含有割合は、硬化遅延性及び塗布性の観点から、重量比で、式（１）で表される化合物：式（２）で表される化合物＝１：９９～９９：１であることが好ましく、式（１）で表される化合物：式（２）で表される化合物＝１０：９０～９０：１０であることがより好ましい。 When the cationic curable resin contains both the compound represented by the formula (1) and the compound represented by the formula (2), it is represented by the compound represented by the formula (1) and the formula (2). The content ratio with the compound is, by weight ratio, the compound represented by the formula (1): the compound represented by the formula (2) = 1: 99 to 99: 1, from the viewpoint of curing retardation and coating properties. It is preferable that the compound represented by the formula (1): the compound represented by the formula (2) = 10: 90 to 90:10.
本発明にかかるカチオン硬化性樹脂のうち、その他のものとしては、例えば、ジシクロペンタジエンジエポキシド、１，２，５，６－ジエポキシシクロオクタン等が挙げられる。 Other examples of the cationic curable resin according to the present invention include dicyclopentadiene diepoxide and 1,2,5,6-diepoxycyclooctane.
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、後述する充填剤の分散性を高めることや得られる有機ＥＬ表示素子用封止剤の粘度を適度に調整すること等を目的として、本発明にかかるカチオン硬化性樹脂に加えて、エポキシ基又はオキセタニル基に含まれる以外のエーテル結合やエステル結合を有するその他のカチオン硬化性樹脂を含有してもよい。
上記その他のカチオン硬化性樹脂としては、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。 The sealing agent for organic EL display elements of the present invention increases the dispersibility of the filler described later and moderately adjusts the viscosity of the resulting sealing agent for organic EL display elements within a range that does not impair the object of the present invention. For the purpose of, etc., in addition to the cationic curable resin according to the present invention, other cationic curable resins having an ether bond or an ester bond other than those contained in the epoxy group or oxetanyl group may be contained.
The other cationic curable resin is at least one selected from the group consisting of 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. A kind of epoxy resin is preferable, an epoxy resin having a bisphenol skeleton is more preferable, and a bisphenol F-type epoxy resin is more preferable.
上記その他のカチオン硬化性樹脂を含有する場合、本発明にかかるカチオン硬化性樹脂の含有量は、カチオン硬化性樹脂全体１００重量部に対して、好ましい下限が１０重量部、好ましい上限が８０重量部である。本発明にかかるカチオン硬化性樹脂の含有量が１０重量部未満又は８０重量部を超えると、得られる有機ＥＬ表示素子用封止剤が塗布性に劣るものとなることがある。本発明にかかるカチオン硬化性樹脂の含有量のより好ましい下限は２０重量部、より好ましい上限は７０重量部である。 When the other cation curable resin is contained, the content of the cation curable resin according to the present invention is preferably 10 parts by weight and preferably 80 parts by weight with respect to 100 parts by weight of the whole cation curable resin. It is. When the content of the cationic curable resin according to the present invention is less than 10 parts by weight or more than 80 parts by weight, the obtained sealing agent for organic EL display elements may be inferior in applicability. The more preferable lower limit of the content of the cationic curable resin according to the present invention is 20 parts by weight, and the more preferable upper limit is 70 parts by weight.
本発明の有機ＥＬ表示素子用封止剤は、カチオン重合開始剤を含有する。
上記カチオン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、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が挙げられる。これらであれば特に限定されず、イオン性酸発生型であってもよいし、非イオン性酸発生型であってもよい。 The sealing agent for organic EL display elements of the present invention contains a cationic polymerization initiator.
Examples of the cationic polymerization initiator include a photocationic polymerization initiator that generates a protonic acid or a Lewis acid by light irradiation, and a thermal cationic polymerization initiator that generates a protonic acid or a Lewis acid by heating. These are not particularly limited as long as they are ionic acid generating types or nonionic acid generating types.
上記光カチオン重合開始剤は、光照射によりプロトン酸又はルイス酸を発生するものであれば特に限定されず、イオン性光酸発生型であってもよいし、非イオン性光酸発生型であってもよい。 The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.
