Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/16—Cyclic ethers having four or more ring atoms
  • C08G65/18—Oxetanes
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
  • H05B33/04—Sealing arrangements, e.g. against humidity
• • H—ELECTRICITY
  • 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
  • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
• • 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
  • H10K59/10—OLED displays

Definitions

• the present invention relates to a sealant for an organic EL display element that can provide an organic EL display element that is excellent in applicability and excellent in reliability.
• organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and the organic light emitting material layer is formed from one electrode on the organic light emitting material layer.
• organic EL organic electroluminescence
• the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.
• Patent Document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element with a laminated film of a silicon nitride film and a resin film formed by a CVD method.
• the resin film has a role of preventing pressure on the organic layer and the electrode due to internal stress of the silicon nitride film.
• Patent Document 1 In the method of sealing with a silicon nitride film disclosed in Patent Document 1, organic light emission occurs when a silicon nitride film is formed due to unevenness on the surface of the organic EL display element, adhesion of foreign matters, generation of cracks due to internal stress, or the like. The material layer or electrode may not be completely covered. If the coating with the silicon nitride film is incomplete, moisture will enter the organic light emitting material layer through the silicon nitride film. As a method for preventing moisture from entering into the organic light emitting material layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film. Patent Document 3 and Patent Document 4 Discloses a method of forming a resin film on an inorganic material film.
• a method for forming a resin film there is a method in which a sealing agent is applied on a substrate using an inkjet method and then the sealing agent is cured. If such a coating method by the ink jet method is used, a resin film can be uniformly formed at high speed.
• the conventional sealant is applied by the ink jet method, if it is applied so as to be thin, uneven coating or missing of coating occurs, resulting in insufficient sealing, and the resulting organic EL display element is inferior in reliability. There were problems such as becoming.
• An object of this invention is to provide the sealing agent for organic EL display elements which can obtain the organic EL display element excellent in applicability
• the present invention is a sealant for an organic EL display device containing a polymerizable compound, and 30 wt% of the polymerizable compound having a surface tension at 25 ° C. of 35 mN / m or more in 100 wt parts of the polymerizable compound.
• the viscosity of the whole sealing agent for organic EL display elements at 25 ° C. is 5 mPa ⁇ s to 50 mPa ⁇ s
• the surface tension of the whole sealing agent for organic EL display elements at 25 ° C. is 35 mN / m.
• It is the sealing agent for organic EL display elements which is the following. The present invention is described in detail below.
• the present inventors use a polymerizable compound having a low surface tension in order to prevent coating unevenness and coating omission of the sealant for organic EL display elements, and improve the wetting and spreading properties by lowering the overall surface tension. It was investigated. However, even when such a sealant is used, particularly when applied to a SiON substrate, application unevenness and application omission may occur without sufficient wetting and spreading. Therefore, the inventors of the present invention have studied to use a specific amount or more of a polymerizable compound having a surface tension higher than a specific value as the total viscosity and surface tension within a specific low range. As a result, the obtained sealing agent for organic EL display elements has excellent wettability, and it has been found that application unevenness and application omission can be prevented, thereby completing the present invention.
• the minimum of the viscosity of the whole sealing agent for organic EL display elements in 25 degreeC is 5 mPa * s, and an upper limit is 50 mPa * s.
• an upper limit is 50 mPa * s.
• the viscosity means a value measured under a condition of 100 rpm using an E-type viscometer (for example, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.)).
• the sealing agent for organic EL display elements of the present invention can be applied using an inkjet application head equipped with a heating mechanism.
• the inkjet coating head equipped with the heating mechanism By using the inkjet coating head equipped with the heating mechanism, the viscosity and the surface tension can be reduced by heating when discharging the sealing agent for organic EL display elements of the present invention. By becoming a range, it can apply
• the inkjet coating head equipped with the heating mechanism for example, KM1024 series manufactured by Konica Minolta, SG1024i series manufactured by Fuji Film Dimatix, and the like are preferably used.
