WO2022019267A1 - Sealant for organic el display element - Google Patents

Sealant for organic el display element 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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WO
WIPO (PCT)
Prior art keywords
organic
display element
meth
examples
sealant
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Application number
PCT/JP2021/026973
Other languages
French (fr)
Japanese (ja)
Inventor
俊隆 吉武
穣 末▲崎▼
真理子 安部
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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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 CN202180039446.3A priority Critical patent/CN115943732A/en
Priority to KR1020227026942A priority patent/KR20230041956A/en
Priority to JP2021544176A priority patent/JPWO2022019267A1/ja
Publication of WO2022019267A1 publication Critical patent/WO2022019267A1/en

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Classifications

    • 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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Abstract

The purpose of the present invention is to provide a sealant for an organic EL display element with which it is possible to obtain an organic EL display element that has exceptional moisture prevention and adhesiveness and that also has exceptional reliability. The present invention is a sealant for an organic EL display element that contains a curable resin and a water-absorbent filler, the sealant being such that: the curable resin contains a (meth) acrylic compound that does not have an isocyanate group or a blocked isocyanate group, and an isocyanate compound or a blocked isocyanate; and the content ratio of the water-absorbent filler is 20 wt% or greater.

Description

有機ＥＬ表示素子用封止剤Encapsulant for organic EL display elements
本発明は、透湿防止性及び接着性に優れ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤に関する。 The present invention relates to a 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.
有機エレクトロルミネッセンス表示素子（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 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.
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る。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 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.
特許文献１には、有機発光材料層を有する積層体を被覆して封止する有機充填層と、該有機充填層の側面を覆う吸湿シール層（封止壁）とを有する構成により、有機ＥＬ表示素子を封止する方法が開示されている。通常、有機ＥＬ表示素子用封止剤として、上記有機充填層には面内封止剤が用いられ、上記封止壁には面内封止剤とは構成成分の異なる周辺封止剤が用いられている。 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. Usually, as 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.
特開２０１４－６７５９８号公報Japanese Unexamined Patent Publication No. 2014-67598
本発明は、透湿防止性及び接着性に優れ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することを目的とする。 It is an object of the present invention to provide 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.
本発明は、硬化性樹脂と吸水性フィラーとを含有し、上記硬化性樹脂は、イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物と、イソシアネート化合物又はブロックイソシアネートとを含み、上記吸水性フィラーの含有割合が２０重量％以上である有機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 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. A sealing agent for an organic EL display element having a content ratio of a sex filler of 20% by weight or more.
The present invention will be described in detail below.
本発明者らは、有機ＥＬ表示素子の表示領域を広く確保すること等の目的で、封止壁を薄くすることを検討した。しかしながら、封止壁を薄くするために周辺封止剤の線幅を狭くして（細線化して）塗布した場合、接着力が充分に得られなかったり、得られる有機ＥＬ表示素子が信頼性に劣るものとなったりすることがあった。特に、透湿防止性を向上させるために周辺封止剤に吸水性フィラーを多量に配合した場合、高温高湿環境下における接着性の低下が顕著であった。そこで本発明者らは、吸水性フィラーを多量に含有する有機ＥＬ表示素子用封止剤について、硬化性樹脂として、イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物と、イソシアネート化合物又はブロックイソシアネートとを含むものとすることを検討した。その結果、得られた有機ＥＬ表示素子用封止剤は、透湿防止性及び接着性に優れ、信頼性に優れる有機ＥＬ表示素子を得ることができるものとなることを見出し、本発明を完成させるに至った。 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. However, when 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. In particular, when a large amount of water-absorbent filler was added to the peripheral sealant in order to improve the moisture permeation prevention property, the adhesiveness was significantly reduced in a high temperature and high humidity environment. Therefore, 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.
本発明の有機ＥＬ表示素子用封止剤は、硬化性樹脂を含有する。
上記硬化性樹脂は、イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物を含む。上記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物を含有することにより、本発明の有機ＥＬ表示素子用封止剤は、硬化性に優れるものとなる。
なお、本明細書において、上記「（メタ）アクリル」は、アクリル又はメタクリルを意味し、上記「（メタ）アクリル化合物」は、（メタ）アクリロイル基を有する化合物を意味し、上記「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味する。 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. By containing the (meth) acrylic compound having no isocyanate group and blocked isocyanate group, the encapsulant for an organic EL display element of the present invention has excellent curability.
In the present specification, the above-mentioned "(meth) acrylic" means acrylic or methacrylic, and the above-mentioned "(meth) acrylic compound" means a compound having a (meth) acryloyl group, and the above-mentioned "(meth)". "Acryloyl" means acryloyl or methacryloyl.
上記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物としては、例えば、ウレタン（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、ノルボルニルメチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、シクロデシル（メタ）アクリレート、４－ｔ－ブチルシクロヘキシル（メタ）アクリレート、トリメチルシクロヘキシル（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシイソプロピル（メタ）アクリレート等が挙げられる。なかでも、上記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物は、得られる有機ＥＬ表示素子用封止剤の接着性及び透湿防止性をより向上させる観点、及び、後述するポリオレフィンとの相溶性を向上させる観点から、脂環式骨格を有する（メタ）アクリル化合物を含むことが好ましい。また、上記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物は、得られる有機ＥＬ表示素子用封止剤の接着性（特に高温高湿環境下における接着性）をより向上させる観点から、多官能（メタ）アクリル化合物を含むことが好ましい。
なお、本明細書において上記「（メタ）アクリレート」は、アクリレート又はメタクリレートを意味し、上記「ウレタン（メタ）アクリレート」は、ウレタン結合と（メタ）アクリロイル基とを有する化合物を意味する。また、「多官能（メタ）アクリル化合物」は、１分子中に２以上の（メタ）アクリロイル基を有する化合物を意味する。 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. (Meta) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclodecyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, trimethyl Examples thereof include cyclohexyl (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxyisopropyl (meth) acrylate. Among them, 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.
In the present specification, the above-mentioned "(meth) acrylate" means acrylate or methacrylate, and the above-mentioned "urethane (meth) acrylate" means a compound having a urethane bond and a (meth) acryloyl group. Further, the "polyfunctional (meth) acrylic compound" means a compound having two or more (meth) acryloyl groups in one molecule.
上記硬化性樹脂全体１００重量部中における上記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物の含有量の好ましい下限は０．０１重量部、好ましい上限は９９．９９重量部である。上記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物の含有量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤が接着性及び保存安定性により優れるものとなる。上記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物の含有量のより好ましい下限は０．１重量部、更に好ましい下限は１０重量部、更により好ましい下限は２０重量部、特に好ましい下限は８０重量部である。 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. When 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.
