TW201938677A - Encapsulating material for display element and cured product thereof, frame encapsulating material for organic el element, and surface encapsulating material for organic el element - Google Patents
Encapsulating material for display element and cured product thereof, frame encapsulating material for organic el element, and surface encapsulating material for organic el element Download PDFInfo
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- TW201938677A TW201938677A TW108108752A TW108108752A TW201938677A TW 201938677 A TW201938677 A TW 201938677A TW 108108752 A TW108108752 A TW 108108752A TW 108108752 A TW108108752 A TW 108108752A TW 201938677 A TW201938677 A TW 201938677A
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- Prior art keywords
- sealing material
- display element
- meth
- acrylic monomer
- group
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- 239000000463 material Substances 0.000 title abstract description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000000178 monomer Substances 0.000 claims abstract description 113
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 63
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 53
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 230000009477 glass transition Effects 0.000 claims abstract description 11
- 239000003566 sealing material Substances 0.000 claims description 193
- -1 2-chloroacetamido, 2-iodoacetamido Chemical group 0.000 claims description 36
- 238000007789 sealing Methods 0.000 claims description 33
- 238000005401 electroluminescence Methods 0.000 claims description 23
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 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 claims description 11
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002540 isothiocyanates Chemical class 0.000 claims description 2
- 125000005641 methacryl group Chemical group 0.000 claims 1
- 125000001312 palmitoyl group Chemical group O=C([*])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 claims 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical class CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005538 encapsulation Methods 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 44
- 239000000758 substrate Substances 0.000 description 40
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- 239000011521 glass Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 125000006850 spacer group Chemical group 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 5
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical group C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000005340 laminated glass Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 2
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- PZDBZAHFEBLPPW-UHFFFAOYSA-N bis(1-ethoxy-1-phenylethyl)diazene Chemical compound N(=NC(C)(OCC)C1=CC=CC=C1)C(C)(C1=CC=CC=C1)OCC PZDBZAHFEBLPPW-UHFFFAOYSA-N 0.000 description 2
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 2
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- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
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- 238000002076 thermal analysis method Methods 0.000 description 2
- XYWDBAKATHNVAA-YZXKGSGOSA-N (2r,3s,6r,8r,10s)-2-[(2s)-butan-2-yl]-8-(2-hydroxyethyl)-3-methyl-1,7-dioxaspiro[5.5]undecan-10-ol Chemical compound C1C[C@H](C)[C@@H]([C@@H](C)CC)O[C@@]21O[C@H](CCO)C[C@H](O)C2 XYWDBAKATHNVAA-YZXKGSGOSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- ZKCNNDSWJDPZDQ-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-octoxy-4-[1-(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl)decyl]piperidine Chemical compound C(CCCCCCC)ON1C(CC(CC1(C)C)C(CCCCCCCCC)C1CC(N(C(C1)(C)C)OCCCCCCCC)(C)C)(C)C ZKCNNDSWJDPZDQ-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- DHNHVRTWXFSWDS-UHFFFAOYSA-N 2,2-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)decanedioic acid Chemical compound C1C(C)(C)N(C)C(C)(C)CC1C(CCCCCCCC(O)=O)(C(O)=O)C1CC(C)(C)N(C)C(C)(C)C1 DHNHVRTWXFSWDS-UHFFFAOYSA-N 0.000 description 1
- ICGDKKACLISIAM-UHFFFAOYSA-N 2,3,5,6-tetramethylpiperazine Chemical compound CC1NC(C)C(C)NC1C ICGDKKACLISIAM-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- MJGLWGBXQWRFCX-UHFFFAOYSA-N 2-[(1-imino-2-methyl-1-pyrrolidin-1-ylpropan-2-yl)diazenyl]-2-methyl-1-pyrrolidin-1-ylpropan-1-imine;dihydrochloride Chemical compound Cl.Cl.C1CCCN1C(=N)C(C)(C)N=NC(C)(C)C(=N)N1CCCC1 MJGLWGBXQWRFCX-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- AEZBIUBWOJAYOA-UHFFFAOYSA-N 2-[2-[2-[2-[1-(2-hydroxyethyl)-4,5-dihydroimidazol-2-yl]propan-2-yldiazenyl]propan-2-yl]-4,5-dihydroimidazol-1-yl]ethanol Chemical compound N=1CCN(CCO)C=1C(C)(C)N=NC(C)(C)C1=NCCN1CCO AEZBIUBWOJAYOA-UHFFFAOYSA-N 0.000 description 1
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BSXGCUHREZFSRY-UHFFFAOYSA-N 3-[[1-amino-2-[[1-amino-1-(2-carboxyethylimino)-2-methylpropan-2-yl]diazenyl]-2-methylpropylidene]amino]propanoic acid;tetrahydrate Chemical compound O.O.O.O.OC(=O)CCNC(=N)C(C)(C)N=NC(C)(C)C(=N)NCCC(O)=O BSXGCUHREZFSRY-UHFFFAOYSA-N 0.000 description 1
- HPFWYRKGZUGGPB-UHFFFAOYSA-N 4,6-dichloro-n-(2,4,4-trimethylpentan-2-yl)-1,3,5-triazin-2-amine Chemical compound CC(C)(C)CC(C)(C)NC1=NC(Cl)=NC(Cl)=N1 HPFWYRKGZUGGPB-UHFFFAOYSA-N 0.000 description 1
- YZXTWMQYSSMUFH-UHFFFAOYSA-N 4-[6-(1-amino-2,2,6,6-tetramethylpiperidin-4-yl)hexyl]-2,2,6,6-tetramethylpiperidin-1-amine Chemical compound C1C(C)(C)N(N)C(C)(C)CC1CCCCCCC1CC(C)(C)N(N)C(C)(C)C1 YZXTWMQYSSMUFH-UHFFFAOYSA-N 0.000 description 1
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- 239000011324 bead Substances 0.000 description 1
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical compound NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- DVXRGUXKOSSOHV-UHFFFAOYSA-N bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl] decanedioate Chemical compound C1C(C)(C)N(OCC(C)(O)C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCC(C)(C)O)C(C)(C)C1 DVXRGUXKOSSOHV-UHFFFAOYSA-N 0.000 description 1
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- IBAHLNWTOIHLKE-UHFFFAOYSA-N cyano cyanate Chemical compound N#COC#N IBAHLNWTOIHLKE-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JMFYZMAVUHNCPW-UHFFFAOYSA-N dimethyl 2-[(4-methoxyphenyl)methylidene]propanedioate Chemical compound COC(=O)C(C(=O)OC)=CC1=CC=C(OC)C=C1 JMFYZMAVUHNCPW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- QPMJENKZJUFOON-PLNGDYQASA-N ethyl (z)-3-chloro-2-cyano-4,4,4-trifluorobut-2-enoate Chemical compound CCOC(=O)C(\C#N)=C(/Cl)C(F)(F)F QPMJENKZJUFOON-PLNGDYQASA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YIMHRDBSVCPJOV-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC YIMHRDBSVCPJOV-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- LKTCWOYIQVKYIV-UHFFFAOYSA-N n-butyl-4-chloro-n-(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,3,5-triazin-2-amine Chemical compound N=1C=NC(Cl)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 LKTCWOYIQVKYIV-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- 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
- 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
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Electroluminescent Light Sources (AREA)
- Sealing Material Composition (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本發明是有關於一種顯示元件用密封材及其硬化物、有機EL元件用框架密封材以及有機EL元件用面密封材。The present invention relates to a sealing material for a display element and a cured product thereof, a frame sealing material for an organic EL element, and a surface sealing material for an organic EL element.
有機電致發光（Electro-Luminescence，EL）元件因消耗電力少而正在用於顯示器或照明裝置等中。有機EL元件容易因大氣中的水分或氧而劣化，因此通常利用各種密封構件加以密封後使用。Organic electro-luminescence (EL) elements are being used in displays, lighting devices, etc. due to low power consumption. Organic EL elements are liable to be deteriorated by moisture or oxygen in the atmosphere. Therefore, they are usually used after being sealed with various sealing members.
有機EL裝置例如可形成為包含基板、配置於該基板上的有機EL元件、以及與基板成對的密封基板的結構體。作為將此種結構體的有機EL元件密封的方法，可列舉如下方法：於配置了有機EL元件的基板（以下，亦稱為「顯示元件側基板」）的外周以框架狀塗佈密封材，並利用該密封材將顯示元件側基板與密封基板貼合（框架密封法）。另外，亦可列舉如下方法：於密封基板與顯示元件側基板之間、及有機EL元件與密封基板之間塗佈密封材，並利用該密封材將顯示元件側基板與密封基板貼合（面密封法）。The organic EL device can be formed, for example, as a structure including a substrate, an organic EL element disposed on the substrate, and a sealed substrate paired with the substrate. As a method of sealing the organic EL element of such a structure, there may be mentioned a method in which a sealing material is applied to the outer periphery of a substrate on which an organic EL element is disposed (hereinafter, also referred to as a "display element side substrate") in a frame shape, Then, the display element-side substrate is bonded to the sealing substrate using the sealing material (frame sealing method). Alternatively, a method may be used in which a sealing material is applied between the sealing substrate and the display element-side substrate, and between the organic EL element and the sealing substrate, and the display element-side substrate and the sealing substrate are bonded together using the sealing material (surface). Sealing method).
作為用以將有機EL元件等各種顯示元件密封的密封材，提出了一種包含脂肪族(甲基)丙烯酸單體、偶氮系聚合起始劑、以及四甲基哌啶自由基衍生物的熱硬化性組成物（專利文獻1）。
[現有技術文獻]
[專利文獻]As a sealing material for sealing various display elements such as organic EL elements, a heat containing an aliphatic (meth) acrylic monomer, an azo-based polymerization initiator, and a tetramethylpiperidine radical derivative has been proposed. Curable composition (Patent Document 1).
[Prior Art Literature]
[Patent Literature]
[專利文獻1]日本專利特開2007-186521號公報[Patent Document 1] Japanese Patent Laid-Open No. 2007-186521
[發明所欲解決之課題]
近年來，為擴大顯示裝置的顯示面積而要求進一步減小配置於顯示面的周圍的框體的框架的寬度。因此，以前，由框體的框架覆蓋的區域亦作為顯示面而露出。而且，於利用以前的密封材對顯示元件進行面密封的情況下，如圖1所示，有時會於顯示區域的外周側（於圖1中表示的是隔堤材11及其附近的密封材的硬化物12）出現花紋般的條紋（以下，亦稱為「條紋不均」）。另外，於將以前的密封材用作框架密封材的情況下，有時亦會產生同樣的條紋不均。此種條紋不均若於顯示面中露出，則存在有損顯示裝置的外觀性的課題。[Problems to be Solved by the Invention]
In recent years, in order to enlarge the display area of a display device, it is required to further reduce the width of the frame of the frame body arranged around the display surface. Therefore, in the past, the area covered by the frame of the housing was also exposed as a display surface. Furthermore, when the display element is surface-sealed with a conventional sealing material, as shown in FIG. 1, the sealing may sometimes be performed on the outer peripheral side of the display area (shown in FIG. 1 is the sealing of the bank material 11 and its vicinity). The hardened material 12) has pattern-like streaks (hereinafter, also referred to as "stripe unevenness"). In addition, when a conventional sealing material is used as a frame sealing material, the same uneven striation may occur. If such unevenness of stripes is exposed on the display surface, there is a problem that the appearance of the display device is impaired.
本發明是鑑於上述情況而成。即，本發明的目的在於提供一種不僅可將顯示元件充分密封，而且於密封後不易產生條紋不均的顯示元件用密封材。
[解決課題之手段]The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a sealing material for a display element which can not only sufficiently seal the display element, but also less likely to cause unevenness in stripes after sealing.
[Means for solving problems]
即，本發明的第一方面是有關於以下的顯示元件用密封材。
[1]一種顯示元件用密封材，包含：（A）脂肪族(甲基)丙烯酸單體、（B）偶氮系聚合起始劑、（C）下述通式（1）所表示的2,2,6,6-四甲基哌啶1-氧基自由基衍生物、以及（D）具有(甲基)丙烯酸基且重量平均分子量為400～500,000的矽烷偶合劑，所述顯示元件用密封材以100℃進行30分鐘加熱而獲得的硬化物的玻璃轉移溫度為46℃以上。
[化1]
（1）
（通式（1）中，R表示選自由H、羥基、橋氧基、胺基、氰基、乙醯胺基、甲氧基、羧基、棕櫚醯胺基、甲基丙烯醯基、異硫代氰酸酯基、2-氯乙醯胺基、2-碘乙醯胺基、(9-吖啶羰基)胺基、及[2-[2-(4-碘苯氧基)乙氧基]羰基]苯甲醯基所組成的群組中的任一種基）That is, the first aspect of the present invention relates to the following sealing material for a display element.
