WO2018131553A1 - Sealant for organic electroluminescent display element - Google Patents
Sealant for organic electroluminescent display element Download PDFInfo
- Publication number
- WO2018131553A1 WO2018131553A1 PCT/JP2018/000158 JP2018000158W WO2018131553A1 WO 2018131553 A1 WO2018131553 A1 WO 2018131553A1 JP 2018000158 W JP2018000158 W JP 2018000158W WO 2018131553 A1 WO2018131553 A1 WO 2018131553A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organic
- surface tension
- sealing agent
- display element
- display elements
- Prior art date
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- 239000000565 sealant Substances 0.000 title abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000007789 sealing Methods 0.000 claims description 69
- 239000003795 chemical substances by application Substances 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 27
- 125000003566 oxetanyl group Chemical group 0.000 claims description 7
- 239000008393 encapsulating agent Substances 0.000 claims description 3
- -1 3,4-epoxycyclohexylmethyl Chemical group 0.000 description 64
- 239000000463 material Substances 0.000 description 42
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- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 16
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
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- HYVNJCOHGOONJK-UHFFFAOYSA-N dibenzyl-methyl-phenylazanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(C)CC1=CC=CC=C1 HYVNJCOHGOONJK-UHFFFAOYSA-N 0.000 description 2
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- 150000004714 phosphonium salts Chemical class 0.000 description 2
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
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- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
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- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- HMKGBOLFVMRQRP-UHFFFAOYSA-N tribenzyl(phenyl)azanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 HMKGBOLFVMRQRP-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
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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Abstract
Description
有機発光材料層内への水分の浸入を防止するための方法として、特許文献2には、無機材料膜と樹脂膜とを交互に蒸着する方法が開示されており、特許文献3や特許文献4には、無機材料膜上に樹脂膜を形成する方法が開示されている。 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.
以下に本発明を詳述する。 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, and 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.
なお、本明細書において上記粘度は、E型粘度計(例えば、VISCOMETER TV-22(東機産業社製)等)を用いて、100rpmの条件で測定される値を意味する。 As for the sealing agent for organic EL display elements of this 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. When the viscosity of the whole sealing agent for organic EL display elements at 25 ° C. is within this range, it can be suitably applied particularly by an ink jet method. The preferable lower limit of the viscosity of the whole sealing agent for organic EL display elements at 25 ° C. is 8 mPa · s, the preferable upper limit is 20 mPa · s, the more preferable lower limit is 10 mPa · s, and the more preferable upper limit is 15 mPa · s.
In the present specification, 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.)).
上記加熱機構を搭載したインクジェット用塗布ヘッドとしては、例えば、コニカミノルタ社製のKM1024シリーズや、富士フィルムDimatix社製のSG1024iシリーズ等が好適に用いられる。
塗布ヘッドの加熱温度としては25℃以上80℃以下であることが好ましい。上記加熱温度がこの範囲にあることにより、有機EL表示素子用封止剤の経時的な粘度上昇を抑制でき、安定的に吐出することができる。 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. 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 | coat suitably by the inkjet method.
As 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.
また、上記25℃における有機EL表示素子用封止剤全体の表面張力の好ましい下限は15mN/m、より好ましい下限は20mN/mである。
なお、本明細書において、上記表面張力は、動的濡れ性試験機(例えば、WET-6100型(レスカ社製)等)により測定することができる。 As for the sealing agent for organic EL display elements of this invention, the upper limit of the surface tension of the whole sealing agent for organic EL display elements in 25 degreeC is 35 mN / m. When 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.
Moreover, 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.
In the present specification, the surface tension can be measured by a dynamic wettability tester (for example, WET-6100 type (manufactured by Reska Co., Ltd.)).
本発明の有機EL表示素子用封止剤は、上記重合性化合物100重量部中に、25℃における表面張力が35mN/m以上である重合性化合物を30重量部以上含有する。上記25℃における表面張力が35mN/m以上である重合性化合物を30重量部以上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、濡れ広がり性に優れ、塗布ムラや塗布抜けを防止することができる。
上記25℃における表面張力が35mN/mである重合性化合物は、分子間の凝集性が高いことから分子の極性が高いことが特徴として挙げられる。 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. By containing 30 parts by weight or more of the polymerizable compound having a surface tension of 35 mN / m or more at 25 ° C., 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.
