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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
  • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
  • H01L23/293—Organic, e.g. plastic
• • 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 cured product that can be used for a sealing wall formed around a laminate having an organic light emitting material layer to obtain an organic EL display element having excellent display performance.
• the present invention also relates to an organic EL display device having the cured product.
• An 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 this 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 light emission.
• organic EL display element has advantages that it has good visibility, can be made thinner, and can be driven at a DC low voltage.
• an organic EL display element has a problem that when the organic light emitting material layer and the electrodes are exposed to the outside air, the light emitting characteristics thereof are rapidly deteriorated and the life is shortened. Therefore, for the purpose of enhancing the stability and durability of the organic EL display element, in the organic EL display element, a sealing technique for shielding the organic light emitting material layer and electrodes from moisture and oxygen in the atmosphere is indispensable. There is.
• Patent Document 1 discloses an organic EL device having an organic filling layer that covers and seals a laminate having an organic light emitting material layer, and a moisture absorption seal layer (sealing wall) that covers the side surface of the organic filling layer.
• a method of sealing a display element is disclosed.
• an organic EL display element sealing agent an in-plane sealing agent is used in the organic filling layer, and a peripheral sealing agent having a constituent component different from that of the in-plane sealing agent is used in the sealing wall. Has been.
• the organic EL display element is sealed using such an in-plane sealing agent and a peripheral sealing agent, even if a peripheral sealing agent having excellent moisture permeability of the cured product is used, There is a problem that the organic EL display element may display defectively due to infiltration of water without sufficient performance.
• the present invention is a cured product of a resin composition for organic EL display element encapsulation, which contains a polyolefin, a curable resin, a polymerization initiator and/or a thermosetting agent, and is represented by the following formula (1).
• a resin composition for organic EL display element encapsulation which contains a polyolefin, a curable resin, a polymerization initiator and/or a thermosetting agent, and is represented by the following formula (1).
• 70 parts by weight of an epoxy compound 30 parts by weight of an oxetane compound represented by the following formula (2), 1.5 parts by weight of dimethylphenyl(4-methoxybenzyl)ammonium hexafluoroantimonate, and 0.2 parts by weight of benzylamine.
• Adhesive strength to a cured product of a liquid resin composition 1 consisting only of 70 parts by weight of an epoxy compound represented by the following formula (3), 30 parts by weight of an oxetane compound represented by the following formula (2), and triphenylsulfonium trifluoride.
• Cured product of liquid resin composition 2 consisting of 1 part by weight of methanesulfonate, 0.5 part by weight of 4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, and 0.2 part by weight of benzylamine
• the adhesive force to the cured product of the liquid resin composition 3 consisting of only benzylamine 0.2 parts by weight is 100 N or more.
• the present invention will be described in detail below.
• the present inventors have found that the cause of display failure in the organic EL display element when the organic EL display element is sealed using the in-plane sealant and the peripheral sealant is a cured product of the in-plane sealant. And that the adhesiveness between the peripheral sealing agent and the cured product is insufficient. Therefore, as a result of intensive investigations by the present inventors, a cured product having a specific three or more in-plane sealing agents having excellent coating properties, viscosity stability, and low outgassing properties and having an adhesive force to the cured product is not less than a specific value is selected.
• the use as a sealing wall was investigated. As a result, it was found that a cured product capable of obtaining an organic EL display element having excellent display performance can be obtained by using it for a sealing wall formed around a laminate having an organic light emitting material layer, and the present invention Has been completed.
• the cured product of the present invention has an adhesive force for the cured product of the resin composition 1, an adhesive force for the cured product of the resin composition 2, and an adhesive force for the cured product of the resin composition 3 of 100 N or more. is there.
• the resin compositions 1, 2, and 3 are preferably used as an in-plane sealant, and have excellent performance such as low outgassing when used alone without being combined with a peripheral sealant. It is a thing. Since the adhesive strength of the resin composition 1 to the cured product, the adhesive strength of the resin composition 2 to the cured product, and the adhesive strength of the resin composition 3 to the cured product are all 100 N or more, By using the cured product as a sealing wall, an organic EL display element having excellent display performance can be obtained.
• the adhesive force of the resin composition 1 to the cured product, the adhesive force of the resin composition 2 to the cured product, and the adhesive force of the resin composition 3 to the cured product are all preferably 150 N or more.