上記イオン性光酸発生型の光カチオン重合開始剤としては、例えば、カチオン部分が芳香族スルホニウム、芳香族ヨードニウム、芳香族ジアゾニウム、芳香族アンモニウム、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カチオンであり、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）で構成されるオニウム塩等が挙げられる。 Examples of the ionic photoacid-generating photocationic polymerization initiator include those having a cation moiety of aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadien-1-yl). ) ((1-methylethyl) benzene) -Fe cation, and the anion portion is BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − (where X is at least two or more fluorine atoms) Or an onium salt composed of a phenyl group substituted with a trifluoromethyl group).
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.
上記非イオン性光酸発生型の光カチオン重合開始剤としては、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ－ヒドロキシイミドスホナート等が挙げられる。 Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate and the like.
上記光カチオン重合開始剤のうち市販されているものとしては、例えば、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）、ＩＲＧＡＣＵＲＥ　２６１、ＩＲＧＡＣＵＲＥ　２９０（いずれもＢＡＳＦ　Ｊａｐａｎ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), IRGACURE 261, IRGACURE 290 (all from BASF Japan), PI 2074 (from Rhodia), and the like.
上記熱カチオン重合開始剤としては、例えば、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）等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、ヨードニウム塩等が挙げられる。なかでも、スルホニウム塩が好ましい。 Examples of the thermal cationic polymerization initiator include BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − (wherein X is substituted with at least two fluorine or trifluoromethyl groups. And a sulfonium salt, a phosphonium salt, a quaternary ammonium salt, a diazonium salt, an iodonium salt, and the like. Of these, sulfonium salts are preferred.
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 hexafluorohexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) ) Borate, methylphenyldibenzylammonium, methylphenyldibenzylammonium hexaf Oroantimonate hexafluorophosphate, methylphenyldibenzylammonium trakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) Borate, antimony N, N-dimethyl-N-benzylanilinium hexafluoride, N, N-diethyl-N-benzylanilinium tetrafluoride, antimony N, N-dimethyl-N-benzylpyridinium 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、アデカオプトンＣＰ－６６、アデカオプトンＣＰ－７７（いずれもＡＤＥＫＡ社製）や、熱活性だけでなく光活性も有している熱カチオン重合開始剤である、サンエイドＳＩ－６０、サンエイドＳＩ－８０、サンエイドＳＩ－１００、サンエイドＳＩ－１１０、サンエイドＳＩ－１８０（いずれも三新化学工業社製）、ＣＸＣ－１６１２、ＣＸＣ－１７３８、ＣＸＣ－１８２１（いずれもキングインダストリーズ社製）等が挙げられる。 Examples of commercially available thermal cationic polymerization initiators include, for example, Adeka Opton CP-66, Adeka Opton CP-77 (both manufactured by ADEKA), and thermal cations having not only thermal activity but also photoactivity. Polymerization initiators such as Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-100, Sun-Aid SI-110, Sun-Aid SI-180 (all manufactured by Sanshin Chemical Industry Co., Ltd.), CXC-1612, CXC-1738, CXC -1821 (all manufactured by King Industries).
上記カチオン重合開始剤の含有量は、上記カチオン硬化性樹脂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。上記カチオン重合開始剤の含有量が０．１重量部未満であると、カチオン重合が充分に進行しなかったり、硬化反応が遅くなりすぎたりすることがある。上記カチオン重合開始剤の含有量が１０重量部を超えると、得られる有機ＥＬ表示素子用封止剤の硬化反応が速くなりすぎて、作業性が低下したり、得られる有機ＥＬ表示素子用封止剤の硬化物が不均一となったりすることがある。上記カチオン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 cationic polymerization initiator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic curable resin. If the content of the cationic polymerization initiator is less than 0.1 parts by weight, the cationic polymerization may not proceed sufficiently, or the curing reaction may become too slow. When the content of the cationic polymerization initiator exceeds 10 parts by weight, the curing reaction of the resulting organic EL display element sealant becomes too fast, resulting in a decrease in workability or the resulting organic EL display element seal. The cured product of the stopper may become uneven. The minimum with more preferable content of the said cationic 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、増感剤を含有してもよい。上記増感剤は、上記カチオン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 cationic polymerization 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、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 thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o- Examples include methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4-benzoyl-4′methyldiphenyl sulfide, and the like.