[1] A sealing material for a display element, comprising: (A) an aliphatic (meth) acrylic monomer, (B) an azo-based polymerization initiator, and (C) 2 represented by the following general formula (1) , 2,6,6-tetramethylpiperidine 1-oxy radical derivative, and (D) a silane coupling agent having a (meth) acrylic group and having a weight average molecular weight of 400 to 500,000, for the display device The glass transition temperature of the hardened | cured material obtained by heating the sealing material at 100 degreeC for 30 minutes is 46 degreeC or more.
[Chemical 1]
(1)
(In the general formula (1), R represents a member selected from the group consisting of H, a hydroxyl group, a bridging oxy group, an amine group, a cyano group, an acetamido group, a methoxy group, a carboxyl group, a palmitoylamino group, a methacrylfluorenyl group, and isosulfur Cyanocyanate, 2-chloroacetamido, 2-iodoacetamido, (9-acridylcarbonyl) amino, and [2- [2- (4-iodophenoxy) ethoxy ] Carbonyl] Any group in the group consisting of benzamidine)
[2]如[1]所述的顯示元件用密封材，其中所述（D）矽烷偶合劑於分子內包含兩個以上的(甲基)丙烯酸基。
[3]如[1]或[2]所述的顯示元件用密封材，其中所述（D）矽烷偶合劑於分子內包含兩個以上的Si原子。
[4]如[1]至[3]中任一項所述的顯示元件用密封材，其中所述（D）矽烷偶合劑於主鏈中包含矽氧烷鍵。[2] The sealing material for a display element according to [1], wherein the (D) silane coupling agent contains two or more (meth) acrylic groups in a molecule.
[3] The sealing material for a display element according to [1] or [2], wherein the (D) silane coupling agent contains two or more Si atoms in a molecule.
[4] The sealing material for a display element according to any one of [1] to [3], wherein the (D) silane coupling agent includes a siloxane bond in a main chain.
[5]如[1]至[4]中任一項所述的顯示元件用密封材，其中以100℃進行30分鐘加熱而獲得的硬化物的35℃～100℃中的線膨脹係數為50以上、250以下。
[6]如[1]至[5]中任一項所述的顯示元件用密封材，其中所述（A）脂肪族(甲基)丙烯酸單體包含5質量%～50質量%的3官能以上的(甲基)丙烯酸單體。[5] The sealing material for a display element according to any one of [1] to [4], wherein a linear expansion coefficient at a temperature of 35 ° C. to 100 ° C. of a cured product obtained by heating at 100 ° C. for 30 minutes is 50 Above and below 250.
[6] The sealing material for a display element according to any one of [1] to [5], wherein the (A) aliphatic (meth) acrylic monomer contains 5 to 50% by mass of trifunctional The above (meth) acrylic monomer.
[7]如[1]至[6]中任一項所述的顯示元件用密封材，其中所述（A）脂肪族(甲基)丙烯酸單體的重量平均分子量為400以上、2000以下。
[8]如[1]至[7]中任一項所述的顯示元件用密封材，其中所述（A）脂肪族(甲基)丙烯酸單體為甲基丙烯酸單體。
[9]如[1]至[8]中任一項所述的顯示元件用密封材，其更包含（A-2）含環結構的(甲基)丙烯酸單體。[7] The sealing material for a display element according to any one of [1] to [6], wherein the weight average molecular weight of the (A) aliphatic (meth) acrylic monomer is 400 or more and 2000 or less.
[8] The sealing material for a display element according to any one of [1] to [7], wherein the (A) aliphatic (meth) acrylic monomer is a methacrylic monomer.
[9] The sealing material for a display element according to any one of [1] to [8], further comprising (A-2) a ring structure-containing (meth) acrylic monomer.
[10]如[9]所述的顯示元件用密封材，其中所述（A-2）含環結構的(甲基)丙烯酸單體包含雙酚A型的結構。
[11]如[1]至[10]中任一項所述的顯示元件用密封材，其更包含調平劑。[10] The sealing material for a display element according to [9], wherein the (A-2) ring-containing (meth) acrylic monomer includes a bisphenol A structure.
[11] The sealing material for a display element according to any one of [1] to [10], further comprising a leveling agent.
本發明的第二方面是有關於以下的有機EL元件用框架密封材、有機EL元件用面密封材、及顯示元件用密封材的硬化物。
[12]一種有機EL元件用框架密封材，包含如所述[1]至[11]中任一項所述的顯示元件用密封材，且用於有機EL元件的框架密封。
[13]一種有機EL元件用面密封材，包含如所述[1]至[11]中任一項所述的顯示元件用密封材，且用於有機EL元件的面密封。
[14]一種顯示元件用密封材的硬化物，所述顯示元件用密封材為如所述[1]至[11]中任一項所述的顯示元件用密封材。
[發明的效果]A second aspect of the present invention relates to a cured product of the following frame sealing material for an organic EL element, a surface sealing material for an organic EL element, and a sealing material for a display element.
[12] A frame sealing material for an organic EL element, comprising the sealing material for a display element according to any one of the above [1] to [11], and used for frame sealing of an organic EL element.
[13] A surface sealing material for an organic EL element, comprising the sealing material for a display element according to any one of the above [1] to [11], and used for the surface sealing of the organic EL element.
[14] A cured product of a sealing material for a display element, the sealing material for a display element being the sealing material for a display element according to any one of [1] to [11].
[Effect of the invention]
根據本發明，可形成一種不僅可將顯示元件充分密封，而且於密封後不易產生條紋不均的顯示元件用密封材。According to the present invention, it is possible to form a sealing material for a display element which can not only sufficiently seal the display element but also is less likely to cause unevenness in stripes after sealing.
本發明的顯示元件用密封材可用作用以對各種顯示元件進行面密封的面密封材或者用以進行框架密封的框架密封材。於對顯示元件進行面密封的情況下，通常沿密封基板或者顯示元件側基板的外周配置隔堤材。然後，於由該隔堤材包圍的區域內塗佈密封材。其後，於使密封基板及顯示元件側基板相向的狀態下，使密封材硬化而將密封基板及顯示元件側基板（以下，亦將該些總稱為「基板」）貼合。然而，若將以前的密封材用於貼合，則容易產生容易於顯示裝置的外周側出現條紋不均的課題。認為其理由如下所述。The sealing material for a display element of the present invention can be used as a surface sealing material for surface sealing various display elements or a frame sealing material for frame sealing. When surface-sealing a display element, a bank material is usually arrange | positioned along the outer periphery of a sealing substrate or a display element side substrate. Then, a sealing material is applied to an area surrounded by the bank material. Thereafter, in a state where the sealing substrate and the display element-side substrate face each other, the sealing material is hardened, and the sealing substrate and the display element-side substrate (hereinafter, also collectively referred to as "substrates") are bonded together. However, if a conventional sealing material is used for bonding, the problem that the unevenness of the stripes on the outer peripheral side of the display device easily occurs. The reason is considered as follows.
基板的貼合通常於真空中（例如1 Pa以下的環境下）進行。此時，密封材中的低分子量成分容易揮發，於以前的密封材中主要是矽烷偶合劑揮發。而且，若矽烷偶合劑揮發，則基板與密封材（或者其硬化物）的接著強度無法充分提高。另一方面，面密封材於硬化時會收縮。因此，若使面密封材硬化，則於基板與面密封材之間容易產生縫隙，該縫隙可被觀察為條紋不均。再者，於基板的外周側如上所述般配置有隔堤材。因此，當面密封材硬化收縮時，於該區域中，基板難以追隨面密封材。因此，認為條紋不均會集中於基板的外周側。此處，認為當使用顯示元件用密封材進行框架密封時亦會產生同樣的課題。The substrates are usually bonded in a vacuum (for example, an environment of 1 Pa or less). At this time, the low-molecular-weight component in the sealing material is volatile easily, and in the conventional sealing material, the silane coupling agent is mainly volatile. In addition, if the silane coupling agent is volatilized, the bonding strength between the substrate and the sealing material (or a cured product thereof) cannot be sufficiently improved. On the other hand, the face seal material shrinks when hardened. Therefore, when the surface sealing material is hardened, a gap is easily generated between the substrate and the surface sealing material, and the gap can be observed as uneven stripes. Moreover, a bank material is arrange | positioned on the outer peripheral side of a board | substrate as mentioned above. Therefore, when the surface sealing material is hardened and contracted, it is difficult for the substrate to follow the surface sealing material in this region. Therefore, it is considered that the unevenness of the stripes is concentrated on the outer peripheral side of the substrate. Here, it is considered that the same problem occurs when the frame is sealed using the sealing material for a display element.
相對於此，本發明的顯示元件用密封材包含（D）具有(甲基)丙烯酸基且重量平均分子量為400～500,000的矽烷偶合劑。該矽烷偶合劑的分子量比較大，因此於真空中亦不易揮發。另外，該矽烷偶合劑更具有(甲基)丙烯酸基，因此與顯示元件用密封材中的其他成分（尤其是（A）脂肪族(甲基)丙烯酸單體）的親和性高。因此，當塗佈顯示元件用密封材時，該矽烷偶合劑不易浮出至表面，且不易揮發。In contrast, the sealing material for a display element of the present invention contains (D) a silane coupling agent having a (meth) acrylic group and a weight average molecular weight of 400 to 500,000. The molecular weight of the silane coupling agent is relatively large, so it is not easily volatile in a vacuum. Moreover, since this silane coupling agent has a (meth) acrylic group more, it has high affinity with other components (especially (A) aliphatic (meth) acrylic monomer) in the sealing material for display elements. Therefore, when the sealing material for a display element is applied, the silane coupling agent does not easily float to the surface and is not easily volatile.
另外，當使顯示元件用密封材硬化時，該（D）矽烷偶合劑的(甲基)丙烯酸基與（A）脂肪族(甲基)丙烯酸單體等進行化學鍵結。另一方面，（D）矽烷偶合劑中的Si原子與玻璃基板等進行矽氧烷鍵結。因此，藉由該（D）矽烷偶合劑，密封材與玻璃基板的接著性變得非常高，於該些之間不易產生縫隙。另外，（D）矽烷偶合劑的分子量大，且具有體積比較大的骨架。因此，亦可獲得顯示元件用密封材的硬化時的收縮得到抑制的效果。When the sealing material for a display element is hardened, the (meth) acrylic group of the (D) silane coupling agent is chemically bonded to the (A) aliphatic (meth) acrylic monomer or the like. On the other hand, the Si atom in the (D) silane coupling agent is siloxane-bonded to a glass substrate or the like. Therefore, with this (D) silane coupling agent, the adhesiveness of a sealing material and a glass substrate becomes very high, and a gap is hard to generate between these. In addition, the (D) silane coupling agent has a large molecular weight and a relatively large volume skeleton. Therefore, the effect which suppresses shrinkage at the time of hardening of the sealing material for display elements can also be acquired.
另外，本發明的顯示元件用密封材的硬化物的玻璃轉移溫度（Tg）為46℃以上。因此，顯示元件用密封材的硬化物於硬化後不易發生變形或收縮，藉由該方面，亦不易產生所述條紋不均。顯示元件用密封材的硬化物的玻璃轉移溫度是針對以條件100℃進行30分鐘加熱而獲得的硬化物，利用熱機械分析裝置（TMA（thermomechanical analysis）裝置）等，以升溫速度5℃/分進行熱分析而確定的值。Moreover, the glass transition temperature (Tg) of the hardened | cured material of the sealing material for display elements of this invention is 46 degreeC or more. Therefore, the hardened | cured material of the sealing material for display elements is hard to deform | transform or shrink | contract after hardening, and in this respect, it is also hard to produce the said unevenness | corrugation. The glass transition temperature of the hardened material of the display element sealing material is a hardened material obtained by heating at a condition of 100 ° C. for 30 minutes. The temperature is increased by 5 ° C./min using a thermomechanical analysis device (TMA (thermomechanical analysis) device). A value determined by thermal analysis.
另外，本發明的顯示元件用密封材主要包含（A）脂肪族(甲基)丙烯酸單體，因此其黏度適度地低，可穩定地進行塗佈。另外，聚合起始劑為（B）偶氮系聚合起始劑，因此可使（A）脂肪族(甲基)丙烯酸單體於短時間內硬化，且於顯示元件用密封材的硬化過程中或硬化後，不易產生對顯示元件帶來影響的氣體。進而，包含（A）脂肪族(甲基)丙烯酸單體的熱硬化型的顯示元件用密封材多數情況下通常穩定性低，但本發明的顯示元件用密封材包含（C）四甲基哌啶自由基衍生物。因此，於保存過程中、或者於塗佈裝置等的內部，（A）脂肪族(甲基)丙烯酸單體與（B）偶氮系聚合起始劑不易發生反應，穩定性亦優異。以下，對顯示元件用密封材所包含的各成分進行說明。In addition, since the sealing material for a display element of the present invention mainly contains (A) an aliphatic (meth) acrylic monomer, its viscosity is moderately low, and coating can be performed stably. In addition, since the polymerization initiator is (B) an azo-based polymerization initiator, (A) an aliphatic (meth) acrylic monomer can be cured in a short time, and during the curing process of a sealing material for a display element After hardening, it is difficult to generate a gas that affects the display element. Furthermore, the sealing material for a thermosetting display element containing (A) an aliphatic (meth) acrylic monomer usually has low stability in many cases, but the sealing material for a display element of the present invention contains (C) tetramethylpiperazine. Pyridine radical derivatives. Therefore, (A) an aliphatic (meth) acrylic monomer and (B) an azo-type polymerization initiator do not react easily during storage, or inside a coating device, etc., and are also excellent in stability. Hereinafter, each component contained in the sealing material for display elements is demonstrated.