• the adhesive force of the resin composition 1 to the cured product, the adhesive force of the resin composition 2 to the cured product, and the adhesive force of the resin composition 3 to the cured product are measured by the following methods. Is the value to be set. That is, first, the resin composition 1, 2, or 3 is applied onto an alkali glass A having a length of 60 mm, a width of 20 mm, and a thickness of 0.7 mm so as to have a length of 20 mm, a width of 20 mm, and a thickness of 30 ⁇ m.
• the resin composition 1, 2 or 3 On the surface of the cured product of the resin composition 1, 2 or 3 formed on the alkaline glass A, the resin composition for encapsulating an organic EL display element, a length of 60 mm, a width of 20 mm and a thickness of 0.7 mm Another alkali glass B is laminated in this order and pressed. At this time, the adhesive area between the cured product of the resin composition 1, 2, or 3 and the resin composition for sealing an organic EL display element is 2 mm 2 , and the thickness of the adhesive layer is 10 ⁇ m.
• the maximum load when the alkali glass B is pulled in the opposite direction is measured, and this is taken as the adhesive force.
• the shear rate between the alkali glasses A and B is 5 mm/s.
• the adhesive force of the resin composition 1 to the cured product, the adhesive force of the resin composition 2 to the cured product, and the adhesive force of the resin composition 3 to the cured product are the types of polyolefins and curable resins described below, and By adjusting the content ratio of these, all can be made 100 N or more.
• organic EL display element encapsulation resin composition of the present invention contains a polyolefin.
• the cured product of the present invention has excellent moisture permeation-preventing property and is hardly dissolved in the in-plane sealing agent.
• the polyolefin preferably contains at least one selected from the group consisting of polyisobutylene, polybutene, and polybutadiene, and more preferably polyisobutylene.
• the above polyolefins may be used alone or in combination of two or more.
• the preferred lower limit of the weight average molecular weight of the polyolefin is 10,000, and the preferred 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 thereof is 70,000.
• the above-mentioned “weight average molecular weight” is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and calculated in terms of polystyrene. Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (Showa Denko KK).
• the preferable lower limit of the content of the polyolefin in the total 100 parts by weight of the polyolefin and the curable resin described below is 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 resin composition for organic EL display element encapsulation becomes more excellent in the moisture permeability of the cured product.
• the content of the polyolefin is 80 parts by weight or less, the obtained resin composition for organic EL display element encapsulation becomes more excellent in coating property and adhesiveness.
• the more preferable lower limit of the content of the polyolefin is 20 parts by weight, and the more preferable upper limit thereof is 70 parts by weight.
• the organic EL display element encapsulating resin composition according to the present invention contains a curable resin.
• the curable resin preferably contains at least one selected from the group consisting of an epoxy compound, an oxetane compound, a (meth)acrylic compound, and a urethane compound, and the epoxy compound and/or It is more preferable to include a (meth)acrylic compound.
• the “(meth)acryl” means acryl or methacryl
• the “(meth)acryl compound” means a compound having a (meth)acryloyl group
• the “(meth)acryl” is "Acryloyl" means acryloyl or methacryloyl.
• Examples of the epoxy compound include glycidyl ether compounds and alicyclic epoxy compounds.
• Examples of the glycidyl ether compound include diethylene glycol diglycidyl ether.
• Examples of the alicyclic epoxy compound include the epoxy compound represented by the above formula (1) and 1,2-epoxy-4-(2-oxiranyl) of 2,2-bis(hydroxymethyl)-1-butanol. Examples include cyclohexane adducts.
• the adhesive strength of the obtained cured product to the cured product of the resin composition 1, the adhesive force to the cured product of the resin composition 2, and the adhesive force to the cured product of the resin composition 3 are all 100 N or more.
• Diethylene glycol diglycidyl ether is preferable because it is easier to obtain
• oxetane compound examples include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, di[2-(3-oxetanyl)butyl]ether, 3-ethyl-3-hydroxy Methyl oxetane etc. are mentioned.
• Examples of the (meth)acrylic compound include isobornyl (meth)acrylate, adamantyl (meth)acrylate, methylcyclohexyl (meth)acrylate, norbornylmethyl (meth)acrylate, and dicyclopenta(meth)acrylate.