上記増感剤の含有量は、上記カチオン硬化性樹脂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重量部未満であると、増感効果が充分に得られないことがある。上記増感剤の含有量が３重量部を超えると、吸収が大きくなりすぎて深部まで光が伝わらないことがある。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 cationic curable resin. When the content of the sensitizer is less than 0.05 parts by weight, the sensitizing effect may not be sufficiently obtained. When the content of the sensitizer exceeds 3 parts by weight, absorption may be excessively increased and light may not be transmitted to the deep part. 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、硬化物の耐湿性を向上させること等を目的として、充填剤を含有することが好ましい。特に本発明にかかるカチオン硬化性樹脂として粘度の低い上記式（１）で表される化合物を用いる場合、塗布性を悪化させることなく充填剤を多く配合することができる。 The sealing agent for organic EL display elements of the present invention preferably contains a filler for the purpose of improving the moisture resistance of the cured product. In particular, when the compound represented by the above formula (1) having a low viscosity is used as the cationic curable resin according to the present invention, a large amount of filler can be blended without deteriorating the coating property.
上記充填剤としては、例えば、タルク、石綿、シリカ、マイカ、珪藻土、スメクタイト、ベントナイト、炭酸カルシウム、炭酸マグネシウム、アルミナ、モンモリロナイト、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、水酸化マグネシウム、水酸化アルミニウム、窒化珪素、硫酸バリウム、石膏、珪酸カルシウム、ガラスビーズ、セリサイト活性白土、ベントナイト、窒化アルミニウム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、耐湿性を向上させる効果に優れることから、タルクが好ましい。 Examples of the filler include talc, asbestos, silica, mica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, and magnesium hydroxide. Inorganic fillers such as aluminum hydroxide, silicon nitride, barium sulfate, gypsum, calcium silicate, glass beads, sericite activated clay, bentonite, aluminum nitride, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, etc. Organic fillers and the like. Of these, talc is preferred because of its excellent effect of improving moisture resistance.
上記充填剤の含有量は、上記カチオン硬化性樹脂１００重量部に対して、好ましい下限が１０重量部、好ましい上限が８０重量部である。上記充填剤の含有量が１０重量部未満であると、耐湿性を向上させる効果が充分に発揮されないことがある。上記充填剤の含有量が８０重量部を超えると、得られる有機ＥＬ表示素子用封止剤の粘度が高くなりすぎ、塗布性が悪化することがある。上記充填剤の含有量のより好ましい下限は１５重量部、より好ましい上限は７０重量部である。 The preferred lower limit of the content of the filler is 10 parts by weight and the preferred upper limit is 80 parts by weight with respect to 100 parts by weight of the cationic curable resin. If the content of the filler is less than 10 parts by weight, the effect of improving moisture resistance may not be sufficiently exhibited. When content of the said filler exceeds 80 weight part, the viscosity of the sealing agent for organic EL display elements obtained will become high too much, and applicability | paintability may deteriorate. The minimum with more preferable content of the said filler is 15 weight part, and a more preferable upper limit is 70 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、上記カチオン硬化性樹脂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０．１重量部未満であると、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が充分に発揮されないことがある。上記シランカップリング剤の含有量が１０重量部を超えると、余剰のシランカップリング剤がブリードアウトすることがある。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 cation curable resin. When the content of the silane coupling agent is less than 0.1 parts by weight, the effect of improving the adhesiveness of the obtained sealing agent for organic EL display elements may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 10 weight part, an excess silane coupling agent may bleed out. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
本発明の有機ＥＬ表示素子用封止剤は、更に、本発明の目的を阻害しない範囲において、熱硬化剤を含有してもよい。上記熱硬化剤を含有することで、本発明の有機ＥＬ表示素子用封止剤に熱硬化性を付与することができる。 The sealing agent for organic EL display elements of the present invention may further contain a thermosetting agent as long as the object of the present invention is not impaired. By containing the said thermosetting agent, thermosetting property can be provided to the sealing agent for organic EL display elements of this invention.
上記熱硬化剤は特に限定されず、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］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。
これらの熱硬化剤は、単独で用いられてもよいし、２種類以上が併用されてもよい。 The thermosetting agent is not particularly limited, and examples thereof 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] and the like.
Examples of the imidazole derivative 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.
