WO2022019267A1 - Agent d'étanchéité pour élément d'affichage électroluminescent organique - Google Patents

Agent d'étanchéité pour élément d'affichage électroluminescent organique Download PDF

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Publication number
WO2022019267A1
WO2022019267A1 PCT/JP2021/026973 JP2021026973W WO2022019267A1 WO 2022019267 A1 WO2022019267 A1 WO 2022019267A1 JP 2021026973 W JP2021026973 W JP 2021026973W WO 2022019267 A1 WO2022019267 A1 WO 2022019267A1
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WIPO (PCT)
Prior art keywords
organic
display element
meth
examples
sealant
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PCT/JP2021/026973
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English (en)
Japanese (ja)
Inventor
俊隆 吉武
穣 末▲崎▼
真理子 安部
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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 JP2021544176A priority Critical patent/JPWO2022019267A1/ja
Priority to CN202180039446.3A priority patent/CN115943732A/zh
Priority to KR1020227026942A priority patent/KR20230041956A/ko
Publication of WO2022019267A1 publication Critical patent/WO2022019267A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity

Definitions

  • the present invention relates to a sealing agent for an organic EL display element capable of obtaining an organic EL display element having excellent moisture permeation prevention property and adhesiveness and excellent reliability.
  • the organic electroluminescence display element (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. Electrons are injected into the organic light emitting material layer from one electrode and holes are injected from the other electrode, so that electrons and holes are combined in the organic light emitting material layer to perform self-luminous emission. Compared to a liquid crystal display element or the like that requires a backlight, it has the advantages of better visibility, thinner size, and low DC voltage drive.
  • an organic EL display element has a problem that when the organic light emitting material layer or the electrode is exposed to the outside air, its light emitting characteristics are rapidly deteriorated and its life is shortened. Therefore, in order to improve the stability and durability of the organic EL display element, a sealing technology that shields the organic light emitting material layer and the electrode from the moisture and oxygen in the atmosphere is indispensable for the organic EL display element. There is.
  • Patent Document 1 includes an organic packed layer that covers and seals a laminate having an organic light emitting material layer, and a moisture-absorbing seal layer (sealing wall) that covers the side surface of the organic packed layer.
  • a method of sealing a display element is disclosed.
  • a sealing agent for an organic EL display element an in-plane sealing agent is used for the organic packed bed, and a peripheral sealing agent having a component different from that of the in-plane sealing agent is used for the sealing wall. Has been done.
  • the present invention contains a curable resin and a water-absorbent filler, and the curable resin contains a (meth) acrylic compound having no isocyanate group and a blocked isocyanate group, and an isocyanate compound or a blocked isocyanate, and the water-absorbing resin.
  • the present inventors have studied to make the sealing wall thin for the purpose of securing a wide display area of the organic EL display element.
  • the line width of the peripheral sealant is narrowed (thinned) and applied in order to make the sealing wall thinner, sufficient adhesive strength cannot be obtained, or the obtained organic EL display element becomes reliable. It was sometimes inferior.
  • the adhesiveness was significantly reduced in a high temperature and high humidity environment.
  • the present inventors have described as a curable resin a (meth) acrylic compound having no isocyanate group and a blocked isocyanate group, an isocyanate compound, or an isocyanate compound or a sealant for an organic EL display element containing a large amount of water-absorbent filler. It was considered to contain blocked isocyanate. As a result, they have found that the obtained sealing agent for an organic EL display element can obtain an organic EL display element having excellent moisture permeation prevention property and adhesiveness and excellent reliability, and completed the present invention. I came to let you.
  • the sealing agent for an organic EL display element of the present invention contains a curable resin.
  • the curable resin contains a (meth) acrylic compound having no isocyanate group and no blocked isocyanate group.
  • the encapsulant for an organic EL display element of the present invention has excellent curability.
  • the above-mentioned "(meth) acrylic” means acrylic or methacrylic
  • the above-mentioned "(meth) acrylic compound” means a compound having a (meth) acryloyl group
  • “Acryloyl” means acryloyl or methacryloyl.
  • Examples of the (meth) acrylic compound having no isocyanate group and blocked isocyanate group include urethane (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and norbornylmethyl.
  • the (meth) acrylic compound having no isocyanate group and a blocked isocyanate group has a viewpoint of further improving the adhesiveness and moisture permeation prevention property of the obtained sealant for an organic EL display element, and the polyolefin described later. From the viewpoint of improving compatibility with, it is preferable to contain a (meth) acrylic compound having an alicyclic skeleton. Further, the (meth) acrylic compound having no isocyanate group and a blocked isocyanate group is from the viewpoint of further improving the adhesiveness (particularly, the adhesiveness in a high temperature and high humidity environment) of the obtained sealing agent for an organic EL display element. , It is preferable to contain a polyfunctional (meth) acrylic compound.