（A）脂肪族(甲基)丙烯酸單體
（A）脂肪族(甲基)丙烯酸單體只要是於分子內具有(甲基)丙烯酸基與脂肪族鏈且藉由加熱而進行聚合的單體，則並無特別限制。（A）脂肪族(甲基)丙烯酸單體亦可為具有直鏈狀及分支鏈狀的任一種結構的(甲基)丙烯酸單體。此處，本說明書中的所謂(甲基)丙烯酸表示丙烯酸及/或甲基丙烯酸。顯示元件用密封材可包含僅一種（A）脂肪族(甲基)丙烯酸單體，亦可包含兩種以上。(A) An aliphatic (meth) acrylic monomer (A) An aliphatic (meth) acrylic monomer is a monomer which has a (meth) acrylic group and an aliphatic chain in a molecule | numerator, and is polymerized by heating. , There are no special restrictions. (A) The aliphatic (meth) acrylic monomer may be a (meth) acrylic monomer having any of a linear structure and a branched structure. Here, (meth) acrylic acid in this specification means acrylic acid and / or methacrylic acid. The sealing material for a display element may include only one (A) aliphatic (meth) acrylic monomer, or may include two or more.
（A）脂肪族(甲基)丙烯酸單體的重量平均分子量較佳為400以上、2000以下，更佳為500以上、1000以下。再者，於本說明書中，「重量平均分子量」可為自單體的結構導出的分子量，亦可為藉由凝膠滲透層析法（gel permeation chromatography，GPC）而測定的值（聚苯乙烯換算）。若（A）脂肪族(甲基)丙烯酸單體的重量平均分子量為2000以下，則顯示元件用密封材的黏度不會過度變高，顯示元件用密封材的塗佈性容易變得良好。另一方面，若（A）脂肪族(甲基)丙烯酸單體的重量平均分子量為400以上，則當塗佈顯示元件用密封材時，（A）脂肪族(甲基)丙烯酸單體不易揮發。再者，於要求（A）脂肪族(甲基)丙烯酸單體更不易揮發的情況下，相對於（A）脂肪族(甲基)丙烯酸單體的總量，較佳為將重量平均分子量未滿400的單體的量設為未滿10質量%，更佳為設為5質量%。(A) The weight average molecular weight of the aliphatic (meth) acrylic monomer is preferably 400 or more and 2000 or less, and more preferably 500 or more and 1,000 or less. In addition, in this specification, "weight average molecular weight" may be the molecular weight derived from the structure of a monomer, or the value (polystyrene) measured by gel permeation chromatography (GPC) Conversion). When the weight average molecular weight of (A) aliphatic (meth) acrylic monomer is 2000 or less, the viscosity of the sealing material for display elements will not become high too much, and the coating property of the sealing material for display elements will become favorable easily. On the other hand, when the weight average molecular weight of the (A) aliphatic (meth) acrylic monomer is 400 or more, the (A) aliphatic (meth) acrylic monomer is less volatile when the sealing material for a display element is applied. . In addition, when the (A) aliphatic (meth) acrylic monomer is required to be less volatile, it is preferable to reduce the weight average molecular weight relative to the total amount of the (A) aliphatic (meth) acrylic monomer. The amount of monomers over 400 is set to less than 10% by mass, and more preferably 5% by mass.
另外，（A）脂肪族(甲基)丙烯酸單體可為具有丙烯酸基及甲基丙烯酸基的任一種基的單體，較佳為具有甲基丙烯酸基的單體，即較佳為甲基丙烯酸單體。甲基丙烯酸單體的反應速度較丙烯酸單體慢，更不易產生停止反應。因此，若顯示元件用密封材包含甲基丙烯酸單體，則當使顯示元件用密封材硬化時分子量容易變大，硬化物的強度容易提高。The (A) aliphatic (meth) acrylic monomer may be a monomer having any of an acrylic group and a methacrylic group, and a monomer having a methacrylic group is preferred, that is, a methyl group is preferred. Acrylic monomer. The reaction rate of methacrylic monomer is slower than that of acrylic monomer, and it is more difficult to stop the reaction. Therefore, when the sealing material for a display element contains a methacrylic monomer, the molecular weight tends to increase when the sealing material for a display element is hardened, and the strength of a cured product is easily improved.
（A）脂肪族(甲基)丙烯酸單體所包含的(甲基)丙烯酸基的個數可為一個，就顯示元件用密封材的硬化物的強度容易提高的觀點而言，較佳為兩個以上。(A) The number of (meth) acrylic groups contained in the aliphatic (meth) acrylic monomer may be one, and from the viewpoint that the strength of the cured product of the sealing material for a display element is likely to increase, two is preferred. More than.
另一方面，（A）脂肪族(甲基)丙烯酸單體所包含的脂肪族鏈可為直鏈狀，亦可為分支鏈狀。另外，亦可為多個聚氧伸乙基或聚氧伸丙基等氧伸烷基連結而成的結構。藉由（A）脂肪族(甲基)丙烯酸單體具有脂肪族鏈，顯示元件用密封材的黏度容易變低，進而，所獲得的硬化物的柔軟性容易提高。On the other hand, the aliphatic chain contained in the (A) aliphatic (meth) acrylic monomer may be linear or branched. In addition, a structure in which a plurality of oxyalkylene groups such as polyoxyethyl groups or polyoxypropyl groups are connected may be used. Since (A) an aliphatic (meth) acrylic monomer has an aliphatic chain, the viscosity of the sealing material for display elements will become low easily, and the flexibility of the hardened | cured material obtained will become easy to improve.
（A）脂肪族(甲基)丙烯酸單體的具體例包括：聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚四亞甲基二醇二(甲基)丙烯酸酯等二(甲基)丙烯酸酯；環氧乙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、丙三醇聚乙二醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、丙三醇聚縮水甘油醚聚(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯等。(A) Specific examples of the aliphatic (meth) acrylic monomer include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) ) Di (meth) acrylates such as acrylate; ethylene oxide modified trimethylolpropane tri (meth) acrylate, glycerol polyethylene glycol tri (meth) acrylate, dipentaerythritol penta ( Multifunctional (meth) acrylates such as meth) acrylates, dipentaerythritol hexa (meth) acrylates, glycerol polyglycidyl ether poly (meth) acrylates, and the like.
此處，就黏度容易適度變低的觀點而言，（A）脂肪族(甲基)丙烯酸單體較佳為包含2官能的(甲基)丙烯酸單體。具體而言，相對於（A）脂肪族(甲基)丙烯酸單體的總量，2官能的(甲基)丙烯酸單體的量較佳為50質量%以上、100質量%以下，更佳為50質量%～95質量%，進而較佳為60質量%～90質量%。若2官能的(甲基)丙烯酸單體的量為該範圍，則顯示元件用密封材的黏度適度變低，塗佈穩定性提高。2官能的（A）脂肪族(甲基)丙烯酸單體特佳為上述中的聚乙二醇二(甲基)丙烯酸酯或聚丙二醇二(甲基)丙烯酸酯。Here, it is preferable that the (A) aliphatic (meth) acrylic monomer contains a bifunctional (meth) acrylic monomer from the viewpoint that the viscosity tends to be moderately low. Specifically, the amount of the bifunctional (meth) acrylic monomer is preferably 50% by mass or more and 100% by mass or less with respect to the total amount of the (A) aliphatic (meth) acrylic monomer, more preferably 50% to 95% by mass, and more preferably 60% to 90% by mass. When the amount of the bifunctional (meth) acrylic monomer is within this range, the viscosity of the sealing material for a display element is moderately reduced, and the coating stability is improved. The bifunctional (A) aliphatic (meth) acrylic acid monomer is particularly preferably a polyethylene glycol di (meth) acrylate or a polypropylene glycol di (meth) acrylate.
另一方面，就於顯示元件用密封材的塗佈時不易揮發、進而容易提高相對於基板的接著強度的觀點而言，（A）脂肪族(甲基)丙烯酸單體亦較佳為包含3官能以上的(甲基)丙烯酸單體。於包含3官能以上的(甲基)丙烯酸單體的情況下，相對於（A）脂肪族(甲基)丙烯酸單體的總量，所述3官能以上的(甲基)丙烯酸單體的量較佳為5質量%以上、50質量%以下，更佳為10質量%～40質量%。另外，尤其較佳為3官能的(甲基)丙烯酸單體的量為所述範圍。作為3官能(甲基)丙烯酸單體，較佳為環氧乙烷改質三羥甲基丙烷三(甲基)丙烯酸酯。On the other hand, from the viewpoint that the sealing material for a display element is less volatile at the time of application and further improves the adhesion strength to the substrate, the (A) aliphatic (meth) acrylic monomer preferably contains 3 Functional (meth) acrylic monomer. When a trifunctional or higher (meth) acrylic monomer is included, the amount of the trifunctional or higher (meth) acrylic monomer relative to the total amount of the (A) aliphatic (meth) acrylic monomer. It is preferably 5 mass% or more and 50 mass% or less, and more preferably 10 mass% to 40 mass%. The amount of the trifunctional (meth) acrylic monomer is particularly preferably within the above range. The trifunctional (meth) acrylic monomer is preferably ethylene oxide modified trimethylolpropane tri (meth) acrylate.
（A-2）含環結構的(甲基)丙烯酸單體
顯示元件用密封材較佳為更包含（A-2）含環結構的(甲基)丙烯酸單體。（A-2）含環結構的(甲基)丙烯酸單體所包含的環結構可為芳香環、脂肪族環（脂環式）、或雜環的任一者。顯示元件用密封材若包含所述（A）脂肪族(甲基)丙烯酸單體以及（A-2）含環結構的(甲基)丙烯酸單體，則顯示元件用密封材的硬化物的強度容易提高。顯示元件用密封材可包含僅一種（A-2）含環結構的(甲基)丙烯酸單體，亦可包含兩種以上。The (A-2) ring-containing (meth) acrylic monomer display element sealing material preferably further contains (A-2) a ring-containing (meth) acrylic monomer. (A-2) The ring structure included in the ring structure-containing (meth) acrylic monomer may be any of an aromatic ring, an aliphatic ring (alicyclic), or a heterocyclic ring. When the sealing material for a display element contains the (A) aliphatic (meth) acrylic monomer and (A-2) a ring-containing (meth) acrylic monomer, the strength of a cured product of the sealing material for a display element Easy to improve. The sealing material for a display element may contain only one (A-2) ring-containing (meth) acrylic monomer, or may contain two or more.
此處，（A-2）含環結構的(甲基)丙烯酸單體的重量平均分子量較佳為400以上、2000以下，更佳為500以上、1000以下。重量平均分子量若為2000以下，則顯示元件用密封材的黏度不會過度提高，顯示元件用密封材的塗佈性容易變得良好。另一方面，若重量平均分子量為400以上，則當塗佈顯示元件用密封材時，（A-2）含環結構的(甲基)丙烯酸單體不易揮發。於要求更不易揮發的情況下，相對於（A）脂肪族(甲基)丙烯酸單體與（A-2）含環結構的(甲基)丙烯酸單體的總量，重量平均分子量未滿400的（A-2）含環結構的(甲基)丙烯酸單體的量較佳設為未滿10質量%，更佳設為未滿5質量%。Here, the weight average molecular weight of the (A-2) ring-containing (meth) acrylic monomer is preferably 400 or more and 2000 or less, and more preferably 500 or more and 1,000 or less. When the weight average molecular weight is 2,000 or less, the viscosity of the sealing material for a display element is not excessively increased, and the applicability of the sealing material for a display element is likely to be good. On the other hand, if the weight average molecular weight is 400 or more, (A-2) a ring structure-containing (meth) acrylic monomer is less volatile when a sealing material for a display element is applied. In the case that it is required to be less volatile, the weight average molecular weight is less than 400 relative to the total amount of (A) aliphatic (meth) acrylic monomer and (A-2) ring-containing (meth) acrylic monomer. The amount of (A-2) ring structure-containing (meth) acrylic monomer is preferably less than 10% by mass, and more preferably less than 5% by mass.