上記硬化性樹脂は、イソシアネート化合物又はブロックイソシアネートを含有する。上記イソシアネート化合物又は上記ブロックイソシアネートを含有し、かつ、後述する吸水性フィラーの含有割合を後述する範囲とすることにより、本発明の有機ＥＬ表示素子用封止剤は、接着性（特に高温高湿環境下における接着性）に優れ、かつ、得られる有機ＥＬ表示素子が信頼性に優れるものとなる。 The curable resin contains an isocyanate compound or a blocked isocyanate. By containing the isocyanate compound or the blocked isocyanate and setting the content ratio of the water-absorbent filler described later to the range described later, 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.
上記イソシアネート化合物又は上記ブロックイソシアネートは、（メタ）アクリロイル基を有するものであってもよいし、（メタ）アクリロイル基を有さないものであってもよい。なかでも、得られる有機ＥＬ表示素子用封止剤の接着性（特に高温高湿環境下における接着性）及び保存安定性をより向上させる観点から、（メタ）アクリロイル基を有することが好ましい。 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.
上記（メタ）アクリロイル基を有するイソシアネート化合物としては、例えば、２－（メタ）アクリロイルオキシエチルイソシアネート、１，１－（ビス（メタ）アクリロイルオキシメチル）エチルイソシアネート等が挙げられる。なかでも、２－（メタ）アクリロイルオキシエチルイソシアネートが好ましい。 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.
上記（メタ）アクリロイル基を有するブロックイソシアネートとしては、例えば、２－（（３，５－ジメチルピラゾリル）カルボニルアミノ）エチル（メタ）アクリレート、２－（Ｏ－（１’－メチルプロピリデンアミノ）カルボキシアミノ）エチル（メタ）アクリレート、２－（Ｏ－（１’－メチルプロピリデンアミノ）カルボキシアミノ）（メタ）アクリレート等が挙げられる。なかでも、２－（（３，５－ジメチルピラゾリル）カルボニルアミノ）エチル（メタ）アクリレートが好ましい。 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.
上記イソシアネート化合物又は上記ブロックイソシアネートのうち、上記（メタ）アクリロイル基を有さないものとしては、例えば、芳香族イソシアネート、芳香環を有する脂肪族イソシアネート、芳香環を有さない脂肪族イソシアネート、脂環族イソシアネート等が挙げられる。
上記芳香族イソシアネートとしては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、メチレンジフェニルジイソシアネート、メチレンジフェニルジイソシアネートの重合体、フェニレンジイソシアネート、ナフタレンジイソシアネート等が挙げられる。
上記芳香環を有する脂肪族イソシアネートとしては、例えば、α，α，α’，α’－テトラメチルキシリレンジイソシアネート等が挙げられる。
上記芳香環を有さない脂肪族イソシアネートとしては、例えば、メチレンジイソシアネート、プロピレンジイソシアネート、リジンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ヘキサメチレンジイソシアネート等が挙げられる。
上記脂環族イソシアネートとしては、例えば、シクロヘキサンジイソシアネート、メチルシクロヘキサンジイソシアネート、イソホロンジイソシアネート、メチレンビス（４－シクロヘキシルイソシアネート）、イソプロピリデンジシクロヘキシルジイソシアネート等が挙げられる。
なかでも、接着性の観点から、メチレンジフェニルジイソシアネート、メチレンジフェニルジイソシアネートの重合体が好ましい。 Among the isocyanate compounds or the blocked isocyanates, 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.
Examples of the 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 α, α, α', α'-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.
Examples of the alicyclic isocyanate include cyclohexanediisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), isopropyridene dicyclohexyldiisocyanate and the like.
Of these, polymers of methylene diphenyl diisocyanate and methylene diphenyl diisocyanate are preferable from the viewpoint of adhesiveness.
上記イソシアネート化合物又は上記ブロックイソシアネートとしては、接着性の観点からは上記イソシアネート化合物が好ましく、保存安定性の観点からは上記ブロックイソシアネートが好ましい。 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.
上記硬化性樹脂全体１００重量部中における上記イソシアネート化合物又は上記ブロックイソシアネートの含有量の好ましい下限は０．０５重量部、好ましい上限は８重量部である。上記イソシアネート化合物又は上記ブロックイソシアネートの含有量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤が接着性（特に高温高湿環境下における接着性）及び保存安定性により優れるものとなる。上記イソシアネート化合物又は上記ブロックイソシアネート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５重量部である。 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. When 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. Become. 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.
上記硬化性樹脂は、上記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物、及び、上記イソシアネート化合物又は上記ブロックイソシアネートに加えて、その他の硬化性樹脂を含んでもよい。 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.
上記その他の硬化性樹脂としては、エポキシ化合物、オキセタン化合物、（メタ）アクリロイル基を有さないウレタン化合物等も挙げられる。 Examples of the other curable resin include epoxy compounds, oxetane compounds, urethane compounds having no (meth) acryloyl group, and the like.
上記エポキシ化合物としては、例えば、グリシジルエーテル化合物、脂環式エポキシ化合物等が挙げられる。
上記グリシジルエーテル化合物としては、例えば、ジエチレングリコールジグリシジルエーテル等が挙げられる。
上記脂環式エポキシ化合物としては、例えば、３，４－エポキシシクロヘキシルメチル（３，４－エポキシ）シクロヘキサンカルボキシレート、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物等が挙げられる。 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.
上記オキセタン化合物としては、例えば、１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、ジ［２－（３－オキセタニル）ブチル］エーテル、３－エチル－３－ヒドロキシメチルオキセタン等が挙げられる。 Examples of the oxetane compound 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.
上記（メタ）アクリロイル基を有さないウレタン化合物としては、例えば、イソシアネート化合物と任意のポリオール化合物の反応物等が挙げられる。
上記イソシアネート化合物としては、例えば、トルエンジイソシアネート化合物、ジフェニルメタンジイソシアネート化合物等が挙げられる。
上記トルエンジイソシアネート化合物としては、例えば、２，４－トリレンジイソシアネート（２，４－ＴＤＩ）、２，６－トリレンジイソシアネート、又は、これらの混合物等が挙げられる。
上記ジフェニルメタンジイソシアネート化合物としては、例えば、４，４’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、又は、これらの混合物等が挙げられる。 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.