  • the above-mentioned “(meth) acrylate” means acrylate or methacrylate
  • the above-mentioned “urethane (meth) acrylate” means a compound having a urethane bond and a (meth) acryloyl group
  • the "polyfunctional (meth) acrylic compound” means a compound having two or more (meth) acryloyl groups in one molecule.
  • the preferable lower limit of the content of the (meth) acrylic compound having no isocyanate group and the blocked isocyanate group in 100 parts by weight of the entire curable resin is 0.01 part by weight, and the preferable upper limit is 99.99 parts by weight.
  • the content of the (meth) acrylic compound having no isocyanate group and the blocked isocyanate group is in this range, the obtained sealing agent for an organic EL display element is excellent in adhesiveness and storage stability.
  • a more preferable lower limit of the content of the (meth) acrylic compound having no isocyanate group and a blocked isocyanate group is 0.1 parts by weight, a further preferable lower limit is 10 parts by weight, and a further preferable lower limit is 20 parts by weight, a particularly preferable lower limit. Is 80 parts by weight.
  • the curable resin contains an isocyanate compound or a blocked isocyanate.
  • the sealing agent for an organic EL display element of the present invention has adhesiveness (particularly high temperature and high humidity).
  • the organic EL display element obtained is excellent in adhesiveness in an environment) and is excellent in reliability.
  • the isocyanate compound or the blocked isocyanate may have a (meth) acryloyl group or may not have a (meth) acryloyl group. Among them, it is preferable to have a (meth) acryloyl group from the viewpoint of further improving the adhesiveness (particularly the adhesiveness in a high temperature and high humidity environment) and the storage stability of the obtained sealing agent for an organic EL display element.
  • Examples of the isocyanate compound having a (meth) acryloyl group include 2- (meth) acryloyloxyethyl isocyanate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate. Of these, 2- (meth) acryloyloxyethyl isocyanate is preferable.
  • Examples of the blocked isocyanate having the (meth) acryloyl group include 2-((3,5-dimethylpyrazolyl) carbonylamino) ethyl (meth) acrylate and 2- (O- (1'-methylpropyrideneamino) carboxy). Examples thereof include amino) ethyl (meth) acrylate, 2- (O- (1'-methylpropanolamino) carboxyamino) (meth) acrylate and the like. Of these, 2-((3,5-dimethylpyrazolyl) carbonylamino) ethyl (meth) acrylate is preferable.
  • those having no (meth) acryloyl group include, for example, aromatic isocyanates, aliphatic isocyanates having an aromatic ring, aliphatic isocyanates having no aromatic ring, and alicyclic rings. Examples thereof include group isocyanates.
  • aromatic isocyanate include tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, polymer of methylene diphenyl diisocyanate, phenylenedi isocyanate, naphthalene diisocyanate and the like.
  • Examples of the aliphatic isocyanate having an aromatic ring include ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate and the like.
  • Examples of the aliphatic isocyanate having no aromatic ring include methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and the like.
  • alicyclic isocyanate examples include cyclohexanediisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), isopropyridene dicyclohexyldiisocyanate and the like.
  • polymers of methylene diphenyl diisocyanate and methylene diphenyl diisocyanate are preferable from the viewpoint of adhesiveness.
  • the isocyanate compound or the blocked isocyanate As the isocyanate compound or the blocked isocyanate, the isocyanate compound is preferable from the viewpoint of adhesiveness, and the blocked isocyanate is preferable from the viewpoint of storage stability.
  • the preferable lower limit of the content of the isocyanate compound or the blocked isocyanate in 100 parts by weight of the entire curable resin is 0.05 parts by weight, and the preferable upper limit is 8 parts by weight.
  • the content of the isocyanate compound or the blocked isocyanate is within this range, the obtained sealing agent for an organic EL display element is excellent in adhesiveness (particularly adhesiveness in a high temperature and high humidity environment) and storage stability.
  • the more preferable lower limit of the content of the isocyanate compound or the blocked isocyanate is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.
  • the curable resin may contain other curable resin in addition to the (meth) acrylic compound having no isocyanate group and the blocked isocyanate group, and the isocyanate compound or the blocked isocyanate.
  • Examples of the other curable resin include epoxy compounds, oxetane compounds, urethane compounds having no (meth) acryloyl group, and the like.
