JP6294522B1 - Sealant for organic EL display element and organic EL display element - Google Patents
Sealant for organic EL display element and organic EL display element Download PDFInfo
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- JP6294522B1 JP6294522B1 JP2017024982A JP2017024982A JP6294522B1 JP 6294522 B1 JP6294522 B1 JP 6294522B1 JP 2017024982 A JP2017024982 A JP 2017024982A JP 2017024982 A JP2017024982 A JP 2017024982A JP 6294522 B1 JP6294522 B1 JP 6294522B1
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- acrylate
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- 239000000565 sealant Substances 0.000 title claims abstract description 10
- 239000011342 resin composition Substances 0.000 claims abstract description 68
- 239000000945 filler Substances 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 238000007789 sealing Methods 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 22
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 13
- 229910052623 talc Inorganic materials 0.000 claims description 12
- 239000000454 talc Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000011164 primary particle Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- YANHNDQLUNRWGA-UHFFFAOYSA-N OC.OC.CC(=C)C(O)=O.CC(=C)C(O)=O Chemical compound OC.OC.CC(=C)C(O)=O.CC(=C)C(O)=O YANHNDQLUNRWGA-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 26
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- VNWOJVJCRAHBJJ-UHFFFAOYSA-N 2-pentylcyclopentan-1-one Chemical compound CCCCCC1CCCC1=O VNWOJVJCRAHBJJ-UHFFFAOYSA-N 0.000 description 2
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 230000035515 penetration Effects 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UENOQWSWMYJKIW-UHFFFAOYSA-N 1,2,2-trimethylcyclohexan-1-ol Chemical compound CC1(C)CCCCC1(C)O UENOQWSWMYJKIW-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
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- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KEDGSDIAPIAOGT-UHFFFAOYSA-N triethoxy-[3-[(3-ethyloxetan-2-yl)methoxy]propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1OCC1CC KEDGSDIAPIAOGT-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- 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
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- 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
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Abstract
【課題】保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物、及び該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤、及び、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子の提供。【解決手段】主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００〜１０万であるポリマーと、脂環式骨格と（メタ）アクリロイル基とを有するモノマーと、光ラジカル重合開始剤と、吸水性フィラーとを含有し、上記ポリマーとモノマーとの合計１００重量部に対して、前記脂環式骨格と（メタ）アクリロイル基とを有するモノマーの含有量が３０〜９０重量部であり、かつ、前記吸水性フィラーの含有量が５〜６０重量部であり、Ｅ型粘度計を用いて２５℃、２．５ｒｐｍの条件で測定される粘度が１〜１０００Ｐａ・ｓである光硬化性樹脂組成物。【選択図】なしA photocurable resin composition having excellent storage stability, coating properties, adhesiveness, and barrier properties, an organic EL display element sealing agent comprising the photocurable resin composition, and the organic EL Providing an organic EL display element using a sealant for a display element. A polymer having a repeating unit represented by the following formula (1) in the main chain and a weight average molecular weight of 5,000 to 100,000, a monomer having an alicyclic skeleton and a (meth) acryloyl group; , Containing a radical photopolymerization initiator and a water-absorbing filler, and the content of the monomer having the alicyclic skeleton and the (meth) acryloyl group is 30 with respect to 100 parts by weight of the total of the polymer and the monomer. -90 parts by weight, and the content of the water-absorbing filler is 5-60 parts by weight, and the viscosity measured at 25 ° C. and 2.5 rpm using an E-type viscometer is 1-1000 Pa · The photocurable resin composition which is s. [Selection figure] None
Description
本発明は、保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物に関する。また、本発明は、該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤、及び、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子に関する。 The present invention relates to a photocurable resin composition having excellent storage stability, coating properties, adhesiveness, and barrier properties. Moreover, this invention relates to the organic EL display element which uses the sealing agent for organic EL display elements which consists of this photocurable resin composition, and this sealing agent for organic EL display elements.
有機エレクトロルミネッセンス（以下、「有機ＥＬ」ともいう）表示素子は、互いに対向する一対の電極間に有機発光材料層が挟持された積層体構造を有し、この有機発光材料層に一方の電極から電子が注入されるとともに他方の電極から正孔が注入されることにより有機発光材料層内で電子と正孔とが結合して発光する。このように有機ＥＬ表示素子は自己発光を行うことから、バックライトを必要とする液晶表示素子等と比較して視認性がよく、薄型化が可能であり、しかも直流低電圧駆動が可能であるという利点を有している。 An organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and the organic light emitting material layer is formed from one electrode on the organic light emitting material layer. When electrons are injected and holes are injected from the other electrode, the electrons and holes are combined in the organic light emitting material layer to emit light. Thus, since the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.
有機ＥＬ表示素子を構成する有機発光材料層や電極は、水分や酸素等により特性が劣化しやすいという問題がある。従って、実用的な有機ＥＬ表示素子を得るためには、有機発光材料層や電極を大気と遮断して長寿命化を図る必要がある。有機発光材料層や電極を大気と遮断する方法として、例えば、特許文献１には、基板上に配列された有機発光材料層を有する積層体の上方を封止部材で覆い、その周囲をシール剤（周辺封止剤）により形成された封止壁で囲む方法が開示されている。このような封止壁の形成に用いられる周辺封止剤には、水分や酸素等を遮断する高度なバリア性、基板上にディスペンス等により塗布する際の塗布性、基板と封止部材とを貼り合せた後、光照射又は加熱により硬化させる際の硬化性、並びに、基板と封止部材とを接着固定し、剥がれやクラックによる欠陥を生じることなく封止を維持する接着性及び強靭性が要求される。 The organic light-emitting material layer and electrodes constituting the organic EL display element have a problem that the characteristics are easily deteriorated by moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to extend the life by blocking the organic light emitting material layer and the electrode from the atmosphere. As a method for blocking the organic light emitting material layer and the electrode from the atmosphere, for example, in Patent Document 1, the upper part of the laminate having the organic light emitting material layer arranged on the substrate is covered with a sealing member, and the periphery thereof is a sealing agent. A method of surrounding with a sealing wall formed by (peripheral sealing agent) is disclosed. The peripheral sealing agent used for forming such a sealing wall has a high barrier property to block moisture, oxygen, etc., applicability when applied on a substrate by dispensing, etc., and a substrate and a sealing member. After bonding, the curability when cured by light irradiation or heating, and the adhesiveness and toughness that adheres and fixes the substrate and the sealing member and maintains the sealing without causing defects due to peeling or cracking. Required.
特許文献２には、周辺封止剤として用いることのできる硬化性樹脂組成物として、高分子量のポリイソブチレン樹脂と多官能性（メタ）アクリレートモノマーとを含有する組成物が開示されている。しかしながら、特許文献２に開示されているような従来の封止剤は、塗布時に溶剤希釈が必要であり、溶剤自体や塗布後に溶剤を除去するための乾燥工程における加熱によって有機ＥＬ表示素子にダメージを発生させ易いという問題があった。また、乾燥工程において封止剤の形状が不均一となり易く、有機発光材料層を有する積層体の周囲を封止する周辺封止剤として用いることが困難であった。 Patent Document 2 discloses a composition containing a high molecular weight polyisobutylene resin and a polyfunctional (meth) acrylate monomer as a curable resin composition that can be used as a peripheral sealing agent. However, the conventional sealant as disclosed in Patent Document 2 requires solvent dilution at the time of application, and the organic EL display element is damaged by heating in the drying process for removing the solvent itself or the solvent after application. There was a problem that it was easy to generate. Moreover, the shape of the sealing agent is likely to be non-uniform in the drying step, and it has been difficult to use the sealing agent as a peripheral sealing agent that seals the periphery of the laminate having the organic light emitting material layer.
本発明は、保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物を提供することを目的とする。また、本発明は、該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤、及び、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子を提供することを目的とする。 An object of this invention is to provide the photocurable resin composition excellent in storage stability, applicability | paintability, adhesiveness, and barrier property. Moreover, this invention aims at providing the organic EL display element which uses the sealing agent for organic EL display elements which consists of this photocurable resin composition, and this sealing agent for organic EL display elements. To do.