上記硬化性樹脂がブロックイソシアネートを含有する場合、更にアミン化合物を含有することが好ましい。アミン化合物を含ませることで、徐々にブロックイソシアネートをイソシアネートに変換することができ、保存安定性と接着性をともに向上させることができる。
上記アミン化合物としては、例えば、１，４－ジアザビシクロ［２．２．２］オクタン等が挙げられる。
上記アミン化合物の添加量は、上記ブロックイソシアネート１００重量部に対して、１重量部以上２０重量部以下であることが好ましい。 When the curable resin contains a blocked isocyanate, it is preferable that the curable resin further contains an amine compound. By including the amine compound, the blocked isocyanate can be gradually converted to isocyanate, and both storage stability and adhesiveness can be improved.
Examples of 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.
本発明の有機ＥＬ表示素子用封止剤は、吸水性フィラーを含有する。上記吸水性フィラーを含有することにより、本発明の有機ＥＬ表示素子用封止剤は、透湿防止性に優れるものとなる。 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.
上記吸水性フィラーとしては、例えば、アルカリ土類金属の酸化物、酸化マグネシウム、モレキュラーシーブ等が挙げられる。
上記アルカリ土類金属の酸化物としては、例えば、酸化カルシウム、酸化ストロンチウム、酸化バリウム等が挙げられる。
なかでも、吸水性の観点から、アルカリ土類金属の酸化物が好ましく、酸化カルシウムがより好ましい。
これらの吸水性フィラーは、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 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.
本発明の有機ＥＬ表示素子用封止剤中における上記吸水性フィラーの含有割合の下限は２０重量％である。上記吸水性フィラーの含有割合が２０重量％以上であることにより、本発明の有機ＥＬ表示素子用封止剤は、透湿防止性に優れるものとなる。また、本発明の有機ＥＬ表示素子用封止剤は、上記イソシアネート化合物又は上記ブロックイソシアネートを含有することにより、上記吸水性フィラーを多量に配合しても、接着性（特に高温高湿環境下における接着性）に優れ、かつ、得られる有機ＥＬ表示素子が信頼性に優れるものとなる。上記吸水性フィラーの含有割合の好ましい下限は３０重量％、より好ましい下限は４０重量％である。
また、塗布性等の観点から、上記吸水性フィラーの含有割合の好ましい上限は７０重量％、より好ましい上限は６０重量％である。 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. When the content ratio of the water-absorbent filler is 20% by weight or more, the sealing agent for an organic EL display element of the present invention has excellent moisture permeation prevention properties. Further, 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.
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、上記吸水性フィラーに加えて、その他のフィラーを含有してもよい。
上記その他のフィラーとしては、無機フィラーや有機フィラーを用いることができる。
上記無機フィラーとしては、例えば、シリカ、タルク、アルミナ等が挙げられる。
上記有機フィラーとしては、例えば、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が挙げられる。なかでも、タルクが好ましい。 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.
As the above-mentioned other filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, and alumina.
Examples of 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.
本発明の有機ＥＬ表示素子用封止剤は、ポリオレフィンを含有することが好ましい。
上記ポリオレフィンを含有することにより、本発明の有機ＥＬ表示素子用封止剤は、透湿防止性により優れるものとなる。 The encapsulant for an organic EL display element of the present invention preferably contains polyolefin.
By containing the above-mentioned polyolefin, the sealing agent for an organic EL display element of the present invention becomes more excellent in moisture permeation prevention property.
上記ポリオレフィンとしては、透湿防止性を更に向上させる観点から、ポリイソブチレン、ポリブテン、及び、ポリブタジエンからなる群より選択される少なくとも１種を含むことが好ましく、ポリイソブチレンを含むことがより好ましい。
上記ポリオレフィンは、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 From the viewpoint of further improving the 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.
上記ポリオレフィンの重量平均分子量の好ましい下限は１万、好ましい上限は４０万である。上記ポリオレフィンの重量平均分子量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤が塗布性、接着性、及び、透湿防止性により優れるものとなる。上記ポリオレフィンの重量平均分子量のより好ましい下限は２万、より好ましい上限は７万である。
なお、本明細書において上記「重量平均分子量」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で溶媒としてテトラヒドロフランを用いて測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による重量平均分子量を測定する際に用いるカラムとしては、例えば、Ｓｈｏｄｅｘ　ＬＦ－８０４（昭和電工社製）等が挙げられる。 The preferable lower limit of the weight average molecular weight of the polyolefin is 10,000, and the preferable upper limit is 400,000. When the weight average molecular weight of the polyolefin is in this range, the obtained sealing agent for an organic EL display element is excellent in coatability, adhesiveness, and moisture permeation prevention property. 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.
In the present specification, 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.
上記硬化性樹脂と上記ポリオレフィンとの合計１００重量部中における上記ポリオレフィンの含有量の好ましい下限は１０重量部、好ましい上限は８０重量部である。上記ポリオレフィンの含有量が１０重量部以上であることにより、得られる有機ＥＬ表示素子用封止剤が透湿防止性により優れるものとなる。上記ポリオレフィンの含有量が８０重量部以下であることにより、得られる有機ＥＬ表示素子用封止剤が塗布性や接着性により優れるものとなる。上記ポリオレフィン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６０重量部である。 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. When 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. When 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.
本発明の有機ＥＬ表示素子用封止剤は、接着性を更に向上させること等を目的として、粘着付与樹脂を含有してもよい。
上記粘着付与樹脂としては、例えば、テルペン樹脂、変性テルペン樹脂、クマロン樹脂、インデン樹脂、石油樹脂等が挙げられる。
上記変性テルペン樹脂としては、例えば、水素添加テルペン樹脂、テルペンフェノール共重合樹脂、芳香族変性テルペン樹脂等が挙げられる。
上記石油樹脂としては、例えば、脂肪族系石油樹脂、水添脂環式石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂、脂環族系石油樹脂、ジシクロペンタジエン系石油樹脂及びその水素化物等が挙げられる。
なかでも、上記粘着付与樹脂としては、有機ＥＬ表示素子用封止剤の接着性、耐透湿性、相溶性等の観点から、テルペン樹脂、芳香族変性テルペン樹脂、テルペンフェノール共重合樹脂、水添脂環式石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂、脂環族系石油樹脂が好ましく、脂環族系石油樹脂がより好ましく、脂環族飽和炭化水素樹脂、脂環族不飽和炭化水素樹脂が更に好ましく、シクロヘキシル環含有飽和炭化水素樹脂、ジシクロペンタジエン変性炭化水素樹脂が特に好ましい。
これらの粘着付与樹脂は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 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.
