WO2019082996A1 - 有機エレクトロルミネッセンス表示素子用封止剤 - Google Patents
有機エレクトロルミネッセンス表示素子用封止剤Info
- Publication number
- WO2019082996A1 WO2019082996A1 PCT/JP2018/039784 JP2018039784W WO2019082996A1 WO 2019082996 A1 WO2019082996 A1 WO 2019082996A1 JP 2018039784 W JP2018039784 W JP 2018039784W WO 2019082996 A1 WO2019082996 A1 WO 2019082996A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- group
- formula
- organic electroluminescent
- Prior art date
Links
- 238000007789 sealing Methods 0.000 title claims abstract description 102
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 144
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 42
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 12
- 230000003068 static effect Effects 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 71
- -1 m-phenoxybenzyl Chemical group 0.000 claims description 65
- 125000001153 fluoro group Chemical group F* 0.000 claims description 63
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000565 sealant Substances 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 23
- 239000011737 fluorine Substances 0.000 claims description 23
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
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- 125000000217 alkyl group Chemical group 0.000 claims description 14
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- 239000003963 antioxidant agent Substances 0.000 claims description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 10
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 5
- 238000005401 electroluminescence Methods 0.000 claims description 5
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 4
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- NSKCTPBWPZPFHW-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane-1,10-diol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CO NSKCTPBWPZPFHW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 156
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- 239000000203 mixture Substances 0.000 description 79
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- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
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- 239000011342 resin composition Substances 0.000 description 6
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- LTVOKYUPTHZZQH-UHFFFAOYSA-N difluoromethane Chemical group F[C]F LTVOKYUPTHZZQH-UHFFFAOYSA-N 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
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- 239000002861 polymer material Substances 0.000 description 5
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- 239000007789 gas Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 150000004866 oxadiazoles Chemical class 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052790 beryllium Inorganic materials 0.000 description 3
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- 230000000903 blocking effect Effects 0.000 description 3
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- TXZNVWGSLKSTDH-XCADPSHZSA-N (1Z,3Z,5Z)-cyclodeca-1,3,5-triene Chemical group C1CC\C=C/C=C\C=C/C1 TXZNVWGSLKSTDH-XCADPSHZSA-N 0.000 description 2
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- 125000006002 1,1-difluoroethyl group Chemical group 0.000 description 1
- NGQSLSMAEVWNPU-YTEMWHBBSA-N 1,2-bis[(e)-2-phenylethenyl]benzene Chemical class C=1C=CC=CC=1/C=C/C1=CC=CC=C1\C=C\C1=CC=CC=C1 NGQSLSMAEVWNPU-YTEMWHBBSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- SHXCHSNZIGEBFL-UHFFFAOYSA-N 1,3-benzothiazole;zinc Chemical compound [Zn].C1=CC=C2SC=NC2=C1 SHXCHSNZIGEBFL-UHFFFAOYSA-N 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical class C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical class C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
-
- 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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
Definitions
- the present invention relates to a sealing agent for an organic electroluminescent (EL) display element.
- EL organic electroluminescent
- OLED Organic electroluminescent
- OLED devices are attracting attention as devices capable of high luminance light emission.
- the OLED element has a problem that it is deteriorated by moisture and light emission characteristics are deteriorated.
- An organic electroluminescence display device (see Patent Document 2) characterized in that the sealing layer is a laminate in which at least a barrier layer, a resin layer, and a barrier layer are sequentially formed (inorganic film and organic film for sealing an organic EL device) And a sealing glass substrate disposed in close contact with the top organic film of the sealing layer and covering all of the top surface of the top organic film.
- An organic EL device (see Patent Document 3) characterized by the above has been proposed.
- JP 10-74583 A JP 2001-307873 A JP, 2009-37812, A JP, 2014-225380, A JP, 2012-190612, A JP 2014-229496 A JP, 2014-196387, A JP, 2014-193970, A JP, 2014-193971, A WO 2014/157642 US2017 / 0062762 publication
- Patent Documents 2 to 3 there is a problem that the thickness of the organic film is 3 ⁇ m or less because the organic film is formed by vapor deposition. If the thickness of the organic film is 3 ⁇ m or less, not only the particles generated at the time of element formation can not be completely covered, but it is also difficult to apply while maintaining the flatness on the inorganic film.
- Patent Document 5 proposes a photocurable sealing agent using an epoxy-based material, but such a material cures with UV light, causing damage to the organic EL element with UV light, and yield There was a problem in
- Patent Documents 6 to 10 describe that the water vapor transmission rate is reduced as a property necessary for such a sealing material, the sealing material itself penetrates from the pinhole of the passivation film, and the organic EL element There is no description about the problem of reducing the reliability of the sealing material
- patent document 11 describes use of cyclic monofunctional (meth) acrylate, the unreacted material becomes outgassing and it has not solved the problem leading to the light emission defect of an organic EL element.
- the present invention can provide the following.
- ⁇ 4> The sealing agent for organic electroluminescent display elements as described in any one of ⁇ 1>- ⁇ 3> which contains the fluorine-containing monomer which has a fluorine atom and a (meth) acryloyl group as (E) component.
- the fluorine-containing monomer is at least one selected from the group consisting of a compound represented by the formula (E-1), a compound represented by the formula (E-2) and a compound represented by the formula (E-3)
- Formula (E-1) [In the formula (E-1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a fluorinated alkyl group or a group in which an oxygen atom is inserted into carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkyl group. Plural R 3 's may be the same or different.
- R 3 represents a hydrogen atom or a methyl group
- R 4 represents a fluorinated alkanediyl group or a group in which an oxygen atom is inserted into carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkanediyl group.
- Plural R 3 's may be the same or different.
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents a single bond, an alkanediyl group, a fluorinated alkanediyl group, or a group in which an oxygen atom is inserted in part of a carbon-carbon bond or carbon-hydrogen bond in an alkanediyl group or a fluorinated alkanediyl group
- R 5 represents a hydrogen atom or a methyl group
- R 61 represents a hydrogen atom or a fluorine atom
- R 62 represents a hydrogen atom or a fluorine atom
- p is an integer of 0 or more Indicates
- Plural R 61 may be the same or different.
- Plural R 62 may be the same or different. However, at least one of R 62 is a fluorine atom.
- the content of the component (E) is in the range of 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B) ⁇ 4> to ⁇
- the component (E) is 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol di ( Characterized in that it contains one or more selected from the group consisting of meta) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, and 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate.
- the sealing agent for organic electroluminescent display elements as described in any one of ⁇ 4>- ⁇ 8>.
- ⁇ 11> Any of ⁇ 1> to ⁇ 10> characterized by not containing a difunctional (meth) acrylate oligomer, a difunctional (meth) acrylate polymer, a polyfunctional (meth) acrylate oligomer, or a polyfunctional (meth) acrylate polymer
- ⁇ 14> Among the components (B), at least two of them have two or more cyclic structures in the molecule, and the sealant for an organic electroluminescent display element according to any one of ⁇ 1> to ⁇ 13>.
- Component (B) is ethoxylated-o-phenylphenol (meth) acrylate, m-phenoxybenzyl (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, ethoxylated bisphenol A represented by the following structural formula
- the sealing agent for an organic electroluminescent display element according to any one of ⁇ 1> to ⁇ 14>, which contains at least one member selected from the group consisting of di (meth) acrylates.
- each R is independently a hydrogen atom or a methyl group.
- ⁇ 16> The sealing agent for an organic electroluminescent display element according to any one of ⁇ 1> to ⁇ 15>, wherein the component (A) is an alkanediol di (meth) acrylate having 12 or less carbon atoms.
- Component (A) is at least one member selected from the group consisting of 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate and 1,12-dodecanediol di (meth) acrylate And a sealing agent for an organic electroluminescent display element as described in any one of ⁇ 1> to ⁇ 16>.
- the sealant for an organic electroluminescent display element according to any one of ⁇ 1> to ⁇ 19>, which further comprises (D) an antioxidant.
- ⁇ 23> The sealant for an organic electroluminescent display element according to any one of ⁇ 1> to ⁇ 22>, which is cured at a wavelength of 395 nm to 500 nm.
- the sealing agent according to the present invention exhibits an effect of being excellent in dischargeability when using an inkjet, and also excellent in reliability of the obtained organic EL element.
- (Meth) acrylate means acrylate or methacrylate, and the notation such as "(meth) acryloyloxy" or "(meth) acrylamide” has the same meaning.
- “Monofunctional (meth) acrylate” refers to (meth) acrylate having one (meth) acrylic group
- "bifunctional (meth) acrylate” refers to (meth) acrylate having two (meth) acrylic groups Point to.
- the "polyfunctional (meth) acrylate” refers to a (meth) acrylate having three or more (meth) acrylic groups, and does not contain a difunctional (meth) acrylate.
- a top emission type organic EL device that emits light from the side opposite to the substrate of the organic EL element formed on the substrate will be described as an example.
- an organic EL element in which an anode, an organic EL layer including a light emitting layer, and a cathode are sequentially stacked on a substrate, and an inorganic film and an organic film covering the entire organic EL element It has the structure where the sealing layer which consists of films
- various substrates such as a glass substrate, a silicon substrate, and a plastic substrate can be used.
- a glass substrate is preferable, and a glass substrate is more preferable.
- Plastics used for plastic substrates include polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole, polyparaphenylene Examples include vinylene, polymethyl methacrylate, polystyrene, polycarbonate, polycycloolefin, polyacrylic and the like.
- polyimides, polyetherimides, polyethylene terephthalates, polyethylene naphthalates, polyoxadiazoles, aromatic polyamides, polybenzimidazoles, polybenzos in that they are excellent in low water permeability, low oxygen permeability, and heat resistance.
- One or more members selected from the group consisting of bisthiazole, polybenzoxazole, polythiazole and polyparaphenylene vinylene are preferable, and polyimide, polyetherimide, polyethylene terephthalate are preferred because they have high permeability to energy rays such as ultraviolet rays or visible rays. And more preferably one or more selected from the group consisting of polyethylene naphthalate.
- a conductive metal oxide film, a semitransparent metal thin film or the like having a relatively large work function preferably having a work function larger than 4.0 eV
- materials for the anode include indium tin oxide (hereinafter referred to as ITO), metal oxides such as tin oxide, gold (Au), platinum (Pt), silver (Ag), copper (Cu) and the like. Or an alloy containing at least one of these metals, an organic transparent conductive film of polyaniline or a derivative thereof, an organic such as polythiophene or a derivative thereof, and the like.
- the anode can be formed by a layer structure of two or more layers if necessary.
- the film thickness of the anode can be appropriately selected in consideration of the electrical conductivity (also in the case of the bottom emission type, the light transmittance).
- the thickness of the anode is preferably 10 nm to 10 ⁇ m, more preferably 20 nm to 1 ⁇ m, and most preferably 50 nm to 500 nm.
- Examples of the method for producing the anode include a vacuum evaporation method, a sputtering method, an ion plating method, and a plating method.
- a reflective film for reflecting light emitted to the substrate side may be provided under the anode.
- the organic EL layer contains at least a light emitting layer made of an organic substance.
- the light emitting layer contains a light emitting material.
- the light emitting material include organic substances (low molecular weight compounds or high molecular weight compounds) which emit fluorescence or phosphorescence.
- the light emitting layer may further contain a dopant material.
- the organic substance include dye-based materials, metal complex-based materials, and polymer materials.