また、封止剤全体の表面張力の調整の容易性等の観点から、上記25℃における表面張力が35mN/m以上である重合性化合物の表面張力の好ましい上限は50mN/m、より好ましい上限は47mN/mである。 From the viewpoint of further improving the effect of preventing coating unevenness and coating omission, 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.
In addition, from the viewpoint of easy adjustment of the surface tension of the entire sealant, 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.
上記ダイセル社製の重合性化合物としては、例えば、セロキサイド2021P、セロキサイド8000、サイクロマーM100等が挙げられる。
上記ADEKA社製の重合性化合物としては、例えば、ED-523L等が挙げられる。
上記日立化成社製の重合性化合物としては、例えば、FA-220A、FA-222A等が挙げられる。
上記三菱化学社製の重合性化合物としては、例えば、YED-216D(三菱化学社製)等が挙げられる。 Among the other polymerizable compounds having a surface tension at 25 ° C. of 35 mN / m or more, 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).
上記重合開始剤としては、用いる重合性化合物の種類等に応じて、光カチオン重合開始剤や、熱カチオン重合開始剤や、光ラジカル重合開始剤や、熱ラジカル重合開始剤が好適に用いられる。なかでも、上記重合性化合物がエポキシ化合物又はオキセタン化合物であり、上記重合開始剤がカチオン重合開始剤であることが好ましい。 It is preferable that the sealing agent for organic EL display elements of this invention contains a polymerization initiator.
As the 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. Especially, it is preferable that the said polymeric compound is an epoxy compound or an oxetane compound, and the said polymerization initiator is a cationic polymerization initiator.
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。 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.
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。 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.
上記BASF社製の光ラジカル重合開始剤としては、例えば、IRGACURE184、IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE819、IRGACURE907、IRGACURE2959、IRGACURE OXE01、ルシリンTPO等が挙げられる。
上記東京化成工業社製の光ラジカル重合開始剤としては、例えば、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。 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.
Examples of 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.
Examples of the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
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。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
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, and peroxydicarbonate.
上記表面改質剤を含有することにより、本発明の有機EL表示素子用封止剤全体の表面張力を容易に調整することができる。
上記表面改質剤としては、例えば、界面活性剤やレベリング剤等が挙げられる。 It is preferable that the sealing agent for organic EL display elements of this invention contains a surface modifier.
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.
Examples of the surface modifier include surfactants and leveling agents.
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、BYK-340、BYK-345(いずれもビックケミー社製)、サーフロンS-611(AGCセイミケミカル社製)等が挙げられる。 Examples of the 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).
上記チオキサントン化合物としては、例えば、2,4-ジエチルチオキサントン等が挙げられる。 Examples of the sensitizer 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.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone.
上記全光線透過率は、例えば、AUTOMATIC HAZE MATER MODEL TC=III DPK(東京電色社製)等の分光計を用いて測定することができる。 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%. When 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 total light transmittance can be measured using a spectrometer such as AUTOMATIC HAZE MATER MODEL TC = III DPK (manufactured by Tokyo Denshoku Co., Ltd.).
上記紫外線を照射する光源としては、例えば、キセノンランプ、カーボンアークランプ等、従来公知の光源を用いることができる。 In the sealing agent for organic EL display elements of the present invention, 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 μm. When 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%.
As 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.
上記含水率の測定方法としては、例えば、JIS K 7251に準拠してカールフィッシャー法により求める方法や、JIS K 7209-2に準拠して吸水後の重量増分を求める等の方法が挙げられる。 Furthermore, 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. When 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.
本発明の有機EL表示素子用封止剤を用いて有機EL表示素子を製造する方法としては、例えば、インクジェット法により、本発明の有機EL表示素子用封止剤を基材に塗布する工程と、塗布した有機EL表示素子用封止剤を光照射及び/又は加熱により硬化させる工程とを有する方法等が挙げられる。 The sealing agent for organic EL display elements of this invention is used suitably for application | coating by the inkjet method.
As 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.