Examples of the tackifier resin include terpene resin, modified terpene resin, kumaron resin, inden resin, petroleum resin and the like.
Examples of the modified terpene resin include hydrogenated terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin and the like.
Examples of 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.
Among them, 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.
上記粘着付与樹脂の含有量は、上記硬化性樹脂（上記ポリオレフィンを含有する場合は上記硬化性樹脂と上記ポリオレフィンとの合計）１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が１００重量部である。上記粘着付与樹脂の含有量がこの範囲であることにより、透湿防止性を維持しつつ、接着性を向上させる効果をより発揮することができる。上記粘着付与樹脂の含有量のより好ましい下限は０．２重量部、より好ましい上限は２０重量部である。 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. When 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.
本発明の有機ＥＬ表示素子用封止剤は、重合開始剤を含有することが好ましい。
上記重合開始剤としては、ラジカル重合開始剤やカチオン重合開始剤を用いることができる。なかでも、ラジカル重合開始剤が好ましい。 The encapsulant for an organic EL display element of the present invention preferably contains a polymerization initiator.
As the polymerization initiator, a radical polymerization initiator or a cationic polymerization initiator can be used. Of these, a radical polymerization initiator is preferable.
上記ラジカル重合開始剤としては、光ラジカル重合開始剤や熱ラジカル重合開始剤が挙げられる。 Examples of the radical polymerization initiator include a photoradical polymerization initiator and a thermal radical polymerization initiator.
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン化合物、アセトフェノン化合物、アシルフォスフィンオキサイド化合物、チタノセン化合物、オキシムエステル化合物、ベンゾインエーテル化合物、チオキサントン化合物等が挙げられる。
上記光ラジカル重合開始剤としては、具体的には例えば、１－ヒドロキシシクロヘキシルフェニルケトン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン、１，２－（ジメチルアミノ）－２－（（４－メチルフェニル）メチル）－１－（４－（４－モルホリニル）フェニル）－１－ブタノン、２，２－ジメトキシ－２－フェニルアセトフェノン、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、１－（４－（２－ヒドロキシエトキシ）－フェニル）－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、１－（４－（フェニルチオ）フェニル）－１，２－オクタンジオン２－（Ｏ－ベンゾイルオキシム）、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等が挙げられる。 Examples of the photoradical polymerization initiator 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). -2-((4-Methylphenyl) Methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2,2-dimethoxy-2-phenylacetophenone, bis (2,4,6-trimethyl) Phenyl) Phenylphosphinoxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2- Methyl-1-propane-1-one, 1- (4- (phenylthio) phenyl) -1,2-octanedione 2- (O-benzoyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoinmethyl Examples thereof include ether, benzoin ethyl ether, benzoin isopropyl ether and the like.
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。
上記アゾ化合物としては、例えば、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、アゾビスイソブチロニトリル等が挙げられる。
上記有機過酸化物としては、例えば、過酸化ベンゾイル、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネート等が挙げられる。 Examples of the thermal radical polymerization initiator include those made of an azo compound, an organic peroxide and the like.
Examples of the azo compound include 2,2'-azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile and the like.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate and the like.
上記熱ラジカル重合開始剤のうち市販されているものとしては、例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１、Ｖ－５０１（いずれも富士フイルム和光純薬社製）等が挙げられる。 Commercially available 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.
上記カチオン重合開始剤としては、光カチオン重合開始剤や熱カチオン重合開始剤が挙げられる。 Examples of the cationic polymerization initiator include a photocationic polymerization initiator and a thermal cationic polymerization initiator.
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 protonic acid or Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type. May be.
上記イオン性光酸発生型の光カチオン重合開始剤のアニオン部分としては、例えば、ＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－（但し、Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す）等が挙げられる。
上記イオン性光酸発生型の光カチオン重合開始剤としては、例えば、上記アニオン部分を有する、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ジアゾニウム塩、芳香族アンモニウム塩、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩等が挙げられる。 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.
Examples of 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.
上記芳香族スルホニウム塩としては、例えば、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロホスフェート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラフルオロボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリアリールスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、トリス（４－（４－アセチルフェニル）チオフェニル）スルホニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4-( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexa Fluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triarylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (di (4- (2-hydroxyethoxy)) phenyl) Sulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, bis (4- (di (4- (4- (2-hydroxyethoxy))) 2-Hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, tris (4- (4-Acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like can be mentioned.
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, and bis. (Dodecylphenyl) Iodineium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4-( 1-Methylethyl) Phenyliodonium tetrakis (pentafluorophenyl) borate and the like 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 and 1-benzyl. -2-Cyanopyridinium tetrakis (pentafluorophenyl) boronate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) Examples thereof include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) volate.
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-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1) -Il) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta) Fluorophenyl) Borate and the like can be mentioned.
上記非イオン性光酸発生型の光カチオン重合開始剤としては、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ－ヒドロキシイミドスルホネート等が挙げられる。 Examples of the nonionic photoacid generation type photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid 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、みどり化学社製の光カチオン重合開始剤、ユニオンカーバイド社製の光カチオン重合開始剤、ＡＤＥＫＡ社製の光カチオン重合開始剤、３Ｍ社製の光カチオン重合開始剤、ＢＡＳＦ社製の光カチオン重合開始剤、ローディア社製の光カチオン重合開始剤等が挙げられる。
上記みどり化学社製の光カチオン重合開始剤としては、例えば、ＤＴＳ－２００等が挙げられる。
上記ユニオンカーバイド社製の光カチオン重合開始剤としては、例えば、ＵＶＩ６９９０、ＵＶＩ６９７４等が挙げられる。
上記ＡＤＥＫＡ社製の光カチオン重合開始剤としては、例えば、ＳＰ－１５０、ＳＰ－１７０等が挙げられる。
上記３Ｍ社製の光カチオン重合開始剤としては、例えば、ＦＣ－５０８、ＦＣ－５１２等が挙げられる。
上記ＢＡＳＦ社製の光カチオン重合開始剤としては、例えば、ＩＲＧＡＣＵＲＥ２６１、ＩＲＧＡＣＵＲＥ２９０等が挙げられる。
上記ローディア社製の光カチオン重合開始剤としては、例えば、ＰＩ２０７４等が挙げられる。 Commercially available 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.
上記熱カチオン重合開始剤としては、アニオン部分がＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－（但し、Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す）で構成される、スルホニウム塩、ホスホニウム塩、アンモニウム塩等が挙げられる。なかでも、スルホニウム塩、アンモニウム塩が好ましい。 As the thermal cationic polymerization initiator, the 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.