- the dopant material is to be doped into the organic substance for the purpose of improving the luminous efficiency of the organic substance or changing the emission wavelength.
- the thickness of the light emitting layer comprising these organic substances and the dopant optionally doped is usually 2 to 200 nm.
- Dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine
- a ring compound, a perinone derivative, a perylene derivative, an oligothiophene derivative, a trifluorolamine derivative, an oxadiazole dimer, a pyrazoline dimer and the like can be mentioned.
- Metal complex materials metal complexes having luminescence from triplet excited state such as iridium complex and platinum complex, aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazolyl zinc complex, benzothiazole zinc complex, azomethyl zinc complex And metal complexes such as porphyrin zinc complex and europium complex.
- the metal complex includes, as central metals, rare earth metals such as terbium (Tb), europium (Eu), dysprosium (Dy), aluminum (Al), zinc (Zn), beryllium (Be), etc.
- metal complexes having a quinoline structure and the like metal complexes having aluminum (Al) as a central metal and having a quinoline structure or the like as a ligand are preferable.
- metal complexes having aluminum (Al) as the central metal and quinoline structure as the ligand tris (8-hydroxyquinolinato) aluminum is preferable.
- Polymer material As the polymer material, polyparaphenylene vinylene derivative, polythiophene derivative, polyparaphenylene derivative, polysilane derivative, polyacetylene derivative, polyfluorene derivative, polyvinyl carbazole derivative, a product obtained by polymerizing the above dye or metal complex light emitting material, etc. Can be mentioned.
- examples of the material emitting blue light include distyrylarylene derivatives, oxadiazole derivatives, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, polymers thereof, and the like.
- polymeric materials are preferred.
- the polymer materials one or more members selected from the group consisting of polyvinylcarbazole derivatives, polyparaphenylene derivatives and polyfluorene derivatives are preferable.
- Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, polyparaphenylene vinylene derivatives, polyfluorene derivatives, polymers of these, and the like.
- polymeric materials are preferred.
- the polymeric materials one or more of the group consisting of polyparaphenylene vinylene derivatives and polyfluorene derivatives is preferred.
- Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyfluorene derivatives, polymers of these, and the like.
- polymeric materials are preferred.
- the polymer materials one or more selected from the group consisting of polyparaphenylene vinylene derivatives, polythiophene derivatives and polyfluorene derivatives is preferable.
- Dopant material examples include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone and the like.
- the organic EL layer can appropriately provide a layer provided between the light emitting layer and the anode and a layer provided between the light emitting layer and the cathode, in addition to the light emitting layer.
- the hole injecting layer for improving the hole injection efficiency from the anode, or the holes injected from the anode or the hole injecting layer are transported to the light emitting layer
- a hole transport layer etc. are mentioned.
- the layer provided between the light emitting layer and the cathode include an electron injecting layer for improving the electron injection efficiency from the cathode, and an electron transporting layer for transporting the electrons injected from the cathode or the electron injecting layer to the light emitting layer.
- Hole injection layer Materials for forming the hole injection layer include phenylamines such as 4 ′, 4 ′ ′-tris ⁇ 2-naphthyl (phenyl) amino ⁇ triphenylamine, starburst type amines, phthalocyanines, vanadium oxide, molybdenum oxide And oxides such as ruthenium oxide and aluminum oxide, amorphous carbon, polyaniline, and polythiophene derivatives.
- phenylamines such as 4 ′, 4 ′ ′-tris ⁇ 2-naphthyl (phenyl) amino ⁇ triphenylamine, starburst type amines, phthalocyanines, vanadium oxide, molybdenum oxide And oxides such as ruthenium oxide and aluminum oxide, amorphous carbon, polyaniline, and polythiophene derivatives.
- hole transport layer Materials for forming the hole transport layer include polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine Derivative, benzidine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, poly (2,5-thienylenevinylene) or derivative thereof Derivatives and the like can be mentioned.
- the hole transport layer or the hole injection layer may be referred to as an electron block layer.
- Electrode transport layer As materials constituting the electron transport layer, oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives Diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline or derivatives thereof, polyquinolines or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like. As a derivative, a metal complex etc. are mentioned.
- 8-hydroxyquinoline or a derivative thereof is preferred.
- tris (8-hydroxyquinolinato) aluminum is preferable in that it can be used as an organic substance that emits fluorescence or phosphorescence contained in the light emitting layer.
- the electron injecting layer may be an electron injecting layer having a single layer structure of a calcium (Ca) layer or a metal of Groups IA and IIA of the periodic table, and the work function is 1 depending on the type of the light emitting layer.
- the electron injection layer etc. which consist of a structure are mentioned.
- Metals or oxides or halides of Group IIA of the periodic table having a work function of 1.5 to 3.0 eV, halides, carbonates such as strontium (Sr), magnesium oxide, magnesium fluoride, strontium fluoride, fluoride Barium, strontium oxide, magnesium carbonate and the like can be mentioned.
- these electron transport layers or electron injection layers have the function of blocking the transport of holes
- these electron transport layers or electron injection layers may be referred to as hole blocking layers.
- a transparent or semitransparent material having a relatively small work function (preferably having a work function smaller than 4.0 eV) and facilitating electron injection to the light emitting layer is preferable.
- Materials for the cathode include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) , Barium (Ba), aluminum (Al), scandium (Sc), vanadium (V), zinc (Zn), yttrium (Y), indium (In), cerium (Ce), samarium (Sm), europium (Eu) , Metals such as terbium (Tb) and ytterbium (Yb), or alloys of two or more of the foregoing metals, or one or more of them, gold (Au), silver (Ag), platinum (Pt), Copper (Cu), chromium (Cr), manganese (M
- the cathode may have a laminated structure of two or more layers.
- the laminated structure of two or more layers include a laminated structure of the above-described metals, metal oxides, fluorides, alloys thereof, and metals such as Al, Ag, and Cr.
- the film thickness of the cathode can be appropriately selected in consideration of the electrical conductivity and the durability.
- the thickness of the cathode is preferably 10 nm to 10 ⁇ m, more preferably 15 nm to 1 ⁇ m, and most preferably 20 nm to 500 nm.
- the method for producing the cathode include a vacuum evaporation method, a sputtering method, and a laminating method of thermocompression bonding of a metal thin film.
- the layers provided between the light emitting layer and the anode and between the light emitting layer and the cathode can be appropriately selected according to the performance required for the organic EL device to be produced.
- the structure of the organic EL element used in the present embodiment can have any one of the layer configurations (i) to (xv) below.
- anode / hole transport layer / light emitting layer / cathode ii) anode / light emitting layer / electron transport layer / cathode (iii) anode / hole transport layer / light emitting layer / electron transport layer / cathode (iv) anode / Hole injection layer / emission layer / cathode (v) anode / emission layer / electron injection layer / cathode (vi) anode / hole injection layer / emission layer / electron injection layer / cathode (vii) anode / hole injection layer / Hole transport layer / emission layer / cathode (viii) anode / hole transport layer / emission layer / electron injection layer / cathode (ix) anode / hole injection layer / hole transport layer / emission layer / electron injection layer / cathode (X) anode / hole injection layer / light emitting layer / electron transport layer
- the sealing layer is provided to seal the organic EL element with a layer having a high barrier property to the gas in order to prevent the gas such as water vapor and oxygen from contacting the organic EL element.
- a layer having a high barrier property to the gas in order to prevent the gas such as water vapor and oxygen from contacting the organic EL element.
- an inorganic film and an organic film are alternately formed from the bottom.
- the inorganic / organic laminate may be repeatedly formed twice or more.
- the unevenness of 0.5 ⁇ m to 3 ⁇ m due to the TFT or the partition dividing the blue, green and red pixels is It exists between the cathode or the anode and the sealing layer.
- the sealing layer is formed by the sealing agent according to the present embodiment, an effect of obtaining excellent flatness can be obtained.
- the inorganic film of the inorganic / organic laminate is a film provided to prevent the organic EL element from being exposed to a gas such as water vapor or oxygen existing in the environment where the organic EL device is placed.
- the inorganic film of the inorganic / organic laminate is preferably a continuous dense film with few defects such as pinholes.
- the organic film of the inorganic / organic laminate is provided to provide flatness to the surface in order to cover defects such as pinholes formed on the inorganic film.
- the organic film is formed in a narrower area than the area where the inorganic film is formed. This is because if the organic substance film is formed to be the same as or wider than the formation area of the inorganic substance film, it deteriorates in the area where the organic substance film is exposed.
- the uppermost organic film formed on the uppermost layer of the entire sealing layer is formed in substantially the same area as the formation area of the inorganic film. Then, the upper surface of the sealing layer is formed to be planarized.
- a composition having a good adhesion function with the above-mentioned inorganic film is used.
- the present embodiment is suitable, for example, for inkjet coating that enables coating with excellent flatness of a film thickness of 3 ⁇ m or more in a short time, excellent dischargeability by inkjet and flatness after inkjet coating, and barrier properties against water vapor
- the sealant itself penetrates from the pinhole on the inorganic film, not only the OLED element around the pinhole no longer emits light, but the sealant also penetrates the organic light emitting material layer during long-term use, and the light emission defect increases. So-called dark spots will occur. That is, the reliability of the OLED element is significantly reduced.
- the penetration depth l to the pinhole is the time after the liquid comes in contact with the solid (t) It depends on the pore diameter (r), the viscosity of the liquid ( ⁇ ), the surface tension of the liquid ( ⁇ ), and the contact angle with the solid surface ( ⁇ ).
- the sealing agent improves the reliability of the organic EL element by controlling the permeation rate according to the formula 2. I found something to do. ⁇ / 2 ⁇ ⁇ 0.9 m / s ⁇ ⁇ ⁇ Formula 2 As described later, in the organic EL element, there is a problem that a dark spot is generated to cause a light emission failure due to the penetration of the sealant. By satisfying the above equation 2, the penetration of such a sealing agent is suppressed.
- the static surface tension of the composition of the present embodiment is preferably 14 mN / m or more and 40 mN / m or less.
- the static surface tension is measured by a plate method, a ring method, a pendant drop method or the like, but the value of the static surface tension specified in this embodiment is a pendant drop method.
- the pendant drop method refers to a method of extruding a liquid from the tip of a tube and calculating the surface tension from the shape of a hanging drop (pendant drop).
- the static surface tension of the composition is more preferably 20 mN / m to 30 mN / m.
- the composition of the present embodiment contains (A) an acyclic alkanediol di (meth) acrylate having 6 or more carbon atoms, (B) a cyclic monomer, and (C) a photopolymerization initiator (meth) It is an acrylic resin composition.
- the component (B) contains at least a cyclic monofunctional (meth) acrylate and a cyclic bifunctional (meth) acrylate.
- Acyclic alkanediol di (meth) acrylate having 6 or more carbon atoms means a difunctional (meth) acrylate in which the carbon number of the alkane as the main chain is 6 or more.
- the component (A) which is acyclic is one having no cyclic molecular structure.
- As the component (A), .alpha.,. Omega.-linear alkanediol di (meth) acrylates are preferable from the viewpoint of low moisture permeability, dischargeability by ink jet, and flatness effect after ink jet application. More preferably, the carbon number of the main chain alkane can be 12 or less.
- ⁇ -linear alkanediol di (meth) acrylates 1,6-hexadiol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate 1
- At least one member selected from the group consisting of acrylate and 1,12-dodecanediol di (meth) acrylate is preferable, and 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate,
- One or more of the group consisting of 1,12-dodecanediol di (meth) acrylate is more preferable, and 1,12-dodecanediol di (meth) acrylate is most preferable.