  • Examples of the epoxy compound include glycidyl ether compounds and alicyclic epoxy compounds.
  • Examples of the glycidyl ether compound include diethylene glycol diglycidyl ether and the like.
  • Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4. -(2-Oxylanyl) cyclohexane adduct and the like can be mentioned.
  • oxetane compound examples include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, di [2- (3-oxetanyl) butyl] ether, and 3-ethyl-3-hydroxy. Methyloxetane and the like can be mentioned.
  • Examples of the urethane compound having no (meth) acryloyl group include a reaction product of an isocyanate compound and an arbitrary polyol compound.
  • Examples of the isocyanate compound include toluene diisocyanate compounds and diphenylmethane diisocyanate compounds.
  • Examples of the toluene diisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate, and a mixture thereof.
  • Examples of the diphenylmethane diisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and a mixture thereof.
  • the curable resin contains a blocked isocyanate
  • the curable resin further contains an amine compound.
  • the blocked isocyanate can be gradually converted to isocyanate, and both storage stability and adhesiveness can be improved.
  • the amine compound include 1,4-diazabicyclo [2.2.2] octane and the like.
  • the amount of the amine compound added is preferably 1 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the blocked isocyanate.
  • the sealing agent for an organic EL display element of the present invention contains a water-absorbent filler. By containing the above-mentioned water-absorbent filler, the sealing agent for an organic EL display element of the present invention has excellent moisture permeation prevention properties.
  • Examples of the water-absorbent filler include oxides of alkaline earth metals, magnesium oxide, molecular sieves and the like.
  • Examples of the oxide of the alkaline earth metal include calcium oxide, strontium oxide, barium oxide and the like. Of these, oxides of alkaline earth metals are preferable, and calcium oxide is more preferable, from the viewpoint of water absorption.
  • These water-absorbent fillers may be used alone or in combination of two or more.
  • the lower limit of the content ratio of the water-absorbent filler in the sealant for an organic EL display element of the present invention is 20% by weight.
  • the sealing agent for an organic EL display element of the present invention has excellent moisture permeation prevention properties.
  • the encapsulant for an organic EL display element of the present invention contains the isocyanate compound or the blocked isocyanate, so that even if a large amount of the water-absorbent filler is blended, the adhesive (particularly in a high temperature and high humidity environment).
  • the organic EL display element obtained is excellent in adhesiveness) and has excellent reliability.
  • the preferable lower limit of the content ratio of the water-absorbent filler is 30% by weight, and the more preferable lower limit is 40% by weight. Further, from the viewpoint of coatability and the like, the preferable upper limit of the content ratio of the water-absorbent filler is 70% by weight, and the more preferable upper limit is 60% by weight.
  • the encapsulant for an organic EL display element of the present invention may contain other fillers in addition to the above water-absorbent filler as long as the object of the present invention is not impaired.
  • an inorganic filler or an organic filler can be used as the above-mentioned other filler.
  • the inorganic filler include silica, talc, and alumina.
  • the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. Of these, talc is preferable.
  • the encapsulant for an organic EL display element of the present invention preferably contains polyolefin.
  • the sealing agent for an organic EL display element of the present invention becomes more excellent in moisture permeation prevention property.
  • the polyolefin preferably contains at least one selected from the group consisting of polyisobutylene, polybutene, and polybutadiene, and more preferably contains polyisobutylene.
  • the above-mentioned polyolefin may be used alone or in combination of two or more.
  • the preferable lower limit of the weight average molecular weight of the polyolefin is 10,000, and the preferable upper limit is 400,000.
  • the more preferable lower limit of the weight average molecular weight of the polyolefin is 20,000, and the more preferable upper limit is 70,000.
  • the above-mentioned "weight average molecular weight” is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.
  • the preferable lower limit of the content of the polyolefin in 100 parts by weight of the curable resin and the polyolefin is preferably 10 parts by weight, and the preferable upper limit is 80 parts by weight.
  • the content of the polyolefin is 10 parts by weight or more, the obtained sealing agent for an organic EL display element becomes more excellent in moisture permeation prevention.
  • the content of the polyolefin is 80 parts by weight or less, the obtained sealing agent for an organic EL display element is excellent in coatability and adhesiveness.
  • the more preferable lower limit of the content of the polyolefin is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.
  • the sealing agent for an organic EL display element of the present invention may contain a tackifier resin for the purpose of further improving the adhesiveness.
  • the tackifier resin include terpene resin, modified terpene resin, kumaron resin, inden resin, petroleum resin and the like.
  • the modified terpene resin include hydrogenated terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin and the like.