上記スルホニウム塩としては、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムヘキサフルオロアンチモネート等が挙げられる。 Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
上記ホスホニウム塩としては、エチルトリフェニルホスホニウムヘキサフルオロアンチモネート、テトラブチルホスホニウムヘキサフルオロアンチモネート等が挙げられる。 Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
上記アンモニウム塩としては、例えば、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロホスフェート、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メトキシベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロホスフェート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロテトラキス（ペンタフルオロフェニル）ボレート、メチルフェニルジベンジルアンモニウムヘキサフルオロホスフェート、メチルフェニルジベンジルアンモニウムヘキサフルオロアンチモネート、メチルフェニルジベンジルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、フェニルトリベンジルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（３，４－ジメチルベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルアニリニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルアニリニウムテトラフルオロボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルピリジニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルピリジニウムトリフルオロメタンスルホン酸等が挙げられる。 Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, and dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl). Borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl Dibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethyl) Benzyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N- Benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid and the like can be mentioned.
上記熱カチオン重合開始剤のうち市販されているものとしては、例えば、三新化学工業社製の熱カチオン重合開始剤、Ｋｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製の熱カチオン重合開始剤等が挙げられる。
上記三新化学工業社製の熱カチオン重合開始剤としては、例えば、サンエイドＳＩ－６０、サンエイドＳＩ－８０、サンエイドＳＩ－Ｂ３、サンエイドＳＩ－Ｂ３Ａ、サンエイドＳＩ－Ｂ４等が挙げられる。
上記Ｋｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製の熱カチオン重合開始剤としては、例えば、ＣＸＣ－１６１２、ＣＸＣ－１８２１等が挙げられる。 Examples of commercially available thermal cationic polymerization initiators include thermal cationic polymerization initiators manufactured by Sanshin Chemical Industry Co., Ltd., thermal cationic polymerization initiators manufactured by King Industries, and the like.
Examples of the thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd. include Sun Aid SI-60, Sun Aid SI-80, Sun Aid SI-B3, Sun Aid SI-B3A, and Sun Aid SI-B4.
Examples of the thermal cationic polymerization initiator manufactured by King Industries include CXC-1612, CXC-1821 and the like.
上記重合開始剤の含有量は、上記硬化性樹脂（上記ポリオレフィンを含有する場合は上記硬化性樹脂と上記ポリオレフィンとの合計）１００重量部に対して、好ましい下限が０．０５重量部、好ましい上限が１０重量部である。上記重合開始剤の含有量が０．０５重量部以上であることにより、得られる有機ＥＬ表示素子用封止剤が硬化性により優れるものとなる。上記重合開始剤の含有量が１０重量部以下であることにより、得られる有機ＥＬ表示素子用封止剤の硬化反応が速くなり過ぎず、作業性により優れるものとなり、硬化物をより均一なものとすることができる。上記重合開始剤の含有量のより好ましい下限は１重量部、より好ましい上限は３重量部である。 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. When 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. When 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. Can be. 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.
本発明の有機ＥＬ表示素子用封止剤は、増感剤を含有してもよい。上記増感剤は、上記重合開始剤の重合開始効率をより向上させて、本発明の有機ＥＬ表示素子用封止剤の硬化反応をより促進させる役割を有する。 The encapsulant for an organic EL display element of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the encapsulant for an organic EL display element of the present invention.
上記増感剤としては、例えば、アントラセン系化合物、チオキサントン系化合物、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、ベンゾフェノン、２，４－ジクロロベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド等が挙げられる。
上記アントラセン系化合物としては、例えば、９，１０－ジブトキシアントラセン等が挙げられる。
上記チオキサントン系化合物としては、例えば、２，４－ジエチルチオキサントン等が挙げられる。
これらの増感剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 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.
上記増感剤の含有量は、上記硬化性樹脂（上記ポリオレフィンを含有する場合は上記硬化性樹脂と上記ポリオレフィンとの合計）１００重量部に対して、好ましい下限が０．０５重量部、好ましい上限が３重量部である。上記増感剤の含有量が０．０５重量部以上であることにより、増感効果がより発揮される。上記増感剤の含有量が３重量部以下であることにより、吸収が大きくなり過ぎずに深部まで光を伝えることができる。上記増感剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は１重量部である。 The content of the sensitizer 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. When the content of the sensitizer is 0.05 parts by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption. The 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.
本発明の有機ＥＬ表示素子用封止剤は、熱硬化剤を含有してもよい。
上記熱硬化剤としては、例えば、ヒドラジド化合物、イミダゾール誘導体、酸無水物、ジシアンジアミド、グアニジン誘導体、変性脂肪族ポリアミン、各種アミンとエポキシ樹脂との付加生成物等が挙げられる。 The sealing agent for an organic EL display element of the present invention may contain a thermosetting agent.
Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.
上記ヒドラジド化合物としては、例えば、１，３－ビス（ヒドラジノカルボエチル）－５－イソプロピルヒダントイン、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、マロン酸ジヒドラジド等が挙げられる。
上記イミダゾール誘導体としては、例えば、１－シアノエチル－２－フェニルイミダゾール、Ｎ－（２－（２－メチル－１－イミダゾリル）エチル）尿素、２，４－ジアミノ－６－（２’－メチルイミダゾリル－（１’））－エチル－ｓ－トリアジン、Ｎ，Ｎ’－ビス（２－メチル－１－イミダゾリルエチル）尿素、Ｎ，Ｎ’－（２－メチル－１－イミダゾリルエチル）－アジポアミド、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール等が挙げられる。
上記酸無水物としては、例えば、テトラヒドロ無水フタル酸、エチレングリコールビス（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種以上が組み合わせて用いられてもよい。 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-). (1'))-Ethyl-s-triazine, N, N'-bis (2-methyl-1-imidazolylethyl) urea, N, N'-(2-methyl-1-imidazolylethyl) -adipamide, 2- Examples thereof include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydrotrimeritate) and the like.
These thermosetting agents may be used alone or in combination of two or more.
上記熱硬化剤のうち市販されているものとしては、例えば、ＳＤＨ（日本ファインケム社製）、ＡＤＨ（大塚化学社製）、アミキュアＶＤＨ、アミキュアＶＤＨ－Ｊ、アミキュアＵＤＨ（いずれも味の素ファインテクノ社製）等が挙げられる。 Commercially available 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.