- the alkane which is the main chain of the component (A) may be linear or branched.
- the component (A) may
- the content of the component (A) is preferably 10 to 85 parts by mass with respect to 100 parts by mass in total of the components (A) and (B).
- the content of (A) is preferably 30 to 70 parts by mass, more preferably 35 to 68 parts by mass, and most preferably 45 to 65 parts by mass from the viewpoint of low moisture permeability and reliability of the organic EL element.
- the cyclic monomer has a group having a cyclic structure in the molecule, and has 1 unsaturated double bond group selected from the group consisting of (meth) acrylate group, (meth) acrylamide group and N-vinyl group It is a monomer having one or more. That is, the component (B) having a cyclic structure is different from the component (A) which is acyclic.
- Examples of such cyclic structures include heterocyclic structures such as cyclic amide groups, tetrahydrofurfuryl groups and piperidinyl groups, cyclic structures of aromatic hydrocarbon systems, and monomers having cyclic structures of aliphatic hydrocarbon systems. .
- At least one member selected from the group consisting of aromatic hydrocarbon-based cyclic structures and aliphatic hydrocarbon-based cyclic structures is preferable in terms of ink jettability and low moisture permeability. More preferably, a cyclic (meth) acrylate monomer having an aromatic hydrocarbon cyclic structure or an aliphatic hydrocarbon cyclic structure can be used as the component (B).
- the component (B) does not have a fluorine atom, and is distinguished from the component (E) described later.
- Examples of (meth) acrylates having an aromatic hydrocarbon cyclic structure include benzyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate and 2,4,5-tetramethylphenyl (meth) ) Acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate (2-HPA), 2- (meth) acryloyl Roxyhexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalic acid, EO modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, PO modified Monofunctional (meth) having one or more aromatic hydrocarbon cyclic structures in the molecule such as
- the sealing agent for an organic electroluminescent display element it is preferable to have two or more cyclic structures in the molecule in view of low moisture permeability and reliability of the organic EL element.
- Examples of (meth) acrylates having two or more aromatic hydrocarbon cyclic structures in the molecule include ethoxylated-o-phenylphenol (meth) acrylate, m-phenoxybenzyl (meth) acrylate, ethoxylated bisphenol A di ( One or more of the group consisting of meta) acrylate is preferred, and one or more of the group consisting of ethoxylated-o-phenylphenol (meth) acrylate and ethoxylated bisphenol A di (meth) acrylate is more preferred.
- Examples of the alicyclic hydrocarbon group in the monomer having an aliphatic hydrocarbon cyclic structure include a group having a dicyclopentadiene skeleton such as a dicyclopentanyl group or a dicyclopentenyl group, a cyclohexyl group, an isobornyl group, a cyclodecatriene Groups, norbornyl groups, adamantyl groups and the like. Among these, a group having a dicyclopentadiene skeleton is preferable.
- (meth) acrylate having an alicyclic hydrocarbon group cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cyclopentenyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate and the like can be mentioned.
- Examples of (meth) acrylates having a dicyclopentadiene skeleton include tricyclodecanedimethanol di (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentenyl oxyethyl (meth) acrylate 1) At least one member in the group consisting of acrylates is preferred, and one or more members in the group consisting of dicyclopentanyl (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate are more preferred in view of low moisture permeability. preferable.
- the cyclic monomer needs to contain a mixture of cyclic monofunctional (meth) acrylate and cyclic difunctional (meth) acrylate in a predetermined ratio. This is due to the following reasons.
- the cyclic monofunctional (meth) acrylate is effective in view of low moisture permeability, but there is a problem that the unreacted substance outgasses and causes the light emission failure of the organic EL element because the boiling point is low.
- cyclic difunctional (meth) acrylates are excellent in low moisture permeability and low in volatility and therefore effective in terms of OLED element reliability, they have a problem of adversely affecting the ink jet discharge performance because the viscosity is relatively high. .
- the present inventor achieves both low moisture permeability that can not be achieved by the prior art and OLED device reliability by using cyclic monofunctional (meth) acrylate and cyclic difunctional (meth) acrylate in combination at a predetermined ratio. It has been found that the effects can be obtained, and is conceived to the present invention.
- the range of 95:90 to 5 is preferable, the range of 40 to 90:60 to 10 is more preferable, and the range of 65 to 85:35 to 15 is the most preferable.
- the cyclic monofunctional (meth) acrylate is preferably any of the following compounds.
- Cyclic monofunctional (meth) acrylate represented by the following structural formula (R 1 in the above formula is each independently a hydrogen atom or a methyl group, and the average value of n is preferably 1 to 10, and particularly preferably n is 1.) and represented by the following structural formula Cyclic monofunctional (meth) acrylate (In the above formula, Y is —CH 2 —, — (CH (R 5 ) CH 2 O) m1 —, — (CH (R 5 ) CH 2 S) m 2 — (where R 5 is a hydrogen atom or a methyl group , M1 and m2 are numbers 1 to 4), R 3 is a hydrogen atom or a methyl group, and R 4 is any substituent represented by the following structural formula).
- an ethoxylated bisphenol A di (meth) acrylate compound represented by the following structural formula is preferable.
- Each R in the following formulas is independently a hydrogen atom or a methyl group.
- m + n is 2 to 10 for m and n in the formula.
- At least one preferably has two or more cyclic structures in the molecule, and more preferably at least two have two or more cyclic structures in the molecule.
- the content of the component (B) is preferably 15 to 90 parts by mass with respect to 100 parts by mass in total of the components (A) and (B).
- the content of (B) is preferably 30 to 70 parts by mass, more preferably 32 to 65 parts by mass, and most preferably 45 to 65 parts by mass from the viewpoint of low moisture permeability and reliability of the organic EL element.
- a photoinitiator is used in order to sensitize by the active ray of a visible ray and an ultraviolet ray, and to accelerate
- a photoinitiator a radical photopolymerization initiator is preferable.
- Photoradical polymerization initiators include benzophenone and derivatives thereof, benzyl and derivatives thereof, enthraquinone and derivatives thereof, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like, Acetophenone derivatives such as diethoxyacetophenone, 4-tert-butyltrichloroacetophenone, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanthone and its derivatives, camphorquinone, 7,7-dimethyl-2,3 -Dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1]
- a photoinitiator can be used in combination of 1 or more type.
- an acyl phosphine oxide derivative is preferable in that it can be cured using only visible light of 390 nm or more at the time of curing and can be cured without damaging the organic electroluminescent display element.
- the acyl phosphine oxide derivatives 2,4,6-trimethylbenzoyl-diphenyl in that it can be cured using only light of 395 nm or more without reduction in visible light transmittance when formed into a display.
- -Phosphine oxide is most preferred. Examples of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide include “Irgacure TPO” manufactured by BASF Japan Ltd.
- the content of the photopolymerization initiator (C) is preferably 0.05 to 6 parts by mass, and more preferably 0.5 to 4 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). 2 to 3.9 parts by mass is most preferable, and 2.5 to 3.5 parts by mass is still more preferable. If the content of the component (C) is 0.05 parts by mass or more, the effect of promoting curing is surely obtained, and if it is 6 parts by mass or less, the transparency to visible light decreases when used in a display There is nothing to do.
- the (meth) acrylate is preferably a monomer from the viewpoint of inkjet dischargeability.
- the components (A) and (B) are preferably monomers.
- the molecular weight of the monomer is preferably 1000 or less.
- bifunctional (meth) acrylate oligomers / polymers and polyfunctional (meth) acrylate oligomers / polymers are contained in 100 parts by mass of (meth) acrylate containing the (A) component and the (B) component. It is preferable to contain by mass part or less, more preferable to contain by 1 part by mass or less, and it is most preferable not to contain.
- a fluorine-containing monomer having a fluorine atom and a (meth) acryloyl group as component (E) is included from the viewpoint of lowering the free energy of the surface after application and obtaining high flatness.
- the (meth) acryloyl group is an acryloyl group or a methacryloyl group.
- the fluorine-containing monomers may be used alone or in combination of two or more.
- the content of the component (E) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 4 parts by mass, with respect to 100 parts by mass in total of the components (A) and (B). 9 to 1.6 parts by weight are even more preferred. If it is 0.1 parts by mass or more, the flatness is secured, and if it is 10 parts by mass or less, good inkjet coatability can be secured.
- the number of fluorine atoms contained in the fluorine-containing monomer which is the component (E) may be one or more, for example, two or more, and preferably three or more.
- the upper limit of the number of fluorine atoms contained in the fluorine-containing monomer is not particularly limited, and may be, for example, 40 or less, preferably 30 or less.
- the content of the fluorine atom with respect to the total amount of the fluorine-containing monomer may be, for example, 1% by mass or more, preferably 2% by mass or more, and more preferably 5% by mass or more.
- the content of fluorine atoms may be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less, based on the total amount of the fluorine-containing monomer.
- the content of fluorine atoms is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, with respect to the total amount of the composition according to the embodiment containing the component (E). If the content of fluorine atoms is within the above range, it is possible to obtain the effect of improving the flatness.
- the number of (meth) acryloyl groups contained in the fluorine-containing monomer may be one or more. From the viewpoint of easily obtaining a cured product having a low glass transition temperature, the number of (meth) acryloyl groups contained in the fluorine-containing monomer may be one. Further, from the viewpoint of easily obtaining a cured product having a high glass transition temperature, the number of (meth) acryloyl groups contained in the fluorine-containing monomer may be two or more.
- the upper limit of the number of (meth) acryloyl groups contained in the fluorine-containing monomer is not particularly limited, and may be, for example, 4 or less, preferably 3 or less, more preferably from the viewpoint of easily obtaining a cured product having excellent flexibility. Is 2 or less.
- R 1 represents a hydrogen atom or a methyl group.
- R 2 represents a fluorinated alkyl group or a group in which an oxygen atom is inserted into carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkyl group.
- the fluorinated alkyl group can be said to be a group in which part or all of the hydrogen atoms contained in the alkyl group are substituted by fluorine atoms.
- the number of carbon atoms of the fluorinated alkyl group is not particularly limited, and may be, for example, one or more, and preferably two or more.
- the carbon atom number of the fluorinated alkyl group may be, for example, 25 or less, and may be 20 or less.
- fluorinated alkyl group a group containing difluoromethylene (—CF 2 —) can be suitably used.
- fluorinated alkyl group examples include difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 1,1,1-trifluoroethyl group, 2,2, 2-trifluoroethyl group, perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, 1,1,2,2,2,3,3 -Hexafluoropropyl group, perfluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2-tetrafluoroethyl group, 2,2,3,3-tetrafluoropropyl group, perfluoro Propyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,1,2,2,3,3-pep Fluor
- a group in which an oxygen atom is inserted into a part of carbon-carbon bond and carbon-hydrogen bond in a fluorinated alkyl group is a group in which an oxygen atom is inserted in one place. Or a group inserted at two or more places.
- an ether bond is formed. Also, when an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, it can also be said that the oxygen-containing group of R 2 contains at least one selected from the group consisting of an ether bond and a hydroxyl group.
- oxygen-containing groups for R 2 include groups represented by the following formula.
- the fluorine atom content in the compound represented by the formula (E-1) may be, for example, 5% by mass or more, preferably 15% by mass or more, and more preferably 30% by mass or more.
- the fluorine atom content in the compound represented by the formula (E-1) may be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less.