本発明は、主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと、脂環式骨格と（メタ）アクリロイル基とを有するモノマーと、光ラジカル重合開始剤と、吸水性フィラーとを含有し、上記主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと上記脂環式骨格と（メタ）アクリロイル基とを有するモノマーとの合計１００重量部に対して、上記脂環式骨格と（メタ）アクリロイル基とを有するモノマーの含有量が３０重量部以上９０重量部以下であり、かつ、上記吸水性フィラーの含有量が５重量部以上６０重量部以下であり、Ｅ型粘度計を用いて２５℃、２．５ｒｐｍの条件で測定される粘度が１Ｐａ・ｓ以上１０００Ｐａ・ｓ以下である光硬化性樹脂組成物である。 The present invention provides a monomer having a repeating unit represented by the following formula (1) in the main chain, a polymer having a weight average molecular weight of 5,000 to 100,000, an alicyclic skeleton, and a (meth) acryloyl group. A polymer containing a radical photopolymerization initiator and a water-absorbing filler, having a repeating unit represented by the following formula (1) in the main chain, and having a weight average molecular weight of 5,000 to 100,000: The content of the monomer having the alicyclic skeleton and the (meth) acryloyl group is 30 parts by weight or more and 90 parts by weight with respect to a total of 100 parts by weight of the monomer having the alicyclic skeleton and the (meth) acryloyl group. The viscosity of the water-absorbent filler is 5 parts by weight or more and 60 parts by weight or less, and the viscosity measured at 25 ° C. and 2.5 rpm using an E-type viscometer is 1 Pa · s or more. 1000 A photocurable resin composition is not more than a · s.
以下に本発明を詳述する。
本発明者らは、樹脂成分として、（メタ）アクリルモノマー又はエポキシモノマーに低分子量のポリイソブチレン系ポリマーを加え、更に、吸水性フィラーを配合することにより、有機溶剤を用いずに塗布性に優れ、バリア性にも優れる封止剤を作製することを検討した。しかしながら、得られた封止剤は相分離し易く、保存安定性に劣るものであったり、硬化物の耐熱試験を行った際にポリイソブチレン系ポリマーがブリードアウトして接着性が低下したりするという問題があった。そこで本発明者らは鋭意検討した結果、重量平均分子量が特定の範囲であるポリイソブチレン系ポリマーと、脂環式骨格と（メタ）アクリロイル基とを有するモノマーと、吸水性フィラーとを特定の含有割合となるように配合し、かつ、粘度が特定の範囲となるようにすることにより、保存安定性、塗布性、接着性、及び、バリア性の全てに優れる光硬化性樹脂組成物を得ることができることを見出し、本発明を完成させるに至った。
なお、本明細書において上記「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味する。
The present invention is described in detail below.
By adding a low molecular weight polyisobutylene polymer to a (meth) acrylic monomer or epoxy monomer as a resin component, and further blending a water-absorbing filler, the present inventors have excellent coating properties without using an organic solvent. Then, the production of a sealant having excellent barrier properties was studied. However, the obtained sealant is easy to phase-separate and is inferior in storage stability, or the polyisobutylene polymer bleeds out when the heat resistance test of the cured product is performed and the adhesiveness is lowered. There was a problem. Therefore, as a result of intensive studies, the present inventors have found that a polyisobutylene polymer having a weight average molecular weight in a specific range, a monomer having an alicyclic skeleton and a (meth) acryloyl group, and a water-absorbing filler are contained in a specific content. A photocurable resin composition having excellent storage stability, applicability, adhesiveness, and barrier properties can be obtained by blending in proportions and setting the viscosity within a specific range. As a result, the present invention has been completed.
In the present specification, the “(meth) acryloyl” means acryloyl or methacryloyl.
本発明の光硬化性樹脂組成物は、主鎖に上記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマー（以下、「本発明にかかるポリイソブチレン系ポリマー」ともいう）を含有する。
本発明にかかるポリイソブチレン系ポリマーは、主鎖に上記式（１）で表される繰り返し単位からなる疎水性で嵩高い骨格を有することにより、非晶性でありながら排除体積が大きく、本発明の光硬化性樹脂組成物がバリア性に優れるものとなる。
The photocurable resin composition of the present invention comprises a polymer having a repeating unit represented by the above formula (1) in the main chain and a weight average molecular weight of from 5,000 to 100,000 (hereinafter referred to as “polyester according to the present invention”). It is also referred to as “isobutylene polymer”.
The polyisobutylene polymer according to the present invention has a hydrophobic and bulky skeleton composed of repeating units represented by the above formula (1) in the main chain, so that the excluded volume is large while being amorphous. This photocurable resin composition is excellent in barrier properties.
本発明にかかるポリイソブチレン系ポリマーは、上記式（１）で表される繰り返し単位以外の他の構成単位を有していてもよい。即ち、本発明にかかるポリイソブチレン系ポリマーは、上記式（１）で表される繰り返し単位を有していれば、末端に上記他の構成単位として（メタ）アクリロイル基等の反応性官能基を有していてもよいし、上記式（１）で表される繰り返し単位に加えて上記他の構成単位を繰り返し単位として有する共重合体であってもよい。 The polyisobutylene polymer according to the present invention may have a structural unit other than the repeating unit represented by the above formula (1). That is, if the polyisobutylene polymer according to the present invention has a repeating unit represented by the above formula (1), a reactive functional group such as a (meth) acryloyl group is added to the terminal as the above other structural unit. You may have, and the copolymer which has the said other structural unit as a repeating unit in addition to the repeating unit represented by the said Formula (1) may be sufficient.
上記他の構成単位を有する場合、バリア性の観点から、本発明にかかるポリイソブチレン系ポリマーは、上記式（１）で表される繰り返し単位を８０重量％以上含むことが好ましく、９０重量％以上含むことがより好ましい。 In the case of having the above other structural unit, from the viewpoint of barrier properties, the polyisobutylene polymer according to the present invention preferably contains 80% by weight or more of the repeating unit represented by the above formula (1), and is 90% by weight or more. More preferably.
本発明にかかるポリイソブチレン系ポリマーの重量平均分子量の下限は５０００、上限は１０万である。本発明にかかるポリイソブチレン系ポリマーの重量平均分子量がこの範囲であることにより、後述する脂環式骨格と（メタ）アクリロイル基とを有するモノマーとの相溶性に優れるものとなって、得られる光硬化性樹脂組成物が保存安定性に優れ、かつ、硬化物からの本発明にかかるポリイソブチレン系ポリマーのブリードアウトが抑制されて接着性にも優れるものとなる。本発明にかかるポリイソブチレン系ポリマーの重量平均分子量の好ましい下限は２万、好ましい上限は８万、より好ましい下限は３万、より好ましい上限は６万である。
なお、本明細書において上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による重量平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ ＬＦ−８０４（昭和電工社製）等が挙げられる。また、ＧＰＣで用いる溶媒としては、テトラヒドロフラン等が挙げられる。
The lower limit of the weight average molecular weight of the polyisobutylene polymer according to the present invention is 5000, and the upper limit is 100,000. When the weight average molecular weight of the polyisobutylene polymer according to the present invention is within this range, the resulting light has excellent compatibility with a monomer having an alicyclic skeleton and a (meth) acryloyl group, which will be described later. The curable resin composition is excellent in storage stability, and the bleed-out of the polyisobutylene polymer according to the present invention from the cured product is suppressed, resulting in excellent adhesion. The preferable lower limit of the weight average molecular weight of the polyisobutylene polymer according to the present invention is 20,000, the preferable upper limit is 80,000, the more preferable lower limit is 30,000, and the more preferable upper limit is 60,000.
In addition, the said weight average molecular weight is a value calculated | required by polystyrene conversion by measuring with a gel permeation chromatography (GPC) in this specification. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.