• the heating temperature of the coating head is preferably 25 ° C. or higher and 80 ° C. or lower. When the heating temperature is in this range, an increase in the viscosity of the organic EL display element sealant over time can be suppressed, and stable discharge can be performed.
• the upper limit of the surface tension of the whole sealing agent for organic EL display elements in 25 degreeC is 35 mN / m.
• the surface tension of the whole sealing agent for organic EL display elements at 25 ° C. is 35 mN / m or less, it can be suitably applied particularly by an ink jet method.
• the upper limit with preferable surface tension of the whole sealing agent for organic EL display elements in the said 25 degreeC is 30 mN / m, and a more preferable upper limit is 28 mN / m.
• the minimum with the preferable surface tension of the whole sealing agent for organic EL display elements in the said 25 degreeC is 15 mN / m, and a more preferable minimum is 20 mN / m.
• the surface tension can be measured by a dynamic wettability tester (for example, WET-6100 type (manufactured by Reska Co., Ltd.)).
• the sealing agent for organic EL display elements of the present invention contains a polymerizable compound.
• the sealing agent for organic EL display elements of the present invention contains 30 parts by weight or more of a polymerizable compound having a surface tension at 25 ° C. of 35 mN / m or more in 100 parts by weight of the polymerizable compound.
• the sealing agent for organic EL display elements of the present invention has excellent wet spreading properties, coating unevenness and coating omission. Can be prevented.
• the polymerizable compound having a surface tension at 25 ° C. of 35 mN / m is characterized by high molecular polarity because of high cohesion between molecules.
• the preferred lower limit of the surface tension of the polymerizable compound having a surface tension at 25 ° C. of 35 mN / m or more is 36 mN / m, and the more preferred lower limit is 37 mN / m. It is.
• the upper limit of the surface tension of the polymerizable compound having a surface tension at 25 ° C. of 35 mN / m or more is preferably 50 mN / m, and more preferably the upper limit is 47 mN / m.
• the polymerizable compound is a polymerizable compound having a surface tension at 25 ° C. of 35 mN / m or more. It is preferable to contain more than one species.
• the polymerizable compound having a surface tension of 35 mN / m at 25 ° C. includes at least one group selected from the group consisting of a hydroxyl group, an ester group, an alicyclic epoxy group, a glycidyl group, and an oxetanyl group in the structure. Those having the following are preferably used. Among these, from the viewpoint of further improving the effect of preventing coating unevenness and coating omission, the polymerizable compound having a surface tension at 25 ° C. of 35 mN / m or more has an oxetanyl group and has a surface tension at 25 ° C. It is preferable to contain the compound whose is 35 mN / m or more.
• the compound having an oxetanyl group and having a surface tension at 25 ° C. of 35 mN / m or more include, for example, 3-ethyl-3-hydroxymethyloxetane (surface tension of 37.1 mN / m at 25 ° C. m) and the like.
• Examples of commercially available compounds having the oxetanyl group and a surface tension at 25 ° C. of 35 mN / m or more include etanacol EHO (manufactured by Ube Industries).
• a cycloalkene oxide type alicyclic epoxy compound having a surface tension at 25 ° C. of 35 mN / m or more is preferable, and 3 ′, 4′-epoxycyclohexanecarboxylic acid 3,4- Epoxycyclohexylmethyl and 3,4,3 ′, 4′-diepoxybicyclohexane are more preferred.
• those commercially available include, for example, a polymerizable compound manufactured by Daicel, a polymerizable compound manufactured by ADEKA, and a product manufactured by Hitachi Chemical. And a polymerizable compound manufactured by Mitsubishi Chemical Corporation.
• Examples of the polymerizable compound manufactured by Daicel Corporation include Celoxide 2021P, Celoxide 8000, Cyclomer M100, and the like.
• Examples of the polymerizable compound manufactured by ADEKA include ED-523L.