具有芳香環的（A-2）含環結構的(甲基)丙烯酸單體的例子包括：(聚)乙氧基改質雙酚A二(甲基)丙烯酸酯、(聚)丙氧基改質雙酚A二(甲基)丙烯酸酯、(聚)乙氧基(聚)丙氧基改質雙酚A二(甲基)丙烯酸酯等具有雙酚A型結構的二(甲基)丙烯酸酯；(聚)乙氧基改質雙酚F二(甲基)丙烯酸酯、(聚)丙氧基改質雙酚F二(甲基)丙烯酸酯、(聚)乙氧基(聚)丙氧基改質雙酚F二(甲基)丙烯酸酯等具有雙酚F型結構的二(甲基)丙烯酸酯；(聚)乙氧基改質雙酚S二(甲基)丙烯酸酯、(聚)丙氧基改質雙酚S二(甲基)丙烯酸酯、(聚)乙氧基(聚)丙氧基改質雙酚S二(甲基)丙烯酸酯等具有雙酚S型結構的二(甲基)丙烯酸酯；聯苯酚(聚)乙氧基二(甲基)丙烯酸酯、聯苯酚(聚)丙氧基二(甲基)丙烯酸酯等具有聯苯酚結構的二(甲基)丙烯酸酯；鄰苯二甲酸改質季戊四醇三(甲基)丙烯酸酯；二羥基萘(聚)乙氧基二(甲基)丙烯酸酯、二羥基萘(聚)丙氧基二(甲基)丙烯酸酯、聯萘酚二(甲基)丙烯酸酯、聯萘酚(聚)乙氧基二(甲基)丙烯酸酯、聯萘酚(聚)丙氧基二(甲基)丙烯酸酯、(聚)己內酯改質聯萘酚二(甲基)丙烯酸酯等具有縮合環的(甲基)丙烯酸酯；雙酚芴二(甲基)丙烯酸酯、雙苯氧基甲醇芴二(甲基)丙烯酸酯、雙苯氧基乙醇芴二(甲基)丙烯酸酯、雙苯氧基(聚)己內酯芴二(甲基)丙烯酸酯等具有多個芳香環的二(甲基)丙烯酸酯；聯苯型苯酚芳烷基環氧樹脂與丙烯酸酸的反應物等。Examples of (A-2) ring-containing (meth) acrylic monomers having an aromatic ring include: (poly) ethoxy modified bisphenol A di (meth) acrylate, (poly) propoxy modified Di (meth) acrylic acid having a bisphenol A structure such as modified bisphenol A di (meth) acrylate and (poly) ethoxy (poly) propoxy modified bisphenol A di (meth) acrylate Esters; (poly) ethoxy modified bisphenol F di (meth) acrylate, (poly) propoxy modified bisphenol F di (meth) acrylate, (poly) ethoxy (poly) acrylic acid Di- (meth) acrylates with bisphenol F structure such as oxy-modified bisphenol F di (meth) acrylate; (poly) ethoxy-modified bisphenol S di (meth) acrylate, ( (Poly) propoxy modified bisphenol S di (meth) acrylate, (poly) ethoxy (poly) propoxy modified bisphenol S di (meth) acrylate, etc. Di (meth) acrylates; di (methyl) with biphenol structure, such as biphenol (poly) ethoxydi (meth) acrylate, biphenol (poly) propoxydi (meth) acrylate, etc. Acrylate; Phthalate modified pentaerythritol tri (meth) acrylate; dihydroxynaphthalene (poly) ethoxybis (methyl) Enoate, dihydroxynaphthalene (poly) propoxydi (meth) acrylate, binaphthol di (meth) acrylate, binaphthol (poly) ethoxydi (meth) acrylate, Naphthol (poly) propoxydi (meth) acrylate, (poly) caprolactone modified binaphthol di (meth) acrylate, etc. (meth) acrylates with condensed rings; bisphenol glyoxal (Meth) acrylate, bisphenoxymethanol, di (meth) acrylate, bisphenoxyethanol, di (meth) acrylate, bisphenoxy (poly) caprolactone, bis (methyl) ) Di (meth) acrylates having a plurality of aromatic rings, such as acrylate; reactants of biphenyl-type phenol aralkyl epoxy resin and acrylic acid, and the like.
具有脂肪族環的（A-2）含環結構的(甲基)丙烯酸酯單體的例子包括：氫化雙酚A(聚)乙氧基二(甲基)丙烯酸酯、氫化雙酚A(聚)丙氧基二(甲基)丙烯酸酯、氫化雙酚F(聚)乙氧基二(甲基)丙烯酸酯、氫化雙酚F(聚)丙氧基二(甲基)丙烯酸酯、氫化雙酚S(聚)乙氧基二(甲基)丙烯酸酯、氫化雙酚S(聚)丙氧基二(甲基)丙烯酸酯等。Examples of the (A-2) ring-containing (meth) acrylate monomer having an aliphatic ring include: hydrogenated bisphenol A (poly) ethoxydi (meth) acrylate, hydrogenated bisphenol A (poly ) Propoxydi (meth) acrylate, hydrogenated bisphenol F (poly) ethoxydi (meth) acrylate, hydrogenated bisphenol F (poly) propoxydi (meth) acrylate, hydrogenated bis Phenol S (poly) ethoxydi (meth) acrylate, hydrogenated bisphenol S (poly) propoxydi (meth) acrylate, and the like.
具有雜環的（A-2）含環結構的(甲基)丙烯酸酯單體的例子包括：異氰脲酸環氧乙烷改質二(甲基)丙烯酸酯、ε-己內酯改質三((甲基)丙烯醯氧基乙基)異氰脲酸酯、異氰脲酸環氧乙烷改質二丙烯酸酯及異氰脲酸環氧乙烷改質三丙烯酸酯、羥基特戊醛改質三羥甲基丙烷二(甲基)丙烯酸酯、螺二醇二(甲基)丙烯酸酯等。Examples of (A-2) ring-containing (meth) acrylate monomers having a heterocyclic ring include: isocyanurate modified ethylene oxide di (meth) acrylate, ε-caprolactone modified Tris ((meth) acryloxyethyl) isocyanurate, isocyanurate ethylene oxide modified diacrylate and isocyanurate ethylene oxide modified triacrylate, hydroxytetramethylene Aldehyde-modified trimethylolpropane di (meth) acrylate, spirodiol di (meth) acrylate, and the like.
上述中，就容易獲取等觀點而言，較佳為具有芳香環的（A-2）含環結構的(甲基)丙烯酸酯單體，特佳為(聚)乙氧基改質雙酚A二(甲基)丙烯酸酯、(聚)丙氧基改質雙酚A二(甲基)丙烯酸酯、(聚)乙氧基(聚)丙氧基改質雙酚A二(甲基)丙烯酸酯等具有雙酚A型結構的單體。Among the above, from the viewpoints of easy availability and the like, the (A-2) ring-containing (meth) acrylate monomer having an aromatic ring is preferred, and (poly) ethoxy-modified bisphenol A is particularly preferred. Di (meth) acrylate, (poly) propoxy modified bisphenol A di (meth) acrylate, (poly) ethoxy (poly) propoxy modified bisphenol A di (meth) acrylic acid A monomer having a bisphenol A structure such as an ester.
（A）脂肪族(甲基)丙烯酸單體與（A-2）含環結構的(甲基)丙烯酸單體的比率（質量比）較佳為20:80～90:10，更佳為30:70～70:30。The ratio (mass ratio) of (A) an aliphatic (meth) acrylic monomer to (A-2) a ring-containing (meth) acrylic monomer is preferably 20:80 to 90:10, more preferably 30 : 70 ～ 70: 30.
此處，相對於顯示元件用密封材100質量份，（A）脂肪族(甲基)丙烯酸單體及（A-2）含環結構的(甲基)丙烯酸單體的總量較佳為90質量份以上、99.9質量份以下，更佳為95質量份以上、99.9質量份以下。若（A）脂肪族(甲基)丙烯酸單體及（A-2）含環結構的(甲基)丙烯酸單體的含量為所述範圍，則藉由顯示元件用密封材的硬化物，各種顯示元件受到充分保護而免受大氣中的氧或水分等的影響。Here, the total amount of (A) the aliphatic (meth) acrylic monomer and (A-2) the ring-containing (meth) acrylic monomer is preferably 90 to 100 parts by mass of the sealing material for a display element. Part by mass or more and 99.9 parts by mass or less, more preferably 95 parts by mass or more and 99.9 parts by mass or less. When the content of (A) an aliphatic (meth) acrylic monomer and (A-2) a ring-containing (meth) acrylic monomer is within the above-mentioned range, the cured product of the sealing material for a display element can be variously produced The display element is sufficiently protected from atmospheric oxygen, moisture, and the like.
（B）偶氮系聚合起始劑
（B）偶氮系聚合起始劑是藉由熱而分解並產生自由基且具有偶氮基的化合物，並且是用以使所述（A）脂肪族(甲基)丙烯酸單體等硬化（聚合）的化合物。一般而言，因自顯示元件用密封材的硬化物揮發出聚合起始劑、或揮發出聚合起始劑的分解物（例如，丙酮或甲苯等低分子量體，具有羥基或胺基的極性物質）等，容易對顯示元件產生影響。相對於此，（B）偶氮系聚合起始劑藉由熱而生成的基團成分不會分解且有助於聚合，因此不易產生低分子量成分。因此，自顯示元件用密封材的塗膜或硬化物不易產生對顯示元件帶來影響的逸氣。顯示元件用密封材可包含僅一種（B）偶氮系聚合起始劑，亦可包含兩種以上。(B) Azo-based polymerization initiator (B) An azo-based polymerization initiator is a compound having an azo group which is decomposed by heat and generates a radical, and is used to make the (A) aliphatic A hardened (polymerized) compound such as a (meth) acrylic monomer. Generally speaking, a polymerization initiator is volatilized from a hardened product of a sealing material for a display element, or a decomposition product of a polymerization initiator (for example, a low molecular weight substance such as acetone or toluene, or a polar substance having a hydroxyl group or an amine group). ), Etc., easily affect the display element. In contrast, (B) the azo-based polymerization initiator does not decompose the group components generated by heat and contributes to the polymerization, so it is difficult to generate low molecular weight components. Therefore, a coating film or a cured product of the sealing material for a display element is less likely to generate outgassing that affects the display element. The sealing material for a display element may contain only one (B) azo-based polymerization initiator, or may contain two or more.
（B）偶氮系聚合起始劑可為偶氮腈化合物、偶氮酯化合物、偶氮醯胺化合物、偶氮脒化合物、偶氮咪唑啉化合物、高分子偶氮系化合物的任一種化合物。(B) The azo-based polymerization initiator may be any of an azonitrile compound, an azo ester compound, an azoamido compound, an azohydrazone compound, an azoimidazoline compound, and a polymer azo-based compound.
偶氮腈化合物的例子包括：2,2'-偶氮雙(異丁腈)、2,2'-偶氮雙-2-甲基異丁腈、1,1'-偶氮雙(環己烷-1-甲腈)、1-[(1-氰基-1-甲基乙基)偶氮]甲醯胺、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2-甲基丁腈)、4,4'-偶氮雙(4-氰基戊酸)等。Examples of azonitrile compounds include: 2,2'-azobis (isobutyronitrile), 2,2'-azobis-2-methylisobutyronitrile, 1,1'-azobis (cyclohexane Alkane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamidine, 2,2'-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 4,4'-couple Nitrogen bis (4-cyanovaleric acid) and the like.
偶氮酯化合物的例子包括：二甲基2,2'-偶氮雙(2-甲基丙酸酯)、二甲基1,1'-偶氮雙(1-環己烷羧酸酯)、1,1'-偶氮雙-(1-乙醯氧基-1-苯基乙烷)等。Examples of the azo ester compound include: dimethyl 2,2'-azobis (2-methylpropionate), dimethyl 1,1'-azobis (1-cyclohexanecarboxylic acid ester) , 1,1'-azobis- (1-ethoxyl-1-phenylethane) and the like.
偶氮醯胺化合物的例子包括：2,2'-偶氮雙[N-(2-丙烯基）-2-甲基丙醯胺]、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)、2,2'-偶氮雙(N-環己基-2-甲基丙醯胺)、2,2'-偶氮雙{2-甲基-N-[1,1-雙(羥基甲基)-2-羥基乙基]丙醯胺、2,2'-偶氮雙[2-甲基-N-(2-羥基乙基)]丙醯胺等。Examples of the azoamido compound include: 2,2'-azobis [N- (2-propenyl) -2-methylpropylamidamine], 2,2'-azobis (N-butyl- 2-methylpropylamidamine), 2,2'-azobis (N-cyclohexyl-2-methylpropylamidamine), 2,2'-azobis {2-methyl-N- [1 1,1-bis (hydroxymethyl) -2-hydroxyethyl] propylamine, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl)] propylamine, and the like.