These thermosetting agents may be used alone or in combination of two or more.
上記熱硬化剤の含有量は、上記カチオン硬化性樹脂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重量部未満であると、得られる有機ＥＬ表示素子用封止剤に充分な熱硬化性を付与できないことがある。上記熱硬化剤の含有量が３０重量部を超えると、得られる有機ＥＬ表示素子用封止剤の保存安定性が不充分となったり、得られる有機ＥＬ表示素子用封止剤の硬化物の耐湿性が悪くなったりすることがある。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 cationic curable resin. When the content of the thermosetting agent is less than 0.5 parts by weight, sufficient thermosetting property may not be imparted to the obtained sealing agent for organic EL display elements. When the content of the thermosetting agent exceeds 30 parts by weight, the storage stability of the obtained sealant for organic EL display elements becomes insufficient, or the cured product of the obtained sealant for organic EL display elements. Moisture resistance may deteriorate. 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、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.
上記界面活性剤や上記レベリング剤としては、例えば、シリコン系、アクリル系、フッ素系等のものが挙げられる。
上記界面活性剤や上記レベリング剤のうち市販されているものとしては、例えば、ＢＹＫ－３４５（ビックケミー・ジャパン社製）、ＢＹＫ－３４０（ビックケミー・ジャパン社製）、サーフロンＳ－６１１（ＡＧＣセイミケミカル社製）等が挙げられる。 Examples of the surfactant and the leveling agent include silicon-based, acrylic-based, and fluorine-based ones.
Examples of commercially available surfactants and leveling agents include BYK-345 (manufactured by BYK Japan), BYK-340 (manufactured by BYK Japan), Surflon S-611 (AGC Seimi Chemical). Etc.).
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、有機ＥＬ表示素子用封止剤中に発生した酸と反応する化合物又は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 reacts with the acid generated in the encapsulant for organic EL display elements in order to improve the durability of the element electrode within a range not impairing the object of the present invention. A compound or an ion exchange resin may be contained.
上記発生した酸と反応する化合物としては、酸と中和する物質、例えば、アルカリ金属の炭酸塩若しくは炭酸水素塩、又は、アルカリ土類金属の炭酸塩若しくは炭酸水素塩等が挙げられる。具体的には例えば、炭酸カルシウム、炭酸水素カルシウム、炭酸ナトリウム、炭酸水素ナトリウム等が用いられる。 Examples of the compound that reacts with the generated acid include substances that neutralize the acid, for example, alkali metal carbonates or bicarbonates, or alkaline earth metal carbonates or bicarbonates. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like are used.
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.
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、カチオン硬化性樹脂と、カチオン重合開始剤と、必要に応じて添加する添加剤とを混合する方法等が挙げられる。 Examples of the method for producing the sealing agent for organic EL display elements of the present invention include a cation curable resin using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll. And a method of mixing a cationic polymerization initiator and an additive to be 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℃、１～１００ｒｐｍの条件で測定した全体の粘度の下限が８０ｍＰａ・ｓ、上限が５０００ｍＰａ・ｓである。上記粘度が８０ｍＰａ・ｓ未満であると、得られる有機ＥＬ表示素子用封止剤が塗布性や塗布後の形状安定性に劣るものとなったり、組成ムラが発生して硬化物が透明性に劣るものとなったりする。上記粘度が５０００ｍＰａ・ｓを超えると、得られる有機ＥＬ表示素子用封止剤が塗布性に劣るものとなる。上記粘度の好ましい下限は１５０ｍＰａ・ｓ、好ましい上限は３０００ｍＰａ・ｓ、より好ましい下限は２００ｍＰａ・ｓ、より好ましい上限は１０００ｍＰａ・ｓである。
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型のコーンプレートにて測定することができる。
また、Ｅ型粘度計を用いて測定する際、粘度が１０００ｍＰａ・ｓ以上５０００ｍＰａ・ｓ未満となる場合は１ｒｐｍの条件で測定し、粘度が５００ｍＰａ・ｓ以上１０００ｍＰａ・ｓ未満となる場合は５ｒｐｍの条件で測定し、粘度が２００ｍＰａ・ｓ以上５００ｍＰａ・ｓ未満となる場合は１０ｒｐｍの条件で測定し、粘度が５０ｍＰａ・ｓ以上２００ｍＰａ・ｓ未満となる場合は２０ｒｐｍの条件で測定し、粘度が５０ｍＰａ・ｓ未満となる場合は１００ｒｐｍの条件で測定することが好ましい。 The sealant for organic EL display elements of the present invention has an overall viscosity lower limit of 80 mPa · s and an upper limit of 5000 mPa · s measured using an E-type viscometer at 25 ° C. and 1 to 100 rpm. When the viscosity is less than 80 mPa · s, the obtained sealing agent for organic EL display elements is inferior in applicability and shape stability after application, composition unevenness occurs, and the cured product becomes transparent. It becomes inferior. When the said viscosity exceeds 5000 mPa * s, the sealing agent for organic EL display elements obtained will be inferior to applicability | paintability. The preferable lower limit of the viscosity is 150 mPa · s, the preferable upper limit is 3000 mPa · s, the more preferable lower limit is 200 mPa · s, and the more preferable upper limit is 1000 mPa · s.