これらの光源は、上記光ラジカル重合開始剤や光カチオン重合開始剤の吸収波長に合わせて適宜選択される。 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.
上記無機材料膜を構成する無機材料としては、従来公知のものを用いることができ、例えば、窒化珪素(SiNx)や酸化珪素(SiOx)等が挙げられる。上記無機材料膜は、1層からなるものであってもよく、複数種の層を積層したものであってもよい。また、上記無機材料膜と本発明の有機EL表示素子用封止剤からなる樹脂膜とを、交互に繰り返して上記積層体を被覆してもよい。 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.
As 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 | cover the said laminated body by repeating alternately the said inorganic material film | membrane and the resin film which consists of the sealing agent for organic EL display elements of this invention.
本発明の有機EL表示素子用封止剤を塗布する基材(以下、「一方の基材」ともいう)は、有機発光材料層を有する積層体の形成されている基材であってもよく、該積層体の形成されていない基材であってもよい。本発明の有機EL表示素子用封止剤は、上記一方の基材としてSiON基板にインクジェット法によって塗布する際に特に濡れ広がり性に優れる。
上記一方の基材が上記積層体の形成されていない基材である場合、上記他方の基材を貼り合わせた際に、上記積層体を外気から保護できるように上記一方の基材に本発明の有機EL表示素子用封止剤を塗布すればよい。即ち、他方の基材を貼り合わせた際に上記積層体の位置となる場所に全面的に塗布するか、又は、他方の基材を貼り合わせた際に上記積層体の位置となる場所が完全に収まる形状に、閉じたパターンの封止剤部を形成してもよい。 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.
When the one substrate is a substrate on which the laminate is not formed, 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. What is necessary is just to apply | 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.
上記有機EL表示素子用封止剤を光照射及び/又は加熱により硬化させる工程を、上記一方の基材と上記他方の基材とを貼り合わせる工程の前に行なう場合、本発明の有機EL表示素子用封止剤は、光照射及び/又は加熱してから硬化反応が進行して接着ができなくなるまでの可使時間が1分以上であることが好ましい。上記可使時間が1分以上であることにより、上記一方の基材と上記他方の基材とを貼り合わせる前に硬化が進行し過ぎることなく、より高い接着強度を得ることができる。 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.
When the step of curing the organic EL display element sealant by light irradiation and / or heating is performed before the step of bonding the one base material and the other base material, the organic EL display of the present invention. The device sealant 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.
上記減圧雰囲気下の真空度の好ましい下限は0.01kPa、好ましい上限は10kPaである。上記減圧雰囲気下の真空度がこの範囲であることにより、真空装置の気密性や真空ポンプの能力から真空状態を達成するのに長時間を費やすことなく、上記一方の基材と上記他方の基材とを貼り合わせる際の本発明の有機EL表示素子用封止剤中の気泡をより効率的に除去することができる。 In the step of bonding the one base material and the other base material, 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. When 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.
表1、2に記載された配合比に従い、各材料を、ホモディスパー型撹拌混合機(プライミクス社製、「ホモディスパーL型」)を用い、撹拌速度3000rpmで均一に撹拌混合することにより、実施例1~10、比較例1~4の各有機EL表示素子用封止剤を作製した。
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(東機産業社製、「VISCOMETER TV-22」)を用いて、25℃、100rpmの条件において測定した全体の粘度、及び、25℃において動的濡れ性試験機(レスカ社製、「WET-6100型」)により測定した全体の表面張力を表1、2に示した。 (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”).
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 evaluation was performed about each sealing agent for organic EL display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
(1-1)インクジェット吐出性
アルカリ洗浄した無アルカリガラス(旭硝子社製、「AN100」)上にプラズマCVD法にてSiONを蒸着し、SiON膜を得た。プラズマCVD法は、原料ガスとしてSiH4ガス、窒素ガス、酸素ガス及びNH3ガスを用い、RFパワーを10W(周波数2.45GHz)、チャンバー内温度を100℃、チャンバー内圧力を0.9Torrとする条件で行った。
実施例及び比較例で得られた各有機EL表示素子用封止剤を、インクジェット吐出装置(マイクロジェット社製、「NanoPrinter500」)を用いて、30ピコリットルの液滴量にて、得られたSiON膜を蒸着した基板上に2cm×2cmで塗布し、3分後、基板を顕微鏡(ニコン社製、「AZ-100」)で観察した。直径0.1mm以上の塗布抜けが2個以下であった場合を「○」、3個以上10個未満であった場合を「△」、10個以上であった場合を「×」として、インクジェット吐出性を評価した。 (1) 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. In the plasma CVD method, SiH 4 gas, nitrogen gas, oxygen gas and NH 3 gas are used as source gases, RF power is 10 W (frequency: 2.45 GHz), chamber temperature is 100 ° C., and 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 “Δ”, and the case of 10 or more is “X”. Ejectability was evaluated.