• Nyl dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, cyclodecyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, etc. Can be mentioned.
• the adhesive strength of the obtained cured product to the cured product of the resin composition 1, the adhesive force to the cured product of the resin composition 2, and the adhesive force to the cured product of the resin composition 3 are all 100 N or more.
• Isobornyl (meth)acrylate is preferable because it is easier to obtain
• the said "(meth)acrylate” means an acrylate or a methacrylate.
• Examples of the urethane compound include a reaction product of an isocyanate compound and an arbitrary polyol compound.
• examples of the isocyanate compound include a toluene diisocyanate compound and a diphenylmethane diisocyanate compound.
• examples of the toluene diisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate, and mixtures thereof.
• Examples of the diphenylmethane diisocyanate compound include 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), or a mixture thereof. ..
• the organic EL display element encapsulating resin composition according to the present invention preferably contains a tackifying resin for the purpose of further improving the adhesiveness.
• a tackifying resin include terpene resin, modified terpene resin, coumarone resin, indene resin, petroleum resin and the like.
• the modified terpene resin include hydrogenated terpene resin, terpene phenol copolymer resin, and aromatic modified terpene resin.
• the petroleum resin include aliphatic petroleum resin, hydrogenated alicyclic petroleum resin, aromatic petroleum resin, aliphatic aromatic copolymer petroleum resin, alicyclic petroleum resin, and dicyclopentadiene petroleum. Examples thereof include resins and hydrides thereof.
• tackifying resin terpene resin, aromatic modified terpene resin, terpene phenol copolymer resin, hydrogenated alicyclic petroleum resin, from the viewpoint of adhesiveness of resin composition, moisture resistance, compatibility, etc.
• Aromatic petroleum resin, aliphatic aromatic copolymer petroleum resin, alicyclic petroleum resin are preferable, alicyclic petroleum resin is more preferable, alicyclic saturated hydrocarbon resin, alicyclic unsaturated carbonization
• a hydrogen resin is more preferable, and a cyclohexyl ring-containing saturated hydrocarbon resin and a dicyclopentadiene-modified hydrocarbon resin are particularly preferable.
• These tackifying resins may be used alone or in combination of two or more kinds.
• the content of the tackifying resin is preferably 0.01 parts by weight and 100 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin.
• the more preferable lower limit of the content of the tackifying resin is 0.2 parts by weight, and the more preferable upper limit thereof is 20 parts by weight.
• the organic EL display element encapsulating resin composition according to the present invention contains a polymerization initiator and/or a thermosetting agent.
• the organic EL display element sealing resin composition according to the present invention preferably contains at least one selected from the group consisting of a radical polymerization initiator, a cationic polymerization initiator, and a thermosetting agent, among others. ..
• radical polymerization initiator examples include a photo radical polymerization initiator and a thermal radical polymerization initiator.
• photoradical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
• Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 1,2-(dimethylamino).
• thermal radical polymerization initiator examples include those composed of azo compounds, organic peroxides, and the like.
• azo compound examples include 2,2′-azobis(2,4-dimethylvaleronitrile) and azobisisobutyronitrile.
• organic peroxide examples include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, and peroxydicarbonate.
• thermal radical polymerization initiators commercially available ones include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, V-501 (all of which are FUJIFILM Wako Pure Chemical Industries, Ltd. Manufactured) and the like.
• Examples of the cationic polymerization initiator include photocationic polymerization initiators and thermal cationic polymerization initiators.
• the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid upon irradiation with light, and may be an ionic photoacid-generating type or a nonionic photoacid-generating type. May be.
• Examples of the anion moiety of the above ionic photoacid-generating photocationic polymerization initiator include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is at least 2 or more). Represents a phenyl group substituted with fluorine or a trifluoromethyl group).
• Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, and Pentadien-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, 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
• aromatic iodonium salt examples include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis (Dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4-(1-methylethyl)phen
• 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 above (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) -Yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadiene-1-yl)((1-methylethyl)benzene)-Fe(II) tetrakis(penta Examples thereof include fluorophenyl)borate.
• nonionic photoacid-generating photocationic polymerization initiator examples include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide sulfonate.
• photocationic polymerization initiator for example, a photocationic polymerization initiator manufactured by Midori Kagaku Co., a photocationic polymerization initiator manufactured by Union Carbide Co., a photocationic polymerization initiator manufactured by ADEKA Co.