The viscosity can be measured, for example, with a CP1 type cone plate using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E type viscometer.
In addition, when measuring using an E-type viscometer, when the viscosity is 1000 mPa · s or more and less than 5000 mPa · s, it is measured under the condition of 1 rpm, and when the viscosity is 500 mPa · s or more and less than 1000 mPa · s, it is 5 rpm. When the viscosity is 200 mPa · s or more and less than 500 mPa · s, the measurement is performed under the condition of 10 rpm. When the viscosity is 50 mPa · s or more and less than 200 mPa · s, the measurement is performed under the condition of 20 rpm, and the viscosity is 50 mPa · s. -When it becomes less than s, it is preferable to measure on the conditions of 100 rpm.
本発明によれば、アウトガスの発生を抑制することができ、かつ、塗布性に優れる有機ＥＬ表示素子用封止剤を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of outgas can be suppressed and the sealing agent for organic EL display elements which is excellent in applicability | paintability can be provided.
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）
カチオン硬化性樹脂として、上記式（４）で表される化合物（ダイセル社製、「セロキサイド８０００」）５０重量部及び上記式（５）で表される化合物（日産化学社製、「ＴＥＰＩＣ－ＶＬ」）５０重量部と、光カチオン重合開始剤として芳香族スルホニウム塩（みどり化学社製、「ＤＴＳ－２００」）１重量部とを混合し、８０℃に加熱した後、撹拌混合機（シンキー社製、「ＡＲ－２５０」）を用い、撹拌速度３０００ｒｐｍで均一に撹拌混合して、有機ＥＬ表示素子用封止剤を作製した。 Example 1
As the cationic curable resin, 50 parts by weight of a compound represented by the above formula (4) (manufactured by Daicel, “Celoxide 8000”) and a compound represented by the above formula (5) (manufactured by Nissan Chemical Co., Ltd., “TEPIC-VL”). ”) 50 parts by weight and 1 part by weight of an aromatic sulfonium salt (manufactured by Midori Chemical Co.,“ DTS-200 ”) as a photocationic polymerization initiator are mixed and heated to 80 ° C., and then stirred and mixed (Sinky Corporation). Manufactured by “AR-250”) and uniformly mixed at a stirring speed of 3000 rpm to prepare an organic EL display element sealing agent.
（実施例２～７、比較例１～６）
表１に記載された各材料を、表１に記載された配合比に従い、実施例１と同様にして撹拌混合して、有機ＥＬ表示素子用封止剤を作製した。 (Examples 2 to 7, Comparative Examples 1 to 6)
Each material described in Table 1 was stirred and mixed in the same manner as in Example 1 in accordance with the blending ratio described in Table 1 to prepare an organic EL display element sealant.
＜評価＞
実施例１～７及び比較例１～６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 evaluations were performed on the sealing agents for organic EL display elements obtained in Examples 1 to 7 and Comparative Examples 1 to 6. The results are shown in Table 1.
（粘度）
実施例１～７及び比較例１～６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」コーンプレート：ＣＰ１型）を用いて、２５℃、１～１００ｒｐｍの条件における粘度を測定した。 (viscosity)
About each sealing agent for organic EL display elements obtained in Examples 1 to 7 and Comparative Examples 1 to 6, an E type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMMETER TV-22” cone plate: CP1 type) was used. The viscosity at 25 ° C. and 1 to 100 rpm was measured.