  • the petroleum resin include aliphatic petroleum resin, hydrogenated alicyclic petroleum resin, aromatic petroleum resin, aliphatic aromatic copolymerized petroleum resin, aliphatic petroleum resin, and dicyclopentadiene petroleum. Examples thereof include resins and hydrides thereof.
  • the tackifier resin includes terpene resin, aromatic-modified terpene resin, terpene phenol copolymer resin, and hydrocarbon from the viewpoints of adhesiveness, moisture permeability resistance, compatibility, etc. of the sealant for organic EL display elements.
  • Alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymerized petroleum resins, alicyclic petroleum resins are preferred, alicyclic petroleum resins are more preferred, alicyclic saturated hydrocarbon resins and fats.
  • a ring-type unsaturated hydrocarbon resin is more preferable, and a cyclohexyl ring-containing saturated hydrocarbon resin and a dicyclopentadiene-modified hydrocarbon resin are particularly preferable.
  • These tackifier resins may be used alone or in combination of two or more.
  • the content of the tackifier resin is such that the preferable lower limit is 0.01 part by weight and the preferable upper limit is 0.01 part by weight with respect to 100 parts by weight of the curable resin (in the case of containing the polyolefin, the total of the curable resin and the polyolefin). Is 100 parts by weight.
  • the content of the tackifier resin is in this range, the effect of improving the adhesiveness can be further exhibited while maintaining the moisture permeation prevention property.
  • the more preferable lower limit of the content of the tackifier resin is 0.2 parts by weight, and the more preferable upper limit is 20 parts by weight.
  • the encapsulant for an organic EL display element of the present invention preferably contains a polymerization initiator.
  • a polymerization initiator a radical polymerization initiator or a cationic polymerization initiator can be used. Of these, a radical polymerization initiator is preferable.
  • radical polymerization initiator examples include a photoradical polymerization initiator and a thermal radical polymerization initiator.
  • photoradical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like.
  • Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and 1,2- (dimethylamino).
  • thermal radical polymerization initiator examples include those made of an azo compound, an organic peroxide and the like.
  • the azo compound examples include 2,2'-azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile and the like.
  • the organic peroxide examples include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate and the like.
  • thermal radical polymerization initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 and V-501 (all of which are Fujifilm Wako Pure Chemical Industries, Ltd.). Made) and the like.
  • Examples of the cationic polymerization initiator include a photocationic polymerization initiator and a thermal cationic polymerization initiator.
  • the photocationic polymerization initiator is not particularly limited as long as it generates protonic acid or Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type. May be.
  • the anionic portion of the ionic photoacid generator type cationic photopolymerization initiator for example, BF 4 -, PF 6 - , SbF 6 -, or, (BX 4) - (where, X is at least two (Representing a phenyl group substituted with a fluorine or trifluoromethyl group) and the like.
  • the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, and aromatic ammonium salts, which have the anion moiety. Examples thereof include pentadiene-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, and bis.
  • 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 and 1-benzyl.
  • Examples of the (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene.
  • nonionic photoacid generation type photocationic polymerization initiator examples include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate and the like.
  • photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd., a photocationic polymerization initiator manufactured by Union Carbide, and a photocationic polymerization initiator manufactured by ADEKA. Examples thereof include a photocationic polymerization initiator manufactured by 3M, a photocationic polymerization initiator manufactured by BASF, and a photocationic polymerization initiator manufactured by Rhodia. Examples of the photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd. include DTS-200 and the like. Examples of the photocationic polymerization initiator manufactured by Union Carbide include UVI6990 and UVI6974.
  • Examples of the photocationic polymerization initiator manufactured by ADEKA include SP-150 and SP-170. Examples of the photocationic polymerization initiator manufactured by 3M include FC-508 and FC-512. Examples of the photocationic polymerization initiator manufactured by BASF include IRGACURE261 and IRGACURE290. Examples of the photocationic polymerization initiator manufactured by Rhodia include PI2074 and the like.
  • the anionic portion is BF 4 -, PF 6 -, SbF 6 -, or, (BX 4) - (where, X is substituted by at least two fluorine or trifluoromethyl group Examples thereof include a sulfonium salt, a phosphonium salt, an ammonium salt, etc., which are composed of (representing a phenyl group). Of these, sulfonium salts and ammonium salts are preferable.
  • sulfonium salt examples include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
  • Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
  • ammonium salt examples include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, and dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl).
  • thermal cationic polymerization initiators examples include thermal cationic polymerization initiators manufactured by Sanshin Chemical Industry Co., Ltd., thermal cationic polymerization initiators manufactured by King Industries, and the like.
  • thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd. examples include Sun Aid SI-60, Sun Aid SI-80, Sun Aid SI-B3, Sun Aid SI-B3A, and Sun Aid SI-B4.
  • thermal cationic polymerization initiator manufactured by King Industries examples include CXC-1612, CXC-1821 and the like.
  • the content of the polymerization initiator has a preferable lower limit of 0.05 parts by weight and a preferable upper limit with respect to 100 parts by weight of the curable resin (in the case of containing the polyolefin, the total of the curable resin and the polyolefin). Is 10 parts by weight.
  • the content of the polymerization initiator is 0.05 parts by weight or more, the obtained sealing agent for an organic EL display element becomes more excellent in curability.
  • the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained sealant for an organic EL display element does not become too fast, the workability is improved, and the cured product becomes more uniform.
  • the more preferable lower limit of the content of the polymerization initiator is 1 part by weight, and the more preferable upper limit is 3 parts by weight.
  • Examples of the sensitizer include anthracene compounds, thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, and methyl o-benzoylbenzoate. Examples thereof include 4,4'-bis (dimethylamino) benzophenone and 4-benzoyl-4'-methyldiphenylsulfide. Examples of the anthracene-based compound include 9,10-dibutoxyanthracene and the like. Examples of the thioxanthone-based compound include 2,4-diethylthioxanthone and the like. These sensitizers may be used alone or in combination of two or more.
  • the content of the sensitizer has a preferable lower limit of 0.05 parts by weight and a preferable upper limit with respect to 100 parts by weight of the curable resin (in the case of containing the polyolefin, the total of the curable resin and the polyolefin). Is 3 parts by weight.
  • 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 more preferable lower limit of the content of the sensitizer is 0.1 parts by weight, and the more preferable upper limit is 1 part by weight.
  • the sealing agent for an organic EL display element of the present invention may contain a thermosetting agent.
  • thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.
  • Examples of the hydrazide compound include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydrandin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
  • Examples of the imidazole derivative include 1-cyanoethyl-2-phenylimidazole, N- (2- (2-methyl-1-imidazolyl) ethyl) urea, and 2,4-diamino-6- (2'-methylimidazole-).
  • thermosetting agents include, for example, SDH (manufactured by Japan Finechem), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Fine-Techno). ) Etc. can be mentioned.
  • the preferable lower limit is 0.01 part by weight and the preferable upper limit is 0.01 part by weight with respect to 100 parts by weight of the curable resin (in the case of containing the polyolefin, the total of the curable resin and the polyolefin). Is 10 parts by weight.
  • the content of the thermosetting agent is 0.01 parts by weight or more, the obtained sealing agent for an organic EL display element becomes more excellent in thermosetting property.
  • the content of the thermosetting agent is 10 parts by weight or less, the obtained sealing agent for an organic EL display element becomes more excellent in storage stability.
  • the more preferable lower limit of the content of the thermosetting agent is 0.5 parts by weight, the more preferable upper limit is 5 parts by weight, the further preferable lower limit is 1 part by weight, and the further preferable upper limit is 3 parts by weight.
  • the sealing agent for an organic EL display element of the present invention may contain a stabilizer. By containing the above stabilizer, the encapsulant for an organic EL display element of the present invention becomes more excellent in storage stability.
  • the stabilizer examples include aromatic amine compounds, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl and the like.
  • the aromatic amine compound examples include benzylamine and aminophenol type epoxy resins. Of these, aromatic amine compounds are preferable, and benzylamine is more preferable. These stabilizers may be used alone or in combination of two or more.
  • the preferable lower limit is 0.001 part by weight and the preferable upper limit is 0.001 part by weight with respect to 100 parts by weight of the curable resin (when the polyolefin is contained, the total of the curable resin and the polyolefin). 2 parts by weight.
  • the content of the stabilizer is in this range, the obtained sealing agent for an organic EL display element becomes more excellent in storage stability while maintaining excellent curability.
  • the more preferable lower limit of the content of the stabilizer is 0.005 parts by weight, and the more preferable upper limit is 1 part by weight.
  • the encapsulant for an organic EL display element of the present invention may contain a silane coupling agent.
  • the silane coupling agent has a role of improving the adhesiveness between the sealing agent for an organic EL display element of the present invention and a substrate or the like.
  • silane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and the like. These silane coupling agents may be used alone or in combination of two or more.
  • the content of the silane coupling agent is preferably 0.1 part by weight, preferably 0.1 part by weight, based on 100 parts by weight of the curable resin (in the case of containing the polyolefin, the total of the curable resin and the polyolefin).