• examples include photocationic polymerization initiators manufactured by 3M, photocationic polymerization initiators manufactured by BASF, and photocationic polymerization initiators manufactured by Rhodia.
• Examples of the photocationic polymerization initiator manufactured by Midori Kagaku include DTS-200.
• the cationic photopolymerization 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 cationic photopolymerization initiator manufactured by 3M include FC-508 and FC-512. Examples of the cationic photopolymerization initiator manufactured by BASF include IRGACURE261 and IRGACURE290. Examples of the photocationic polymerization initiator manufactured by Rhodia include PI2074 and the like.
• thermal cationic polymerization initiator examples include an anion moiety of BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is substituted with at least two or more fluorine or trifluoromethyl groups).
• 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, 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 Co., Ltd., and the like.
• thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd. examples include San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, and San-Aid SI-B4.
• thermal cationic polymerization initiator manufactured by King Industries, Inc. examples include CXC-1612 and CXC-1821.
• the content of the polymerization initiator has a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin.
• the content of the polymerization initiator is 0.05 parts by weight or more, the obtained resin composition for organic EL display element encapsulation has more excellent curability.
• the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained resin composition for organic EL display element encapsulation does not become too fast, the workability becomes excellent, and the cured product becomes more uniform. It can be anything.
• the more preferable lower limit of the content of the polymerization initiator is 1 part by weight, and the more preferable upper limit thereof is 3 parts by weight.
• thermosetting agent examples include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, addition products of various amines with epoxy resins, and the like.
• hydrazide compound examples include 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
• imidazole derivative examples include 1-cyanoethyl-2-phenylimidazole, N-(2-(2-methyl-1-imidazolyl)ethyl)urea, 2,4-diamino-6-(2'-methylimidazolyl- (1′))-Ethyl-s-triazine, N,N′-bis(2-methyl-1-imidazolylethyl)urea, N,N′-(2-methyl-1-imidazolylethyl)-adipamide, 2- Examples thereof include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
• acid anhydride examples include tetrahydrophthalic anhydride, ethylene glycol bis(anhydrotrimellitate) and the like. These thermosetting agents may be used alone or in combination of two or more.
• thermosetting agents include, for example, SDH (manufactured by Nippon Finechem Co., Ltd.), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.). ) And the like.
• the content of the thermosetting agent is preferably 0.01 parts by weight and 10 parts by weight with respect to a total of 100 parts by weight of the polyolefin and the curable resin.
• the content of the thermosetting agent is 0.01 parts by weight or more, the obtained organic EL display element encapsulating resin composition becomes more excellent in thermosetting property.
• the content of the thermosetting agent is 10 parts by weight or less, the obtained resin composition for organic EL display element encapsulation 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 still more preferable lower limit is 1 part by weight, and the still more preferable upper limit is 3 parts by weight.
• the resin composition for organic EL display element encapsulation according to the present invention preferably contains a water absorbing filler.
• a water absorbing filler By containing the above water-absorbing filler, the cured product of the present invention becomes more excellent in moisture permeation preventive property.
• Examples of the water absorbent filler include oxides of alkaline earth metals, magnesium oxide, and molecular sieves.
• Examples of the alkaline earth metal oxides include calcium oxide, strontium oxide, and barium oxide. Among them, from the viewpoint of water absorption, alkaline earth metal oxides are preferable, and calcium oxide is more preferable.
• These water-absorbing fillers may be used alone or in combination of two or more.
• the content of the water-absorbing filler has a preferable lower limit of 10 parts by weight and a preferable upper limit of 500 parts by weight with respect to 100 parts by weight of the total of the polyolefin and the curable resin.
• the content of the water-absorbing filler is within this range, the obtained organic EL display element encapsulating resin composition suppresses panel peeling, and the cured product has more excellent moisture permeation preventive properties. ..
• the more preferable lower limit of the content of the water-absorbing filler is 20 parts by weight, and the more preferable upper limit thereof is 150 parts by weight.
• the organic EL display element encapsulating resin composition according to the present invention contains, in addition to the water-absorbing filler, other fillers, for the purpose of improving adhesiveness, etc., within a range not impairing the object of the present invention. You may.