偶氮脒化合物的例子包括：2,2'-偶氮雙(2-甲基丙脒)二鹽酸鹽、2,2'-偶氮雙(N-(2-羧基乙基)-2-甲基丙脒)四水合物、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2'-偶氮雙(1-亞胺基-1-吡咯啶基-2-甲基丙烷)二鹽酸鹽等。Examples of the azophosphonium compound include: 2,2'-azobis (2-methylpropane) dihydrochloride, 2,2'-azobis (N- (2-carboxyethyl) -2- Methylpropionamidine) tetrahydrate, 2,2'-azobis (2-fluorenylpropane) dihydrochloride, 2,2'-azobis (1-imino-1-pyrrolidinyl- 2-methylpropane) dihydrochloride and the like.
偶氮咪唑啉酮化合物的例子包括：2,2'-偶氮雙[2-[1-(2-羥基乙基)-2-咪唑啉-2-基]丙烷]二羥基氯、2,2'-偶氮雙[2-(2-咪唑啉-2-基)丙烷]、2,2-偶氮雙[2-(2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2-偶氮雙[2-(2-咪唑啉-2-基)丙烷]二硫酸鹽二水合物等。Examples of the azoimidazolinone compound include: 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydroxy chloride, 2,2 '-Azobis [2- (2-imidazolin-2-yl) propane], 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2, 2-Azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate and the like.
高分子偶氮系化合物的例子包括：商品名VPE-0201、商品名VPE-0401、商品名VPE-0601、商品名VPS-1001（均為和光純藥公司製造）等。
上述中，較佳為偶氮腈化合物或偶氮酯化合物。Examples of the polymer azo-based compound include: a trade name of VPE-0201, a trade name of VPE-0401, a trade name of VPE-0601, a trade name of VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.), and the like.
Among the above, an azonitrile compound or an azoester compound is preferred.
（B）偶氮系聚合起始劑較佳為分解溫度高，具體而言，10小時半衰期溫度（分解溫度）較佳為45℃～85℃，更佳為55℃～70℃。若（B）偶氮系聚合起始劑的分解溫度高，則即便於無氧環境、40℃以下將顯示元件用密封材保持一定期間的情況下，顯示元件用密封材亦不易變質，可穩定地進行顯示元件用密封材的塗佈等。(B) The azo-based polymerization initiator preferably has a high decomposition temperature. Specifically, the 10-hour half-life temperature (decomposition temperature) is preferably 45 ° C to 85 ° C, and more preferably 55 ° C to 70 ° C. If the decomposition temperature of the (B) azo-based polymerization initiator is high, the sealing material for a display element is not easily deteriorated and stable even when the sealing material for a display element is held for a certain period of time in an oxygen-free environment at 40 ° C or lower. Coating and the like of a sealing material for a display element are performed.
相對於（A）脂肪族(甲基)丙烯酸單體及（A-2）含環結構的(甲基)丙烯酸單體的總量100質量份，較佳為包含0.05質量份以上、5質量份以下的（B）偶氮系聚合起始劑，更佳為包含0.1質量份以上、3質量份以下的（B）偶氮系聚合起始劑。若包含所述範圍的（B）偶氮系聚合起始劑，則可使（A）脂肪族(甲基)丙烯酸單體或（A-2）含環結構的(甲基)丙烯酸單體充分熱硬化。The content of (A) an aliphatic (meth) acrylic monomer and (A-2) a ring structure-containing (meth) acrylic monomer is 100 parts by mass, preferably 0.05 part by mass or more and 5 parts by mass The following (B) azo-based polymerization initiator more preferably contains (B) an azo-based polymerization initiator in an amount of 0.1 part by mass or more and 3 parts by mass or less. When the (B) azo-based polymerization initiator is included in the above range, (A) an aliphatic (meth) acrylic monomer or (A-2) a cyclic structure-containing (meth) acrylic monomer can be sufficiently obtained. Heat hardened.
（C）四甲基哌啶自由基衍生物
（C）四甲基哌啶自由基衍生物於顯示元件用密封材中作為聚合抑制劑發揮功能。因此，若顯示元件用密封材包含該化合物，則顯示元件用密封材的貯存時間（pot life）提高。顯示元件用密封材可包含僅一種（C）四甲基哌啶自由基衍生物，亦可包含兩種以上。(C) Tetramethylpiperidine radical derivative (C) The tetramethylpiperidine radical derivative functions as a polymerization inhibitor in the sealing material for display elements. Therefore, when the sealing material for a display element contains the compound, the pot life of the sealing material for a display element is improved. The sealing material for a display element may include only one (C) tetramethylpiperidine radical derivative, or may include two or more.
此處，本發明的顯示元件用密封材所包含的（C）四甲基哌啶自由基衍生物為下述通式（1）所表示的化合物。
[化2]
（1）
所述通式（1）中，R表示一價、或二價的基，具體而言，表示選自由H、羥基、橋氧基、胺基、氰基、乙醯胺基、甲氧基、羧基、棕櫚醯胺基、甲基丙烯醯基、異硫代氰酸酯基、2-氯乙醯胺基、2-碘乙醯胺基、(9-吖啶羰基)胺基、及[2-[2-(4-碘苯氧基)乙氧基]羰基]苯甲醯基所組成的群組中的任一種基。Here, the (C) tetramethylpiperidine radical derivative contained in the sealing material for display elements of this invention is a compound represented by following General formula (1).
[Chemical 2]
(1)
In the general formula (1), R represents a monovalent or divalent group, and specifically, it represents a group selected from the group consisting of H, a hydroxyl group, a bridging oxy group, an amine group, a cyano group, an acetamido group, a methoxy group, Carboxy, palmitoylamino, methacrylomethyl, isothiocyanate, 2-chloroacetamido, 2-iodoacetamido, (9-acridylcarbonyl) amino, and [2 Any one of the groups consisting of-[2- (4-iodophenoxy) ethoxy] carbonyl] benzyl.
另外，上述中，就容易獲取等觀點而言，較佳為通式（1）中的R為H、橋氧基、或羥基的化合物。In addition, from the viewpoints of easy availability and the like, a compound in which R in the general formula (1) is H, a bridging oxy group, or a hydroxyl group is preferred.
相對於（A）脂肪族(甲基)丙烯酸單體及（A-2）含環結構的(甲基)丙烯酸單體的總量100質量份，較佳為包含0.0005質量份以上、0.2質量份以下的（C）四甲基哌啶自由基衍生物，更佳為包含0.001質量份以上、0.1質量份以下的（C）四甲基哌啶自由基衍生物。若包含所述範圍的（C）四甲基哌啶自由基衍生物，則可延長顯示元件用密封材的貯存時間。另外，若（C）四甲基哌啶自由基衍生物的量過剩，則顯示元件用密封材的熱硬化性有時降低，但若相對於（A）脂肪族(甲基)丙烯酸單體與（A-2）含環結構的(甲基)丙烯酸單體的總量100質量份而為0.2質量份以下，則可使顯示元件用密封材的熱硬化性良好。The content of (A) aliphatic (meth) acrylic monomer and (A-2) ring structure-containing (meth) acrylic monomer is preferably 100 parts by mass, preferably 0.0005 parts by mass or more and 0.2 parts by mass The following (C) tetramethylpiperidine radical derivative more preferably contains (C) a tetramethylpiperidine radical derivative in an amount of 0.001 part by mass or more and 0.1 part by mass or less. When the range (C) tetramethylpiperidine radical derivative is included, the storage time of the sealing material for a display element can be extended. In addition, if the amount of the (C) tetramethylpiperidine radical derivative is excessive, the thermosetting property of the sealing material for a display device may be reduced. However, when compared with (A) an aliphatic (meth) acrylic monomer and (A-2) The total amount of the ring-containing (meth) acrylic monomer is 100 parts by mass and 0.2 part by mass or less, and the thermosetting property of the sealing material for a display element can be made good.
（D）矽烷偶合劑
（D）矽烷偶合劑只要為具有(甲基)丙烯酸基且重量平均分子量為400～500,000的矽烷偶合劑，則並無特別限制。如上所述，若顯示元件用密封材包含（D）矽烷偶合劑，則顯示元件用密封材的硬化物與基板的接著強度提高。(D) Silane coupling agent (D) The silane coupling agent is not particularly limited as long as it is a silane coupling agent having a (meth) acrylic group and a weight average molecular weight of 400 to 500,000. As described above, when the sealing material for a display element contains (D) a silane coupling agent, the bonding strength between the cured product of the sealing material for a display element and the substrate is improved.
（D）矽烷偶合劑只要具有(甲基)丙烯酸基即可，較佳為於分子內具有兩個以上的(甲基)丙烯酸基。另外，(甲基)丙烯酸基的當量較佳為100 g/mol～15,000 g/mol，(甲基)丙烯酸基的當量更佳為120 g/mol～1,000 g/mol。若（D）矽烷偶合劑包含多個(甲基)丙烯酸基，則（D）矽烷偶合劑的相對於（A）脂肪族(甲基)丙烯酸單體的親和性提高。其結果，當塗佈顯示元件用密封材時，（D）矽烷偶合劑不易揮發。進而，若(甲基)丙烯酸基的個數為所述範圍，則於顯示元件用密封材的硬化時，（D）矽烷偶合劑中的(甲基)丙烯酸基與（A）脂肪族(甲基)丙烯酸單體充分進行化學鍵結。（D）矽烷偶合劑中的(甲基)丙烯酸基的個數或(甲基)丙烯酸基的當量可藉由核磁共振（nuclear magnetic resonance，NMR）、紅外（infrared，IR）法等來確定。(D) The silane coupling agent may have a (meth) acrylic group, and preferably has two or more (meth) acrylic groups in the molecule. The equivalent of the (meth) acrylic group is preferably 100 g / mol to 15,000 g / mol, and the equivalent of the (meth) acrylic group is more preferably 120 g / mol to 1,000 g / mol. When the (D) silane coupling agent contains a plurality of (meth) acrylic groups, the affinity of the (D) silane coupling agent to the (A) aliphatic (meth) acrylic monomer is improved. As a result, when the sealing material for a display element is applied, the (D) silane coupling agent is less volatile. Furthermore, when the number of (meth) acrylic groups is within the above range, the (meth) acrylic group and (A) aliphatic (formaldehyde) in the (D) silane coupling agent are cured when the sealing material for a display device is cured. Group) The acrylic monomer is sufficiently chemically bonded. (D) The number of (meth) acrylic groups or the equivalent of (meth) acrylic groups in the silane coupling agent can be determined by nuclear magnetic resonance (NMR), infrared (IR), or the like.
另一方面，（D）矽烷偶合劑於分子內可包含僅一個Si原子，較佳為於分子內包含兩個以上的Si原子。若（D）矽烷偶合劑於分子內包含多個Si原子，則顯示元件用密封材的硬化物與基板容易進行矽氧烷鍵結，該些的接著強度容易提高。其結果，於顯示元件用密封材的硬化物與基板之間不易產生縫隙，從而不易產生所述條紋不均。On the other hand, the (D) silane coupling agent may contain only one Si atom in the molecule, and preferably contains two or more Si atoms in the molecule. When the (D) silane coupling agent contains a plurality of Si atoms in the molecule, the cured product of the sealing material for a display element and the substrate are easily siloxane-bonded, and the bonding strength of these is easily improved. As a result, a gap is less likely to occur between the hardened material of the sealing material for a display element and the substrate, and the unevenness of the stripes is less likely to occur.
進而，（D）矽烷偶合劑可為於主鏈中包含矽氧烷鍵（-Si-O-Si-）的化合物，亦可為於主鏈中包含有機鏈的化合物。另外，主鏈可為直線狀，亦可為分支鏈狀，亦可具有網眼結構等。Furthermore, the (D) silane coupling agent may be a compound containing a siloxane bond (-Si-O-Si-) in the main chain, or a compound containing an organic chain in the main chain. The main chain may be linear, branched, or may have a mesh structure.
（D）矽烷偶合劑的分子量只要為400～500,000即可。若（D）矽烷偶合劑的分子量為400以上，則即便於真空中，自顯示元件用密封材亦不易揮發出（D）矽烷偶合劑。另外，其結構容易成為大體積，容易抑制顯示元件用密封材的硬化收縮。另一方面，若分子量為500,000以下，則顯示元件用密封材的黏度不會過度提高，進而與顯示元件用密封材中的成分容易相容。（D）矽烷偶合劑的所述分子量為重量平均分子量，且是藉由GPC而確定的值。(D) The molecular weight of the silane coupling agent should just be 400-500,000. When the molecular weight of the (D) silane coupling agent is 400 or more, the (D) silane coupling agent is not easily volatilized from the sealing material for a display element even in a vacuum. In addition, its structure tends to be bulky, and it is easy to suppress the curing shrinkage of the sealing material for a display element. On the other hand, when the molecular weight is 500,000 or less, the viscosity of the sealing material for a display element does not increase excessively, and further it is easily compatible with the components in the sealing material for a display element. The molecular weight of the (D) silane coupling agent is a weight average molecular weight, and is a value determined by GPC.