（塗布性及び塗布形状安定性）
ディスペンサー（武蔵エンジニアリング社製、「ＳＨＯＴＭＡＳＴＥＲ３００」）を用い、ディスペンスノズルを４００μｍ、ノズルギャップを３０μｍ、塗出圧を３００ｋＰａに固定し、ガラス基板上に実施例１～７及び比較例１～６で得られた各有機ＥＬ表示素子用封止剤を塗布した。塗布後、紫外線照射装置（オーク社製、「ＪＬ－４３００－３Ｓ」）を用いて紫外線を１５００ｍＪ／ｃｍ２照射し、その後１００℃で１５分間加熱を行うことで樹脂を硬化させた。なお、実施例４～６、比較例２、５で得られた有機ＥＬ表示素子用封止剤については、紫外線の照射を行わずに１００℃で３０分間加熱硬化させた。封止剤を塗布してから硬化反応が起こるまでの重量変化を熱重量測定装置（ＴＡ－ＩＮＳＴＲＵＭＥＮＴＳ社製、「ＴＧＡ」）を用いて確認した。
かすれやダレがなく塗布でき、かつ、硬化反応が起こるまでに重量減少がほとんど起こらなかった場合を「○」、塗布状態がかすれやダレが生じた場合や、硬化反応が起こるまでに５％未満の重量減少が起こった場合を「△」、塗布状態が大きな塗布切れや塗布ムラが生じたり、全く塗布できなかったりした場合や、硬化反応起こるまでに５％以上の重量減少が起こった場合を「×」として塗布性及び塗布形状安定性を評価した。 (Coating properties and coating shape stability)
Using a dispenser (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.), the dispensing nozzle was fixed at 400 μm, the nozzle gap was fixed at 30 μm, and the coating pressure was fixed at 300 kPa, and obtained in Examples 1 to 7 and Comparative Examples 1 to 6 Each obtained sealing agent for organic EL display elements was apply | coated. After application, the resin was cured by irradiating with ultraviolet rays at 1500 mJ / cm 2 using an ultraviolet irradiation device (Oak Corp., “JL-4300-3S”) and then heating at 100 ° C. for 15 minutes. The organic EL display element sealants obtained in Examples 4 to 6 and Comparative Examples 2 and 5 were cured by heating at 100 ° C. for 30 minutes without irradiation with ultraviolet rays. The change in weight from the application of the sealant to the occurrence of the curing reaction was confirmed using a thermogravimetric apparatus (TA-INSTRUMENTS, “TGA”).
Can be applied without fading or sagging, and when there is almost no weight loss before the curing reaction occurs, “○”, when the coating state is faint or sagging, or less than 5% before the curing reaction occurs “△” when the weight loss of the coating occurs, when the coating state is largely out of application, uneven coating occurs, or when the coating cannot be applied at all, or when the weight reduction of 5% or more occurs before the curing reaction occurs The coating property and the coating shape stability were evaluated as “X”.
（アウトガス防止性）
実施例１～７及び比較例１～６で得られた各有機ＥＬ表示素子用封止剤を、バイアル瓶中に３００ｍｇ計量して封入した後、紫外線照射装置（オーク社製、「ＪＬ－４３００－３Ｓ」）を用いて紫外線を１５００ｍＪ／ｃｍ２照射し、その後１００℃で１５分間加熱を行うことで樹脂を硬化させた。更にこのバイアル瓶を８５℃の恒温オーブンで１００時間加熱し、バイアル瓶中の気化成分を、ガスクロマトグラフ質量分析計（日本電子社製、「ＪＭＳ－ｋ９」）を用いて測定した。なお、実施例４～６、比較例２、５で得られた有機ＥＬ表示素子用封止剤については、紫外線の照射を行わずに１００℃で３０分間加熱硬化させた。
その結果、気化成分量が２０ｐｐｍ未満であった場合を「○」、２０ｐｐｍ以上１００ｐｐｍ未満であった場合を「△」、１００ｐｐｍ以上であった場合を「×」としてアウトガス防止性を評価した。 (Outgas prevention)
300 mg of each organic EL display element sealant obtained in Examples 1 to 7 and Comparative Examples 1 to 6 was weighed and sealed in a vial, and then an ultraviolet irradiation device (manufactured by Oak Co., “JL-4300”). −3S ”) was irradiated with ultraviolet rays at 1500 mJ / cm 2 and then heated at 100 ° C. for 15 minutes to cure the resin. Further, the vial was heated in a constant temperature oven at 85 ° C. for 100 hours, and the vaporized components in the vial were measured using a gas chromatograph mass spectrometer (“JMS-k9” manufactured by JEOL Ltd.). The organic EL display element sealants obtained in Examples 4 to 6 and Comparative Examples 2 and 5 were cured by heating at 100 ° C. for 30 minutes without irradiation with ultraviolet rays.