• Examples of the polymerizable compound manufactured by Hitachi Chemical Co., Ltd. include FA-220A and FA-222A.
• Examples of the polymerizable compound manufactured by Mitsubishi Chemical Corporation include YED-216D (manufactured by Mitsubishi Chemical Corporation).
• the lower limit of the content of the polymerizable compound having a surface tension at 25 ° C. of 35 mN / m or more in 100 parts by weight of the polymerizable compound is 30 parts by weight.
• the organic EL display element sealant of the present invention has excellent wettability and coating unevenness. And omission of coating can be prevented.
• the minimum with preferable content of the polymeric compound whose surface tension in said 25 degreeC is 35 mN / m or more is 35 weight part, and a more preferable minimum is 40 weight part.
• the polymerizable compound may contain a polymerizable compound having a surface tension at 25 ° C. of less than 35 mN / m from the viewpoint of easy adjustment of the surface tension of the entire sealant.
• a polymerizable compound having a surface tension at 25 ° C. of less than 35 mN / m is contained, the content of the polymerizable compound having a surface tension at 25 ° C. of less than 35 mN / m in 100 parts by weight of the polymerizable compound is A preferred lower limit is 30 parts by weight, and a more preferred lower limit is 35 parts by weight.
• Examples of the polymerizable compound having a surface tension of less than 35 mN / m at 25 ° C. include 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane (surface tension at 25 ° C. 33.0 mN / m), 2- (2-vinyloxyethoxy) ethyl acrylate (surface tension 34.3 mN / m at 25 ° C.), allyloxyoxetane (surface tension 31.3 mN / m at 25 ° C.), etc. It is done.
• the sealing agent for organic EL display elements of this invention contains a polymerization initiator.
• a polymerization initiator a photocationic polymerization initiator, a thermal cationic polymerization initiator, a photoradical polymerization initiator, or a thermal radical polymerization initiator is suitably used depending on the type of polymerizable compound used.
• the said polymeric compound is an epoxy compound or an oxetane compound, and the said polymerization initiator is a cationic polymerization initiator.
• the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.
• Examples of the anion portion of the ionic photoacid-generating photocationic polymerization initiator include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , (BX 4 ) ⁇ (where X is at least two or more fluorine atoms) Or a phenyl group substituted with 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 having the above anion moiety, and (2,4-cyclohexane). And pentadien-1-yl) ((1-methylethyl) benzene) -Fe salt.
• aromatic sulfonium salt examples include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetraflu
• aromatic iodonium salt examples include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethy
• aromatic diazonium salt examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
• aromatic ammonium salt examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl)
• Examples include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
• Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene.
• nonionic photoacid-generating photocationic polymerization initiator examples include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like.
• Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., a photocationic polymerization initiator manufactured by Union Carbide, 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. Examples of the cationic photopolymerization initiator manufactured by Union Carbide include UVI6990, UVI6974, and the like.
• Examples of the photocation polymerization initiator manufactured by ADEKA include SP-150 and SP-170. Examples of the cationic photopolymerization initiator manufactured by 3M include FC-508, FC-512, and the like. Examples of the cationic photopolymerization initiator manufactured by BASF include IRGACURE261, IRGACURE290, and the like. Examples of the photocationic polymerization initiator manufactured by Rhodia include PI 2074.
• the anion moiety is BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is substituted with at least two fluorine or trifluoromethyl groups
• a sulfonium salt, a phosphonium salt, an ammonium salt, and the like 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, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl).
• thermal cationic polymerization initiators include, for example, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, Sun-Aid SI-B4 (all of which are Sanshin Chemical Industry Co., Ltd.). CXC1612, CXC1821 (all manufactured by King Industries) and the like.
• photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone compounds, and the like.
• the radical photopolymerization initiator by BASF As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF, the radical photopolymerization initiator by Tokyo Chemical Industry, etc. are mentioned, for example.