所述（D）矽烷偶合劑例如可為市售的矽烷偶合劑，市售品的例子包括：商品名X-12-1048、商品名X-12-1050、商品名X-40-9296、KR-513（均為信越矽利光（ShinEtsu Silicone）公司製造）。The (D) silane coupling agent may be, for example, a commercially available silane coupling agent. Examples of commercially available products include: trade name X-12-1048, trade name X-12-1050, trade name X-40-9296, and KR. -513 (both manufactured by ShinEtsu Silicone).
此處，相對於（A）脂肪族(甲基)丙烯酸單體及（A-2）含環結構的(甲基)丙烯酸單體的總量100質量份，較佳為包含0.1質量份以上、10質量份以下的（D）矽烷偶合劑，更佳為包含0.5質量份以上、5質量份以下的（D）矽烷偶合劑。若包含所述範圍的（D）矽烷偶合劑，則可提高顯示元件用密封材的硬化物與基板的接著強度。Here, it is preferable to contain 0.1 mass part or more with respect to 100 mass parts of total amount of (A) aliphatic (meth) acrylic monomer and (A-2) ring structure-containing (meth) acrylic monomer. (D) The silane coupling agent is 10 mass parts or less, More preferably, it contains the (D) silane coupling agent of 0.5 mass part or more and 5 mass parts or less. When the (D) silane coupling agent is included in the above range, the bonding strength between the cured product of the sealing material for a display element and the substrate can be improved.
（E）調平劑
顯示元件用密封材可更包含（D）調平劑。（E）調平劑為如下化合物：其於顯示元件用密封材的塗膜表面進行配向而使該塗膜表面的表面張力均勻化，並使得不易產生排斥等而容易於被塗佈物上潤濕擴展。(E) Leveling agent The sealing material for display elements may further contain (D) a leveling agent. (E) A leveling agent is a compound that aligns on the surface of a coating film of a sealing material for a display element to uniformize the surface tension of the surface of the coating film, makes it difficult for repellence, etc. to occur, and makes it easy to wet the coated object Wet expansion.
若（E）調平劑對顯示元件用密封材的塗膜表面的表面張力進行調整，則組成物相對於被塗佈物的潤濕性得到改善，塗膜面的流動性或消泡性容易得到改善。再者，多數情況下，藉由少量的添加量便可表現出該些效果。因此，作為（E）調平劑，較佳為使用表面改質作用比較小的矽酮系聚合物或丙烯酸酯系聚合物。此種矽酮系聚合物或丙烯酸酯系聚合物可使用公知者。When the (E) leveling agent adjusts the surface tension of the coating film surface of the sealing material for a display element, the wettability of the composition with respect to the coating object is improved, and the flowability or defoaming property of the coating film surface is easy. Improved. Moreover, in many cases, these effects can be exhibited with a small amount of addition. Therefore, as the (E) leveling agent, it is preferable to use a silicone polymer or an acrylate polymer having a relatively small surface modification effect. As such a silicone-based polymer or an acrylate-based polymer, a known one can be used.
相對於（A）脂肪族(甲基)丙烯酸單體及（A-2）含環結構的(甲基)丙烯酸單體的總量100質量份，較佳為包含0.01質量份～1質量份的（E）調平劑，更佳為0.05質量份～0.5質量份。若（E）調平劑的含量為一定以上，則充分量的調平劑容易於顯示元件用密封材的塗膜表面進行配向，容易獲得充分的調平效果。另一方面，若（E）調平劑的含量為一定以下，則不易損害（E）調平劑與（A）脂肪族(甲基)丙烯酸單體或（A-2）含環結構的(甲基)丙烯酸單體的相容性、或硬化物的透明性。Relative to 100 parts by mass of the total amount of (A) the aliphatic (meth) acrylic monomer and (A-2) the cyclic structure-containing (meth) acrylic monomer, it is preferably 0.01 to 1 part by mass. (E) Leveling agent, more preferably 0.05 to 0.5 parts by mass. When the content of the leveling agent (E) is equal to or more than a certain level, a sufficient amount of the leveling agent is easily aligned on the surface of the coating film of the sealing material for a display element, and a sufficient leveling effect is easily obtained. On the other hand, if the content of the (E) leveling agent is less than or equal to a certain level, the (E) leveling agent and the (A) aliphatic (meth) acrylic monomer or (A-2) ring-containing ( Compatibility of meth) acrylic monomer, or transparency of hardened material.
（F）其他成分
顯示元件用密封材可於不大幅損害本發明的效果的範圍內包含其他樹脂。其他樹脂例如可設為熱硬化性樹脂等。熱硬化性樹脂的例子包括：環氧樹脂、酚樹脂、鄰苯二甲酸二烯丙酯樹脂、脲樹脂、聚酯樹脂等。顯示元件用密封材可包含僅一種熱硬化性樹脂，亦可包含兩種以上。(F) The sealing material for other component display elements may contain other resins as long as the effect of the present invention is not significantly impaired. The other resin can be, for example, a thermosetting resin. Examples of the thermosetting resin include epoxy resin, phenol resin, diallyl phthalate resin, urea resin, polyester resin, and the like. The sealing material for a display element may contain only one type of thermosetting resin, or may contain two or more types.
顯示元件用密封材可包含填充材。顯示元件用密封材所包含的填充材的例子包括：玻璃珠粒、苯乙烯系聚合物粒子、甲基丙烯酸酯系聚合物粒子、乙烯系聚合物粒子、丙烯系聚合物粒子等。顯示元件用密封材可包含僅一種填充材，亦可包含兩種以上。The sealing material for a display element may include a filler. Examples of the filler included in the sealing material for a display element include glass beads, styrene-based polymer particles, methacrylate-based polymer particles, ethylene-based polymer particles, and propylene-based polymer particles. The sealing material for a display element may include only one type of filler, or may include two or more types.
顯示元件用密封材可包含改質劑或穩定劑。改質劑的具體例包括：抗老化劑、調平劑、潤濕性改良劑、界面活性劑、塑化劑等。該些改質劑可單獨使用一種或組合使用兩種以上。另一方面，穩定劑的具體例包括：紫外線吸收劑、防腐劑、抗菌劑等。顯示元件用密封材可包含僅一種所述改質劑或穩定劑，亦可包含兩種以上。The sealing material for a display element may contain a modifier or a stabilizer. Specific examples of the modifier include an anti-aging agent, a leveling agent, a wettability improver, a surfactant, a plasticizer, and the like. These modifiers may be used alone or in combination of two or more. On the other hand, specific examples of the stabilizer include ultraviolet absorbers, preservatives, antibacterial agents, and the like. The sealing material for a display element may include only one of the modifiers or stabilizers described above, or may include two or more of them.
顯示元件用密封材可包含抗氧化劑。所謂抗氧化劑，是指使因電漿照射或日光照射而產生的基團失活者（受阻胺類光穩定劑（Hindered Amine Light Stabilizer，HALS））、或將過氧化物分解者等。抗氧化劑具有防止顯示元件用密封材的硬化物的變色的功能。抗氧化劑的例子包括：受阻胺、酚系抗氧化劑、磷系抗氧化劑等。The sealing material for a display element may contain an antioxidant. The term "antioxidant" refers to a group (Hindered Amine Light Stabilizer (HALS)) that deactivates groups generated by plasma or solar radiation, or a group that decomposes peroxides. The antioxidant has a function of preventing discoloration of a cured product of a sealing material for a display element. Examples of the antioxidant include hindered amines, phenol-based antioxidants, phosphorus-based antioxidants, and the like.
受阻胺的例子包括：雙(2,2,6,6-四甲基哌啶-4-基)癸二酸酯、2,4-二氯-6-第三辛基胺基-均三嗪與4,4'-六亞甲基雙(胺基-2,2,6,6-四甲基哌啶)的縮聚產物、雙[1-(2-羥基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基]癸二酸酯。Examples of hindered amines include: bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,4-dichloro-6-tertiary octylamino-s-triazine Polycondensation product with 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate.
酚系抗氧化劑的例子包括：2,6-二-第三丁基-對甲酚等單酚類、2,2'-亞甲基雙(4-甲基-6-第三丁基酚)等雙酚類、1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷等高分子型酚類。Examples of phenolic antioxidants include monophenols such as 2,6-di-tertiary-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-tertiary-butylphenol) Such as bisphenols, 1,1,3-tris (2-methyl-4-hydroxy-5-third butylphenyl) butane and other polymer phenols.
磷系抗氧化劑的例子包括：選自亞磷酸鹽類的抗氧化劑、及選自氧雜磷雜菲氧化物（oxaphosphaphenanthrene oxide）類的抗著色劑。Examples of the phosphorus-based antioxidant include an antioxidant selected from the phosphite type and an anti-colorant selected from the oxaphosphaphenanthrene oxide type.
尤其於賦予對紫外線的耐受性的方面，較佳為地奴彬（Tinuvin）123（雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸）、地奴彬（Tinuvin）765（雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸與甲基1,2,2,6,6-五甲基-4-哌啶基癸二酸的混合物）、豪斯他彬（Hostavin）PR25（二甲基4-甲氧基苯亞甲基丙二酸酯（dimethyl 4-methoxy benzyl idenemalonate））、地奴彬（Tinuvin）312或豪斯他彬（Hostavin）vsu（乙烷二醯胺N-(2-乙氧基苯基)-N'-(2-乙基苯基)）、智瑪索伯（CHIMASSORB）119 FL（N,N'-雙(3-胺基丙基)乙二胺-2,4-雙[N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基]-6-氯-1,3,5-三嗪縮合物。In particular, in terms of imparting resistance to ultraviolet rays, Tinuvin 123 (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) decane) is preferred. Diacid), Tinuvin 765 (bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacic acid and methyl 1,2,2,6,6- A mixture of pentamethyl-4-piperidyl sebacic acid), Hostavin PR25 (dimethyl 4-methoxy benzyl idenemalonate) , Tinuvin 312 or Hostavin vsu (ethanediamine N- (2-ethoxyphenyl) -N '-(2-ethylphenyl)), Zhima Sauber (CHIMASSORB) 119 FL (N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6- Pentamethyl-4-piperidinyl) amino] -6-chloro-1,3,5-triazine condensate.
顯示元件用密封材視需要可包含溶劑。溶劑具有使各成分均勻地分散或溶解的功能。溶劑的例子包括：甲苯、二甲苯等芳香族溶媒；丙酮、甲基乙基酮、甲基異丁基酮等酮系溶媒；醚、二丁基醚、四氫呋喃、二噁烷、乙二醇單烷基醚等醚類；N-甲基吡咯啶酮等非質子性極性溶媒；乙酸乙酯、乙酸丁酯等酯類等。The sealing material for a display element may contain a solvent as needed. The solvent has a function of dispersing or dissolving each component uniformly. Examples of the solvent include: aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers, dibutyl ether, tetrahydrofuran, dioxane, and ethylene glycol mono Ethers such as alkyl ethers; aprotic polar solvents such as N-methylpyrrolidone; esters such as ethyl acetate and butyl acetate.
（G）顯示元件用密封材的物性等
本發明的顯示元件用密封材的、利用E型黏度計以25℃、2.5 rpm測定而得的黏度為5 mPa･s以上、400 mPa･s以下，較佳為5 mPa･s～200 mPa･s。若顯示元件用密封材的黏度為所述範圍，則將各種顯示元件密封時的流動性容易變得充分。所述黏度例如可利用博菲勒（BROOKFIELD）公司製造的數位流變計（digital rheometer）型號DII-III ULTRA等來測定。(G) Physical properties of the sealing material for display elements, etc. The viscosity of the sealing material for display elements of the present invention measured by an E-type viscometer at 25 ° C and 2.5 rpm is 5 mPa ･ s or more and 400 mPa ･ s or less, It is preferably 5 mPa200s to 200 mPa ･ s. If the viscosity of the sealing material for a display element is in the said range, the fluidity | liquidity at the time of sealing various display elements will become sufficient easily. The viscosity can be measured using, for example, a digital rheometer model DII-III ULTRA manufactured by BROOKFIELD.
可藉由對顯示元件用密封材中所含的各成分的含量進行調整而將顯示元件用密封材的黏度調整成所述範圍。另外，為了將顯示元件用密封材的黏度調整為所述範圍，亦有效的是對（A）脂肪族(甲基)丙烯酸單體或（A-2）含環結構的(甲基)丙烯酸單體的重量平均分子量進行調整。The viscosity of the sealing material for a display element can be adjusted to the above range by adjusting the content of each component contained in the sealing material for a display element. In addition, in order to adjust the viscosity of the sealing material for display elements to the above range, it is also effective to (A) an aliphatic (meth) acrylic monomer or (A-2) a ring-containing (meth) acrylic monomer. The weight average molecular weight is adjusted.