• An inorganic filler or an organic filler can be used as the other filler.
• the inorganic filler include silica, talc, alumina and the like.
• 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 preferred.
• the organic EL display element sealing resin composition according to 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 organic EL display element encapsulating resin composition according to the present invention.
• Examples of the sensitizer include anthracene compounds, thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 2,4-dichlorobenzophenone, and methyl o-benzoylbenzoate. 4,4′-bis(dimethylamino)benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide and the like can be mentioned.
• Examples of the anthracene compound include 9,10-dibutoxyanthracene.
• Examples of the thioxanthone compound include 2,4-diethylthioxanthone.
• the content of the sensitizer is preferably 0.05 parts by weight and 3 parts by weight with respect to 100 parts by weight of the total amount of the polyolefin and the curable resin.
• the content of the sensitizer is 0.05 parts by weight or more, the sensitizing effect is more exerted.
• the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep portion without excessive absorption.
• the more preferable lower limit of the content of the sensitizer is 0.1 part by weight, and the more preferable upper limit thereof is 1 part by weight.
• the resin composition for sealing an organic EL display element according to the present invention preferably contains a stabilizer.
• the organic EL display element encapsulating resin composition according to the present invention becomes more excellent in storage stability.
• the stabilizer examples include aromatic amine compounds, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and the like.
• the aromatic amine compound examples include benzylamine and aminophenol type epoxy resin. 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.
• a preferable lower limit is 0.001 part by weight and a preferable upper limit is 2 parts by weight with respect to a total of 100 parts by weight of the polyolefin and the curable resin.
• the content of the above stabilizer is in this range, the obtained resin composition for organic EL display element encapsulation 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 thereof is 1 part by weight.
• the organic EL display element sealing resin composition according to the present invention may contain a silane coupling agent.
• the silane coupling agent has a role of improving the adhesiveness between the resin composition for sealing an organic EL display element according to the present invention and a substrate or the like.
• silane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatepropyltrimethoxysilane. 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 and 10 parts by weight with respect to 100 parts by weight of the total amount of the polyolefin and the curable resin.
• the content of the silane coupling agent is in this range, the effect of improving the adhesiveness of the obtained organic EL display element encapsulating resin composition while preventing bleeding out of the excess silane coupling agent is obtained. It will be excellent.
• the more preferable lower limit of the content of the silane coupling agent is 0.5 part by weight, and the more preferable upper limit thereof is 5 parts by weight.
• the organic EL display element encapsulating resin composition according to the present invention may contain a surface modifier within a range not impairing the object of the present invention.
• a surface modifier within a range not impairing the object of the present invention.
• the flatness of the coating film of the organic EL display element encapsulating resin composition according to the present invention can be improved.
• the surface modifier include a surfactant and a leveling agent.
• Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based agents.
• Examples of commercially available surface modifiers include, for example, a surface modifier manufactured by Big Chemie Japan, a surface modifier manufactured by Kusumoto Kasei, and a surface modifier manufactured by AGC Seimi Chemical. Can be mentioned.
• Examples of the surface modifier manufactured by Big Chemie Japan include BYK-300, BYK-302, and BYK-331.
• Examples of the surface modifier manufactured by Kusumoto Chemicals include UVX-272.
• Examples of the surface modifier manufactured by AGC Seimi Chemical Co., Ltd. include Surflon S-611.
• the resin composition for encapsulating an organic EL display element according to the present invention is a compound and/or ion exchange that reacts with an acid generated in the resin composition for encapsulating an organic EL display element within a range that does not impair the object of the present invention. It may contain a resin.
• Examples of the compound that reacts with the generated acid include a substance that neutralizes with an acid, for example, an alkali metal carbonate or hydrogen carbonate, or an alkaline earth metal carbonate or hydrogen carbonate.
• an acid for example, an alkali metal carbonate or hydrogen carbonate, or an alkaline earth metal carbonate or hydrogen carbonate.
• calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate or the like is used.
• any of a cation exchange type, an anion exchange type, and both ion exchange types can be used, and in particular, a cation exchange type or both ion exchange types capable of adsorbing chloride ions. Is preferred.
• the resin composition for encapsulating an organic EL display element according to the present invention is, as necessary, a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, and an ultraviolet absorbing agent within a range that does not impair the object of the present invention.