本発明にかかるポリイソブチレン系ポリマーのうち市販されているものとしては、例えば、エピオン２００Ａ（カネカ社製、重量平均分子量６９００）、エピオン４００Ａ（カネカ社製、重量平均分子量１３０００）、エピオン６００Ａ（カネカ社製、重量平均分子量１９０００）、テトラックス３Ｔ（ＪＸ日鉱日石エネルギー社製、重量平均分子量４９０００）、テトラックス４Ｔ（ＪＸ日鉱日石エネルギー社製、重量平均分子量５９０００）、テトラックス５Ｔ（ＪＸ日鉱日石エネルギー社製、重量平均分子量６９０００）、テトラックス６Ｔ（ＪＸ日鉱日石エネルギー社製、重量平均分子量８００００）、ハイモール４Ｈ（ＪＸ日鉱日石エネルギー社製、重量平均分子量５０００以上１０万以下）、ハイモール５Ｈ（ＪＸ日鉱日石エネルギー社製、重量平均分子量５０００以上１０万以下）、ハイモール５．５Ｈ（ＪＸ日鉱日石エネルギー社製、重量平均分子量５０００以上１０万以下）、ハイモール６Ｈ（ＪＸ日鉱日石エネルギー社製、重量平均分子量５０００以上１０万以下）、Ｏｐｐａｎｏｌ Ｂ１０（ＢＡＳＦ社製、重量平均分子量３６０００）、Ｏｐｐａｎｏｌ Ｂ１１（ＢＡＳＦ社製、重量平均分子量４６０００）、Ｏｐｐａｎｏｌ Ｂ１２（ＢＡＳＦ社製、重量平均分子量５１０００）、Ｏｐｐａｎｏｌ Ｂ１３（ＢＡＳＦ社製、重量平均分子量６万）、Ｏｐｐａｎｏｌ Ｂ１４（ＢＡＳＦ社製、重量平均分子量６５０００）、Ｏｐｐａｎｏｌ Ｂ１５（ＢＡＳＦ社製、重量平均分子量７５０００）等が挙げられる。 Among commercially available polyisobutylene polymers according to the present invention, for example, Epion 200A (manufactured by Kaneka Corporation, weight average molecular weight 6900), Epion 400A (manufactured by Kaneka Corporation, weight average molecular weight 13000), Epion 600A (Kaneka) Manufactured by Co., Ltd., weight average molecular weight 19000), Tetrax 3T (manufactured by JX Nippon Mining & Energy Corporation, weight average molecular weight 49000), Tetrax 4T (manufactured by JX Nippon Mining & Energy Corporation, weight average molecular weight 59000), Tetrax 5T (JX Nippon Mining & Energy Corporation, weight average molecular weight 69000), Tetrax 6T (manufactured by JX Nippon Mining & Energy Corporation, weight average molecular weight 80000), High Mall 4H (manufactured by JX Nippon Mining & Energy Corporation, weight average molecular weight 5,000 to 100,000) Below), High Mall 5H (JX Nippon Oil & Energy Corporation) Made by Gee Co., Ltd., weight average molecular weight 5000 or more and 100,000 or less), Hymor 5.5H (manufactured by JX Nippon Mining & Energy Corporation, weight average molecular weight 5000 or more and 100,000 or less), Hymor 6H (manufactured by JX Nippon Mining & Energy Corporation, Weight average molecular weight 5000 to 100,000), Oppanol B10 (manufactured by BASF, weight average molecular weight 36000), Opanol B11 (manufactured by BASF, weight average molecular weight 46000), Oppanol B12 (manufactured by BASF, weight average molecular weight 51000), Oppanol B13 (manufactured by BASF, weight average molecular weight 60,000), Oppanol B14 (manufactured by BASF, weight average molecular weight 65000), Opanol B15 (manufactured by BASF, weight average molecular weight 75000) and the like.
本発明の光硬化性樹脂組成物は、本発明の目的を阻害しない範囲で、本発明にかかるポリイソブチレン系ポリマー以外の他のポリマーを含有してもよい。 The photocurable resin composition of the present invention may contain a polymer other than the polyisobutylene polymer according to the present invention as long as the object of the present invention is not impaired.
上記他のポリマーとしては、例えば、ポリブテン系ポリマー、ポリイソプレン系ポリマー、水添ポリイソプレン系ポリマー、ポリブタジエン系ポリマー、水添ポリブタジエン系ポリマー、重量平均分子量が１０万を超えるポリイソブチレン系ポリマー、及び、これらの共重合体や変性体等が挙げられる。なかでも、バリア性の観点からは、重量平均分子量が１０万を超えるポリイソブチレン系ポリマーが好ましく、反応性の観点からは、末端に（メタ）アクリロイル基を有するポリブタジエン系ポリマー、及び、末端に（メタ）アクリロイル基を有するポリイソプレン系ポリマーが好ましい。 Examples of the other polymer include a polybutene polymer, a polyisoprene polymer, a hydrogenated polyisoprene polymer, a polybutadiene polymer, a hydrogenated polybutadiene polymer, a polyisobutylene polymer having a weight average molecular weight exceeding 100,000, and These copolymers, modified products and the like can be mentioned. Among them, a polyisobutylene polymer having a weight average molecular weight exceeding 100,000 is preferable from the viewpoint of barrier properties, and a polybutadiene polymer having a (meth) acryloyl group at the terminal and a terminal ( A polyisoprene-based polymer having a (meth) acryloyl group is preferred.
上記重量平均分子量が１０万を超えるポリイソブチレン系ポリマーのうち市販されているものとしては、例えば、Ｏｐｐａｎｏｌ Ｂ３０ＳＦ、Ｏｐｐａｎｏｌ Ｂ５０、Ｏｐｐａｎｏｌ Ｂ５０ＳＦ、Ｏｐｐａｎｏｌ Ｂ８０、Ｏｐｐａｎｏｌ Ｂ１００、Ｏｐｐａｎｏｌ Ｂ１５０、Ｏｐｐａｎｏｌ Ｂ２００（いずれもＢＡＳＦ社製）等が挙げられる。
上記末端に（メタ）アクリロイル基を有するポリブタジエン系ポリマーのうち市販されているものとしては、例えば、ＣＮ３０７、ＣＮ９０１４ＮＳ（いずれもアルケマ社製）、ＢＡＣ−４５（大阪有機化学工業社製）、ＴＥ−２０００、ＴＥＡＩ−１０００（いずれも日本曹達社製）等が挙げられる。
上記末端に（メタ）アクリロイル基を有するポリイソプレン系ポリマーのうち市販されているものとしては、例えば、クラプレン ＵＣ−１０２Ｍ（クラレ社製）等が挙げられる。
Examples of commercially available polyisobutylene polymers having a weight average molecular weight exceeding 100,000 include, for example, Opanol B30SF, Opanol B50, Opanol B50SF, Opanol B80, Opanol B100, Opanol B150, Oppanol B200 (all BA Manufactured) and the like.
Examples of commercially available polybutadiene-based polymers having a (meth) acryloyl group at the terminal include CN307, CN9014NS (all manufactured by Arkema), BAC-45 (manufactured by Osaka Organic Chemical Industry), TE- 2000, TEAI-1000 (all manufactured by Nippon Soda Co., Ltd.) and the like.
Examples of commercially available polyisoprene polymers having a (meth) acryloyl group at the terminal include Claprene UC-102M (manufactured by Kuraray Co., Ltd.).
本発明の光硬化性樹脂組成物は、脂環式骨格と（メタ）アクリロイル基とを有するモノマー（以下、「本発明にかかる（メタ）アクリルモノマー」ともいう）を含有する。
本発明にかかる（メタ）アクリルモノマーは、本発明にかかるポリイソブチレン系ポリマーとの相溶性に優れるため、本発明にかかる（メタ）アクリルモノマーを含有することにより、硬化物からの本発明にかかるポリイソブチレン系ポリマーのブリードアウトが抑制され、得られる光硬化性樹脂組成物が接着性に優れるものとなり、かつ、保存安定性にも優れるものとなる。
なお、本明細書において上記「（メタ）アクリル」は、アクリル又はメタクリルを意味する。
The photocurable resin composition of the present invention contains a monomer having an alicyclic skeleton and a (meth) acryloyl group (hereinafter also referred to as “(meth) acrylic monomer according to the present invention”).
Since the (meth) acrylic monomer according to the present invention is excellent in compatibility with the polyisobutylene-based polymer according to the present invention, the (meth) acrylic monomer according to the present invention contains the (meth) acrylic monomer according to the present invention from the cured product. Bleed-out of the polyisobutylene polymer is suppressed, and the resulting photocurable resin composition has excellent adhesiveness and storage stability.
In the present specification, the “(meth) acryl” means acryl or methacryl.
本発明にかかる（メタ）アクリルモノマーの有する脂環式骨格は、バリア性等の観点から、有橋脂環式骨格であることが好ましい。 The alicyclic skeleton of the (meth) acrylic monomer according to the present invention is preferably a bridged alicyclic skeleton from the viewpoint of barrier properties and the like.
また、本発明にかかる（メタ）アクリルモノマーは、バリア性の観点から、（メタ）アクリロイル基としてメタクリル基を有することが好ましい。 Moreover, it is preferable that the (meth) acryl monomer concerning this invention has a methacryl group as a (meth) acryloyl group from a viewpoint of barrier property.
本発明にかかる（メタ）アクリルモノマーの分子量の好ましい上限は１０００である。本発明にかかる（メタ）アクリルモノマーの分子量が１０００以下であることにより、得られる光硬化性樹脂組成物が光硬化性により優れるものとなる。本発明にかかる（メタ）アクリルモノマーの分子量のより好ましい上限は５００である。
本発明にかかる（メタ）アクリルモノマーの分子量の好ましい下限は特にないが、実質的な下限は１５０である。
The upper limit with preferable molecular weight of the (meth) acryl monomer concerning this invention is 1000. When the molecular weight of the (meth) acrylic monomer according to the present invention is 1000 or less, the resulting photocurable resin composition is more excellent in photocurability. A more preferred upper limit of the molecular weight of the (meth) acrylic monomer according to the present invention is 500.
Although there is no particular lower limit of the molecular weight of the (meth) acrylic monomer according to the present invention, the substantial lower limit is 150.