另外，對顯示元件用密封材以100℃進行30分鐘加熱而獲得的硬化物的玻璃轉移溫度（Tg）如上所述般為46℃以上，較佳為46℃～100℃，更佳為46℃～80℃。The glass transition temperature (Tg) of the cured product obtained by heating the sealing material for a display element at 100 ° C for 30 minutes is 46 ° C or higher as described above, preferably 46 ° C to 100 ° C, and more preferably 46 ° C. ~ 80 ° C.
另一方面，顯示元件用密封材的硬化物的35℃～100℃中的線膨脹係數較佳為50以上、250以下，更佳為80 ppm/℃～250 ppm/℃，進而較佳為100 ppm/℃～200 ppm/℃。若顯示元件用密封材的硬化物的線膨脹係數為該範圍，則顯示元件用密封材於其硬化時或硬化後不易收縮，不易產生所述條紋不均。顯示元件用密封材的硬化物的線膨脹係數是針對以100℃對顯示元件用密封材進行30分鐘加熱而獲得的硬化物，利用熱機械分析裝置（TMA裝置）等，以升溫速度5℃/分進行熱分析而確定的值。On the other hand, the linear expansion coefficient of the cured product of the sealing material for a display element at 35 ° C to 100 ° C is preferably 50 or more and 250 or less, more preferably 80 ppm / ° C to 250 ppm / ° C, and even more preferably 100. ppm / ℃ ～ 200 ppm / ℃. If the linear expansion coefficient of the hardened | cured material of the sealing material for display elements is this range, the sealing material for display elements will not shrink easily at the time of hardening or after hardening, and it will become difficult to produce the said unevenness | corrugation. The linear expansion coefficient of the hardened material of the sealing material for display elements is a hardened material obtained by heating the sealing material for display elements at 100 ° C for 30 minutes, using a thermomechanical analysis device (TMA device), etc., at a temperature increase rate of 5 ° C / The value determined by thermal analysis.
所述顯示元件用密封材可藉由將（A）脂肪族(甲基)丙烯酸單體、（B）偶氮系聚合起始劑、（C）四甲基哌啶自由基衍生物、及（D）矽烷偶合劑、以及視需要的其他成分（（A-2）含環結構的(甲基)丙烯酸單體等）利用公知的方法加以混合而製造。混合順序並無特別限制，例如，較佳為使（C）四甲基哌啶自由基衍生物或（D）矽烷偶合劑溶解於（A）脂肪族(甲基)丙烯酸單體或（A-2）含環結構的(甲基)丙烯酸單體中後，再混合（B）偶氮系聚合起始劑。The sealing material for a display element can be obtained by (A) an aliphatic (meth) acrylic monomer, (B) an azo-based polymerization initiator, (C) a tetramethylpiperidine radical derivative, and ( D) Silane coupling agent and other components ((A-2) ring structure-containing (meth) acrylic monomer, etc.), if necessary, are produced by mixing by a known method. The mixing order is not particularly limited. For example, (C) a tetramethylpiperidine radical derivative or (D) a silane coupling agent is preferably dissolved in (A) an aliphatic (meth) acrylic acid monomer or (A- 2) After the (meth) acrylic monomer having a ring structure, (B) an azo-based polymerization initiator is mixed.
（H）顯示元件用密封材的用途
本發明的顯示元件用密封材用於將各種顯示元件密封。各種顯示元件的例子包括：無機發光二極體（Light Emitting Diode，LED）元件、液晶元件、有機EL元件等，較佳為有機EL元件。藉由利用所述顯示元件用密封材將各種顯示元件密封，可抑制該些顯示元件因水分等而劣化。(H) Use of sealing material for display element The sealing material for display element of this invention is used for sealing various display elements. Examples of the various display elements include: an inorganic light emitting diode (Light Emitting Diode, LED) element, a liquid crystal element, an organic EL element, etc., preferably an organic EL element. By sealing the various display elements with the display element sealing material, it is possible to suppress deterioration of these display elements due to moisture and the like.
如前所述，本發明的顯示元件用密封材可作為用以對各種顯示元件進行面密封的面密封材，亦可作為用以進行框架密封的框架密封材。例如，將液狀的顯示元件用密封材塗佈於被密封物（顯示元件側基板或顯示元件）上後，使顯示元件側基板與密封基板相向而使顯示元件用密封材硬化等，藉此可對顯示元件進行面密封。於該情況下，顯示元件用密封材可藉由網版印刷法、噴墨印刷法、分配器塗佈等來塗佈。As described above, the sealing material for a display element of the present invention can be used as a surface sealing material for surface sealing various display elements or as a frame sealing material for frame sealing. For example, after the liquid-state sealing element for a display element is applied to a to-be-sealed object (display element-side substrate or display element), the display element-side substrate faces the sealing substrate to harden the sealing element for the display element. The display element can be face-sealed. In this case, the sealing material for a display element can be applied by a screen printing method, an inkjet printing method, a dispenser coating, or the like.
另外，亦可將顯示元件用密封材預先成形為膜狀，並將該膜層壓於被密封物（基板或顯示元件）上。於該情況下，於膜狀的顯示元件用密封材上進一步載置密封基板，並使顯示元件用密封材硬化。藉此，可對顯示元件進行面密封。In addition, the sealing material for a display element may be formed into a film shape in advance, and the film may be laminated on an object to be sealed (a substrate or a display element). In this case, a sealing substrate is further placed on the film-shaped display element sealing material, and the display element sealing material is hardened. Thereby, the display element can be surface-sealed.
本發明的顯示元件用密封材可於無氧環境、40℃以下使用。而且，即便於此種環境下使用，顯示元件用密封材中的成分亦不易揮發，黏度變化亦少。The sealing material for a display element of the present invention can be used in an oxygen-free environment at 40 ° C or lower. Moreover, even if it is used in such an environment, the components in the sealing material for a display element are not easily volatile, and the viscosity changes are small.
再者，所述顯示元件用密封材的硬化可藉由加熱來進行。加熱溫度可適宜設定，可考慮被密封物的耐熱溫度或效率等而適宜設定，通常可設為80℃～130℃，較佳設為90℃～110℃。根據本發明的顯示元件用密封材，即便以所述溫度進行加熱，於硬化過程中或硬化後，亦不易產生對顯示元件帶來影響的逸氣。進而，所獲得的硬化物中不易產生條紋不均，故可獲得外觀性亦優異的高品質的顯示裝置。
[實施例]The sealing material for the display element may be hardened by heating. The heating temperature can be appropriately set, and can be appropriately set in consideration of the heat-resistant temperature or efficiency of the sealed object, and it can be generally set to 80 ° C to 130 ° C, preferably 90 ° C to 110 ° C. According to the sealing material for a display element of the present invention, even if heating is performed at the above-mentioned temperature, outgass that affect the display element are hardly generated during or after curing. Furthermore, since unevenness is less likely to occur in the obtained cured product, a high-quality display device that is also excellent in appearance can be obtained.
[Example]
以下參照實施例對本發明進行說明。本發明的範圍並不由實施例限定性地解釋。Hereinafter, the present invention will be described with reference to examples. The scope of the present invention is not limitedly interpreted by the examples.
[材料]
於實施例及比較例中使用以下的材料。[material]
The following materials were used in the examples and comparative examples.
（A）脂肪族(甲基)丙烯酸單體
･9PG：下述式所表示的聚丙二醇#400二甲基丙烯酸酯（新中村化學工業公司製造 分子量536）
[化3]
m+n=7
･TMPT-3EO：下述式所表示的環氧乙烷（ethylene oxide，EO）改質三羥甲基丙烷三甲基丙烯酸酯（新中村化學工業製造 分子量470）
[化4]
･FA-137M：下述式所表示的EO改質三羥甲基丙烷三甲基丙烯酸酯（日立化成製造 分子量1263）
[化5]
(A) Aliphatic (meth) acrylic monomer ･ 9PG: polypropylene glycol # 400 dimethacrylate represented by the following formula (molecular weight 536 manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
[Chemical 3]
m + n = 7
･ TMPT-3EO: Ethylene oxide (EO) modified trimethylolpropane trimethacrylate represented by the following formula (molecular weight 470 manufactured by Shin Nakamura Chemical Industry)
[Chemical 4]
･ FA-137M: EO modified trimethylolpropane trimethacrylate represented by the following formula (Hitachi Chemical Co., Ltd. molecular weight 1263)
[Chemical 5]
（A-2）含環結構的(甲基)丙烯酸單體
･BPE-500：下述式所表示的乙氧基化雙酚A二甲基丙烯酸酯（新中村化學公司製造 分子量804）
[化6]
m+n=10
･DCP：下述式所表示的三環癸烷甲醇二甲基丙烯酸酯（新中村化學工業製造 分子量332）
[化7]
(A-2) Ring-containing (meth) acrylic monomer ･ BPE-500: ethoxylated bisphenol A dimethacrylate represented by the following formula (molecular weight 804 manufactured by Shin Nakamura Chemical Co., Ltd.)
[Chemical 6]
m + n = 10
･ DCP: Tricyclodecane methanol dimethacrylate represented by the following formula (molecular weight 332 manufactured by Shin Nakamura Chemical Industry)
[Chemical 7]
（B）偶氮系聚合起始劑
･OTAZO：下述化學式所表示的1,1'-偶氮雙-(1-乙醯氧基-1-苯基乙烷)（大塚化學公司製造 分子量354.4，融點106℃～110℃，分解點106℃～110℃，10小時半衰期的溫度61℃）
[化8]
(B) Azo-based polymerization initiator ･ OTAZO: 1,1'-azobis- (1-ethoxyl-1-phenylethane) represented by the following chemical formula (molecular weight 354.4 manufactured by Otsuka Chemical Co., Ltd.) , Melting point 106 ℃ ～ 110 ℃, decomposition point 106 ℃ ～ 110 ℃, 10-hour half-life temperature 61 ℃)
[Chemical 8]
（C）四甲基哌啶自由基衍生物
･4H-TEMPO：下述化學式所表示的4-羥基-2,2,6,6-四甲基哌啶1-氧基自由基
[化9]
(C) Tetramethylpiperidine radical derivative ･ 4H-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical represented by the following chemical formula
[Chemical 9]
（D）矽烷偶合劑
･X-12-1048：有機鏈類型的多官能基型矽烷偶合劑（信越矽利光（ShinEtsu Silicone）公司製造，黏度33 mm2
/s，反應性官能基當量300 g/mol，分子量2,500（推算））
･X-12-1050：有機鏈類型的多官能基型矽烷偶合劑（信越矽利光（ShinEtsu Silicone）公司製造，黏度6,000 mm2
/s，反應性官能基當量150 g/mol，分子量14萬（推算））
･X-40-9296：矽氧烷鏈類型的多官能基型矽烷偶合劑（信越矽利光（ShinEtsu Silicone）公司製造，黏度20 mm2
/s，反應性官能基當量230 g/mol，分子量1,500（推算））
･KBM-5103：下述化學式所表示的3-丙烯醯氧基丙基三甲氧基癸烷（信越矽利光（ShinEtsu Silicone）公司製造，分子量258）
[化10]
(D) Silane coupling agent X-12-1048: organic chain type multifunctional silane coupling agent (manufactured by ShinEtsu Silicone), viscosity 33 mm 2 / s, reactive functional group equivalent 300 g / mol, molecular weight 2,500 (estimated)
-12X-12-1050: Organic chain type multifunctional silane coupling agent (manufactured by ShinEtsu Silicone), viscosity 6,000 mm 2 / s, reactive functional group equivalent 150 g / mol, molecular weight 140,000 ( Calculation))
· X-40-9296: Silicon siloxane chain type of polyfunctional group-containing silicon silane coupling agent (Shin-Etsu Silicone Toshimitsu (ShinEtsu Silicone) Corporation, viscosity 20 mm 2 / s, the reactive functional group equivalent 230 g / mol, a molecular weight of 1,500 (Estimated))
･ KBM-5103: 3-propenyloxypropyltrimethoxydecane represented by the following chemical formula (manufactured by ShinEtsu Silicone, molecular weight 258)
[Chemical 10]
（E）調平劑
･LS-460 （楠本化成公司製造）(E) Leveling agent ･ LS-460 (manufactured by Kusumoto Chemical Co., Ltd.)
[實施例1]
對作為（A）脂肪族(甲基)丙烯酸單體的9PG 45 g、TMPT-3EO 10 g，作為（A-2）含環結構的(甲基)丙烯酸單體的BPE-500 45 g，作為（C）四甲基哌啶自由基衍生物的4H-TEMPO 0.03 g，以及作為（D）矽烷偶合劑的X-12-1048 3 g進行混合･攪拌。其後，加入作為（B）偶氮系聚合起始劑的OTAZO 0.3 g，進一步進行混合･攪拌，製備顯示元件用密封材。[Example 1]
45 g of 9PG as the (A) aliphatic (meth) acrylic monomer and 10 g of TMPT-3EO, and 45 g of the BPE-500 as the (A-2) ring-containing (meth) acrylic monomer as (C) 0.03 g of 4H-TEMPO of the tetramethylpiperidine radical derivative and 3 g of X-12-1048 as the (D) silane coupling agent were mixed and stirred. Thereafter, 0.3 g of OTAZO as the (B) azo-based polymerization initiator was added, and further mixed and stirred to prepare a sealing material for a display element.