  • the upper limit is 10 parts by weight.
  • the more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and the more preferable upper limit is 5 parts by weight.
  • the encapsulant for an organic EL display element 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 above-mentioned surface modifier, the flatness of the coating film of the sealing agent for an organic EL display element of the present invention can be improved.
  • the surface modifier include a surfactant, a leveling agent and the like.
  • Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based agents.
  • commercially available ones include, for example, a surface modifier manufactured by Big Chemie Japan, a surface modifier manufactured by Kusumoto Kasei Co., Ltd., and a surface modifier manufactured by AGC Seimi Chemical Co., Ltd. Can be mentioned.
  • Examples of the surface modifier manufactured by Big Chemie Japan Co., Ltd. include BYK-300, BYK-302, BYK-331 and the like.
  • Examples of the surface modifier manufactured by Kusumoto Kasei Co., Ltd. include UVX-272 and the like.
  • Examples of the surface modifier manufactured by AGC Seimi Chemical Co., Ltd. include Surflon S-611 and the like.
  • the encapsulant for an organic EL display element of the present invention contains a compound that reacts with an acid generated in the encapsulant for an organic EL display element and / or an ion exchange resin to the extent that the object of the present invention is not impaired. May be good.
  • Examples of the compound that reacts with the generated acid include substances that neutralize the acid, such as alkali metal carbonates or bicarbonates, or alkaline earth metal carbonates or bicarbonates.
  • alkali metal carbonates or bicarbonates such as 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 biion exchange type can be used, and in particular, a cation exchange type or a biion exchange type capable of adsorbing chloride ions can be used. Is preferable.
  • the sealant for an organic EL display element of the present invention is a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an oxidation, if necessary, as long as the encapsulant for an organic EL display element of the present invention is not impaired. It may contain various known additives such as an inhibitor.
  • the encapsulant for an organic EL display element of the present invention preferably does not contain a solvent from the viewpoint of further suppressing the generation of outgas.
  • the encapsulant for an organic EL display element of the present invention can be excellent in coatability even if it does not contain a solvent.
  • solvent-free means that the solvent content is less than 1000 ppm.
  • a method for producing the encapsulant for an organic EL display element of the present invention for example, a polyolefin, a curable resin, a water-absorbent filler, a polymerization initiator and / or a thermosetting agent, or a necessary one, using a mixer.
  • a mixer examples thereof include a method of mixing with an additive such as a silane coupling agent to be added according to the above.
  • the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
  • the sealant for an organic EL display element of the present invention has a preferable upper limit of viscosity measured at 25 ° C. and 2.5 rpm using an E-type viscometer at 1000 Pa ⁇ s.
  • the viscosity is 1000 Pa ⁇ s or less, the obtained sealing agent for an organic EL display element has excellent coatability.
  • a more preferable upper limit of the viscosity is 500 Pa ⁇ s.
  • a practical lower limit is 100 Pa ⁇ s.
  • the sealant for an organic EL display element of the present invention has a preferable lower limit of 0.8 kgf / cm 2 in the adhesive force of the cured product to glass after being stored in an environment of 85 ° C. and 85% RH for 500 hours.
  • the adhesive force of the cured product to the glass after storage in the environment of 85 ° C. and 85% RH for 500 hours is 0.8 kgf / cm 2 or more, so that the sealant for an organic EL display element of the present invention can be used. It can be suitably used as a peripheral sealant for an organic EL display element.
  • a more preferable lower limit of the adhesive force of the cured product to the glass after storage in the environment of 85 ° C. and 85% RH for 500 hours is 1.2 kgf / cm 2 .
  • the cured product of the sealant for an organic EL display element of the present invention is preferably used for a sealing wall surrounding the peripheral edge of the organic EL display element. That is, the encapsulant for an organic EL display element of the present invention is preferably used as a peripheral encapsulant for an organic EL display element for forming a sealing wall around a laminate having an organic light emitting material layer.
  • the peripheral encapsulant for an organic EL display element is usually used in combination with an in-plane encapsulant for an organic EL display element that covers the laminate.
  • the sealing wall made of the cured product of the sealing agent for the organic EL display element of the present invention is preferably thick in the line width direction from the viewpoint of securing a wide display area of the obtained organic EL display element. It is 5 mm or less, more preferably 3 mm or less, still more preferably 2 mm or less. Since the sealing agent for an organic EL display element of the present invention is excellent in moisture permeation prevention property, adhesiveness and reliability, the sealing wall can be made to have a thickness equal to or less than the above upper limit.