実施例及び比較例で得られた各有機EL表示素子用封止剤を、インクジェット吐出装置(マイクロジェット社製、「NanoPrinter500」)を用いて、30ピコリットルの液滴量にて、上記「(1-1)インクジェット吐出性」と同様にしてSiON膜を蒸着した基板上に、5m/秒の速度にて500μmピッチで1000滴塗布した。次いで、塗布から3分後の基板上の液滴の直径を測定した。液滴の直径が200μm以上であった場合を「○」、液滴の直径が100μm以上200μm未満であった場合を「△」、液滴の直径が100μm未満であった場合を「×」として濡れ広がり性を評価した。 (1-2) Wetting and spreading property 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). In the same manner as in “(1-1) Inkjet ejection properties”, 1000 droplets were applied at a rate of 5 m / sec. Next, the diameter of the droplet on the substrate 3 minutes after coating was measured. When the diameter of the droplet is 200 μm or more, “◯”, when the diameter of the droplet is 100 μm or more and less than 200 μm, “△”, and when the diameter of the droplet is less than 100 μm, “×” Wet spreadability was evaluated.
実施例及び比較例で得られた各有機EL表示素子用封止剤の硬化物の加熱時に発生するアウトガスをヘッドスペース法によるガスクロマトグラフにより測定した。各有機EL表示素子用封止剤100mgをアプリケーターにて300μmの厚さに塗工した後に、LEDランプにて波長365nmの紫外線を3000mJ/cm2照射して封止剤を硬化した後、ヘッドスペース用バイアルに硬化させた封止剤硬化物を入れてバイアルを封止し、100℃で30分間加熱して、ヘッドスペース法により発生ガスを測定した。
発生したガスが300ppm未満であった場合を「○」、300ppm以上500ppm未満であった場合を「△」、500ppm以上であった場合を「×」として低アウトガス性を評価した。 (2) Low outgassing property The outgas generated during heating of the cured products of the sealing agents for organic EL display elements obtained in Examples and Comparative Examples was measured by a gas chromatograph by the headspace method. After coating 100 mg of each organic EL display element sealant with an applicator to a thickness of 300 μm, the ultraviolet light with a wavelength of 365 nm was irradiated with 3000 mJ / cm 2 with an LED lamp to cure the sealant, and then headspace The cured sealant cured product was put in the vial for sealing, the vial was sealed, heated at 100 ° C. for 30 minutes, and the generated gas was measured by the headspace method.
The case where the generated gas was less than 300 ppm was evaluated as “◯”, the case where it was 300 ppm or more and less than 500 ppm as “Δ”, and the case where it was 500 ppm or more as “x”, and the low outgassing property was evaluated.