• a curing retarder e.g., a curing retarder, a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, and an ultraviolet absorbing agent within a range that does not impair the object of the present invention.
• Various known additives such as agents and antioxidants may be contained.
• the organic EL display element encapsulating resin composition according to the present invention preferably contains no solvent from the viewpoint of further suppressing the generation of outgas.
• the resin composition for encapsulating an organic EL display element according to the present invention can have excellent coatability without containing a solvent.
• "containing no solvent” means that the content of the solvent is less than 1000 ppm.
• Examples of the method for producing the resin composition for organic EL display element encapsulation according to the present invention include, for example, using a mixer, a polyolefin, a curable resin, a polymerization initiator and/or a thermosetting agent, and water absorption. Examples thereof include a method of mixing with a filler and an additive such as a silane coupling agent added as necessary.
• Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
• the cured product of the present invention is preferably used for a sealing wall that surrounds the peripheral portion of the organic EL display element. That is, the resin composition for organic EL display element encapsulation according to the present invention is 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. Is preferred.
• the above-mentioned peripheral sealant for organic EL display element is usually used in combination with an in-plane sealant for organic EL display element which covers the laminate.
• the in-plane sealing agent for an organic EL display element used in combination when the resin composition for sealing an organic EL display element according to the present invention is used as a peripheral sealing agent for an organic EL display element the above resin composition 1 is used. 2, or 3 is preferable.
• the thickness of the sealing wall made of the cured product of the present invention is preferably 5 mm or less from the viewpoint of securing a wide display area of the obtained organic EL display element.
• the organic EL display device having the cured product of the present invention is also one aspect of the present invention.
• the organic EL display element of the present invention preferably has a display area having a diagonal size of 40 inches or more and 60 inches or less.
• the present invention it is possible to provide a cured product capable of obtaining an organic EL display element having excellent display performance by using the sealing wall formed around the laminate having the organic light emitting material layer. Further, according to the present invention, it is possible to provide an organic EL display device having the cured product.
• Examples 1 to 10 Comparative Examples 1 to 4
• the respective materials were stirred and mixed using a stirring mixer at a stirring speed of 2000 rpm for 3 minutes, and then further kneaded with a three-roll mill to compare Examples 1 to 10 with each other.
• Resin compositions for organic EL display element encapsulation of Examples 1 to 4 were produced.
• AR-250 manufactured by Shinky Co., Ltd.
• NR-42A manufactured by Noritake Co.
• the calcium oxide used in the above examples was dry batch pulverized by a ball mill (“ANZ-53D” manufactured by Nitto Kagaku Co., Ltd.) so that the particle diameter was 10 ⁇ m or less.
• the adhesive strength of the cured product to the cured resin composition 1, 2, or 3 was measured by the following method. First, the resin composition 1, 2, or 3 is applied onto an alkali glass A having a length of 60 mm, a width of 20 mm, and a thickness of 0.7 mm so that the length is 20 mm, the width is 20 mm, and the thickness is 30 ⁇ m. It heated at 100 degreeC for 30 minute(s), and hardened
• the resin composition for encapsulating an organic EL display element On the surface of the cured product of the resin composition 1, 2, or 3 formed on the alkali glass A, the resin composition for encapsulating an organic EL display element, the length of 60 mm, the width of 20 mm, the thickness of 0.7 mm Another alkali glass B was laminated in this order and pressed. At this time, the adhesive area between the cured product of the resin composition 1, 2, or 3 and the resin composition for sealing an organic EL display element was 2 mm 2 , and the thickness of the adhesive layer was 10 ⁇ m.
• the organic EL display element encapsulating resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were cured by heating at 100° C. for 30 minutes.
• the organic EL display element encapsulating resin compositions obtained in Examples 7 to 10 and Comparative Examples 3 and 4 were irradiated with UV light having a wavelength of 365 nm from the alkali glass B side at 3000 mJ/cm 2 with a UV-LED irradiation device. And cured. While pulling the alkali glass A at 25° C. in the horizontal direction with the interface (bonding surface) between the cured product of the resin composition 1, 2 or 3 and the cured product of the resin composition for sealing an organic EL display element, The maximum load when the alkali glass B was pulled in the opposite direction was measured using a universal testing machine, and this was taken as the adhesive strength. Tensilon (manufactured by Orientec Co., Ltd.) was used as a universal testing machine, and the shear rate between the alkali glasses A and B was 5 mm/s. The obtained adhesive strengths are shown in Tables 2 and 3.