As a result, the outgassing prevention property was evaluated as “◯” when the vaporized component amount was less than 20 ppm, “Δ” when it was 20 ppm or more and less than 100 ppm, and “X” when it was 100 ppm or more.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
本発明によれば、アウトガスの発生を抑制することができ、かつ、塗布性に優れる有機ＥＬ表示素子用封止剤を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of outgas can be suppressed and the sealing agent for organic EL display elements which is excellent in applicability | paintability can be provided.

Claims (5)

  1. カチオン硬化性樹脂と、カチオン重合開始剤とを含有する有機ＥＬ表示素子用封止剤であって、
    前記カチオン硬化性樹脂は、エポキシ基又はオキセタニル基を有し、かつ、エポキシ基又はオキセタニル基に含まれる以外のエーテル結合、及び、エステル結合を有さないものであり、
    Ｅ型粘度計を用いて、２５℃、１～１００ｒｐｍの条件で測定した有機ＥＬ表示素子用封止剤全体の粘度が８０～５０００ｍＰａ・ｓである
    ことを特徴とする有機ＥＬ表示素子用封止剤。     A sealing agent for an organic EL display element containing a cationic curable resin and a cationic polymerization initiator,
    The cationic curable resin has an epoxy group or oxetanyl group, and has no ether bond other than that contained in the epoxy group or oxetanyl group, and has no ester bond,
    Sealing for organic EL display elements, characterized in that the viscosity of the whole sealing agent for organic EL display elements measured with an E-type viscometer at 25 ° C. and 1 to 100 rpm is 80 to 5000 mPa · s. Agent.
  2. カチオン硬化性樹脂は、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を特徴とする請求項１記載の有機ＥＬ表示素子用封止剤。
    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。
    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。
    Figure JPOXMLDOC01-appb-C000003
     式（３－１）中、Ｒ２２は、水素原子又はメチル基である。     The cationic curable resin contains a compound represented by the following formula (1) and / or a compound represented by the following formula (2): The sealing agent for organic EL display elements according to claim 1, .
    Figure JPOXMLDOC01-appb-C000001
     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.
    Figure JPOXMLDOC01-appb-C000002
     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
     In formula (3-1), R 22 represents a hydrogen atom or a methyl group.
  3. カチオン硬化性樹脂は、式（１）で表される化合物及び式（２）で表される化合物を含有することを特徴とする請求項２記載の有機ＥＬ表示素子用封止剤。 The sealing agent for organic EL display elements according to claim 2, wherein the cationic curable resin contains a compound represented by the formula (1) and a compound represented by the formula (2).
  4. 式（１）で表される化合物として下記式（４）で表される化合物を含有することを特徴とする請求項２又は３記載の有機ＥＬ表示素子用封止剤。
    Figure JPOXMLDOC01-appb-C000004
         The compound represented by the following formula (4) as a compound represented by the formula (1) is contained, The sealing agent for organic EL display elements according to claim 2 or 3.
    Figure JPOXMLDOC01-appb-C000004
  5. 式（２）で表される化合物として下記式（５）で表される化合物を含有することを特徴とする請求項２、３又は４記載の有機ＥＬ表示素子用封止剤。
    Figure JPOXMLDOC01-appb-C000005
         The compound represented by the following formula (5) is contained as the compound represented by the formula (2), the sealing agent for organic EL display elements according to claim 2, 3 or 4.
    Figure JPOXMLDOC01-appb-C000005
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