上記熱硬化剤の含有量は、上記硬化性樹脂（上記ポリオレフィンを含有する場合は上記硬化性樹脂と上記ポリオレフィンとの合計）１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が１０重量部である。上記熱硬化剤の含有量が０．０１重量部以上であることにより、得られる有機ＥＬ表示素子用封止剤が熱硬化性により優れるものとなる。上記熱硬化剤の含有量が１０重量部以下であることにより、得られる有機ＥＬ表示素子用封止剤が保存安定性により優れるものとなる。上記熱硬化剤の含有量のより好ましい下限は０．５重量部、より好ましい上限は５重量部、更に好ましい下限は１重量部、更に好ましい上限は３重量部である。 Regarding the content of the thermosetting agent, 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. When 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. When 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.
本発明の有機ＥＬ表示素子用封止剤は、安定剤を含有してもよい。上記安定剤を含有することにより、本発明の有機ＥＬ表示素子用封止剤は、より保存安定性に優れるものとなる。 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.
上記安定剤としては、例えば、芳香族アミン化合物、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン－１－オキシル等が挙げられる。
上記芳香族アミン化合物としては、例えば、ベンジルアミン、アミノフェノール型エポキシ樹脂等が挙げられる。
なかでも、芳香族アミン化合物が好ましく、ベンジルアミンがより好ましい。
これらの安定剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 Examples of the stabilizer include aromatic amine compounds, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl and the like.
Examples of the aromatic amine compound 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.
上記安定剤の含有量は、上記硬化性樹脂（上記ポリオレフィンを含有する場合は上記硬化性樹脂と上記ポリオレフィンとの合計）１００重量部に対して、好ましい下限が０．００１重量部、好ましい上限が２重量部である。上記安定剤の含有量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤が優れた硬化性を維持したまま保存安定性により優れるものとなる。上記安定剤の含有量のより好ましい下限は０．００５重量部、より好ましい上限は１重量部である。 Regarding the content of the stabilizer, 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. When 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.
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 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.
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種以上が組み合わせて用いられてもよい。 Examples of the silane coupling agent 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.
上記シランカップリング剤の含有量は、上記硬化性樹脂（上記ポリオレフィンを含有する場合は上記硬化性樹脂と上記ポリオレフィンとの合計）１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記シランカップリング剤の含有量がこの範囲であることにより、余剰のシランカップリング剤のブリードアウトを防止しつつ、得られる有機ＥＬ表示素子用封止剤の接着性を向上させる効果により優れるものとなる。上記シランカップリング剤の含有量のより好ましい下限は０．５重量部、より好ましい上限は５重量部である。 The content of the silane coupling agent is preferably 0.1 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. When the content of the silane coupling agent is in this range, it is more excellent in the effect of improving the adhesiveness of the obtained sealing agent for organic EL display elements while preventing the bleed-out of the excess silane coupling agent. Will be. 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.
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表示素子用封止剤の塗膜の平坦性を向上させることができる。
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 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. 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.
Examples of the surface modifier include a surfactant, a leveling agent and the like.
上記表面改質剤としては、例えば、シリコーン系、アクリル系、フッ素系等のものが挙げられる。
上記表面改質剤のうち市販されているものとしては、例えば、ビックケミー・ジャパン社製の表面改質剤、楠本化成社製の表面改質剤、ＡＧＣセイミケミカル社製の表面改質剤等が挙げられる。
上記ビックケミー・ジャパン社製の表面改質剤としては、例えば、ＢＹＫ－３００、ＢＹＫ－３０２、ＢＹＫ－３３１等が挙げられる。
上記楠本化成社製の表面改質剤としては、例えば、ＵＶＸ－２７２等が挙げられる。
上記ＡＧＣセイミケミカル社製の表面改質剤としては、例えば、サーフロンＳ－６１１等が挙げられる。 Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based agents.
Among the above surface modifiers, 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.
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、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及び／又はイオン交換樹脂を含有してもよい。 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.
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, such as 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 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.
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。 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.
本発明の有機ＥＬ表示素子用封止剤は、アウトガスの発生をより抑制する観点から、溶剤を含有しないことが好ましい。本発明の有機ＥＬ表示素子用封止剤は、溶剤を含有しなくても、塗布性に優れるものとすることができる。
なお、本明細書において「溶剤を含有しない」とは、溶剤の含有量が１０００ｐｐｍ未満であることを意味する。 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.
In the present specification, "solvent-free" means that the solvent content is less than 1000 ppm.
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、混合機を用いて、ポリオレフィンと、硬化性樹脂と、吸水性フィラーと、重合開始剤及び／又は熱硬化剤や必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。
上記混合機としては、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本ロール等が挙げられる。 As 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. Examples thereof include a method of mixing with an additive such as a silane coupling agent to be added according to the above.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
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℃、２．５ｒｐｍの条件で測定される粘度の好ましい上限は１０００Ｐａ・ｓである。上記粘度が１０００Ｐａ・ｓ以下であることにより、得られる有機ＥＬ表示素子用封止剤が塗布性に優れるものとなる。上記粘度のより好ましい上限は５００Ｐａ・ｓである。
また、上記粘度の好ましい下限は特にないが、実質的な下限は１００Ｐａ・ｓである。 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. When 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.
Further, although there is no particular preferable lower limit of the viscosity, a practical lower limit is 100 Pa · s.
本発明の有機ＥＬ表示素子用封止剤は、８５℃、８５％ＲＨの環境下で５００時間保管した後の硬化物のガラスに対する接着力の好ましい下限が０．８ｋｇｆ／ｃｍ２である。上記８５℃、８５％ＲＨの環境下で５００時間保管した後の硬化物のガラスに対する接着力が０．８ｋｇｆ／ｃｍ２以上であることにより、本発明の有機ＥＬ表示素子用封止剤は、有機ＥＬ表示素子用周辺封止剤として好適に用いることができる。上記８５℃、８５％ＲＨの環境下で５００時間保管した後の硬化物のガラスに対する接着力のより好ましい下限は１．２ｋｇｆ／ｃｍ２である。
上記８５℃、８５％ＲＨの環境下で５００時間保管した後の硬化物のガラスに対する接着力の好ましい上限は特にないが、実質的な上限は３．０ｋｇｆ／ｃｍ２である。 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 .
There is no particular preferable upper limit of the adhesive strength of the cured product to the glass after storage in the environment of 85 ° C. and 85% RH for 500 hours, but the practical upper limit is 3.0 kgf / cm 2 .