本発明にかかる（メタ）アクリルモノマーとしては、具体的には例えば、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、トリメチルシクロヘキサノール（メタ）アクリレート、ノルボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジシクロペンタジエンジメタノールジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート等が挙げられる。なかでも、イソボルニル（メタ）アクリレート及び／又はジシクロペンタジエンジメタノールジ（メタ）アクリレートが好ましく、イソボルニルメタクリレート及び／又はジシクロペンタジエンジメタノールジメタクリレートがより好ましい。これらの（メタ）アクリルモノマーは、単独で用いられてもよく、２種以上が併用されてもよい。 Specific examples of the (meth) acrylic monomer according to the present invention include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, trimethylcyclohexanol (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) ) Acrylate, dicyclopentadiene dimethanol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, and the like. Of these, isobornyl (meth) acrylate and / or dicyclopentadiene dimethanol di (meth) acrylate is preferable, and isobornyl methacrylate and / or dicyclopentadiene dimethanol dimethacrylate is more preferable. These (meth) acrylic monomers may be used alone or in combination of two or more.
本発明にかかる（メタ）アクリルモノマーの含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部のうち、下限が３０重量部、上限が９０重量部である。本発明にかかる（メタ）アクリルモノマーの含有量が３０重量部以上であることにより、得られる光硬化性樹脂組成物が塗布性、硬化性、及び、接着性に優れるものとなる。本発明にかかる（メタ）アクリルモノマーの含有量が９０重量部以下であることにより、得られる光硬化性樹脂組成物がバリア性に優れるものとなる。本発明にかかる（メタ）アクリルモノマーの含有量の好ましい下限は３５重量部、好ましい上限は８０重量部、より好ましい下限は４０重量部、より好ましい上限は７０重量部である。 The content of the (meth) acrylic monomer according to the present invention is such that the lower limit is 30 parts by weight and the upper limit is 90 parts out of a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Parts by weight. When the content of the (meth) acrylic monomer according to the present invention is 30 parts by weight or more, the resulting photocurable resin composition is excellent in applicability, curability, and adhesiveness. When the content of the (meth) acrylic monomer according to the present invention is 90 parts by weight or less, the resulting photocurable resin composition has excellent barrier properties. The minimum with preferable content of the (meth) acryl monomer concerning this invention is 35 weight part, a preferable upper limit is 80 weight part, a more preferable minimum is 40 weight part, and a more preferable upper limit is 70 weight part.
本発明の光硬化性樹脂組成物は、接着性をより向上させる等の目的で、本発明にかかる（メタ）アクリルモノマーに加えて、相溶性を損なわない範囲で他の重合性モノマーを含有してもよい。
上記他の重合性モノマーとしては、本発明にかかる（メタ）アクリルモノマー以外の他の（メタ）アクリルモノマーが好ましい。
In addition to the (meth) acrylic monomer according to the present invention, the photocurable resin composition of the present invention contains other polymerizable monomers as long as the compatibility is not impaired. May be.
As said other polymerizable monomer, other (meth) acryl monomers other than the (meth) acryl monomer concerning this invention are preferable.
上記他の（メタ）アクリルモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、２−ブトキシエチル（メタ）アクリレート、２−フェノキシエチル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−テトラフルオロプロピル（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、イミド（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、２−（メタ）アクリロイロキシエチルコハク酸、２−（メタ）アクリロイロキシエチルホスフェート、グリシジル（メタ）アクリレート、１，３−ブタンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、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、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、２−ｎ−ブチル−２−エチル−１，３−プロパンジオールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＦジ（メタ）アクリレート、２−ヒドロキシ−３−（メタ）アクリロイロキシプロピル（メタ）アクリレート、カーボネートジオールジ（メタ）アクリレート、ポリエーテルジオールジ（メタ）アクリレート、ポリエステルジオールジ（メタ）アクリレート、ポリカプロラクトンジオールジ（メタ）アクリレート、ポリブタジエンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、カプロラクトン変性トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、プロピレンオキシド付加グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 Examples of the other (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth). ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, Stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2 , 3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di ( Meta) Acu Relate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide added bisphenol A di (meth) acrylate, propylene oxide added Bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) ) Acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, glycerin tri (meth) Acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples include penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. It is.
本発明の光硬化性樹脂組成物は、光ラジカル重合開始剤を含有する。
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、ベンジル、チオキサントン等が挙げられる。
The photocurable resin composition of the present invention contains a photoradical polymerization initiator.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone, and the like.
上記光ラジカル重合開始剤のうち市販されているものとしては、例えば、ＩＲＧＡＣＵＲＥ１８４、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ３７９、ＩＲＧＡＣＵＲＥ６５１、ＩＲＧＡＣＵＲＥ８１９、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ２９５９、ＩＲＧＡＣＵＲＥ ＯＸＥ０１、ルシリンＴＰＯ（いずれもＢＡＳＦ社製）、ベンソインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル（いずれも東京化成工業社製）等が挙げられる。 Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucin TPO (all manufactured by BASF Methyl, Examples include benzoin ethyl ether and benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.).
上記光ラジカル重合開始剤の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記光ラジカル重合開始剤の含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が、硬化性、保存安定性、及び、バリア性により優れるものとなる。上記光ラジカル重合開始剤の含有量のより好ましい下限は０．２重量部、より好ましい上限は５重量部、更に好ましい下限は０．５重量部、更に好ましい上限は３重量部である。 The content of the radical photopolymerization initiator is preferably 0.1 parts by weight, preferably the upper limit with respect to 100 parts by weight of the total of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Is 10 parts by weight. When the content of the radical photopolymerization initiator is within this range, the resulting photocurable resin composition is more excellent in curability, storage stability, and barrier properties. The more preferable lower limit of the content of the radical photopolymerization initiator is 0.2 parts by weight, the more preferable upper limit is 5 parts by weight, the still more preferable lower limit is 0.5 parts by weight, and the still more preferable upper limit is 3 parts by weight.
本発明の光硬化性樹脂組成物は、吸水性フィラーを含有する。
上記吸水性フィラーを含有することにより、本発明の光硬化性樹脂組成物は、バリア性に優れるものとなる。
The photocurable resin composition of the present invention contains a water-absorbing filler.
By containing the water-absorbing filler, the photocurable resin composition of the present invention has excellent barrier properties.
上記吸水性フィラーの平均一次粒子径の好ましい下限は０．５μｍ、好ましい上限は５μｍである。上記吸水性フィラーの平均一次粒子径がこの範囲であることにより、得られる光硬化性樹脂組成物が、有機ＥＬ表示素子用封止剤として用いた際にパネル剥がれを抑制しつつバリア性により優れるものとなる。上記吸水性フィラーの平均一次粒子径のより好ましい下限は０．８μｍ、より好ましい上限は３μｍである。
なお、本明細書において上記「平均一次粒子径」は、動的光散乱式粒子径測定装置（大塚電子社製、「ＥＬＳＺ−１０００Ｓ」）等により測定することができる。
The minimum with a preferable average primary particle diameter of the said water absorbing filler is 0.5 micrometer, and a preferable upper limit is 5 micrometers. When the average primary particle diameter of the water-absorbing filler is within this range, the resulting photocurable resin composition is more excellent in barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. It will be a thing. The minimum with a more preferable average primary particle diameter of the said water absorbing filler is 0.8 micrometer, and a more preferable upper limit is 3 micrometers.
In the present specification, the “average primary particle diameter” can be measured by a dynamic light scattering particle diameter measuring apparatus (“ELSZ-1000S” manufactured by Otsuka Electronics Co., Ltd.) or the like.
上記吸水性フィラーの比重の好ましい下限は１．５ｇ／ｃｍ３、好ましい上限は３．３ｇ／ｃｍ３である。上記吸水性フィラーの比重がこの範囲であることにより、得られる光硬化性樹脂組成物が、有機ＥＬ表示素子用封止剤として用いた際にパネル剥がれを抑制しつつバリア性により優れるものとなる。上記吸水性フィラーの比重のより好ましい下限は２．０ｇ／ｃｍ３、より好ましい上限は３．０ｇ／ｃｍ３である。
なお、上記「比重」は、ＪＩＳ Ｚ８８０７に準じた方法により測定される値を意味する。
The preferable lower limit of the specific gravity of the water-absorbing filler is 1.5 g / cm 3 , and the preferable upper limit is 3.3 g / cm 3 . When the specific gravity of the water-absorbing filler is within this range, the resulting photocurable resin composition is superior in barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. . A more preferable lower limit of the specific gravity of the water-absorbing filler is 2.0 g / cm 3 , and a more preferable upper limit is 3.0 g / cm 3 .
The “specific gravity” means a value measured by a method according to JIS Z8807.