• the photo radical polymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucyrin TPO.
• the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
• thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
• the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, and the like.
• the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
• thermal radical polymerization initiators examples include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.). ) And the like.
• the content of the polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound.
• the content of the polymerization initiator is 0.01 parts by weight or more, the obtained sealing agent for organic EL display elements is more excellent in curability.
• the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained sealing agent for organic EL display elements does not become too fast, and the workability is improved, and the cured product is more uniform. It can be.
• the minimum with more preferable content of the said polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
• the sealing agent for organic EL display elements of this invention contains a surface modifier.
• the surface modifying agent By containing the surface modifying agent, the surface tension of the whole sealing agent for organic EL display elements of the present invention can be easily adjusted.
• the surface modifier include surfactants and leveling agents.
• Examples of the surface modifier include silicone-based and fluorine-based ones.
• Examples of commercially available surface modifiers include BYK-340, BYK-345 (both manufactured by Big Chemie), and Surflon S-611 (manufactured by AGC Seimi Chemical).
• the content of the surface modifier is preferably 0.01 parts by weight and preferably 5 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the surface modifier is within this range, the surface tension of the whole sealing agent for organic EL display elements of the present invention can be adjusted more easily.
• the minimum with more preferable content of the said surface modifier is 0.1 weight part, and a more preferable upper limit is 3 weight part.
• the sealing agent for organic EL display elements of the present invention may contain a sensitizer.
• the sensitizer has a role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the sealing agent for organic EL display elements of the present invention.
• sensitizer examples include thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4 ′ -Bis (dimethylamino) benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like.
• thioxanthone compound include 2,4-diethylthioxanthone.
• the content of the sensitizer is preferably 0.01 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the polymerizable compound.
• the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited.
• the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption.
• the minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
• the sealing agent for organic EL display elements of the present invention may contain a silane coupling agent.
• the said silane coupling agent has a role which improves the adhesiveness of the sealing agent for organic EL display elements of this invention, a board
• silane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used independently and 2 or more types may be used together.
• the content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the excess silane coupling agent from bleeding out.
• the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
• the encapsulant for organic EL display elements of the present invention may contain a solvent for the purpose of adjusting the viscosity, but problems such as deterioration of the organic light emitting material layer and generation of outgas due to the remaining solvent. Therefore, it is preferable that the solvent is not contained or the solvent content is 0.05% by weight or less.
• the sealing agent for organic EL display elements of this invention contains well-known various additives, such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, a ultraviolet absorber, antioxidant, as needed. May be.
• Examples of the method for producing the sealing agent for organic EL display elements of the present invention include a polymerizable compound using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. And a method of mixing a polymerization initiator and an additive such as a silane coupling agent added if necessary.
• a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
• a method of mixing a polymerization initiator and an additive such as a silane coupling agent added if necessary.
• the preferable lower limit of the total light transmittance of light at a wavelength of 380 to 800 nm of the cured product of the encapsulant for organic EL display elements of the present invention is 80%.
• the total light transmittance is 80% or more, the obtained organic EL display element has superior optical characteristics.
• a more preferable lower limit of the total light transmittance is 85%.
• the transmittance at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours is preferably 85% or more at an optical path length of 20 ⁇ m.
• the transmittance after irradiating the ultraviolet rays for 100 hours is 85% or more, the transparency is high, the loss of light emission is small, and the color reproducibility is excellent.
• a more preferable lower limit of the transmittance after irradiation with the ultraviolet rays for 100 hours is 90%, and a more preferable lower limit is 95%.
• the light source for irradiating the ultraviolet rays a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
• the sealant for an organic EL display device of the present invention has a moisture permeability of 100 g / 100 ⁇ m when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours in accordance with JIS Z 0208.
• m is preferably 2 or less.
• the moisture permeability is 100 g / m 2 or less, the effect of preventing moisture from reaching the organic light emitting material layer and the generation of dark spots is improved, and the resulting organic EL display element is more reliable. It will be a thing.