本発明の有機ＥＬ表示素子用封止剤の硬化物は、有機ＥＬ表示素子の周縁部を囲む封止壁に用いられることが好ましい。即ち、本発明の有機ＥＬ表示素子用封止剤は、有機発光材料層を有する積層体の周囲に封止壁を形成するための有機ＥＬ表示素子用周辺封止剤として用いられることが好ましい。上記有機ＥＬ表示素子用周辺封止剤は、通常、該積層体を被覆する有機ＥＬ表示素子用面内封止剤と組み合わせて用いられる。 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.
本発明の有機ＥＬ表示素子用封止剤の硬化物を用いてなる封止壁は、得られる有機ＥＬ表示素子の表示領域を広く確保する等の観点から、線幅方向の厚さが好ましくは５ｍｍ以下、より好ましくは３ｍｍ以下、更に好ましくは２ｍｍ以下である。本発明の有機ＥＬ表示素子用封止剤は透湿防止性、接着性及び信頼性に優れるため、封止壁を上記上限以下の厚さとすることができる。封止壁の線幅方向の厚さの下限は特に限定されないが、例えば、０．５ｍｍである。 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.
本発明によれば、透湿防止性及び接着性に優れ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することができる。 According to the present invention, it is possible to provide 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.
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, but the present invention is not limited to these examples.
（実施例１～９、比較例１、２）
表１、２に記載された配合比に従い、各材料を、撹拌混合機を用い、撹拌速度２０００ｒｐｍで３分間撹拌混合して、実施例１～９、比較例１、２の有機ＥＬ表示素子用封止剤を作製した。上記撹拌混合機としては、ＡＲ－２５０（シンキー社製）を用いた。
なお、表１、２における酸化カルシウムとしては、粒径が１０μｍ以下になるようにボールミル（日陶科学社製、「ＡＮＺ－５３Ｄ」）によって乾式バッチ粉砕したものを使用した。 (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. As the stirring mixer, AR-250 (manufactured by Shinky Co., Ltd.) was used.
As 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 μm or less.
＜評価＞
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤について、以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluations were performed on the sealants for each organic EL display element obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.
（１）粘度及び保存安定性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤について、Ｅ型粘度計を用いて、２５℃にて、製造直後の初期粘度を測定した。
また、各有機ＥＬ表示素子用封止剤を製造後２週間冷凍保管した後、解凍して２５℃における粘度を測定し、（２週間冷凍保管後の粘度）／（初期粘度）を粘度変化率とした。粘度変化率が１．１未満であった場合を「◎」、１．１以上１．３未満であった場合を「○」、１．３以上１．５未満であった場合を「△」、１．５以上であった場合を「×」として保存安定性を評価した。
上記Ｅ型粘度計としては、ＶＩＳＣＯＭＥＴＥＲ　ＴＶ－２２（東機産業社製）を用いた。 (1) 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.
（２）接着性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤１０ｇに対して、直径１０μｍのスペーサー粒子０．０３ｇを加え、撹拌混合機を用いて均一に分散させた。上記スペーサー粒子としては、ミクロパールＳＰ－２１０（積水化学工業社製）を用い、上記撹拌混合機としては、ＡＲＶ－３１０（シンキー社製）を用いた。スペーサー粒子を分散させた有機ＥＬ表示素子用封止剤をガラス基板Ａ上の中心部に塗布した後、ガラス基板Ｂを十字になるように交差させて貼り付け、加圧して厚みを均一にした。加圧して厚みが均一になった後の有機ＥＬ表示素子用封止剤が直径５．０～７．０ｍｍの円形となるように、有機ＥＬ表示素子用封止剤の塗布量を調整した。上記ガラス基板Ａ、Ｂは、長さ６０ｍｍ、幅３０ｍｍ、厚さ５ｍｍのガラスの表面をアセトンで洗浄した後、乾燥させたものである。次いで、ＵＶ－ＬＥＤ照射装置にて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して有機ＥＬ表示素子用封止剤を硬化させることにより、ガラス基板Ａとガラス基板Ｂとを接着し、初期接着性評価用の試験片を得た。また、初期接着性評価用の試験片と同様にしてガラス基板Ａとガラス基板Ｂとを接着した後、８５℃、８５％ＲＨの高温高湿条件に５００時間暴露して高温高湿環境に曝した後の接着性評価用の試験片を得た。
それぞれの試験片について、ガラス基板Ｂが下になるように配置してガラス基板Ａの両端を下から固定し、ガラス基板Ｂの両端を精密万能試験機にて２３℃、速度５ｍｍ／分の条件で上から圧縮することで、ガラス基板Ａとガラス基板Ｂとの接着力を測定した。圧縮する箇所は、ガラス基板Ｂの両端から７．２５ｍｍの位置を中心として、縦２０ｍｍ、横幅５ｍｍの範囲とした。上記精密万能試験機としては、オートグラフＡＧ－Ｘｐｌｕｓ（島津製作所製）を用いた。
接着力は、精密万能試験機による圧縮開始からガラス基板Ａとガラス基板Ｂが完全にはがれるまでの最大荷重を、試験片の有機ＥＬ表示素子用封止剤の面積で割った値とした。接着力が２．０ｋｇｆ／ｃｍ２以上であった場合を「◎」、２．０ｋｇｆ／ｃｍ２未満１．５ｋｇｆ／ｃｍ２以上であった場合を「○」、１．５ｋｇｆ／ｃｍ２未満０．８ｋｇｆ／ｃｍ２以上であった場合を「△」、０．８ｋｇｆ／ｃｍ２未満であった場合を「×」として、初期接着性、及び、高温高湿環境に曝した後の接着性を評価した。 (2) Adhesiveness 0.03 g of spacer particles having a diameter of 10 μm 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. Next, 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. Further, after 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. As 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. "◎" when the adhesive strength is 2.0 kgf / cm 2 or more, "○" when the adhesive strength is less than 2.0 kgf / cm 2 1.5 kgf / cm 2 or more, less than 1.5 kgf / cm 2 0 The initial adhesiveness and the adhesiveness after exposure to a high temperature and high humidity environment are defined as "△" when the weight is 8 kgf / cm 2 or more and "x" when the weight is less than 0.8 kgf / cm 2. evaluated.