- R 1 represents a hydrogen atom or a methyl group
- R 21 represents a hydrogen atom or a fluorine atom
- n represents an integer of 1 or more.
- Plural R 21 may be the same or different. However, at least one of R 21 is a fluorine atom.
- n may be 1 or more, preferably 2 or more. Further, the upper limit of n is not particularly limited, and may be, for example, 25 or less, or 20 or less.
- R 21 Although a plurality of R 21 are present in the formula (E-1-1), at least one of them is a fluorine atom. Further, two or more of R 21 are preferably fluorine atoms, and three or more are more preferably fluorine atoms. R 21 may be all fluorine atoms.
- the ratio of the number of fluorine atoms to the total number of R 21 may be, for example, 4% or more, preferably 8% or more, and more preferably 12% or more.
- the ratio may be, for example, 100% or less, preferably 80% or less, and more preferably 75% or less.
- At least one of the divalent groups (—C (R 21 ) 2 —) in the parentheses to which n is attached is difluoromethylene (—CF 2 — Is preferred.
- fluorine-containing monomer is a compound represented by the following formula (E-2).
- R 3 represents a hydrogen atom or a methyl group.
- R 4 represents a fluorinated alkanediyl group or a group in which an oxygen atom is inserted into a part of carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkanediyl group.
- Plural R 3 's may be the same or different.
- the fluorinated alkanediyl group can be said to be a group in which part or all of the hydrogen atoms of the alkanediyl group are substituted with a fluorine atom.
- the carbon atom number of the fluorinated alkanediyl group is not particularly limited, and may be, for example, 1 or more, preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.
- the carbon atom number of the fluorinated alkanediyl group may be, for example, 17 or less, preferably 12 or less, more preferably 10 or less.
- fluorinated alkanediyl group a group containing difluoromethylene (—CF 2 —) can be suitably used.
- fluorinated alkanediyl group examples include linear or branched fluorinated alkanediyl groups having 1 to 17 carbon atoms (eg, 2, 2, 3, 3, 4, 4, 5, 5, 6) And 6,7,7,8,8,9,9,9-hexadecafluoro-1,10-decanediyl group), fluorinated cycloalkanediyl groups having 1 to 17 carbon atoms, and the like.
- an oxygen atom is inserted in one place It may be a group, or may be a group inserted at two or more places.
- the oxygen-containing group of R 4 can also be said to be a group including at least one selected from the group consisting of an ether bond and a hydroxyl group.
- oxygen-containing groups of R 4 are, for example, groups represented by the following formula.
- the fluorine atom content in the compound represented by the formula (E-2) may be, for example, 4% by mass or more, preferably 8% by mass or more, and more preferably 12% by mass or more. Further, the fluorine atom content in the compound represented by the formula (E-2) may be, for example, 90% by mass or less, preferably 75% by mass or less, and more preferably 65% by mass or less.
- R 3 represents a hydrogen atom or a methyl group
- R 41 represents a hydrogen atom or a fluorine atom
- m represents an integer of 1 or more.
- Plural R 41 may be the same or different.
- Plural R 3 's may be the same or different.
- at least one of R 41 is a fluorine atom.
- m may be 1 or more, preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.
- the upper limit of m is not particularly limited, and may be, for example, 20 or less, preferably 17 or less, and more preferably 15 or less.
- a plurality of R 41 is present in the formula (E-2-1), at least one of which is a fluorine atom. Moreover, it is preferable that two or more of R 41 be a fluorine atom, and it is more preferable that four or more be a fluorine atom. R 41 may be all fluorine atoms.
- the ratio of the number of fluorine atoms to the total number of R 41 may be, for example, 1% or more, preferably 5% or more, and more preferably 10% or more.
- the ratio may be, for example, 100% or less, preferably 95% or less, more preferably 90% or less.
- At least one of the divalent groups (—C (R 41 ) 2 —) in the parentheses with m attached thereto is difluoromethylene (—CF 2 — Is preferred.
- fluorine-containing monomer is a compound represented by the following formula (E-3).
- R 5 represents a hydrogen atom or a methyl group.
- R 6 is a single bond, an alkanediyl group, a fluorinated alkanediyl group, or an oxygen atom inserted in part of a carbon-carbon bond or carbon-hydrogen bond in an alkanediyl group or a fluorinated alkanediyl group Group.
- Ar 1 represents a fluorinated aryl group.
- R 6 represents a single bond
- the fluorinated aryl group of Ar 1 is preferably a fluorinated phenyl group. It can also be said that a fluorinated phenyl group or a group in which 1 to 5 of the hydrogen atoms in the phenyl group are substituted with a fluorine atom.
- the fluorinated phenyl group may have one or more fluorine atoms, or may have five.
- the carbon atom number of the alkanediyl group of R 6 is not particularly limited, and may be, for example, one or more.
- the number of carbon atoms of the alkanediyl group of R 6 may be, for example, 17 or less, preferably 15 or less, and more preferably 12 or less.
- alkanediyl group examples include linear or branched alkanediyl groups having 1 to 17 carbon atoms (eg, methylene group, ethylene group etc.), cycloalkanediyl groups having 1 to 17 carbon atoms, etc.
- alkanediyl group examples include linear or branched alkanediyl groups having 1 to 17 carbon atoms (eg, methylene group, ethylene group etc.), cycloalkanediyl groups having 1 to 17 carbon atoms, etc.
- the fluorinated alkanediyl group of R 6 can be said to be a group in which part or all of the hydrogen atoms of the alkanediyl group described above are substituted with a fluorine atom.
- the carbon atom number of the fluorinated alkanediyl group of R 6 is not particularly limited, and may be, for example, one or more.
- the carbon atom number of the fluoroalkanediyl group of R 6 may be, for example, 17 or less, preferably 15 or less, more preferably 12 or less.
- fluorinated alkanediyl group for R 6 a group containing difluoromethylene (—CF 2 —) can be suitably used.
- an alkanediyl group or a fluorinated alkanediyl group a group in which an oxygen atom is inserted in part of a carbon-carbon bond or a carbon-hydrogen bond (hereinafter also referred to as an oxygen-containing group of R 6 ) has one oxygen atom. Or a group inserted into two or more sites.
- an ether bond is formed. Also, when an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, it can also be said that the oxygen-containing group of R 6 contains at least one selected from the group consisting of an ether bond and a hydroxyl group.
- oxygen-containing group of R 6 for example, a group containing —CH 2 CH 2 O— and the like can be mentioned.
- the fluorine atom content in the compound represented by the formula (E-3) may be, for example, 3% by mass or more, preferably 7% by mass or more, and more preferably 15% by mass or more. Further, the fluorine atom content in the compound represented by the formula (E-3) may be, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less.
- R 5 represents a hydrogen atom or a methyl group
- R 61 represents a hydrogen atom or a fluorine atom
- R 62 represents a hydrogen atom or a fluorine atom
- p represents an integer of 0 or more. Show. When p is 1 or more, a plurality of R 61 may be the same or different. In addition, a plurality of R 62 may be the same or different. However, at least one of R 62 is a fluorine atom.
- p represents an integer of 0 or more.
- p of 0 indicates that the benzene ring and the oxygen atom are directly bonded.
- p may be an integer of 1 or more.
- the upper limit of p is not particularly limited, and may be, for example, 17 or less, preferably 15 or less, and more preferably 12 or less.
- R 61 When R 61 is present in formula (E-3-1) (that is, when p is an integer of 1 or more), R 61 may be all hydrogen atoms or all fluorine atoms. And one part may be a hydrogen atom and the other part may be a fluorine atom.
- a plurality of R 62 are present in formula (E-3-1), at least one of which is a fluorine atom. Also, two or more of R 62 may be a fluorine atom, and three or more may be a fluorine atom or more. In addition, all (five) of R 62 may be a fluorine atom.
- the ratio of the number of fluorine atoms to the total number of R 61 and R 62 may be, for example, 5% or more, preferably 10% or more, and more preferably 20% or more.
- the ratio may be, for example, 100% or less, preferably 95% or less, and more preferably 80% or less.
- fluorine-containing monomers preferred are 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9 from the viewpoint of low moisture permeability and inkjet coatability.
- the glass transition temperature of the cured product obtained from the composition of the present embodiment is preferably 65 ° C. or more and 120 ° C. or less, more preferably 65 ° C. or more and 110 ° C. or less, and 70 ° C. or more 100 C. or less is most preferable.
- the glass transition temperature of the cured product is in the range of 65 ° C. or more and 120 ° C. or less, the stress is relaxed when an inorganic passivation film is formed on the cured product of the composition of this embodiment by a method such as CVD.
- the reliability of the organic EL element is improved because the inorganic film and the OLED element are difficult to peel off.
- cured material obtained from the composition of this embodiment does not have a restriction
- tan ⁇ a temperature showing a peak top of loss tangent
- the glass transition temperature is considered to be -150 ° C or less or a certain temperature (Ta ° C)
- a composition having a glass transition temperature of -150.degree. C. or less can not be considered because of its structure, and therefore, it can be made above a certain temperature (Ta.degree. C.).
- the composition of the present embodiment can use (D) an antioxidant to improve the storage stability.
- an antioxidant methyl hydroquinone, hydroquinone, octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate, 2,2-methylene-bis (4-methyl-6-tert-butylphenol ), Catechol, hydroquinone monomethyl ether, mono tert-butyl hydroquinone, 2,5-di tert-butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di tert-butyl-p-benzoquinone Picric acid, citric acid, phenothiazine, tert-butyl catechol, 2-butyl-4-hydroxy anisole, 2,6-di-tert-butyl-p-cresol and the like.
- the antioxidant is preferably a combination of two or more.
- phenol-based antioxidants are preferable in that they have large effects such as transparency and storage stability.
- hindered phenolic antioxidants are preferred.
- As hindered phenol-based antioxidants octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate and 2,2-methylene-bis (4-methyl-6-tert-butylphenol) It is preferable that at least one member be selected from the group consisting of octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate and 2,2-methylene-bis (4-methyl-6-tert- More preferably, it contains butylphenol).
- Examples of octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate include “Irganox 1076” manufactured by BASF Japan Ltd. and the like.
- Examples of 2,2-methylene-bis (4-methyl-6-tert-butylphenol) include “SUMILIZER MDP-S” manufactured by Sumitomo Chemical Co., Ltd.
- the content of the antioxidant is preferably 0.001 to 3 parts by mass, and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). If it is 0.001 parts by mass or more, storage stability is secured, and if it is 3 parts by mass or less, good adhesiveness is obtained and there is no possibility of being uncured.
- composition according to the present embodiment may further contain an additive used in the relevant technical field, such as an antioxidant, a metal deactivator, a filler, a stabilizer, a neutralizer, a lubricant, an antibacterial agent, etc. May be contained.
- an additive used in the relevant technical field such as an antioxidant, a metal deactivator, a filler, a stabilizer, a neutralizer, a lubricant, an antibacterial agent, etc. May be contained.
- the composition of the present embodiment can be used as a resin composition.
- the composition of the present embodiment can be used as a photocurable resin composition.
- the composition of the present embodiment can be used as a sealing agent for an organic EL display element.
- Examples of the method of curing the composition by irradiation with visible light or ultraviolet light include a method of curing by irradiating the composition with at least one of visible light or ultraviolet light.