上記吸水性フィラーの平均比表面積の好ましい下限は５ｍ２／ｇ、好ましい上限は２０ｍ２／ｇである。上記吸水性フィラーの平均比表面積がこの範囲であることにより、得られる光硬化性樹脂組成物が、有機ＥＬ表示素子用封止剤として用いた際にパネル剥がれを抑制しつつバリア性により優れるものとなる。上記吸水性フィラーの平均比表面積のより好ましい下限は１０ｍ２／ｇ、より好ましい上限は１８ｍ２／ｇである。
なお、上記「吸水性フィラーの平均比表面積」は、比表面積測定装置（例えば、島津製作所社製、「ＡＳＡＰ−２０００」等）で窒素ガスを用いたＢＥＴ法により測定することができる。
The preferable lower limit of the average specific surface area of the water-absorbing filler is 5 m 2 / g, and the preferable upper limit is 20 m 2 / g. When the average specific surface area of the water-absorbing filler is within this range, the resulting photocurable resin composition has excellent barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. It becomes. The minimum with a more preferable average specific surface area of the said water absorbing filler is 10 m < 2 > / g, and a more preferable upper limit is 18 m < 2 > / g.
The “average specific surface area of the water-absorbing filler” can be measured by a BET method using nitrogen gas with a specific surface area measuring device (for example, “ASAP-2000” manufactured by Shimadzu Corporation).
本発明の光硬化性樹脂組成物１００ｇ当たりの上記吸水性フィラーの総表面積の好ましい下限は１０ｍ２、好ましい上限は１００ｍ２である。上記吸水性フィラーの総表面積がこの範囲であることにより、得られる光硬化性樹脂組成物が、有機ＥＬ表示素子用封止剤として用いた際にパネル剥がれを抑制しつつバリア性により優れるものとなる。上記吸水性フィラーの総表面積のより好ましい下限は２０ｍ２、より好ましい上限は８０ｍ２である。
なお、上記「吸水性フィラーの総表面積」は、上記吸水性フィラーの含有量と上記吸水性フィラーの平均比表面積とから算出することができる。
A preferable lower limit of the total surface area of the water-absorbing filler per 100 g of the photocurable resin composition of the present invention is 10 m 2 , and a preferable upper limit is 100 m 2 . When the total surface area of the water-absorbing filler is within this range, the resulting photocurable resin composition has excellent barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. Become. A more preferable lower limit of the total surface area of the water-absorbing filler is 20 m 2 , and a more preferable upper limit is 80 m 2 .
The “total surface area of the water-absorbing filler” can be calculated from the content of the water-absorbing filler and the average specific surface area of the water-absorbing filler.
上記吸水性フィラーの吸水率の好ましい下限は１０重量％である。上記吸水性フィラーの吸水率が１０重量％以上であることにより、得られる光硬化性樹脂組成物がバリア性により優れるものとなる。上記吸水性フィラーの吸水率のより好ましい下限は２０重量％である。
また、上記吸水性フィラーの吸水率の好ましい上限は特にないが、実質的な上限は５０重量％である。
なお、上記「吸水率」は、温度８５℃、湿度８５％の雰囲気下で２４時間放置する高温高湿試験を行った場合における重量の変化率を意味する。具体的には、高温高湿試験（８５℃−８５％、２４時間）前の重量をＷ１、高温高湿試験後の重量をＷ２とした場合、下記式（Ｉ）により算出される。
吸水率（重量％）＝（（Ｗ２−Ｗ１）／Ｗ１）×１００ （Ｉ）
The minimum with the preferable water absorption rate of the said water absorptive filler is 10 weight%. When the water absorption rate of the water-absorbing filler is 10% by weight or more, the resulting photocurable resin composition is more excellent in barrier properties. A more preferable lower limit of the water absorption rate of the water-absorbing filler is 20% by weight.
Further, there is no particular upper limit of the water absorption rate of the water-absorbing filler, but the substantial upper limit is 50% by weight.
The “water absorption rate” means the rate of change in weight when a high temperature and high humidity test is performed for 24 hours in an atmosphere at a temperature of 85 ° C. and a humidity of 85%. Specifically, when the weight before the high-temperature and high-humidity test (85 ° C.-85%, 24 hours) is W 1 and the weight after the high-temperature and high-humidity test is W 2 , it is calculated by the following formula (I).
Water absorption rate (% by weight) = ((W 2 −W 1 ) / W 1 ) × 100 (I)
上記吸水性フィラーを構成する材料としては、例えば、酸化カルシウム、酸化ストロンチウム、酸化バリウム等のアルカリ土類金属の酸化物、酸化マグネシウム、モレキュラーシーブ等が挙げられる。なかでも、吸水性の観点から、アルカリ土類金属の酸化物が好ましく、酸化カルシウムがより好ましい。 Examples of the material constituting the water-absorbing filler include alkaline earth metal oxides such as calcium oxide, strontium oxide, and barium oxide, magnesium oxide, and molecular sieve. Among these, from the viewpoint of water absorption, an alkaline earth metal oxide is preferable, and calcium oxide is more preferable.
上記吸水性フィラーの含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、下限が５重量部、上限が７０重量部である。上記吸水性フィラーの含有量がこの範囲であることにより、得られる光硬化性樹脂組成物がバリア性と接着性とを両立する効果に優れるものとなる。上記吸水性フィラーの含有量の好ましい下限は１０重量部、好ましい上限は６０重量部、より好ましい下限は１５重量部、より好ましい上限は５０重量部である。 The content of the water-absorbing filler is such that the lower limit is 5 parts by weight and the upper limit is 70 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. . When the content of the water-absorbing filler is within this range, the resulting photocurable resin composition has an excellent effect of achieving both barrier properties and adhesiveness. The minimum with preferable content of the said water absorbing filler is 10 weight part, a preferable upper limit is 60 weight part, a more preferable minimum is 15 weight part, and a more preferable upper limit is 50 weight part.
本発明の光硬化性樹脂組成物は、バリア性や塗布性を更に向上させること等を目的として、上記吸水性フィラー以外の他のフィラーを含有してもよい。
上記他のフィラーとしては、例えば、タルク、シリカ、アルミナ等の無機フィラーや、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機フィラー等が挙げられる。なかでも、タルク及び／又はシリカを含有することが好ましく、タルク及び／又はフュームドシリカを含有することがより好ましい。
The photocurable resin composition of the present invention may contain a filler other than the water-absorbing filler for the purpose of further improving the barrier property and coating property.
Examples of the other fillers include inorganic fillers such as talc, silica, and alumina, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. Especially, it is preferable to contain a talc and / or silica, and it is more preferable to contain a talc and / or fumed silica.
上記他のフィラーとしてタルクを用いる場合、バリア性及び塗布性の観点から、該タルクの平均一次粒子径の好ましい下限は５μｍ、好ましい上限は５０μｍ、より好ましい上限は１２μｍである。
上記他のフィラーとしてシリカを用いる場合、塗布性の観点から、該シリカの平均一次粒子径の好ましい下限は７ｎｍ、好ましい上限は１０μｍ、より好ましい下限は１０ｎｍ、より好ましい上限は１μｍである。
When talc is used as the other filler, the preferred lower limit of the average primary particle diameter of the talc is 5 μm, the preferred upper limit is 50 μm, and the more preferred upper limit is 12 μm from the viewpoint of barrier properties and coatability.
When silica is used as the other filler, from the viewpoint of coatability, the preferred lower limit of the average primary particle diameter of the silica is 7 nm, the preferred upper limit is 10 μm, the more preferred lower limit is 10 nm, and the more preferred upper limit is 1 μm.
上記タルクのうち市販されているものとしては、例えば、ＭＩＣＲＯ ＡＣＥ Ｐ−４、ＭＩＣＲＯ ＡＣＥ Ｐ−６、ＭＩＣＲＯ ＡＣＥ Ｐ−８（いずれも日本タルク社製）等が挙げられる。
上記シリカのうち市販されているものとしては、例えば、アエロジル２００、アエロジル３００、アエロジル３８０（いずれも日本アエロジル社製）等が挙げられる。
Examples of commercially available talc include MICRO ACE P-4, MICRO ACE P-6, and MICRO ACE P-8 (all manufactured by Nippon Talc Co., Ltd.).
Examples of commercially available silica include Aerosil 200, Aerosil 300, Aerosil 380 (all manufactured by Nippon Aerosil Co., Ltd.) and the like.
上記他のフィラーの含有量は、得られる光硬化性樹脂組成物の粘度等に応じて適宜調整すればよい。
上記他のフィラーとしてタルクを用いる場合、上記タルクの含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が５重量部、好ましい上限が５０重量部である。上記タルクの含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が接着性及びバリア性を両立する効果により優れるものとなる。上記タルクの含有量のより好ましい下限は１０重量部、より好ましい上限は４０重量部である。
上記他のフィラーとしてシリカを用いる場合、上記シリカの含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が３０重量部である。上記シリカの含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が塗布性及びバリア性を両立する効果により優れるものとなる。上記シリカの含有量のより好ましい下限は１重量部、より好ましい上限は２０重量部である。
What is necessary is just to adjust content of said other filler suitably according to the viscosity etc. of the photocurable resin composition obtained.