• the sealing agent for organic EL display elements of the present invention may have a moisture content of less than 0.5% when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours. preferable.
• the moisture content of the cured product is less than 0.5%, the effect of preventing the deterioration of the organic light emitting material layer due to moisture in the cured product is excellent, and the obtained organic EL display element is excellent in reliability. It becomes.
• a more preferable upper limit of the moisture content of the cured product is 0.3%.
• Examples of the method for measuring the moisture content include a method of obtaining by a Karl Fischer method in accordance with JIS K 7251, and a method of obtaining a weight increment after water absorption in accordance with JIS K 7209-2.
• the sealing agent for organic EL display elements of this invention is used suitably for application
• a method for producing an organic EL display element using the sealing agent for organic EL display elements of the present invention for example, a step of applying the sealing agent for organic EL display elements of the present invention to a substrate by an inkjet method, And a method of curing the applied sealing agent for organic EL display elements by light irradiation and / or heating.
• the organic EL display element sealant of the present invention may be applied to the entire surface of the substrate, or on a part of the substrate. It may be applied.
• the shape of the sealing portion of the sealing agent for organic EL display elements of the present invention formed by coating is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air. A shape that completely covers the body may be formed, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape in which a partial opening is provided in the peripheral portion of the laminate. It may be formed.
• the organic EL display sealant element of the present invention When curing the organic EL display element sealing agent of the present invention by light irradiation, the organic EL display sealant element of the present invention, 300 nm or more 400nm or less wavelength and 300 mJ / cm 2 or more 3000 mJ / cm 2 or less of It can be suitably cured by irradiating with an accumulated amount of light.
• Examples of the light source used for the light irradiation include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, and a xenon.
• a lamp, an LED lamp, a fluorescent lamp, sunlight, an electron beam irradiation apparatus, etc. are mentioned.
• These light sources may be used independently and 2 or more types may be used together. These light sources are appropriately selected according to the absorption wavelength of the photo radical polymerization initiator or the photo cationic polymerization initiator.
• Examples of the light irradiation means to the organic EL display element sealant of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, and the like. Any irradiation means may be used.
• the cured product obtained by the step of curing the organic EL display element sealing agent by light irradiation and / or heating may be further coated with an inorganic material film.
• the inorganic material forming the inorganic material layer can be a conventionally known, for example, silicon nitride (SiN x), silicon oxide (SiO x), and the like.
• the inorganic material film may be a single layer or may be a laminate of a plurality of types of layers. Moreover, you may coat
• the method for producing the organic EL display element comprises a step of bonding a base material (hereinafter also referred to as “one base material”) coated with the organic EL display element sealing agent of the present invention and the other base material. You may have.
• the substrate on which the sealing agent for organic EL display elements of the present invention is applied (hereinafter also referred to as “one substrate”) may be a substrate on which a laminate having an organic light emitting material layer is formed. A base material on which the laminate is not formed may be used.
• the sealing agent for organic EL display elements of the present invention is particularly excellent in wet spreadability when applied to the SiON substrate as the one base material by an ink jet method.
• the present invention is applied to the one substrate so that the laminate can be protected from the outside air when the other substrate is bonded.
• coat the sealing agent for organic EL display elements That is, apply the entire surface to the location of the laminate when the other substrate is bonded, or the location of the laminate is complete when the other substrate is bonded.
• the sealing agent portion having a closed pattern may be formed in a shape that fits in the shape.
• the step of curing the organic EL display element sealant by light irradiation and / or heating may be performed before the step of bonding the one base material and the other base material, You may perform after the process of bonding a base material and said other base material.
• the organic EL display of the present invention preferably has a pot life of 1 minute or longer after irradiation with light and / or heating until the curing reaction proceeds and adhesion becomes impossible. When the pot life is 1 minute or longer, higher adhesion strength can be obtained without excessive curing before the one base material and the other base material are bonded together.