• the glass substrate A has a length of 50 mm, a width of 25 mm, and a thickness of 0.7 mm, and the surface of the glass has been washed with acetone and then dried.
• the glass substrate B has a length of 5 mm, a width of 5 mm, and a thickness of 5 mm.
• a 0.7 mm glass was immersed in acetone for cleaning, and then dried. Then, the glass substrate A and the glass substrate B were adhered by curing the resin composition for sealing an organic EL display element.
• the organic EL display element encapsulating resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were cured by heating at 100° C. for 30 minutes.
• the organic EL display element encapsulating resin compositions obtained in Examples 7 to 10 and Comparative Examples 3 and 4 were irradiated with UV light having a wavelength of 365 nm from the alkali glass B side at 3000 mJ/cm 2 with a UV-LED irradiation device. And cured.
• the shear adhesive force between the glass substrate A and the glass substrate B was measured by a die shear tester under the conditions of 23° C. and a shear rate of 200 ⁇ m/sec.
• a bond tester 4000 manufactured by Daiji
• Adhesiveness was evaluated as “ ⁇ ” when the shear adhesive strength was 200 N or more, “ ⁇ ” when it was less than 200 N and 100 N or more, and “ ⁇ ” when it was less than 100 N.
• 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 machine.
• the conditions of vapor deposition were such that the pressure inside the vapor deposition apparatus of the vacuum vapor deposition apparatus was reduced to 2 ⁇ 10 ⁇ 3 Pa and 2000 Ca of Ca was deposited at a vapor deposition rate of 5.0 L/s.
• a glass substrate on which Ca is vapor-deposited is moved into a glove box controlled at a dew point (-60° C.
• the organic EL display element encapsulating resin compositions obtained in Examples 7 to 10 and Comparative Examples 3 and 4 were irradiated with UV light having a wavelength of 365 nm from the alkali glass B side at 3000 mJ/cm 2 with a UV-LED irradiation device. And cured.
• the obtained Ca-TEST substrate was exposed to a high temperature and high humidity condition of 85° C. and 85% RH to obtain a layer composed of a cured product of the resin composition for encapsulating an organic EL display element from the end surface of the glass substrate for each hour. The water penetration distance was observed from the disappearance of Ca.
• UV-ozone cleaner As the UV-ozone cleaner, NL-UV253 (manufactured by Nippon Laser Electronics Co., Ltd.) was used. Next, the substrate after the immediately preceding treatment was fixed to a substrate holder of a vacuum evaporation system, and 200 mg of N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine ( ⁇ -NPD) was put into a cruciform crucible. Then, 200 mg of tris(8-quinolinolato)aluminum (Alq 3 ) was put into another unglazed crucible, and the pressure in the vacuum chamber was reduced to 1 ⁇ 10 ⁇ 4 Pa.
• ⁇ -NPD N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine
• Alq 3 tris(8-quinolinolato)aluminum
• the crucible containing ⁇ -NPD was heated to deposit ⁇ -NPD on the substrate at a vapor deposition rate of 15 ⁇ /s to form a hole transport layer having a film thickness of 600 ⁇ .
• the crucible containing Alq 3 was heated to form an organic light emitting material layer having a film thickness of 600 ⁇ at a vapor deposition rate of 15 ⁇ /s.
• the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum evaporation apparatus having a tungsten resistance heating boat, and lithium fluoride is placed in one of the tungsten resistance heating boats in the vacuum evaporation apparatus.
• Organic EL display element Light emitting state of organic EL display element
• the obtained organic EL display element was exposed to an environment of 85° C. and 85% RH for 1000 hours, and then a voltage of 10 V was applied to change the light emitting state (whether there is dark spot or extinction around the pixel) of the organic EL display element. It was visually observed.
• the display performance of the device was evaluated.
• the present invention it is possible to provide a cured product capable of obtaining an organic EL display element having excellent display performance by using the sealing wall formed around the laminate having the organic light emitting material layer. Further, according to the present invention, it is possible to provide an organic EL display device having the cured product.

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• 2020
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