[實施例2～實施例6、及比較例1～比較例7]
除設為表1及表2所示的材料及組成以外，與實施例1同樣地製備顯示元件用密封材。[Examples 2 to 6 and Comparative Examples 1 to 7]
A sealing material for a display element was prepared in the same manner as in Example 1 except that the materials and compositions shown in Tables 1 and 2 were used.
[評價]
對各實施例及比較例中所製備的顯示元件用密封材的黏度進行測定。進而，藉由以下的方法來進行硬化物的玻璃轉移溫度（Tg）的測定、硬化物的線膨脹係數的測定、硬化後的條紋不均的確認、及接著強度的評價。將結果示於表1及表2中。[Evaluation]
The viscosity of the sealing material for display elements prepared by each Example and the comparative example was measured. Further, the measurement of the glass transition temperature (Tg) of the cured product, the measurement of the linear expansion coefficient of the cured product, the confirmation of the unevenness of streaks after curing, and the evaluation of the adhesive strength were performed by the following methods. The results are shown in Tables 1 and 2.
･黏度測定
利用E型黏度計（博菲勒（BROOKFIELD）公司製造的數位流變計型號DII-III ULTRA），測定25℃、2.5 rpm下的顯示元件用密封材的黏度。･ Viscosity measurement The viscosity of a sealing material for a display element at 25 ° C. and 2.5 rpm was measured using an E-type viscometer (digital rheometer model DII-III ULTRA manufactured by BROOKFIELD).
･硬化物的玻璃轉移溫度（Tg）及線膨脹係數
對顯示元件用密封材以條件100℃進行30分鐘加熱而使其硬化。對硬化樣品切出長度50 mm×寬度4 mm，利用TMA測定裝置（TMA SS6000 精工儀器（Seiko instruments）公司製造），以升溫速度5℃/分進行測定。然後，利用分析軟體確定出Tg及35℃～100℃中的線膨脹係數。The glass transition temperature (Tg) and linear expansion coefficient of the hardened material are cured by heating the sealing material for a display element at a temperature of 100 ° C. for 30 minutes. The hardened sample was cut out by a length of 50 mm × width of 4 mm, and measured with a TMA measuring device (TMA SS6000 Seiko instruments) at a temperature rising rate of 5 ° C / min. Then, the analysis software was used to determine the Tg and the coefficient of linear expansion at 35 ° C to 100 ° C.
･硬化後的條紋不均的確認
（樣品的製作方法）
於25 mm×45 mm×厚度0.7 mm的無鹼玻璃上載置適量的顯示元件用密封材並放入真空腔室內，利用真空泵減壓至1.2 Pa為止。其後，於玻璃的兩端載置厚度15 μm、寬度5 mm的間隔物。於評價樣品中使用間隔物來代替隔堤材。然後，自該間隔物之上載置與上述相同大小的無鹼玻璃（25 mm×45 mm×厚度0.7 mm）。然後，利用夾具夾持兩端而使密封材於相向的玻璃之間擴展。對所述玻璃積層體於氮吹洗烘箱（大和科學（Yamato Scientific）製造的DN4101）中以100℃進行30分鐘加熱，使顯示元件用密封材硬化。确认 Confirmation of uneven streaks after hardening (How to make samples)
An appropriate amount of sealing material for display elements was placed on 25 mm × 45 mm × 0.7 mm thick non-alkali glass and placed in a vacuum chamber. The vacuum pump was used to reduce the pressure to 1.2 Pa. Thereafter, a spacer having a thickness of 15 μm and a width of 5 mm was placed on both ends of the glass. A spacer was used in the evaluation sample instead of a bank. Then, an alkali-free glass (25 mm × 45 mm × thickness 0.7 mm) of the same size as above was placed on the spacer. Then, both ends are clamped by a jig to expand the sealing material between the opposing glasses. The glass laminate was heated in a nitrogen purging oven (DN4101 manufactured by Yamato Scientific) at 100 ° C for 30 minutes to harden the sealing material for a display element.
（條紋不均的評價）
利用顯微鏡，自玻璃面側對玻璃積層體的間隔物與密封材的界面附近進行確認，並如以下般進行評價。同時，將實施例1及比較例1中所製作的樣品（間隔物13附近的顯示元件用密封材的硬化物12）的相片分別示於圖2A及圖2B。
未產生不均：A
於距界面為寬度500 μm以下的範圍內產生不均：B
於距界面超過寬度500 μm的範圍內產生不均：C(Evaluation of uneven stripes)
Using a microscope, the vicinity of the interface between the spacer and the sealing material of the glass laminate was confirmed from the glass surface side, and evaluated as follows. At the same time, photographs of the samples (the cured product 12 of the sealing material for a display element near the spacer 13) produced in Example 1 and Comparative Example 1 are shown in FIGS. 2A and 2B, respectively.
No unevenness: A
Unevenness occurs within a width of 500 μm from the interface: B
Unevenness in a range of more than 500 μm from the interface: C
･接著強度的評價
於所述條紋不均的確認中所製作的玻璃積層體的玻璃與玻璃之間插入鑷子，如以下般對剝離界面進行確認。再者，相比於玻璃與顯示元件用密封材的硬化物的界面處發生剝離的情況，顯示元件用密封材破壞或玻璃破裂的情況可謂接著強度更高。
於玻璃與顯示元件用密封材之間發生剝離的情況：△（界面剝離）
玻璃破裂的情況：○（材料破壞）(2) Evaluation of the strength of the adhesion. The tweezers were inserted between the glass and the glass of the glass laminate produced in the above-mentioned confirmation of uneven streaks, and the peeling interface was confirmed as follows. In addition, compared with the case where peeling occurs at the interface between the glass and the hardened material of the sealing material for a display element, the case where the sealing material for a display element is broken or the glass is broken can be said to have higher bonding strength.
When peeling occurs between the glass and the sealing material for display elements: △ (Interfacial peeling)
Glass breakage: ○ (material damage)
[表1]
[表2]
如表1及圖2A所示，包含（A）脂肪族(甲基)丙烯酸單體、（B）偶氮系聚合起始劑、（C）四甲基哌啶自由基衍生物、以及（D）具有(甲基)丙烯酸基且分子量為400～500,000的矽烷偶合劑，且硬化後的玻璃轉移溫度為46℃以上的顯示元件用密封材中未產生條紋不均（實施例1～實施例6）。認為因所述（D）矽烷偶合劑即便於真空環境下亦不易揮發，密封材的硬化物與玻璃基板的接著性非常高，且於硬化時或硬化後密封材（或其硬化物）不易變形等，故於顯示元件用密封材的硬化物與玻璃之間不易產生縫隙（條紋不均）。As shown in Table 1 and FIG. 2A, (A) an aliphatic (meth) acrylic monomer, (B) an azo-based polymerization initiator, (C) a tetramethylpiperidine radical derivative, and (D) ) A silane coupling agent having a (meth) acrylic group and a molecular weight of 400 to 500,000, and no unevenness in streaks occurred in a sealing material for a display element having a glass transition temperature of 46 ° C or higher after curing (Examples 1 to 6) ). It is considered that (D) the silane coupling agent is not easily volatile even in a vacuum environment, the adhesion between the hardened material of the sealing material and the glass substrate is very high, and the sealing material (or its hardened material) is not easily deformed during or after hardening. As a result, gaps (stripe unevenness) are unlikely to occur between the cured product of the sealing material for display elements and glass.
另外，如所述表1所示，若與所述（D）矽烷偶合劑一同包含3官能的（A）脂肪族(甲基)丙烯酸單體，則接著強度尤其容易提高（實施例1、實施例2、實施例5、及實施例6）。In addition, as shown in Table 1, if the trifunctional (A) aliphatic (meth) acrylic monomer is included together with the (D) silane coupling agent, the adhesion strength is particularly easily improved (Example 1, implementation Example 2, Example 5, and Example 6).
另一方面，如表2及圖2B所示，於不包含所述（D）矽烷偶合劑的情況（比較例1、比較例2）、或所述（D）矽烷偶合劑的分子量未滿400的情況（比較例3）下，不僅玻璃基板與密封材的接著強度未提高，而且亦產生了條紋不均。另外，於即便包含了所述成分（A）～成分（D），但顯示元件用密封材的硬化後的玻璃轉移溫度未滿46℃的情況（比較例4～比較例7）下，亦容易產生條紋不均。推測若玻璃轉移溫度低，則顯示元件用密封材的硬化物於硬化後容易發生變形或收縮，從而容易產生條紋不均。
[工業上之可利用性]On the other hand, as shown in Table 2 and FIG. 2B, when the (D) silane coupling agent is not included (Comparative Example 1, Comparative Example 2), or the molecular weight of the (D) silane coupling agent is less than 400 In the case (Comparative Example 3), not only the bonding strength between the glass substrate and the sealing material was not improved, but unevenness in stripes also occurred. In addition, even when the components (A) to (D) are included, the glass transition temperature after curing of the sealing material for a display element is less than 46 ° C (Comparative Example 4 to Comparative Example 7). Stripe unevenness occurs. It is estimated that when the glass transition temperature is low, the cured product of the sealing material for a display element is likely to be deformed or shrunk after being cured, and streaks are likely to occur.
[Industrial availability]
本發明的顯示元件用密封材不僅可將顯示元件充分密封，而且於密封後不易產生條紋不均。因此，可適用於多種顯示元件。The sealing material for a display element of the present invention can not only sufficiently seal the display element, but also less likely to cause uneven stripes after sealing. Therefore, it can be applied to various display elements.
11‧‧‧隔堤材11‧‧‧ Embankment material
12‧‧‧顯示元件用密封材的硬化物 12‧‧‧ Hardened product of sealing material for display element
13‧‧‧間隔物 13‧‧‧ spacer
圖1是表示利用以前的顯示元件用密封材對顯示元件進行面密封時的、隔堤材附近的顯示元件用密封材的硬化物的相片。FIG. 1 is a photograph showing a cured product of a sealing material for a display element near a bank material when a display element is surface-sealed with a conventional sealing material for a display element.
圖2A是表示實施例1的條紋不均評價樣品的間隔物附近的顯示元件用密封材的硬化物的相片，圖2B是表示比較例1的條紋不均評價樣品的間隔物附近的顯示元件用密封材的硬化物的相片。 FIG. 2A is a photograph showing a cured product of a sealing material for a display element near a spacer of a streak unevenness evaluation sample of Example 1. FIG. 2B is a display element for a display element near a spacer of a streak unevenness evaluation sample of Comparative Example 1. Photo of the hardened material of the seal.
Claims (14)
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| KR100776721B1 (en) * | 2005-10-05 | 2007-11-28 | 주식회사 두산 | Sealantcomposition for use of LCD device and seals using the same |
| KR20090032361A (en) * | 2007-09-27 | 2009-04-01 | 동우 화인켐 주식회사 | Curable resin composition and liquid crystal display device |
| JP5449176B2 (en) * | 2008-09-29 | 2014-03-19 | 三井化学株式会社 | Sealant, sealing member, and organic EL device |
| CN102210192B (en) * | 2008-11-28 | 2014-07-30 | 三井化学株式会社 | Organic el element surface sealant, method for producing display, and display |
| JP2012184353A (en) * | 2011-03-07 | 2012-09-27 | Yokohama Rubber Co Ltd:The | Heat-curable silicone resin composition for sealing optical semiconductor and optical semiconductor package using the same |
| JP5808599B2 (en) * | 2011-07-28 | 2015-11-10 | 株式会社ダイセル | Primer composition and optical semiconductor device using the primer composition |
| CA2994085C (en) * | 2015-07-30 | 2023-08-22 | Threebond Co., Ltd. | Photocurable resin composition, fuel cell, and sealing method |
| JP6822863B2 (en) * | 2016-03-31 | 2021-01-27 | 三井化学株式会社 | Thermosetting composition, encapsulant containing the same, frame encapsulant for organic EL element, surface encapsulant for organic EL element, and cured product thereof. |
| WO2018030113A1 (en) * | 2016-08-10 | 2018-02-15 | パナソニックＩｐマネジメント株式会社 | Acrylic composition for sealing, sheet material, multilayer sheet, cured product, semiconductor device and method for manufacturing semiconductor device |
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| WO2019181592A1 (en) | 2019-09-26 |
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| JPWO2019181592A1 (en) | 2020-12-03 |
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| KR20200123195A (en) | 2020-10-28 |
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