- energy irradiation sources for irradiating such visible light or ultraviolet light deuterium lamps, high pressure mercury lamps, ultra high pressure mercury lamps, low pressure mercury lamps, xenon lamps, xenon-mercury hybrid lamps, halogen lamps, excimer lamps, Energy irradiation sources such as indium lamps, thallium lamps, LED lamps, and electrodeless discharge lamps can be mentioned.
- the composition of the present embodiment is preferably cured at a wavelength of 380 nm or more, more preferably at a wavelength of 395 nm or more, and preferably cured at a wavelength of 395 nm, from the point of hardly damaging the organic EL element.
- the wavelength of the energy irradiation source is preferably 500 nm or less because the temperature of the irradiation portion rises by emitting infrared light and the organic EL element may be damaged.
- an LED lamp having a single emission wavelength is preferable.
- the composition is irradiated with visible light or ultraviolet light to cure the composition
- it is preferable that the composition is irradiated with energy radiation of 100 to 8000 mJ / cm 2 at a wavelength of 395 nm. If it is 100 to 8000 mJ / cm 2 , the composition cures and sufficient adhesive strength can be obtained. 100 mJ / cm 2 or more value, if the composition is sufficiently cured, does not damage the organic EL element if 8000 mJ / cm 2 or less.
- the amount of energy for curing the composition is more preferably 300 to 2000 mJ / cm 2 .
- the spectral transmittance in the ultraviolet-visible light region of 360 nm or more and 800 nm or less is preferably 95% or more and 97% or more. More preferably, 99% or more is the most preferable. If it is 95% or more, an organic EL device excellent in luminance and contrast can be provided.
- the sealing layer made of the composition of the present embodiment is preferably 1 to 5 sets when counting the inorganic / organic laminates as one set. When the number of sets of inorganic / organic laminates is six or more, the sealing effect on the organic EL element is substantially the same as in the case of five sets.
- the thickness of the inorganic film of the inorganic / organic laminate is preferably 50 nm to 1 ⁇ m.
- the thickness of the organic film of the inorganic / organic laminate is preferably 1 to 15 ⁇ m, and more preferably 3 to 10 ⁇ m. If the thickness of the organic film is less than 1 ⁇ m, it may not be possible to completely cover the particles generated at the time of element formation, and it may be difficult to coat the inorganic film with good flatness. When the thickness of the organic film exceeds 15 ⁇ m, water may intrude from the side surface of the organic film, and the reliability of the organic EL element may be reduced.
- the sealing substrate is formed in close contact so as to cover the entire top surface of the uppermost organic film of the sealing layer.
- the above-mentioned substrate is mentioned as this sealing substrate.
- a substrate transparent to visible light is preferred.
- the substrates (transparent sealing substrates) transparent to visible light one or more members in the group consisting of a glass substrate and a plastic substrate are preferable, and a glass substrate is more preferable.
- the thickness of the transparent sealing substrate is preferably 1 ⁇ m or more and 1 mm or less, more preferably 10 ⁇ m or more and 800 ⁇ m or less, and most preferably 50 ⁇ m or more and 300 ⁇ m or less.
- an anode patterned in a predetermined shape, an organic EL layer including a light emitting layer, and a cathode are sequentially formed on a first substrate by a conventionally known method to form an organic EL element.
- a bank is formed to divide the light emitting region in a matrix, and an organic EL layer including a light emitting layer is formed in a region surrounded by the bank.
- the substrate on which the organic EL element is formed it has a predetermined thickness by a film forming method such as a PVD (Physical Vapor Deposition) method such as a sputtering method or a CVD method such as a plasma CVD (Chemical Vapor Deposition) method.
- a film forming method such as a PVD (Physical Vapor Deposition) method such as a sputtering method or a CVD method such as a plasma CVD (Chemical Vapor Deposition) method.
- a first inorganic film is formed.
- the composition of the present embodiment is attached onto the first inorganic substance film by using a coating film forming method such as a solution coating method or a spray coating method, a flash evaporation method, an inkjet method or the like.
- the inkjet method is preferable in terms of productivity.
- the composition is cured by irradiation with energy rays such as ultraviolet rays, electron beams, and plasma, and the first organic film is formed.
- energy rays such as ultraviolet rays, electron beams, and plasma
- the first organic film is formed.
- the curing rate of the composition is not particularly limited as long as the effects of the present embodiment are exhibited, but can be, for example, 90% or more, preferably 95% or more, in the value obtained according to the measurement method described later.
- the formation process of the inorganic / organic laminate shown above is repeated a predetermined number of times.
- the composition is deposited on the upper surface of the inorganic film by a coating method, a flash evaporation method, an inkjet method, etc. so that the upper surface is planarized. Also good.
- a transparent sealing substrate is attached to the surface of the substrate to which the composition is attached.
- perform alignment Thereafter, energy ray is irradiated from the transparent sealing substrate side to cure the composition of the present embodiment present between the inorganic film of the uppermost layer and the transparent sealing substrate.
- the composition is cured to form the uppermost organic film, and the uppermost organic film and the transparent sealing substrate are adhered.
- the method of manufacturing the organic EL device is completed.
- partial energy irradiation may be performed to polymerize the composition. By doing this, it is possible to prevent the shape of the composition that is to be the uppermost organic film from being deformed when the transparent sealing substrate is placed.
- the thickness of the inorganic substance film and the thickness of the organic substance film may be the same for each inorganic / organic laminate, or may be different for each inorganic / organic laminate.
- the top emission type organic EL device has been described as an example.
- the present embodiment can also be applied to a bottom emission type organic EL device that emits light generated in the organic EL layer from the substrate side.
- the organic EL element of the present embodiment can be used as a planar light source, a segment display, or a dot matrix display.
- the sealing layer for shielding the organic EL element formed on the first substrate from the air is formed, and the transparent sealing substrate is disposed on the sealing layer, the organic A sealed structure having sufficient water vapor and oxygen barrier properties to the EL element can be obtained. According to the embodiment of the present embodiment, it is possible to obtain a sealing structure having sufficient adhesive strength between the transparent sealing substrate and the sealing layer.
- the transparent sealing substrate is placed without curing the composition, and then the composition is formed. Since the object is cured, adhesion between the sealing layer and the transparent sealing substrate can be performed simultaneously with the formation of the uppermost organic film constituting the sealing layer. As a result, this embodiment has an effect that the process can be simplified as compared with the case where the sealing layer and the transparent sealing substrate are bonded with an adhesive.
- the composition of this embodiment has a moisture permeability of 350 g / l at a thickness of 100 ⁇ m measured by exposing the cured product to an environment of 85 ° C. and 85% RH for 24 hours according to JIS Z 0208: 1976.
- m is preferably 2 or less. When the moisture permeability exceeds 350 g / m 2 , water may reach the organic light emitting material layer, and a dark spot may occur.
- the sealing agent for organic EL display elements which is excellent in the reliability of the OLED element, the transparency of a hardening object, and barrier property can be provided.
- the manufacturing method of the organic EL display element using the sealing agent for organic EL display elements can be provided.
- the ink jet method refers to a method in which fine droplets are discharged from a nozzle and applied to a target without contact.
- composition The materials used in Table 1 were used.
- the compositions were prepared by mixing the materials used in the compositions shown in Tables 2-3. Using the obtained composition, E-type viscosity, surface tension, moisture permeability, coating area expansion ratio, curing ratio, flatness, transparency, glass transition temperature, organic EL evaluation according to the evaluation methods shown below It measured. The results are shown in Tables 2-3.
- the abbreviations shown in Table 1 were used for the composition names in Tables 2-3.
- the fluorine atom content shown in Tables 2 to 3 is calculated from the composition and is shown on the basis of the total amount of the composition.
- E-type viscosity ⁇ The viscosity of the composition was measured using an E-type viscometer (cone plate type: cone angle 1 ° 34 ', radius 24 mm of cone rotor) at a temperature of 25 ° C. and a rotational speed of 100 rpm.
- the composition was cured under the following light irradiation conditions.
- the composition is photocured and cured by an LED lamp (UV-LED LIGHT SOURCE H-4 MLH 200-V1 manufactured by HOYA) emitting a wavelength of 395 nm under the condition of the integrated light quantity of 1,500 mJ / cm 2 at a wavelength of 395 nm I got a body.
- an LED lamp UV-LED LIGHT SOURCE H-4 MLH 200-V1 manufactured by HOYA
- Moisture permeability A sheet-like cured product having a thickness of 0.1 mm was prepared under the above-mentioned photo-curing conditions, and calcium chloride (anhydrous) as a moisture absorbent according to JIS Z 0208: 1976 "Moisture Moisture Test Method for Moisture-proof Packaging Material (Cup Method)".
- the ambient temperature was 85.degree. C., and the relative humidity was 85%.
- the composition was applied in a size of 10 mm ⁇ 10 mm on the alkali-free glass washed by the above-mentioned method so as to have a thickness of 10 ⁇ m using the above-mentioned ink jet apparatus with respect to the composition obtained in each experimental example
- the resin was cured under the photocuring conditions in a nitrogen atmosphere having an oxygen concentration of less than 0.1%, and the curing rate was measured by the following procedure.
- the composition after curing and the composition before curing were measured using an infrared spectrometer (manufactured by Thermo Scientific, Nicolet is 5, DTGS detector, resolution 4 cm ⁇ 1 ), and infrared light was applied to the measurement sample. The incident infrared spectrum was measured.
- the composition obtained in each experimental example is formed into a thickness of 10 ⁇ m between two 25 mm ⁇ 25 mm ⁇ 1 mm t (mm thick) glass plates (alkali glass, Eagle XG manufactured by Corning), and an LED lamp is used.
- the resultant was cured by irradiation with ultraviolet light having a wavelength of 395 nm so as to give an irradiation amount of 1500 mJ / cm 2 to obtain a cured product.
- the obtained cured product was measured for spectral transmittance at 380 nm, 412 nm, and 800 nm with an ultraviolet-visible spectrophotometer (“UV-2550” manufactured by Shimadzu Corporation) to obtain transparency.
- UV-2550 ultraviolet-visible spectrophotometer
- the composition obtained in each experimental example was sandwiched between PET films using a silicon sheet of 1 mm thickness as a mold.
- the composition was cured from the top under the photocuring conditions, and then cured from the bottom under the photocuring conditions to prepare a cured product of the composition having a thickness of 1 mm.
- the produced cured product was cut into a length of 50 mm and a width of 5 mm with a cutter to obtain a cured product for glass transition temperature measurement.
- the obtained cured product is subjected to stress and strain in the tensile direction of 1 Hz in a nitrogen atmosphere by a dynamic viscoelasticity measuring apparatus “DMS 210” manufactured by Seiko Instruments Inc., and the temperature rise rate is 2 ° C./min.
- the tan ⁇ was measured while raising the temperature from ⁇ 150 ° C. to 200 ° C. at a rate of 10%, and the temperature at the peak top of the tan ⁇ was taken as the glass transition temperature.
- the peak top of tan ⁇ is the maximum value in the region where tan ⁇ is 0.3 or more.
- the peak top of tan ⁇ was assumed to exceed 200 ° C., and the glass transition temperature was 200 ° C. (200 ⁇ ).
- a recess of 25 ⁇ m ⁇ 25 ⁇ m ⁇ 3 ⁇ mt is etched on a 70 mm ⁇ 70 mm ⁇ 0.7 mm t substrate (alkali-free glass (Corning Eagle XG)) to align 10 ⁇ m intervals in front, back, left, and right Made.