（３）透湿防止性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤について、以下のＣａ－ＴＥＳＴを行った。
まず、実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤１０ｇに対して、直径１０μｍのスペーサー粒子０．０３ｇを加え、撹拌混合機を用いて均一に分散させた。上記スペーサー粒子としては、ミクロパールＳＰ－２１０（積水化学工業社製）を用い、上記撹拌混合機としては、ＡＲＶ－３１０（シンキー社製）を用いた。次いで、スペーサー粒子を分散させた有機ＥＬ表示素子用封止剤をガラス基板の表面に塗布した。
次に、３０ｍｍ×３０ｍｍの大きさの別のガラス基板に２ｍｍ×２ｍｍの開口部を複数有するマスクを被せ、Ｃａを真空蒸着装置により蒸着させた。蒸着の条件は、真空蒸着装置の蒸着器内を２×１０－３Ｐａまで減圧してＣａを５．０Å／ｓの蒸着速度で２０００Å成膜するものとした。Ｃａを蒸着したガラス基板を露点（－６０℃以上）に管理されたグローブボックス内に移動させ、表面に有機ＥＬ表示素子用封止剤を塗布したガラス基板と、Ｃａを蒸着したガラス基板とを、有機ＥＬ表示素子用封止剤がＣａの蒸着パターン上となるようにして貼り合わせた。加圧して有機ＥＬ表示素子用封止剤層の厚みを均一にした後、ＵＶ－ＬＥＤ照射装置にて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して有機ＥＬ表示素子用封止剤を硬化させ、Ｃａ－ＴＥＳＴ基板を作製した。
得られたＣａ－ＴＥＳＴ基板を、８５℃、８５％ＲＨの高温高湿条件に暴露し、有機ＥＬ表示素子用封止剤の硬化物からなる層へのガラス基板端面からの水分の浸入距離をＣａの消失から観測した。
その結果、高温高湿条件の暴露時間が９００時間のときの、水分の浸入距離が１．８ｍｍ未満であった場合を「◎」、１．８ｍｍ以上２．１ｍｍ未満であった場合を「○」、２．１ｍｍ以上２．４ｍｍ未満であった場合を「△」、２．４ｍｍ以上であった場合を「×」として透湿防止性を評価した。 (3) Moisture Permeability Prevention The following Ca-TEST was performed on each of the sealants for organic EL display elements obtained in Examples and Comparative Examples.
First, 0.03 g of spacer particles having a diameter of 10 μm was added to 10 g of the encapsulant 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. Next, a sealing agent for an organic EL display element in which spacer particles were dispersed was applied to the surface of the glass substrate.
Next, another glass substrate having a size of 30 mm × 30 mm was covered with a mask having a plurality of openings of 2 mm × 2 mm, and Ca was vapor-deposited by a vacuum vapor deposition apparatus. The conditions for vapor deposition were such that the inside of the vapor deposition device of the vacuum vapor deposition apparatus was depressurized to 2 × 10 -3 Pa to form 2000 Å of Ca at a vapor deposition rate of 5.0 Å / s. 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. After pressurizing to make the thickness of the sealant layer for the organic EL display element uniform, 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.
As a result, when 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 “Δ”, and the case of 2.4 mm or more was evaluated as “x” to evaluate the moisture permeation prevention property.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
本発明によれば、透湿防止性及び接着性に優れ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することができる。 According to the present invention, it is possible to provide 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.

Claims (9)

  1. 硬化性樹脂と吸水性フィラーとを含有し、
    前記硬化性樹脂は、イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物と、イソシアネート化合物又はブロックイソシアネートとを含み、
    前記吸水性フィラーの含有割合が２０重量％以上である
    ことを特徴とする有機ＥＬ表示素子用封止剤。     Contains curable resin and water-absorbent filler,
    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.
    A sealing agent for an organic EL display element, wherein the content ratio of the water-absorbent filler is 20% by weight or more.
  2. 前記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物は、脂環式骨格を有する（メタ）アクリル化合物を含む請求項１記載の有機ＥＬ表示素子用封止剤。 The sealant for an organic EL display element according to claim 1, wherein the (meth) acrylic compound having no isocyanate group and a blocked isocyanate group contains a (meth) acrylic compound having an alicyclic skeleton.
  3. 前記イソシアネート基及びブロックイソシアネート基を有さない（メタ）アクリル化合物は、多官能（メタ）アクリル化合物を含む請求項１又は２記載の有機ＥＬ表示素子用封止剤。 The sealant for an organic EL display element according to claim 1 or 2, wherein the (meth) acrylic compound having no isocyanate group and a blocked isocyanate group is a polyfunctional (meth) acrylic compound.
  4. 前記イソシアネート化合物又は前記ブロックイソシアネートは、（メタ）アクリロイル基を有する請求項１、２又は３記載の有機ＥＬ表示素子用封止剤。 The sealant for an organic EL display element according to claim 1, 2 or 3, wherein the isocyanate compound or the blocked isocyanate has a (meth) acryloyl group.
  5. 前記吸水性フィラーは、酸化カルシウムを含む請求項１、２、３又は４記載の有機ＥＬ表示素子用封止剤。 The sealant for an organic EL display element according to claim 1, 2, 3 or 4, wherein the water-absorbent filler contains calcium oxide.
  6. 更に、ポリオレフィンを含有する請求項１、２、３、４又は５記載の有機ＥＬ表示素子用封止剤。 The sealant for an organic EL display element according to claim 1, 2, 3, 4 or 5, further containing a polyolefin.
  7. Ｅ型粘度計を用いて、２５℃、２．５ｒｐｍの条件で測定される粘度が１０００Ｐａ・ｓ以下である請求項１、２、３、４、５又は６記載の有機ＥＬ表示素子用封止剤。 The encapsulation for an organic EL display element according to claim 1, 2, 3, 4, 5 or 6, wherein the viscosity measured at 25 ° C. and 2.5 rpm using an E-type viscometer is 1000 Pa · s or less. Agent.
  8. ８５℃、８５％ＲＨの環境下で５００時間保管した後の硬化物のガラスに対する接着力が０．８ｋｇｆ／ｃｍ２以上である請求項１、２、３、４、５、６又は７記載の有機ＥＬ表示素子用封止剤。 The invention according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the cured product has an adhesive force of 0.8 kgf / cm 2 or more after being stored in an environment of 85 ° C. and 85% RH for 500 hours. Encapsulant for organic EL display elements.
  9. 有機発光材料層を有する積層体の周囲に封止壁を形成するための有機ＥＬ表示素子用周辺封止剤として用いられる請求項１、２、３、４、５、６、７又は８記載の有機ＥＬ表示素子用封止剤。 The invention according to claim 1, 2, 3, 4, 5, 6, 7 or 8, which is used as a peripheral sealant for an organic EL display element for forming a sealing wall around a laminate having an organic light emitting material layer. Encapsulant for organic EL display elements.
PCT/JP2021/026973 2020-07-22 2021-07-19 Sealant for organic el display element WO2022019267A1 (en)

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