• a method of bonding the one base material and the other base material is not particularly limited, but it is preferable to bond them in a reduced-pressure atmosphere.
• the preferable lower limit of the degree of vacuum in the reduced-pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa.
• the degree of vacuum in the reduced-pressure atmosphere is within this range, the one base material and the other base material are not spent for a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump. Bubbles in the sealing agent for organic EL display elements of the present invention when the material is bonded can be more efficiently removed.
• the sealing agent for organic EL display elements which can obtain the organic EL display element excellent in applicability
• Examples 1 to 10, Comparative Examples 1 to 4 According to the blending ratios described in Tables 1 and 2, each material was stirred and mixed uniformly at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Primix Co., Ltd., “Homodisper L type”). Sealants for organic EL display elements of Examples 1 to 10 and Comparative Examples 1 to 4 were produced. About each sealing agent for organic EL display elements obtained in Examples and Comparative Examples, measurement was performed using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) at 25 ° C. and 100 rpm. Tables 1 and 2 show the overall viscosity and the overall surface tension measured at 25 ° C. with a dynamic wettability tester (Reska, “WET-6100”).
• Inkjet coating properties (1-1) Inkjet discharge properties SiON was deposited by plasma CVD on alkali-free glass (“AN100” manufactured by Asahi Glass Co., Ltd.) that had been subjected to alkali cleaning to obtain a SiON film.
• AN100 alkali-free glass
• RF power 10 W (frequency: 2.45 GHz)
• chamber temperature is 100 ° C.
• chamber pressure is 0.9 Torr. I went under the conditions to do.
• Each sealing agent for organic EL display elements obtained in Examples and Comparative Examples was obtained in a droplet amount of 30 picoliters using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet Co., Ltd.).
• the substrate was applied at 2 cm ⁇ 2 cm on the substrate on which the SiON film was deposited, and after 3 minutes, the substrate was observed with a microscope (manufactured by Nikon Corporation, “AZ-100”). Ink jets when the number of coating omissions with a diameter of 0.1 mm or more is 2 or less is “ ⁇ ”, the case of 3 or more and less than 10 is “ ⁇ ”, and the case of 10 or more is “X”. Ejectability was evaluated.
• each of the sealing agents for organic EL display elements obtained in the examples and comparative examples is a liquid of 30 picoliters using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet).
• NanoPrinter500 manufactured by Microjet
• 1000 droplets were applied at a rate of 5 m / sec.
• the diameter of the droplet on the substrate 3 minutes after coating was measured.
• the diameter of the droplet is 200 ⁇ m or more, “ ⁇ ”, when the diameter of the droplet is 100 ⁇ m or more and less than 200 ⁇ m, “ ⁇ ”, and when the diameter of the droplet is less than 100 ⁇ m, “ ⁇ ” Wet spreadability was evaluated.
• the substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, respectively, then washed with boiled isopropyl alcohol for 10 minutes, and a UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd.). The last treatment was performed with “NL-UV253”).
• this substrate is fixed to the substrate folder of the vacuum evaporation apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -NPD) is added to the unglazed crucible.
• the substrate on which the hole transport layer and the organic light emitting material layer are laminated is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and an aluminum wire is added to another tungsten boat. 1.0 g was added.
• the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 ⁇ 10 ⁇ 4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did.
• the inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer of 10 mm ⁇ 10 mm was arranged was taken out.
• a mask having an opening of 13 mm ⁇ 13 mm is installed so as to cover the entire laminated body on the substrate on which the obtained laminated body is arranged, and inorganic by plasma CVD method.
• a material film A was formed.
• SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
• the formed inorganic material film A had a thickness of about 1 ⁇ m.
• the sealing agent for organic EL display elements which can obtain the organic EL display element excellent in applicability

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• 2018
  • 2018-01-09 WO PCT/JP2018/000158 patent/WO2018131553A1/ja active Application Filing
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