- the substrate was washed with acetone and isopropanol respectively, and then washed for 5 minutes with UV-208, a UV ozone cleaner manufactured by Technovision.
- a SiN film of 200 nm was formed by plasma CVD on the substrate provided with the recess.
- a sealant was applied in a pattern so as to be 50 mm ⁇ 50 mm ⁇ 10 ⁇ mt. After pattern application, it was left for 5 minutes under conditions of temperature 23 ° C. and relative humidity 50%, and the shape of the sealant coating was observed. The flatness of the sealant was determined by the following equation. The results are shown in Table 1.
- Flatness (%) (area of sealant film after left for 5 minutes) / (50 mm ⁇ 50 mm)
- the flatness of 50% means that a part of the pattern-applied sealing agent is repelled and the SiN film is exposed in half (50%) of the 50 mm ⁇ 50 mm range.
- Anode ITO, 150 nm film thickness of anode ⁇ Hole injection layer 4,4 ′, 4 ′ ′-tris ⁇ 2-naphthyl (phenyl) amino ⁇ triphenylamine (2-TNATA) ⁇ Hole transport layer N, N'-diphenyl-N, N'-dinaphthylbenzidine ( ⁇ -NPD)
- Light-emitting layer Tris (8-hydroxyquinolinato) aluminum (metal complex material) film thickness of 1000 ⁇ of the light-emitting layer, the light-emitting layer also functions as an electron transport layer.
- Electron injection layer Lithium fluoride ⁇ Cathode aluminum Film thickness 150 nm
- the thickness of the formed SiN (inorganic substance film) was about 1 ⁇ m. Then, using a 30 mm ⁇ 30 mm ⁇ 25 ⁇ mt transparent base material-less double-sided tape, it was bonded to a 30 mm ⁇ 30 mm ⁇ 0.7 mm t alkali-free glass (Eagle XG manufactured by Corning) to produce an organic EL element (organic EL evaluation) ).
- the diameter of the dark spot can be taken as an index for evaluating the degree of penetration of the sealant into the pinholes of the passivation layer and the degree to which the water in the sealant is discharged as outgassing.
- the diameter of the dark spot is preferably 300 ⁇ m or less, more preferably 50 ⁇ m or less, and evaluated as most preferable that the dark spot does not exist.
- the composition according to the present embodiment can provide a composition excellent in the reliability of the organic EL element, the dischargeability by high-precision ink jet, and the shape maintainability after ink jet application, and excellent in low moisture permeability.
- Formulas (I) to (III) are obtained using (a) an acyclic alkanediol dimethacrylate having 6 or more carbon atoms, (b) cyclic monofunctional (meth) acrylate and cyclic difunctional (meth) acrylate, In the case where both were satisfied, the reliability, the ink jet dischargeability, the shape maintainability, and the low moisture permeability were excellent (Experimental Examples 1 to 3 and 10 to 11).
- Acyclic alkanediol dimethacrylate having 6 or more carbon atoms is used as (A), and two cyclic (meth) acrylates are used as (B), satisfying the formulas (II) to (III) and having a viscosity of 50 mPa ⁇ s
- “super" although it is excellent in low moisture permeability, the inkjet discharge can not be performed, and the reliability and the shape retention can not be evaluated
- the cyclic difunctional (meth) acrylate was not used as (B)
- only the cyclic monofunctional acrylate was used, and the formulas (I) to (III) were satisfied, the transparency and the shape retention were inferior (Experimental Example) 16).
- the composition of the present embodiment is excellent in high-precision inkjet dischargeability and flatness after inkjet application, has low moisture permeability and transparency, and does not degrade the organic EL element.
- This embodiment can perform inkjet coating in a short time.
- the composition of this embodiment is an electronic product, particularly, a display part such as an organic EL (for example, a flexible display or organic EL device used for a wearable product etc.), an electronic such as an image sensor such as a CCD or CMOS It can apply suitably in adhesion
- composition described above is an aspect of the present embodiment, and the sealing agent for an organic EL element, the cured product, the organic EL device, the display, the method for producing the same, and the like of the present embodiment also have the same configuration and effects.
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Abstract
Description
(A)非環式の炭素数6以上のアルカンジオールジ(メタ)アクリレートと、(B)環状モノマーと、(C)光重合開始剤を含有し、
(B)環状モノマーは、環状単官能(メタ)アクリレートと環状2官能(メタ)アクリレートとを含有し、
下記の数式(I)及び(III)を共に満たす有機エレクトロルミネッセンス表示素子用封止剤。
8mPa・s≦η≦50mPa・s ・・・(I)
γ/2η<0.9m/s ・・・(III)
(式中、ηは25℃においてE型粘度計により測定される粘度を表し、γはペンダントドロップ法により測定された静的表面張力を表す。)
(A)非環式の炭素数6以上のアルカンジオールジ(メタ)アクリレートと、(B)環状モノマーと、(C)光重合開始剤を含有し、
(A)成分と(B)成分の合計100質量部に対して、(A)成分を10~85質量部、(B)成分を15~90質量部含有し、
(B)環状モノマーは、環状単官能(メタ)アクリレートと環状2官能(メタ)アクリレートとを含有し、
環状単官能(メタ)アクリレートと環状2官能(メタ)アクリレートの含有比率は、環状単官能(メタ)アクリレートと環状2官能(メタ)アクリレートの合計100質量部中、質量比で、環状単官能(メタ)アクリレート:環状2官能(メタ)アクリレート=10~95:90~5であり、かつ
下記の数式(I)、(II)及び(III)を共に満たす有機エレクトロルミネッセンス表示素子用封止剤。
8mPa・s≦η≦50mPa・s ・・・(I)
14mN/m≦γ≦40mN/m ・・・(II)
γ/2η<0.9m/s ・・・(III)
(式中、ηは25℃においてE型粘度計により測定される粘度を表し、γはペンダントドロップ法により測定された静的表面張力を表す。)
(B)環状モノマーが1種類以上の脂環式モノマーを含むことを特徴とする<1>又は<2>に記載の有機エレクトロルミネッセンス表示素子用封止剤。
(E)成分として、フッ素原子及び(メタ)アクリロイル基を有する含フッ素モノマーを含有する、<1>~<3>のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
前記含フッ素モノマーのフッ素原子含有量が、前記含フッ素モノマーの全量基準で、2~70質量%である、<4>に記載の有機エレクトロルミネッセンス表示素子用封止剤。
前記含フッ素モノマーが、式(E-1)で表される化合物、式(E-2)で表される化合物及び式(E-3)で表される化合物からなる群より選択される少なくとも一種を含む、<4>又は<5>に記載の有機エレクトロルミネッセンス表示素子用封止剤。
式(E-1)
R1は、水素原子又はメチル基を示し、
R2は、フッ化アルキル基、又は、フッ化アルキル基における炭素-炭素結合及び炭素-水素結合の一部に酸素原子が挿入された基、を示す。複数存在するR3は、互いに同一でも異なっていてもよい。]
式(E-2)
R3は、水素原子又はメチル基を示し、
R4は、フッ化アルカンジイル基、又は、フッ化アルカンジイル基における炭素-炭素結合及び炭素-水素結合の一部に酸素原子が挿入された基、を示す。複数存在するR3は、互いに同一でも異なっていてもよい。]
式(E-3)
R5は水素原子又はメチル基を示し、
R6は、単結合、アルカンジイル基、フッ化アルカンジイル基、又は、アルカンジイル基若しくはフッ化アルカンジイル基における炭素-炭素結合及び炭素-水素結合の一部に酸素原子が挿入された基、を示し、
Ar1はフッ化アリール基を示す。]
前記含フッ素モノマーが、式(E-1-1)で表される化合物、式(E-2-1)で表される化合物及び式(E-3-1)で表される化合物からなる群より選択される少なくとも一種を含む、<6>に記載の有機エレクトロルミネッセンス表示素子用封止剤。
式(E-1-1)
式(E-2-1)
式(E-3-1)
(E)成分の含有量が、(A)成分と(B)成分の合計100質量部に対して、0.1質量部~10質量部の範囲にあることを特徴とする<4>~<7>のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
(E)成分が、2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-ヘキサデカフルオロ-1,10-デカンジオールジ(メタ)アクリレート、1H,1H,5H-オクタフルオロペンチル(メタ)アクリレート、及び1H,1H,2H,2H-トリデカフルオロオクチル(メタ)アクリレートからなる群から選択される一種以上を含むことを特徴とする<4>~<8>のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
インクジェット法を用いて塗布することを特徴とする<1>~<9>のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