  • the lower limit of the thickness of the sealing wall in the line width direction is not particularly limited, but is, for example, 0.5 mm.
  • a sealing agent for an organic EL display element capable of obtaining an organic EL display element having excellent moisture permeation prevention property and adhesiveness and excellent reliability.
  • Examples 1 to 9, Comparative Examples 1 and 2 According to the compounding ratios shown in Tables 1 and 2, each material is stirred and mixed for 3 minutes at a stirring speed of 2000 rpm using a stirring mixer for the organic EL display elements of Examples 1 to 9 and Comparative Examples 1 and 2. A sealant was prepared.
  • the stirring mixer AR-250 (manufactured by Shinky Co., Ltd.) was used.
  • the calcium oxide in Tables 1 and 2 dry batch pulverized with a ball mill (“ANZ-53D” manufactured by Nikko Kagaku Co., Ltd.) was used so that the particle size was 10 ⁇ m or less.
  • Viscosity and storage stability For each of the sealants for organic EL display elements obtained in Examples and Comparative Examples, the initial viscosity immediately after production was measured at 25 ° C. using an E-type viscometer. Further, after each organic EL display element sealant is frozen and stored for 2 weeks after production, it is thawed and the viscosity at 25 ° C. is measured, and (viscosity after freezing and storage for 2 weeks) / (initial viscosity) is the viscosity change rate. And said. If the viscosity change rate is less than 1.1, it is " ⁇ ", if it is 1.1 or more and less than 1.3, it is " ⁇ ", and if it is 1.3 or more and less than 1.5, it is " ⁇ ". , 1.5 or more was evaluated as "x" to evaluate the storage stability. As the E-type viscometer, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) was used.
  • Adhesiveness 0.03 g of spacer particles having a diameter of 10 ⁇ m was added to 10 g of the sealant for each organic EL display element obtained in Examples and Comparative Examples, and the particles were uniformly dispersed using a stirring mixer. .. Micropearl SP-210 (manufactured by Sekisui Chemical Co., Ltd.) was used as the spacer particles, and ARV-310 (manufactured by Shinky Co., Ltd.) was used as the stirring mixer. After applying a sealing agent for an organic EL display element in which spacer particles are dispersed to the central portion on the glass substrate A, the glass substrate B is crossed and pasted so as to form a cross, and pressed to make the thickness uniform. ..
  • the amount of the sealant for the organic EL display element applied was adjusted so that the sealant for the organic EL display element after being pressurized to have a uniform thickness had a circular shape with a diameter of 5.0 to 7.0 mm.
  • the glass substrates A and B have a length of 60 mm, a width of 30 mm, and a thickness of 5 mm.
  • the surface of the glass is washed with acetone and then dried.
  • the glass substrate A and the glass substrate B are adhered by irradiating the UV-LED irradiator with ultraviolet rays having a wavelength of 365 nm at 3000 mJ / cm 2 to cure the sealant for the organic EL display element, and the initial adhesiveness is obtained.
  • a test piece for evaluation was obtained.
  • the glass substrate A and the glass substrate B are adhered in the same manner as the test piece for initial adhesiveness evaluation, the glass substrate A and the glass substrate B are exposed to a high temperature and high humidity condition of 85 ° C. and 85% RH for 500 hours to be exposed to a high temperature and high humidity environment.
  • a test piece for evaluation of adhesiveness was obtained. For each test piece, place the glass substrate B so that it faces down, fix both ends of the glass substrate A from below, and use a precision universal testing machine to fix both ends of the glass substrate B at 23 ° C and a speed of 5 mm / min.
  • the adhesive strength between the glass substrate A and the glass substrate B was measured by compressing from above.
  • the location to be compressed was set to a range of 20 mm in length and 5 mm in width, centered on a position of 7.25 mm from both ends of the glass substrate B.
  • the precision universal testing machine Autograph AG-Xplus (manufactured by Shimadzu Corporation) was used.
  • the adhesive force was defined as the maximum load from the start of compression by the precision universal testing machine to the complete peeling of the glass substrate A and the glass substrate B divided by the area of the sealant for the organic EL display element of the test piece.
  • the glass substrate on which Ca is vapor-deposited is moved into a glove box controlled at a dew point (-60 ° C or higher), and the glass substrate on which the sealing agent for an organic EL display element is coated on the surface and the glass substrate on which Ca is vapor-deposited are separated.
  • the sealant for the organic EL display element was bonded so as to be on the vapor deposition pattern of Ca.