When talc is used as the other filler, the content of the talc is preferably 5% by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Parts, and the preferred upper limit is 50 parts by weight. When the content of the talc is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both adhesiveness and barrier properties. The minimum with more preferable content of the said talc is 10 weight part, and a more preferable upper limit is 40 weight part.
When silica is used as the other filler, the preferred lower limit of the silica content is 0.00 with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. 1 part by weight, the preferred upper limit is 30 parts by weight. When the content of the silica is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both applicability and barrier properties. A more preferable lower limit of the silica content is 1 part by weight, and a more preferable upper limit is 20 parts by weight.
上記吸水性フィラーと上記他のフィラーとの合計の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、１００重量部以下であることが好ましい。上記吸水性フィラーと上記他のフィラーとの合計の含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が接着性及びバリア性を両立する効果により優れるものとなる。上記吸水性フィラーと上記他のフィラーとの合計の含有量のより好ましい上限は８０重量部である。 The total content of the water-absorbing filler and the other filler is 100 parts by weight or less with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Preferably there is. When the total content of the water-absorbing filler and the other filler is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both adhesiveness and barrier properties. A more preferable upper limit of the total content of the water-absorbing filler and the other filler is 80 parts by weight.
本発明の光硬化性樹脂組成物は、粘着付与剤を含有することが好ましい。
上記粘着付与剤としては、例えば、テルペン樹脂、変性テルペン樹脂、クマロン樹脂、インデン樹脂、石油樹脂等が挙げられる。
上記変性テルペン樹脂としては、例えば、水素添加テルペン樹脂、テルペンフェノール共重合樹脂、芳香族変性テルペン樹脂等が挙げられる。
上記石油樹脂としては、例えば、脂環族系石油樹脂、非環式脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂等が挙げられる。
なかでも、他の成分との相溶性や、得られる光硬化性樹脂組成物の接着性、バリア性等の観点から、上記粘着付与剤としては、石油樹脂が好ましく、脂環族系石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂がより好ましく、脂環族系石油樹脂が特に好ましい。
The photocurable resin composition of the present invention preferably contains a tackifier.
Examples of the tackifier include terpene resins, modified terpene resins, coumarone resins, indene resins, and petroleum resins.
Examples of the modified terpene resin include a hydrogenated terpene resin, a terpene phenol copolymer resin, and an aromatic modified terpene resin.
Examples of the petroleum resin include alicyclic petroleum resins, acyclic aliphatic petroleum resins, aromatic petroleum resins, and aliphatic aromatic copolymer petroleum resins.
Among these, from the viewpoints of compatibility with other components, adhesiveness of the resulting photocurable resin composition, barrier properties, etc., the tackifier is preferably a petroleum resin, an alicyclic petroleum resin, Aromatic petroleum resins and aliphatic aromatic copolymer petroleum resins are more preferred, and alicyclic petroleum resins are particularly preferred.
上記脂環族系石油樹脂のうち市販されているものとしては、例えば、Ｑｕｉｎｔｏｎｅ１３２５、Ｑｕｉｎｔｏｎｅ１３４５（いずれも日本ゼオン社製）、アルコンＰ−１００、アルコンＰ−１２５、アルコンＰ−１４０（いずれも荒川化学社製）、Ｅｓｃｏｒｅｚ５３００シリーズ、５６００シリーズ（いずれもエクソンモービル社製）等が挙げられる。
上記芳香族系石油樹脂のうち市販されているものとしては、例えば、ＥＮＤＥＸ１５５（イーストマン社製）等が挙げられる。
上記脂肪族芳香族共重合系石油樹脂のうち市販されているものとしては、例えば、ＱｕｉｎｔｏｎｅＤ１００（日本ゼオン社製）等が挙げられる。
Examples of commercially available alicyclic petroleum resins include, for example, Quintone 1325, Quintone 1345 (all manufactured by Nippon Zeon), Alcon P-100, Alcon P-125, Alcon P-140 (all Arakawa Chemical). Co., Ltd.), Escorez 5300 series, 5600 series (both manufactured by ExxonMobil).
As what is marketed among the said aromatic petroleum resin, ENDEX155 (made by Eastman) etc. are mentioned, for example.
As what is marketed among the said aliphatic aromatic copolymerization petroleum resin, QuintoneD100 (made by Nippon Zeon) etc. are mentioned, for example.
上記粘着付与剤の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が１重量部、好ましい上限が１５重量部である。上記粘着付与剤の含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が優れた硬化性及びバリア性を維持しつつ、接着性により優れるものとなる。上記粘着付与剤の含有量のより好ましい下限は５重量部、より好ましい上限は１０重量部である。 The content of the tackifier is preferably 1 part by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and preferably 15 parts by weight with respect to the upper limit. It is. When the content of the tackifier is within this range, the resulting photocurable resin composition is more excellent in adhesiveness while maintaining excellent curability and barrier properties. The minimum with more preferable content of the said tackifier is 5 weight part, and a more preferable upper limit is 10 weight part.
本発明の光硬化性樹脂組成物は、増感剤を含有してもよい。上記増感剤は、上記光ラジカル重合開始剤の重合開始効率をより向上させて、本発明の光硬化性樹脂組成物の硬化反応をより促進させる役割を有する。 The photocurable resin composition of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the photoradical polymerization initiator and further promoting the curing reaction of the photocurable resin composition of the present invention.
上記増感剤としては、例えば、９，１０−ジブトキシアントラセン等のアントラセン系化合物や、２，４−ジエチルチオキサントン等のチオキサントン系化合物や、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、ベンゾフェノン、２，４−ジクロロベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４，４’−ビス（ジメチルアミノ）ベンゾフェノン、４−ベンゾイル−４’メチルジフェニルサルファイド等が挙げられる。 Examples of the sensitizer include anthracene compounds such as 9,10-dibutoxyanthracene, thioxanthone compounds such as 2,4-diethylthioxanthone, and 2,2-dimethoxy-1,2-diphenylethane-1. -One, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4-benzoyl-4'methyldiphenyl sulfide and the like.
上記増感剤の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限は０．０５重量部、好ましい上限は３重量部である。上記増感剤の含有量が０．０５重量部以上であることにより、増感効果がより発揮される。上記増感剤の含有量が３重量部以下であることにより、吸収が大きくなり過ぎずに深部まで光を伝えることができる。上記増感剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は１重量部である。 The content of the sensitizer is preferably 0.05 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and the preferable upper limit is 3 parts. Parts by weight. When the content of the sensitizer is 0.05 parts by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption. The minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
本発明の光硬化性樹脂組成物は、シランカップリング剤を含有してもよい。上記シランカップリング剤は、本発明の光硬化性樹脂組成物と基板等との接着性を向上させる役割を有する。 The photocurable resin composition of the present invention may contain a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of the photocurable resin composition of this invention, a board | substrate, etc.
上記シランカップリング剤としては、本発明にかかるポリオレフィン系ポリマーと相溶可能な公知のシランカップリング剤を用いることができ、例えば、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−エチル−（（トリエトキシシリルプロポキシ）メチル）オキセタン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン等が挙げられる。 As said silane coupling agent, the well-known silane coupling agent compatible with the polyolefin-type polymer concerning this invention can be used, for example, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ethyl-((triethoxysilylpropoxy) methyl) oxetane, vinyltrimethoxysilane, vinyl Examples include triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
上記シランカップリング剤の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が５重量部である。上記シランカップリング剤の含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が優れたバリア性を維持しつつ、の接着性により優れるものとなる。上記シランカップリング剤の含有量のより好ましい下限は０．３重量部、より好ましい上限は３重量部である。 The content of the silane coupling agent is preferably 0.1 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and preferably has an upper limit. 5 parts by weight. When the content of the silane coupling agent is within this range, the resulting photocurable resin composition is more excellent in adhesiveness while maintaining excellent barrier properties. The minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 3 weight part.
本発明の光硬化性樹脂組成物は、溶剤を含有しないことが好ましい。
本発明の光硬化性樹脂組成物は、該溶剤を含有しなくても塗布性に優れるため、有機ＥＬ表示素子等の製造に用いた場合でも、乾燥工程を必要とせず、アウトガスの発生等による素子や装置へのダメージを抑制することができる。
The photocurable resin composition of the present invention preferably contains no solvent.
Since the photocurable resin composition of the present invention is excellent in coatability even without containing the solvent, it does not require a drying step even when used in the production of an organic EL display element, etc. Damage to elements and devices can be suppressed.