2官能(メタ)アクリレートオリゴマー、2官能(メタ)アクリレートポリマー、多官能(メタ)アクリレートオリゴマー、又は多官能(メタ)アクリレートポリマーを含有しないことを特徴とする<1>~<10>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
硬化体のガラス転移温度が65℃以上120℃以下であることを特徴とする<1>~<11>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
(B)成分のうち、少なくとも1個は環状構造を分子内に2個以上有することを特徴とする<1>~<12>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
(B)成分のうち、少なくとも2個は環状構造を分子内に2個以上有することを特徴とする<1>~<13>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
(B)成分が、エトキシ化-o-フェニルフェノール(メタ)アクリレート、m-フェノキシベンジル(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリレート、下記の構造式で表されるエトキシ化ビスフェノールAジ(メタ)アクリレートからなる群のうちの1種以上を含有することを特徴とする<1>~<14>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
(A)成分が、炭素数12以下のアルカンジオールジ(メタ)アクリレートであることを特徴とする<1>~<15>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
(A)成分が、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、1,12-ドデカンジオールジ(メタ)アクリレートからなる群のうちの1種以上を含有することを特徴とする<1>~<16>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
(C)成分が、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイドを含有することを特徴とする<1>~<17>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
(C)成分の含有量が、0.5~4質量部であることを特徴とする<1>~<18>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
更に(D)酸化防止剤を含有することを特徴とする<1>~<19>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
(D)成分がヒンダードフェノール系酸化防止剤であることを特徴とする<20>に記載の有機エレクトロルミネッセンス表示素子用封止剤。
(D)成分を2種以上含有することを特徴とする<20>又は<21>に記載の有機エレクトロルミネッセンス表示素子用封止剤。
395nm以上500nm以下の波長で硬化させることを特徴とする<1>~<22>のいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤。
395nmのLEDランプで硬化させることを特徴とする<23>に記載の有機エレクトロルミネッセンス表示素子用封止剤。
<1>~<24>のうちのいずれかに記載の有機エレクトロルミネッセンス表示素子用封止剤を硬化してなる硬化体。
<25>に記載の硬化体を含む有機EL装置。
<25>に記載の硬化体を含むディスプレイ。
<25>に記載の硬化体を含む、フレキシブル性を有するディスプレイ。
<25>に記載の硬化体を含む、フレキシブル性を有する有機EL装置。
色素系材料としては、シクロペンダミン誘導体、テトラフェニルブタジエン誘導体化合物、トリフェニルアミン誘導体、オキサジアゾール誘導体、ピラゾロキノリン誘導体、ジスチリルベンゼン誘導体、ジスチリルアリーレン誘導体、ピロール誘導体、チオフェン環化合物、ピリジン環化合物、ペリノン誘導体、ペリレン誘導体、オリゴチオフェン誘導体、トリフマニルアミン誘導体、オキサジアゾールダイマー、ピラゾリンダイマー等が挙げられる。
金属錯体系材料としては、イリジウム錯体、白金錯体等の三重項励起状態からの発光を有する金属錯体、アルミキノリノール錯体、ベンゾキノリノールベリリウム錯体、ベンゾオキサゾリル亜鉛錯体、ベンゾチアゾール亜鉛錯体、アゾメチル亜鉛錯体、ポルフィリン亜鉛錯体、ユーロピウム錯体等といった、金属錯体等が挙げられる。金属錯体としては、中心金属に、テルビウム(Tb)、ユウロピウム(Eu)、ジスプロシウム(Dy)等の希土類金属、アルミニウム(Al)、亜鉛(Zn)、ベリリウム(Be)等を有し、配位子に、オキサジアゾール、チアジアゾール、フェニルピリジン、フェニルベンゾイミダゾール、キノリン構造等を有する金属錯体等が挙げられる。これらの中では、中心金属にアルミニウム(Al)を有し、配位子にキノリン構造等を有する金属錯体が好ましい。中心金属にアルミニウム(Al)を有し、配位子にキノリン構造等を有する金属錯体の中では、トリス(8-ヒドロキシキノリナト)アルミニウムが好ましい。
高分子材料としては、ポリパラフェニレンビニレン誘導体、ポリチオフェン誘導体、ポリパラフェニレン誘導体、ポリシラン誘導体、ポリアセチレン誘導体、ポリフルオレン誘導体、ポリビニルカルバゾール誘導体、上記色素体や金属錯体系発光材料を高分子化した物等が挙げられる。
ドーパント材料としては、ペリレン誘導体、クマリン誘導体、ルブレン誘導体、キナクリドン誘導体、スクアリウム誘導体、ポルフィリン誘導体、スチリル系色素、テトラセン誘導体、ピラゾロン誘導体、デカシクレン、フェノキサゾン等が挙げられる。
正孔注入層を形成する材料としては、4’,4”-トリス{2-ナフチル(フェニル)アミノ}トリフェニルアミン等のフェニルアミン系、スターバースト型アミン系、フタロシアニン系、酸化バナジウム、酸化モリブデン、酸化ルテニウム、酸化アルミニウム等の酸化物、アモルファスカーボン、ポリアニリン、ポリチオフェン誘導体等が挙げられる。
正孔輸送層を構成する材料としては、ポリビニルカルバゾール若しくはその誘導体、ポリシラン若しくはその誘導体、側鎖若しくは主鎖に芳香族アミンを有するポリシロキサン誘導体、ピラゾリン誘導体、アリールアミン誘導体、スチルベン誘導体、トリフェニルジアミン誘導体、ベンジジン誘導体、ポリアニリン若しくはその誘導体、ポリチオフェン若しくはその誘導体、ポリアリールアミン若しくはその誘導体、ポリピロール若しくはその誘導体、ポリ(p-フェニレンビニレン)若しくはその誘導体、ポリ(2,5-チエニレンビニレン)若しくはその誘導体等が挙げられる。
電子輸送層を構成する材料としては、オキサジアゾール誘導体、アントラキノジメタン若しくはその誘導体、ベンゾキノン若しくはその誘導体、ナフトキノン若しくはその誘導体、アントラキノン若しくはその誘導体、テトラシアノアントラキノジメタン若しくはその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン若しくはその誘導体、ジフェノキノン誘導体、8-ヒドロキシキノリン若しくはその誘導体、ポリキノリン若しくはその誘導体、ポリキノキサリン若しくはその誘導体、ポリフルオレン若しくはその誘導体等が挙げられる。誘導体としては、金属錯体等が挙げられる。これらの中では、8-ヒドロキシキノリン若しくはその誘導体が好ましい。8-ヒドロキシキノリン若しくはその誘導体の中では、発光層中に含有する、蛍光又は燐光を発光する有機物としても使用できる点で、トリス(8-ヒドロキシキノリナト)アルミニウムが好ましい。
電子注入層としては、発光層の種類に応じて、カルシウム(Ca)層の単層構造からなる電子注入層、又は、周期律表IA族とIIA族の金属であり、且つ、仕事関数が1.5~3.0eVの金属及びその金属の酸化物、ハロゲン化物及び炭酸化物からなる群のうちの1種以上で形成された層の単層構造、又は、周期律表IA族とIIA族の金属であり、且つ、仕事関数が1.5~3.0eVの金属及びその金属の酸化物、ハロゲン化物及び炭酸化物からなる群のうちの1種以上で形成された層とCa層との積層構造からなる電子注入層等が挙げられる。仕事関数が1.5~3.0eVの、周期律表IA族の金属又はその酸化物、ハロゲン化物、炭酸化物としては、リチウム(Li)、フッ化リチウム、酸化ナトリウム、酸化リチウム、炭酸リチウム等が挙げられる。仕事関数が1.5~3.0eVの、周期律表IIA族の金属又はその酸化物、ハロゲン化物、炭酸化物としては、ストロンチウム(Sr)、酸化マグネシウム、フッ化マグネシウム、フッ化ストロンチウム、フッ化バリウム、酸化ストロンチウム、炭酸マグネシウム等が挙げられる。
(i)陽極/正孔輸送層/発光層/陰極
(ii)陽極/発光層/電子輸送層/陰極
(iii)陽極/正孔輸送層/発光層/電子輸送層/陰極
(iv)陽極/正孔注入層/発光層/陰極
(v)陽極/発光層/電子注入層/陰極
(vi)陽極/正孔注入層/発光層/電子注入層/陰極
(vii)陽極/正孔注入層/正孔輸送層/発光層/陰極
(viii)陽極/正孔輸送層/発光層/電子注入層/陰極
(ix)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
(x)陽極/正孔注入層/発光層/電子輸送層/陰極
(xi)陽極/発光層/電子輸送層/電子注入層/陰極
(xii)陽極/正孔注入層/発光層/電子輸送層/電子注入層/陰極
(xiii)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/陰極
(xiv)陽極/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
(xv)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
(ここで、「/」は各層が隣接して積層されていることを示す。以下同じ。)
γ/2η<0.9m/s ・・・ 式2
後述するように、有機EL素子においては封止剤の浸透によって、ダークスポットが発生し発光不良を起こす問題がある。上記式2の条件を満たすことにより、このような封止剤の浸透が抑制される。
下記構造式で表される環状単官能(メタ)アクリレート
以下の方法により組成物を作製し、評価した。
表1の使用材料を用いた。表2~3に示す組成で各使用材料を混合して、組成物を調製した。得られた組成物を使用して、以下に示す評価方法にてE型粘度、表面張力、透湿度、塗布面積の拡大率、硬化率、平坦性、透明性、ガラス転移温度、有機EL評価の測定を行った。結果を表2~3に示す。表2~3の組成物名には、表1に示す略号を用いた。表2~3に示すフッ素原子含有量は、組成から計算したものであり、組成物全量基準で示す。
組成物の粘度はE型粘度計(コ-ンプレート型:コーン角度1°34′、コーンロータの半径24mm)を用い、温度25℃、回転数100rpmの条件下で測定した。
組成物の表面張力は23℃の雰囲気下、接触角計(協和界面科学社製DM500)を用いて、ペンダントドロップ法により測定した。
組成物の硬化物性の評価に際し、下記光照射条件により、組成物を硬化させた。395nmの波長を発光するLEDランプ(HOYA社製UV-LED LIGHT SOURCE H-4MLH200-V1)により、395nmの波長の積算光量1,500mJ/cm2の条件にて、組成物を光硬化させ、硬化体を得た。
厚さ0.1mmのシート状の硬化体を前記光硬化条件にて作製し、JIS Z0208:1976「防湿包装材料の透湿度試験方法(カップ法)」に準じ、吸湿剤として塩化カルシウム(無水)を用い、雰囲気温度85℃、相対湿度85%の条件で測定した。
各実験例で得られた組成物に対して、上記インクジェット装置を使用して10μmの厚みとなるように上述の方法で洗浄した無アルカリガラス上に、組成物を10mm×10mmの大きさに塗布し、酸素濃度0.1%未満の窒素雰囲気中にて前記光硬化条件で硬化させ、硬化率を以下の手順で測定した。
硬化後の上記組成物及び硬化前の上記組成物に、赤外分光装置(サーモサイエンティフィック社製、Nicolet is5、DTGS検出器、分解能4cm-1)を用い、該測定試料に赤外光を入射して赤外分光スペクトルを測定した。得られた赤外分光スペクトルにて、硬化前後でピーク変化を生じない、2950cm-1付近に観測されるメチレン基の炭素-水素結合の伸縮振動ピークを内部標準とし、この内部標準の硬化前後のピーク面積と、(メタ)アクリレートの炭素-炭素二重結合に結合する炭素-水素結合の面外変角振動のピークに帰属される、810cm-1付近のピークの硬化前後の面積から、次式を用い硬化率を算出した。
硬化率(%)=[1-(Ax/Bx)/(Ao/Bo)]×100
ここで、
Ao:810cm-1付近の硬化前のピーク面積を表す。
Ax:810cm-1付近の硬化後のピーク面積を表す。
Bo:2950cm-1付近の硬化前のピーク面積を表す。
Bx:2950cm-1付近の硬化後のピーク面積を表す。
各実験例で得られた組成物をそれぞれ25mm×25mm×1mmt(mm厚)のガラス板(無アルカリガラス、Corning社製 Eagle XG)2枚の間に10μmの厚みに形成し、LEDランプを用いて波長395nmの紫外線を照射量が1500mJ/cm2となるように照射することにより硬化させて硬化体を得た。得られた硬化体について、紫外-可視分光光度計(島津製作所社製「UV-2550」)にて380nm、412nm、800nmの分光透過率を測定し、透明性とした。
各実験例で得られた組成物を、1mm厚のシリコンシートを型枠とし、PETフィルムに挟み込んだ。該組成物を、前記光硬化条件にて、上面から硬化させた後、更に下から前記光硬化条件にて、硬化させ、厚さ1mmの該組成物の硬化体を作製した。作製した硬化体をカッターにて長さ50mm幅5mmに切断し、ガラス転移温度測定用硬化体とした。得られた硬化体をセイコー電子産業社製、動的粘弾性測定装置「DMS210」により、窒素雰囲気中にて前記硬化体に1Hzの引張方向の応力及び歪みを加え、昇温速度毎分2℃の割合で-150℃から200℃まで昇温しながらtanδを測定し、該tanδのピークトップの温度をガラス転移温度とした。tanδのピークトップはtanδが0.3以上の領域における最大値とした。tanδが-150℃から200℃の領域で0.3以下であった場合、tanδのピークトップは200℃を超えるとし、ガラス転移温度は200℃を超える(200<)とした。