  • the UV-LED irradiation device irradiates ultraviolet rays having a wavelength of 365 nm 2 at 3000 mJ / cm to cure the sealant for the organic EL display element.
  • Ca-TEST substrate was prepared.
  • the obtained Ca-TEST substrate is exposed to high temperature and high humidity conditions of 85 ° C. and 85% RH to determine the penetration distance of moisture from the end face of the glass substrate into the layer made of the cured product of the sealant for the organic EL display element. Observed from the disappearance of Ca.
  • the exposure time under high temperature and high humidity conditions was 900 hours, the case where the moisture penetration distance was less than 1.8 mm was " ⁇ ", and the case where it was 1.8 mm or more and less than 2.1 mm was " ⁇ ".
  • the case of 2.1 mm or more and less than 2.4 mm was evaluated as “ ⁇ ”, and the case of 2.4 mm or more was evaluated as “x” to evaluate the moisture permeation prevention property.
  • a sealing agent for an organic EL display element capable of obtaining an organic EL display element having excellent moisture permeation prevention property and adhesiveness and excellent reliability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)

Abstract

Le but de la présente invention est de fournir un agent d'étanchéité pour un élément d'affichage électroluminescent organique grâce auquel il serait possible d'obtenir un élément d'affichage électroluminescent organique ayant d'excellentes propriétés en termes de prévention contre l'humidité et de collage et présentant aussi une excellente fiabilité. La présente invention concerne un matériau d'étanchéité pour un élément d'affichage électroluminescent organique qui contient une résine durcissable et un élément de remplissage absorbant l'eau, l'agent d'étanchéité étant tel que : la résine durcissable contient un composé (meth) acrylique qui ne possède pas de groupe isocyanate ou un groupe isocyanate bloqué, et un composé isocyanate ou un isocyanate bloqué ; et le rapport de teneur de l'élément de remplissage absorbant l'eau est de 20 % en poids ou plus.
PCT/JP2021/026973 2020-07-22 2021-07-19 Agent d'étanchéité pour élément d'affichage électroluminescent organique WO2022019267A1 (fr)

Priority Applications (3)

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JP2021544176A JPWO2022019267A1 (fr) 2020-07-22 2021-07-19
CN202180039446.3A CN115943732A (zh) 2020-07-22 2021-07-19 有机el显示元件用密封剂
KR1020227026942A KR20230041956A (ko) 2020-07-22 2021-07-19 유기 el 표시 소자용 봉지제

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KR20140085262A (ko) * 2012-12-27 2014-07-07 제일모직주식회사 유기발광소자용 충진제 및 이를 포함하는 유기발광장치
JP2015504580A (ja) * 2011-11-18 2015-02-12 エルジー・ケム・リミテッド 有機電子装置封止用光硬化型粘接着フィルム、有機電子装置及びその封止方法
JP2016037599A (ja) * 2014-08-05 2016-03-22 古河電気工業株式会社 電子デバイス封止用硬化性吸湿性樹脂組成物、封止樹脂および電子デバイス
KR20190064134A (ko) * 2017-11-30 2019-06-10 (주)엘지하우시스 장식 시트용 점접착 조성물, 표시소자 백커버용 필름 및 표시소자 백커버
WO2019124923A1 (fr) * 2017-12-18 2019-06-27 주식회사 엘지화학 Dispositif électronique organique
JP2019149312A (ja) * 2018-02-27 2019-09-05 味の素株式会社 封止用組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6098091B2 (ja) 2012-09-26 2017-03-22 凸版印刷株式会社 有機エレクトロルミネッセンスパネルの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015504580A (ja) * 2011-11-18 2015-02-12 エルジー・ケム・リミテッド 有機電子装置封止用光硬化型粘接着フィルム、有機電子装置及びその封止方法
KR20140085262A (ko) * 2012-12-27 2014-07-07 제일모직주식회사 유기발광소자용 충진제 및 이를 포함하는 유기발광장치
JP2016037599A (ja) * 2014-08-05 2016-03-22 古河電気工業株式会社 電子デバイス封止用硬化性吸湿性樹脂組成物、封止樹脂および電子デバイス
KR20190064134A (ko) * 2017-11-30 2019-06-10 (주)엘지하우시스 장식 시트용 점접착 조성물, 표시소자 백커버용 필름 및 표시소자 백커버
WO2019124923A1 (fr) * 2017-12-18 2019-06-27 주식회사 엘지화학 Dispositif électronique organique
JP2019149312A (ja) * 2018-02-27 2019-09-05 味の素株式会社 封止用組成物

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CN115943732A (zh) 2023-04-07

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