また、本発明の光硬化性樹脂組成物は、本発明の目的を阻害しない範囲で、必要に応じて、紫外線吸収剤、光安定剤、酸化防止剤、着色剤等の公知の各種添加剤を含有してもよい。 In addition, the photocurable resin composition of the present invention contains various known additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, and a colorant as necessary, as long as the object of the present invention is not impaired. You may contain.
本発明の光硬化性樹脂組成物を製造する方法としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、本発明にかかるポリイソブチレン系ポリマーと、本発明にかかる（メタ）アクリルモノマーと、光ラジカル重合開始剤と、吸水性フィラーと、粘着付与剤や必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。 Examples of the method for producing the photocurable resin composition of the present invention include a polyisobutylene according to the present invention using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. Of mixing a polymer, a (meth) acrylic monomer according to the present invention, a radical photopolymerization initiator, a water-absorbing filler, and an additive such as a tackifier or a silane coupling agent added as necessary Etc.
本発明の光硬化性樹脂組成物は、Ｅ型粘度計を用いて２５℃、２．５ｒｐｍの条件で測定される粘度の下限が１Ｐａ・ｓ、上限が１０００Ｐａ・ｓである。上記粘度がこの範囲であることにより、本発明の光硬化性樹脂組成物が塗布性及び形状保持性に優れるものとなる。上記粘度の好ましい下限は１０Ｐａ・ｓ、好ましい上限は８００Ｐａ・ｓ、より好ましい下限は５０Ｐａ・ｓ、より好ましい上限は５００Ｐａ・ｓである。 The lower limit of the viscosity of the photocurable resin composition of the present invention measured using an E-type viscometer at 25 ° C. and 2.5 rpm is 1 Pa · s, and the upper limit is 1000 Pa · s. When the viscosity is within this range, the photocurable resin composition of the present invention is excellent in applicability and shape retention. The preferable lower limit of the viscosity is 10 Pa · s, the preferable upper limit is 800 Pa · s, the more preferable lower limit is 50 Pa · s, and the more preferable upper limit is 500 Pa · s.
本発明の光硬化性樹脂組成物は、有機ＥＬ表示素子用封止剤として好適に用いることができる。本発明の光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤もまた、本発明の１つである。 The photocurable resin composition of this invention can be used suitably as a sealing agent for organic EL display elements. The sealing agent for organic EL display elements which consists of the photocurable resin composition of this invention is also one of this invention.
本発明の有機ＥＬ表示素子用封止剤により形成される封止部の形状としては、有機発光材料層を有する積層体を外気から保護しうる形状であれば特に限定されず、該積層体を完全に被覆する形状であってもよいし、該積層体の周囲に封止壁を形成してもよい。なかでも、本発明の有機ＥＬ表示素子用封止剤は、該封止壁を形成するため有機ＥＬ表示素子用周辺封止剤として好適に用いることができる。 The shape of the sealing portion formed by the organic EL display element sealant of the present invention is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air, and the laminate is not limited. The shape may be completely covered, or a sealing wall may be formed around the laminate. Especially, since the sealing agent for organic EL display elements of this invention forms this sealing wall, it can be used suitably as a periphery sealing agent for organic EL display elements.
本発明の有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子もまた、本発明の１つである。 The organic EL display element using the sealing agent for organic EL display elements of the present invention is also one aspect of the present invention.
本発明によれば、保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物を提供することができる。また、本発明によれば、該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤、及び、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition excellent in storage stability, applicability | paintability, adhesiveness, and barrier property can be provided. Moreover, according to this invention, the organic EL display element which uses the sealing agent for organic EL display elements which consists of this photocurable resin composition, and this sealing agent for organic EL display elements is provided. it can.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１〜１３、比較例１〜１１）
表１、２に記載された配合比に従い、各材料を、各材料を撹拌混合機（シンキー社製、「ＡＲ−２５０」）を用い、撹拌速度２０００ｒｐｍで撹拌混合した後、更に３本ロール（ノリタケ社製、「ＮＲ−４２Ａ」）を用いて混練することにより、実施例１〜１３、比較例１〜１１の光硬化性樹脂組成物を作製した。
得られた各光硬化性樹脂組成物について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ ＴＶ−２２」）を用いて、２５℃、２．５ｒｐｍの条件において測定した粘度を表１、２に示した。
(Examples 1-13, Comparative Examples 1-11)
According to the blending ratios described in Tables 1 and 2, each material was stirred and mixed at a stirring speed of 2000 rpm using a stirring mixer (“AR-250” manufactured by Sinky Corporation), and then three rolls ( The photocurable resin compositions of Examples 1 to 13 and Comparative Examples 1 to 11 were prepared by kneading using “NR-42A” manufactured by Noritake Co., Ltd.
About each obtained photocurable resin composition, the viscosity measured on condition of 25 degreeC and 2.5 rpm using E-type viscosity meter (the Toki Sangyo company make, "VISCOMETER TV-22") is Table 1, It was shown in 2.
＜評価＞
実施例及び比較例で得られた各光硬化性樹脂組成物について、以下の評価を行った。結果を表１、２に示した。
<Evaluation>
The following evaluation was performed about each photocurable resin composition obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
（保存安定性（相分離））
実施例及び比較例で得られた各光硬化性樹脂組成物を、ドクターブレードを用いてガラス板上に１００μｍの厚さに塗布した。２５℃で１０分間放置した後、光学顕微鏡（倍率２０倍）で塗膜を観察し、相分離が見られなかった場合を「○」、相分離が見られた場合を「△」、光学顕微鏡を使用せずに目視で相分離が観察された場合を「×」として保存安定性を評価した。
(Storage stability (phase separation))
Each photocurable resin composition obtained in Examples and Comparative Examples was applied to a thickness of 100 μm on a glass plate using a doctor blade. After standing at 25 ° C. for 10 minutes, the coating film was observed with an optical microscope (magnification 20 times), “◯” when phase separation was not observed, “Δ” when phase separation was observed, optical microscope The storage stability was evaluated as “x” when the phase separation was observed visually without using.
（接着性）
実施例及び比較例で得られた各光硬化性樹脂組成物１０ｇに対して、直径１０μｍのスペーサー粒子（積水化学工業社製、「ミクロパールＳＰ−２１０」）０．０３ｇ加え、撹拌混合機（シンキー社製、「ＡＲ−２５０」）を用いて均一に分散させた。ガラス基板Ａ（長さ５０ｍｍ、幅２５ｍｍ、厚さ０．７ｍｍのガラス表面をアセトンで洗浄後乾燥したもの）上に該スペーサー粒子を分散させた光硬化性樹脂組成物を塗布した後、ガラス基板Ｂ（長さ５ｍｍ、幅５ｍｍ、厚さ０．７ｍｍのガラスをアセトンに浸漬洗浄し、乾燥したもの）を貼り付け、加圧して厚みを均一にした後、ＵＶ−ＬＥＤ照射装置にて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して光硬化性樹脂組成物を硬化させることにより、ガラス基板Ａとガラス基板Ｂとを接着した。ガラス基板Ａとガラス基板Ｂとの剪断接着力をダイシェアテスター（デイジ社製、「ボンドテスター４０００」）にて２３℃、２００μｍ／秒の剪断速度条件で測定した。
剪断接着力が２００Ｎ以上であった場合を「○」、２００Ｎ未満１００Ｎ以上であった場合を「△」、１００Ｎ未満であった場合を「×」として接着性を評価した。
(Adhesiveness)
To 10 g of each photocurable resin composition obtained in the Examples and Comparative Examples, 0.03 g of spacer particles having a diameter of 10 μm (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SP-210”) was added, and a stirring mixer ( It was uniformly dispersed using “AR-250” manufactured by Shinky Corporation. After applying the photocurable resin composition in which the spacer particles are dispersed on a glass substrate A (a glass surface having a length of 50 mm, a width of 25 mm, and a thickness of 0.7 mm washed with acetone and dried), the glass substrate B (A glass with a length of 5 mm, a width of 5 mm, and a thickness of 0.7 mm is dipped in acetone, dried, and dried) is applied and pressed to make the thickness uniform, and then the wavelength is 365 nm with a UV-LED irradiation device. The glass substrate A and the glass substrate B were adhered by irradiating the ultraviolet ray of 3000 mJ / cm 2 to cure the photocurable resin composition. The shear adhesive strength between the glass substrate A and the glass substrate B was measured with a die shear tester (manufactured by Daisy Corporation, “Bond Tester 4000”) at a shear rate of 23 ° C. and 200 μm / second.
The adhesiveness was evaluated as “◯” when the shear adhesive force was 200 N or more, “Δ” when the shear adhesive force was less than 200 N and 100 N or more, and “X” when it was less than 100 N.