各実験例で得られた組成物を70mm×70mm×0.7mmtの基材(無アルカリガラス(Corning社製 Eagle XG))上にインクジェット吐出装置(武蔵エンジニアリング社製MID500B、溶剤系ヘッド「MIDヘッド」)を用いて4mm×4mm×10μmtとなるようにパターン塗布した。無アルカリガラスは使用前に、アセトン、イソプロパノールそれぞれを用いて洗浄し、その後にテクノビジョン社製UVオゾン洗浄装置UV-208を用いて5分間洗浄した。パターン塗布直後に雰囲気温度23℃、相対湿度50%の条件で5分間放置し、塗布面積の拡大率(下記式参照)によりインクジェット塗布後の平坦性を評価した。塗布面積の拡大率が小さい程、塗布後の形状が維持され、位置制御性に優れ、好ましいと評価した。
(塗布面積の拡大率)=((パターン塗布してから5分後に、基材表面に接触した組成物の接触面積)/(パターン塗布直後の、基材表面に接触した組成物の接触面積))×100(%)
70mm×70mm×0.7mmtの基材(無アルカリガラス(Corning社製 Eagle XG))上に、25μm×25μm×3μmtの凹みを前後左右に10μmの間隔を開けて整列するようにエッチング法にて作製した。なお、基材は使用前に、アセトン、イソプロパノールそれぞれを用いて洗浄し、その後にテクノビジョン社製UVオゾン洗浄装置UV-208を用いて5分間洗浄した。次いで、凹みを設けた基板上に、プラズマCVD法にて200nmのSiN膜を形成した。次に、インクジェット吐出装置(武蔵エンジニアリング社製MID500B、溶剤系ヘッド「MIDヘッド」)を用いて50mm×50mm×10μmtとなるように封止剤をパターン塗布した。パターン塗布後、温度23℃、相対湿度50%の条件で5分間放置し、封止剤塗膜の形状を観察した。封止剤の平坦性を、以下の式で求めた。結果を表1に示す。
平坦性(%)=(5分間放置後の封止剤塗膜の面積)/(50mm×50mm)
なお、例えば、平坦性50%とは、パターン塗布した封止剤の一部が弾かれて、50mm×50mmの範囲の半分(50%)で、SiN膜が露出したことを示す。
30mm角のITO電極付きガラス基板(厚さ700μm)を、アセトン、イソプロパノールそれぞれを用いて洗浄した。その後、真空蒸着法にて以下の化合物を薄膜となるように順次蒸着し、陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極からなる2mm角の有機EL素子を有する基板を得た。各層の構成は以下の通りである。
・陽極 ITO、陽極の膜厚150nm
・正孔注入層 4,4’,4”-トリス{2-ナフチル(フェニル)アミノ}トリフェニルアミン(2-TNATA)
・正孔輸送層 N,N’-ジフェニル-N,N’-ジナフチルベンジジン(α-NPD)
・発光層 トリス(8-ヒドロキシキノリナト)アルミニウム(金属錯体系材料)、発光層の膜厚1000Å、発光層は電子輸送層としても機能する。
・電子注入層 フッ化リチウム
・陰極 アルミニウム 膜厚150nm
その後、2mm×2mmの有機EL素子を覆うように、10mm×10mmの開口部を有するマスク(覆い)を設置し、プラズマCVD法にてSiN膜を形成した。次に、各実験例で得られた組成物(有機物膜)を、窒素雰囲気下にて上記インクジェット装置を用いて2mm×2mmの有機EL素子を覆うように厚み10μmで塗布し、前記光硬化条件にて、この組成物を硬化させた後、該硬化体の全体を覆うように、10mm×10mmの開口部を有するマスク(覆い)を設置し、プラズマCVD法にてSiN膜を形成して有機EL表示素子を得た。
作製した直後の有機EL素子に6Vの電圧を印加し、有機EL素子の発光状態を目視と顕微鏡で観察し、ダークスポットの直径を測定した。
作製した直後の有機EL素子を、85℃、相対湿度85質量%の条件下にて70時間暴露した後、6Vの電圧を印加し、有機EL素子の発光状態を目視と顕微鏡で観察し、ダークスポットの直径を測定した。
Claims (29)
- (A)非環式の炭素数6以上のアルカンジオールジ(メタ)アクリレートと、(B)環状モノマーと、(C)光重合開始剤を含有し、
(B)環状モノマーは、環状単官能(メタ)アクリレートと環状2官能(メタ)アクリレートとを含有し、
下記の数式(I)及び(III)を共に満たす有機エレクトロルミネッセンス表示素子用封止剤。
8mPa・s≦η≦50mPa・s ・・・(I)
γ/2η<0.9m/s ・・・(III)
(式中、ηは25℃においてE型粘度計により測定される粘度を表し、γはペンダントドロップ法により測定された静的表面張力を表す。) - (A)非環式の炭素数6以上のアルカンジオールジ(メタ)アクリレートと、(B)環状モノマーと、(C)光重合開始剤を含有し、
(A)成分と(B)成分の合計100質量部に対して、(A)成分を10~85質量部、(B)成分を15~90質量部含有し、
(B)環状モノマーは、環状単官能(メタ)アクリレートと環状2官能(メタ)アクリレートとを含有し、
環状単官能(メタ)アクリレートと環状2官能(メタ)アクリレートの含有比率は、環状単官能(メタ)アクリレートと環状2官能(メタ)アクリレートの合計100質量部中、質量比で、環状単官能(メタ)アクリレート:環状2官能(メタ)アクリレート=10~95:90~5であり、かつ
下記の数式(I)、(II)及び(III)を共に満たす有機エレクトロルミネッセンス表示素子用封止剤。
8mPa・s≦η≦50mPa・s ・・・(I)
14mN/m≦γ≦40mN/m ・・・(II)
γ/2η<0.9m/s ・・・(III)
(式中、ηは25℃においてE型粘度計により測定される粘度を表し、γはペンダントドロップ法により測定された静的表面張力を表す。) - (B)環状モノマーが1種類以上の脂環式モノマーを含むことを特徴とする請求項1又は2に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (E)成分として、フッ素原子及び(メタ)アクリロイル基を有する含フッ素モノマーを含有する、請求項1~3のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- 前記含フッ素モノマーのフッ素原子含有量が、前記含フッ素モノマーの全量基準で、2~70質量%である、請求項4に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- 前記含フッ素モノマーが、式(E-1)で表される化合物、式(E-2)で表される化合物及び式(E-3)で表される化合物からなる群より選択される少なくとも一種を含む、請求項4又は5に記載の有機エレクトロルミネッセンス表示素子用封止剤。
式(E-1)
R1は、水素原子又はメチル基を示し、
R2は、フッ化アルキル基、又は、フッ化アルキル基における炭素-炭素結合及び炭素-水素結合の一部に酸素原子が挿入された基、を示す。]
式(E-2)
R3は、水素原子又はメチル基を示し、
R4は、フッ化アルカンジイル基、又は、フッ化アルカンジイル基における炭素-炭素結合及び炭素-水素結合の一部に酸素原子が挿入された基、を示す。複数存在するR3は、互いに同一でも異なっていてもよい。]
式(E-3)
R5は水素原子又はメチル基を示し、
R6は、単結合、アルカンジイル基、フッ化アルカンジイル基、又は、アルカンジイル基若しくはフッ化アルカンジイル基における炭素-炭素結合及び炭素-水素結合の一部に酸素原子が挿入された基、を示し、
Ar1はフッ化アリール基を示す。] - 前記含フッ素モノマーが、式(E-1-1)で表される化合物、式(E-2-1)で表される化合物及び式(E-3-1)で表される化合物からなる群より選択される少なくとも一種を含む、請求項6に記載の有機エレクトロルミネッセンス表示素子用封止剤。
式(E-1-1)
式(E-2-1)
式(E-3-1)
- (E)成分の含有量が、(A)成分と(B)成分の合計100質量部に対して、0.1質量部~10質量部の範囲にあることを特徴とする請求項4~7のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (E)成分が、2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-ヘキサデカフルオロ-1,10-デカンジオールジ(メタ)アクリレート、1H,1H,5H-オクタフルオロペンチル(メタ)アクリレート、及び1H,1H,2H,2H-トリデカフルオロオクチル(メタ)アクリレートからなる群から選択される一種以上を含むことを特徴とする請求項4~8のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- インクジェット法を用いて塗布することを特徴とする請求項1~9のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- 2官能(メタ)アクリレートオリゴマー、2官能(メタ)アクリレートポリマー、多官能(メタ)アクリレートオリゴマー、又は多官能(メタ)アクリレートポリマーを含有しないことを特徴とする請求項1~10のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- 硬化体のガラス転移温度が65℃以上120℃以下であることを特徴とする請求項1~11のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (B)成分のうち、少なくとも1個は環状構造を分子内に2個以上有することを特徴とする請求項1~12のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (B)成分のうち、少なくとも2個は環状構造を分子内に2個以上有することを特徴とする請求項1~13のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (A)成分が、炭素数12以下のアルカンジオールジ(メタ)アクリレートであることを特徴とする請求項1~15のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (A)成分が、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、1,12-ドデカンジオールジ(メタ)アクリレートからなる群のうちの1種以上を含有することを特徴とする請求項1~16のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (C)成分が、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイドを含有することを特徴とする請求項1~17のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (C)成分の含有量が、0.5~4質量部であることを特徴とする請求項1~18のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- 更に(D)酸化防止剤を含有することを特徴とする請求項1~19のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (D)成分がヒンダードフェノール系酸化防止剤であることを特徴とする請求項20に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- (D)成分を2種以上含有することを特徴とする請求項20~21のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- 395nm以上500nm以下の波長で硬化させることを特徴とする請求項1~22のいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- 395nmのLEDランプで硬化させることを特徴とする請求項23に記載の有機エレクトロルミネッセンス表示素子用封止剤。
- 請求項1~24のうちのいずれか一項に記載の有機エレクトロルミネッセンス表示素子用封止剤を硬化してなる硬化体。
- 請求項25に記載の硬化体を含む有機EL装置。
- 請求項25に記載の硬化体を含むディスプレイ。
- 請求項25に記載の硬化体を含む、フレキシブル性を有するディスプレイ。
- 請求項25に記載の硬化体を含む、フレキシブル性を有する有機EL装置。
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JPWO2022059738A1 (ja) * | 2020-09-18 | 2022-03-24 | ||
KR20230022968A (ko) | 2020-09-18 | 2023-02-16 | 미쓰이 가가쿠 가부시키가이샤 | 표시 소자용 봉지제 및 그의 경화물 |
KR20230022967A (ko) | 2020-09-18 | 2023-02-16 | 미쓰이 가가쿠 가부시키가이샤 | 표시 소자용 봉지제, 그의 경화물 및 표시 장치 |
KR20230022434A (ko) | 2020-09-18 | 2023-02-15 | 미쓰이 가가쿠 가부시키가이샤 | 자외선 경화성 수지 조성물 |
JP7451740B2 (ja) | 2020-09-18 | 2024-03-18 | 三井化学株式会社 | 表示素子用封止剤、その硬化物および表示装置 |
WO2022059738A1 (ja) * | 2020-09-18 | 2022-03-24 | 三井化学株式会社 | 表示素子用封止剤、その硬化物および表示装置 |
WO2022107692A1 (ja) * | 2020-11-18 | 2022-05-27 | 三井化学株式会社 | 有機el表示素子用封止材、その硬化物および有機el表示装置 |
JP7493058B2 (ja) | 2020-11-18 | 2024-05-30 | 三井化学株式会社 | 有機el表示素子用封止材、その硬化物および有機el表示装置 |
CN115340825A (zh) * | 2022-08-30 | 2022-11-15 | 浙江福斯特新材料研究院有限公司 | Oled器件封装用的密封剂及其应用 |
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TWI773843B (zh) | 2022-08-11 |
KR102626849B1 (ko) | 2024-01-18 |
TW201923018A (zh) | 2019-06-16 |
JP7203903B2 (ja) | 2023-01-13 |
JP6936330B2 (ja) | 2021-09-15 |
JPWO2019082996A1 (ja) | 2020-12-17 |
JP2021153061A (ja) | 2021-09-30 |
CN111345116A (zh) | 2020-06-26 |
KR20200078559A (ko) | 2020-07-01 |
CN111345116B (zh) | 2023-04-04 |
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