(3-1)有機発光材料層を有する積層体が配置された基板の作製
上記「(1-1)インクジェット吐出性」と同様にしてSiON膜を蒸着した基板(長さ25mm、幅25mm、厚さ0.7mm)にITO電極を1000Åの厚さで成膜したものを、正孔輸送層及び有機発光材料層を積層する基板とした。上記基板をアセトン、アルカリ水溶液、イオン交換水、イソプロピルアルコールにてそれぞれ15分間超音波洗浄した後、煮沸させたイソプロピルアルコールにて10分間洗浄し、更に、UV-オゾンクリーナ(日本レーザー電子社製、「NL-UV253」)にて直前処理を行った。
次に、この基板を真空蒸着装置の基板フォルダに固定し、素焼きの坩堝にN,N’-ジ(1-ナフチル)-N,N’-ジフェニルベンジジン(α-NPD)を200mg、別の素焼き坩堝にトリス(8-キノリノラト)アルミニウム(Alq3)を200mg入れ、真空チャンバー内を、1×10-4Paまで減圧した。その後、α-NPDの入った坩堝を加熱し、α-NPDを蒸着速度15Å/sで基板に堆積させ、膜厚600Åの正孔輸送層を成膜した。次いで、Alq3の入った坩堝を加熱し、15Å/sの蒸着速度で膜厚600Åの有機発光材料層を成膜した。その後、正孔輸送層及び有機発光材料層が積層された基板を別の真空蒸着装置に移し、この真空蒸着装置内のタングステン製抵抗加熱ボートにフッ化リチウム200mg、別のタングステン製ボートにアルミニウム線1.0gを入れた。その後、真空蒸着装置の蒸着器内を2×10-4Paまで減圧してフッ化リチウムを0.2Å/sの蒸着速度で5Å成膜した後、アルミニウムを20Å/sの速度で1000Å成膜した。窒素により蒸着器内を常圧に戻し、10mm×10mmの有機発光材料層を有する積層体が配置された基板を取り出した。 (3) Reliability of organic EL display element (3-1) Fabrication of substrate on which laminated body having organic light emitting material layer is arranged SiON film was deposited in the same manner as “(1-1) Inkjet ejection property”. A substrate in which an ITO electrode was formed to a thickness of 1000 mm on a substrate (length 25 mm, width 25 mm, thickness 0.7 mm) was a substrate on which a hole transport layer and an organic light emitting material layer were laminated. 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”).
Next, 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 (α-NPD) is added to the unglazed crucible. 200 mg of tris (8-quinolinolato) aluminum (Alq 3 ) was put in the crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa. Thereafter, the crucible containing α-NPD was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 s / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, 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. After that, 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.
得られた積層体が配置された基板における該積層体全体を覆うように、13mm×13mmの開口部を有するマスクを設置し、プラズマCVD法にて無機材料膜Aを形成した。
プラズマCVD法は、原料ガスとしてSiH4ガス及び窒素ガスを用い、各々の流量をSiH4ガス10sccm、窒素ガス200sccmとし、RFパワーを10W(周波数2.45GHz)、チャンバー内温度を100℃、チャンバー内圧力を0.9Torrとする条件で行った。
形成された無機材料膜Aの厚さは、約1μmであった。 (3-2) Coating with Inorganic Material Film A 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.
In the plasma CVD method, 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 μm.
得られた基板に対し、実施例及び比較例で得られた各有機EL表示素子用封止剤を、インクジェット吐出装置(マイクロジェット社製、「NanoPrinter500」)を使用して基板にパターン塗布した。
その後、LEDランプを用いて波長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て樹脂保護膜を形成した。 (3-3) Formation of Resin Protective Film Each of the organic EL display element sealants obtained in Examples and Comparative Examples was applied to the obtained substrate using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet). Was used to apply a pattern to the substrate.
Thereafter, an ultraviolet ray having a wavelength of 365 nm was irradiated with 3000 mJ / cm 2 using an LED lamp to cure the organic EL display element sealant to form a resin protective film.
樹脂保護膜を形成した後、該樹脂保護膜の全体を覆うように、12mm×12mmの開口部を有するマスクを設置し、プラズマCVD法にて無機材料膜Bを形成して有機EL表示素子を得た。
プラズマCVD法は、上記「(3-2)無機材料膜Aによる被覆」と同様の条件で行った。
形成された無機材料膜Bの厚さは、約1μmであった。 (3-4) After forming the coating resin protective film with the inorganic material film B, a mask having an opening of 12 mm × 12 mm is installed so as to cover the entire resin protective film, and the inorganic material is formed by plasma CVD. Film B was formed to obtain an organic EL display element.
The plasma CVD method was performed under the same conditions as in “(3-2) Coating with inorganic material film A”.
The formed inorganic material film B had a thickness of about 1 μm.