（バリア性）
実施例及び比較例で得られた各光硬化性樹脂組成物について、以下のＣａ−ＴＥＳＴを行った。
まず、３０ｍｍ×３０ｍｍのガラス基板に２ｍｍ×２ｍｍの開口部を複数有するマスクを被せ、Ｃａを真空蒸着機により蒸着させた。蒸着の条件は、真空蒸着装置の蒸着器内を２×１０−３Ｐａまで減圧してＣａを５．０Å／ｓの蒸着速度で２０００Å成膜するものとした。Ｃａを蒸着したガラス基板を露点（−６０℃以上）に管理されたグローボックス内に移動させ、表面に実施例及び比較例で得られた各光硬化性樹脂組成物を塗布したガラス基板を貼り合わせた。この時、ガラス基板端面から２ｍｍ、４ｍｍ、６ｍｍの位置に蒸着したＣａが存在するように貼り合わせた。次いで、３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射することにより光硬化性樹脂組成物を硬化させ、Ｃａ−ＴＥＳＴ基板を作製した。
得られたＣａ−ＴＥＳＴ基板を、８５℃、８５％ＲＨの高温高湿条件に暴露し、時間毎の水分の浸入距離をＣａの消失から観測した結果、水分の浸入距離が６ｍｍに達するまでの時間が１０００時間以上であった場合を「○」、５００時間以上１０００時間未満であった場合を「△」、５００時間未満であった場合を「×」としてバリア性を評価した。
なお、比較例１１で得られた光硬化性樹脂組成物は、Ｃａ−ＴＥＳＴ中にガラス基板が剥離したため、バリア性を評価することができなかった。
(Barrier properties)
The following Ca-TEST was performed about each photocurable resin composition obtained by the Example and the comparative example.
First, a mask having a plurality of openings of 2 mm × 2 mm was put on a 30 mm × 30 mm glass substrate, and Ca was vapor-deposited by a vacuum vapor deposition machine. The conditions for the vapor deposition were that the inside of the vapor deposition unit of the vacuum vapor deposition apparatus was depressurized to 2 × 10 −3 Pa and a film of 2000 μm of Ca was formed at a vapor deposition rate of 5.0 kg / s. The glass substrate on which Ca was vapor-deposited was moved into a glow box controlled to a dew point (−60 ° C. or higher), and a glass substrate coated with each photocurable resin composition obtained in Examples and Comparative Examples was attached to the surface. Combined. At this time, bonding was performed so that the deposited Ca exists at positions of 2 mm, 4 mm, and 6 mm from the end face of the glass substrate. Next, the photocurable resin composition was cured by irradiating ultraviolet light of 365 nm at 3000 mJ / cm 2 to prepare a Ca-TEST substrate.
The obtained Ca-TEST substrate was exposed to high temperature and high humidity conditions of 85 ° C. and 85% RH, and the moisture penetration distance per hour was observed from the disappearance of Ca. As a result, the moisture penetration distance reached 6 mm. The barrier property was evaluated as “◯” when the time was 1000 hours or more, “Δ” when the time was 500 hours or more and less than 1000 hours, and “X” when the time was less than 500 hours.
In addition, since the glass substrate peeled during Ca-TEST, the photocurable resin composition obtained in Comparative Example 11 could not be evaluated for barrier properties.
本発明によれば、保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物を提供することができる。また、本発明によれば、該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤、及び、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition excellent in storage stability, applicability | paintability, adhesiveness, and barrier property can be provided. Moreover, according to this invention, the organic EL display element which uses the sealing agent for organic EL display elements which consists of this photocurable resin composition, and this sealing agent for organic EL display elements is provided. it can.
Claims (9)
主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと、脂環式骨格と（メタ）アクリロイル基とを有するモノマーと、光ラジカル重合開始剤と、吸水性フィラーとを含有し、溶剤を含有せず、
前記主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと前記脂環式骨格と（メタ）アクリロイル基とを有するモノマーとの合計１００重量部に対して、前記脂環式骨格と（メタ）アクリロイル基とを有するモノマーの含有量が３０重量部以上９０重量部以下であり、かつ、前記吸水性フィラーの含有量が５重量部以上６０重量部以下であり、
Ｅ型粘度計を用いて２５℃、２．５ｒｐｍの条件で測定される粘度が１Ｐａ・ｓ以上１０００Ｐａ・ｓ以下である光硬化性樹脂組成物を含有する
ことを特徴とする有機ＥＬ表示素子用封止剤。
A polymer having a repeating unit represented by the following formula (1) in the main chain and having a weight average molecular weight of from 5,000 to 100,000, a monomer having an alicyclic skeleton and a (meth) acryloyl group, a photo radical Contains a polymerization initiator and a water-absorbing filler, does not contain a solvent,
The total of the polymer which has a repeating unit represented by following formula (1) in the said principal chain, and whose weight average molecular weight is 5000 or more and 100,000 or less, the said alicyclic skeleton, and a (meth) acryloyl group The content of the monomer having the alicyclic skeleton and the (meth) acryloyl group is from 30 parts by weight to 90 parts by weight with respect to 100 parts by weight, and the water-absorbing filler content is 5 parts by weight. 60 parts by weight or less,
An organic material comprising a photocurable resin composition having a viscosity of 1 Pa · s or more and 1000 Pa · s or less measured at 25 ° C and 2.5 rpm using an E-type viscometer. Sealant for EL display element .
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| JP2017024982A JP6294522B1 (en) | 2017-02-14 | 2017-02-14 | Sealant for organic EL display element and organic EL display element |
| KR1020197035290A KR102355058B1 (en) | 2017-02-14 | 2018-02-08 | Photocurable resin composition, sealing agent for organic el display elements, organic el display element, sealing agent for quantum dot devices, and quantum dot device |
| CN202210169452.7A CN114539479A (en) | 2017-02-14 | 2018-02-08 | Sealing agent for organic EL display element and organic EL display element |
| JP2018510529A JPWO2018151002A1 (en) | 2017-02-14 | 2018-02-08 | Photocurable resin composition, sealant for organic EL display element, organic EL display element, sealant for quantum dot device, and quantum dot device |
| CN201880004317.9A CN109937214B (en) | 2017-02-14 | 2018-02-08 | Photocurable resin composition, sealing agent for organic EL display element, sealing agent for quantum dot device, and quantum dot device |
| PCT/JP2018/004353 WO2018151002A1 (en) | 2017-02-14 | 2018-02-08 | Photocurable resin composition, sealing agent for organic el display elements, organic el display element, sealing agent for quantum dot devices, and quantum dot device |
| KR1020197003092A KR20190018731A (en) | 2017-02-14 | 2018-02-08 | A photocurable resin composition, a sealing agent for an organic EL display element, an organic EL display element, a sealing agent for a quantum dot device, and a quantum dot device |
| KR1020227000585A KR102549655B1 (en) | 2017-02-14 | 2018-02-08 | Photocurable resin composition, sealing agent for organic el display elements, organic el display element, sealing agent for quantum dot devices, and quantum dot device |
| TW107104896A TWI750317B (en) | 2017-02-14 | 2018-02-12 | Photocurable resin composition, sealant for organic EL display element, organic EL display element, sealant for quantum dot device, and quantum dot device |
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| JPWO2018151002A1 (en) * | 2017-02-14 | 2020-03-26 | 積水化学工業株式会社 | Photocurable resin composition, sealant for organic EL display element, organic EL display element, sealant for quantum dot device, and quantum dot device |
| JP2021015902A (en) * | 2019-07-12 | 2021-02-12 | 積水化学工業株式会社 | Perovskite Solar Cell Encapsulant and Perovskite Solar Cell |
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| JP6590269B1 (en) * | 2018-09-27 | 2019-10-16 | パナソニックＩｐマネジメント株式会社 | UV curable resin composition for sealing organic EL element, method for producing organic EL light emitting device, organic EL light emitting device, and touch panel |
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| JPWO2020149358A1 (en) * | 2019-01-18 | 2021-12-02 | 積水化学工業株式会社 | Organic EL display element Encapsulating resin composition, cured product, and organic EL display element |
| KR20210116427A (en) * | 2019-01-18 | 2021-09-27 | 세키스이가가쿠 고교가부시키가이샤 | Resin composition for sealing organic electroluminescent display element, hardened|cured material, and organic electroluminescent display element |
| WO2020149360A1 (en) * | 2019-01-18 | 2020-07-23 | 積水化学工業株式会社 | Cured product and organic el display element |
| JPWO2020149362A1 (en) * | 2019-01-18 | 2021-11-25 | 積水化学工業株式会社 | Cured product and organic EL display element |
| WO2021002375A1 (en) * | 2019-07-04 | 2021-01-07 | 積水化学工業株式会社 | Sealant for organic el display element |
| KR20230022968A (en) * | 2020-09-18 | 2023-02-16 | 미쓰이 가가쿠 가부시키가이샤 | Encapsulant for display element and cured product thereof |
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