得られた有機EL表示素子を、温度85℃、湿度85%の環境下で100時間暴露した後、3Vの電圧を印加し、有機EL表示素子の発光状態(ダークスポット及び画素周辺消光の有無)を目視で観察した。ダークスポットや周辺消光が無く均一に発光した場合を「○」、ダークスポットや周辺消光はないものの輝度に僅かな低下が認められた場合を「△」、ダークスポットや周辺消光が認められた場合を「×」として有機EL表示素子の発光状態を評価した。 (3-5) Light-emitting state of organic EL display element The obtained organic EL display element was exposed for 100 hours in an environment of a temperature of 85 ° C. and a humidity of 85%, and then a voltage of 3 V was applied to the organic EL display element. The light emission state (the presence or absence of dark spots and pixel periphery quenching) was visually observed. “○” when there is no dark spot or peripheral quenching, and “△” when there is no dark spot or peripheral quenching, but “△” when there is a slight decrease in brightness, when dark spot or peripheral quenching is observed Was evaluated as the light emission state of the organic EL display element.
Claims (5)
- 重合性化合物を含有する有機EL表示素子用封止剤であって、
前記重合性化合物100重量部中に、25℃における表面張力が35mN/m以上である重合性化合物を30重量部以上含有し、
25℃における有機EL表示素子用封止剤全体の粘度が5mPa・s以上50mPa・s以下であり、25℃における有機EL表示素子用封止剤全体の表面張力が35mN/m以下である
ことを特徴とする有機EL表示素子用封止剤。 A sealing agent for organic EL display elements containing a polymerizable compound,
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 viscosity of the whole sealing agent for organic EL display elements at 25 ° C. is 5 mPa · s to 50 mPa · s, and the surface tension of the whole sealing agent for organic EL display elements at 25 ° C. is 35 mN / m or less. A sealing agent for organic EL display elements, which is characterized. - 前記重合性化合物は、前記25℃における表面張力が35mN/m以上である重合性化合物を2種以上含有することを特徴とする請求項1記載の有機EL表示素子用封止剤。 2. The encapsulant for an organic EL display device according to claim 1, wherein the polymerizable compound contains two or more polymerizable compounds having a surface tension at 25 ° C. of 35 mN / m or more.
- 前記25℃における表面張力が35mN/m以上である重合性化合物として、オキセタニル基を有し、かつ、25℃における表面張力が35mN/m以上である化合物を含有することを特徴とする請求項1又は2記載の有機EL表示素子用封止剤。 The polymerizable compound having a surface tension at 25 ° C of 35 mN / m or more contains a compound having an oxetanyl group and having a surface tension at 25 ° C of 35 mN / m or more. Or the sealing agent for organic EL display elements of 2.
- 25℃における有機EL表示素子用封止剤全体の粘度が20mPa・s以下であることを特徴とする請求項1、2又は3記載の有機EL表示素子用封止剤。 The organic EL display element sealing agent according to claim 1, 2 or 3, wherein the viscosity of the whole organic EL display element sealing agent at 25 ° C is 20 mPa · s or less.
- インクジェット法による塗布に用いられることを特徴とする請求項1、2、3又は4記載の有機EL表示素子用封止剤。 The sealing agent for organic EL display elements according to claim 1, 2, 3, or 4, which is used for coating by an ink jet method.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018503681A JP7303628B2 (en) | 2017-01-12 | 2018-01-09 | Sealant for organic EL display element |
KR1020197001615A KR102662808B1 (en) | 2017-01-12 | 2018-01-09 | Encapsulant for organic EL display elements |
CN201880005879.5A CN110169201A (en) | 2017-01-12 | 2018-01-09 | Organic EL display element sealant |
JP2023079272A JP2023109860A (en) | 2017-01-12 | 2023-05-12 | Encapsulant for organic el display element |
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KR (1) | KR102662808B1 (en) |
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- 2018-01-09 JP JP2018503681A patent/JP7303628B2/en active Active
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TW201831605A (en) | 2018-09-01 |
JPWO2018131553A1 (en) | 2019-11-07 |
KR102662808B1 (en) | 2024-05-02 |
CN110169201A (en) | 2019-08-23 |
KR20190100155A (en) | 2019-08-28 |
JP7303628B2 (en) | 2023-07-05 |
JP2023109860A (en) | 2023-08-08 |
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