JP2012236938A - Sealant, and molded article, optical element and light-emitting diode using the same - Google Patents
Sealant, and molded article, optical element and light-emitting diode using the same Download PDFInfo
- Publication number
- JP2012236938A JP2012236938A JP2011107593A JP2011107593A JP2012236938A JP 2012236938 A JP2012236938 A JP 2012236938A JP 2011107593 A JP2011107593 A JP 2011107593A JP 2011107593 A JP2011107593 A JP 2011107593A JP 2012236938 A JP2012236938 A JP 2012236938A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- sealing material
- group
- aliphatic cyclic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims description 8
- 239000000565 sealant Substances 0.000 title abstract 3
- 239000004814 polyurethane Substances 0.000 claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 claims abstract description 53
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 35
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 101
- 239000003566 sealing material Substances 0.000 claims description 94
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 229920001228 polyisocyanate Polymers 0.000 claims description 32
- 239000005056 polyisocyanate Substances 0.000 claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 25
- 125000001931 aliphatic group Chemical group 0.000 claims description 24
- 125000002723 alicyclic group Chemical group 0.000 claims description 20
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 16
- 229920005862 polyol Polymers 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 229920001187 thermosetting polymer Polymers 0.000 claims description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 7
- CVDUUPMTIHXQKC-UHFFFAOYSA-N ethene 1,3,5-triazinane-2,4,6-trione Chemical group C=C.O=C1NC(=O)NC(=O)N1 CVDUUPMTIHXQKC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000016 photochemical curing Methods 0.000 claims description 6
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 4
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 3
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical compound [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 22
- 150000003254 radicals Chemical class 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- -1 acrylate compound Chemical class 0.000 description 21
- 238000001723 curing Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 235000019645 odor Nutrition 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 229940119545 isobornyl methacrylate Drugs 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- HZRPIZSSEMKEEW-UHFFFAOYSA-N C1CO1.O=C1NC(=O)NC(=O)N1 Chemical compound C1CO1.O=C1NC(=O)NC(=O)N1 HZRPIZSSEMKEEW-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000008393 encapsulating agent Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 description 2
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
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- 239000003759 ester based solvent Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
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- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
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- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
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- BMIMOHQDMVRREN-UHFFFAOYSA-N 2-(2-hydroxyethylamino)-4-methylbenzaldehyde Chemical compound CC1=CC=C(C=O)C(NCCO)=C1 BMIMOHQDMVRREN-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- OADIZUFHUPTFAG-UHFFFAOYSA-N 2-[2-(2-ethylhexoxy)ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCO OADIZUFHUPTFAG-UHFFFAOYSA-N 0.000 description 1
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Abstract
Description
本発明は、ラジカル重合性の封止材およびそれを用いた成形品に関する。本発明は、特に、低温での硬化性に優れ、熱による封止材硬化物の変色が極めて少なく、臭気の少ない封止材に関し、透明電気注型用、LED封止用等の透明性を有する光学分野を含め幅広く使用される。 The present invention relates to a radically polymerizable sealing material and a molded article using the same. The present invention particularly relates to a sealing material that is excellent in curability at low temperature, has very little discoloration of a cured sealing material due to heat, and has little odor, and has transparency such as for transparent electrocasting and for LED sealing. Widely used including the optical field.
不飽和ポリエステル系樹脂、エポキシ(メタ)クリレート系樹脂、アクリル系樹脂、ウレタン(メタ)アクリレート系樹脂等に代表されるラジカル重合性組成物は、ラジカル重合性に起因する優れた速硬化性を活かし、モーター等の電気封止部材等の製造場面で幅広く使用されている。
一方、封止材は、近年、前記技術分野以外にも、LEDやレンズ、ディスプレイ等の光学部材を製造する場面で使用することが検討されており、かかる分野で使用される光学部材用の封止材には、透明性と耐熱変色性に優れることが求められる場合が多い。
しかし、前記したようなラジカル重合性組成物は、速硬化性に優れるものの、耐熱変色性の点で十分でないため、特に光学部材の製造場面で使用されるには至っていないのが実情である。
前記透明性や耐熱変色性の良好な封止材としては、例えば脂環式エポキシ樹脂と、硬化剤としての酸無水物を含む組成物が知られている。
しかし、前記脂環式エポキシ樹脂と硬化剤との組み合わせでは、それらを完全硬化するために高い温度で長時間反応を継続する必要がある等、ラジカル重合性樹脂に比較し硬化性に劣り、また耐熱変色性も未だ十分といえるものではなかった。
Radical polymerizable compositions typified by unsaturated polyester resins, epoxy (meth) acrylate resins, acrylic resins, urethane (meth) acrylate resins, etc. make use of the excellent rapid curability resulting from radical polymerizability. It is widely used in manufacturing scenes for electrical sealing members such as motors.
On the other hand, in recent years, it has been studied that the sealing material is used in the field of manufacturing optical members such as LEDs, lenses, displays, etc. in addition to the above technical fields. Stop materials are often required to have excellent transparency and heat discoloration.
However, although the radically polymerizable composition as described above is excellent in rapid curability, it is not sufficient in terms of heat discoloration, so that it is not actually used in the production of optical members.
As the sealing material having good transparency and heat discoloration, for example, a composition containing an alicyclic epoxy resin and an acid anhydride as a curing agent is known.
However, in the combination of the alicyclic epoxy resin and the curing agent, it is necessary to continue the reaction at a high temperature for a long time in order to completely cure them. The heat discoloration was still not sufficient.
このような問題を解決するために、脂環式構造とエチレン性不飽和基を有する樹脂を含むLED封止用硬化性樹脂組成物が提案されている(例えば、特許文献1)。
また、芳香族多価イソシアネートを使用したウレタン(メタ)アクリレート化合物から構成される硬化性樹脂組成物の経時による黄変、及び成形物の保護層としての性能劣化を抑制しうる硬化性樹脂組成物が提案されている(例えば、特許文献2)。
In order to solve such a problem, a curable resin composition for LED encapsulation containing a resin having an alicyclic structure and an ethylenically unsaturated group has been proposed (for example, Patent Document 1).
Moreover, the curable resin composition which can suppress yellowing with the passage of time of the curable resin composition comprised from the urethane (meth) acrylate compound which uses aromatic polyvalent isocyanate, and the performance deterioration as a protective layer of a molded article Has been proposed (for example, Patent Document 2).
しかし、特許文献1に記載の硬化性樹脂組成物においては、ラジカル重合性に起因して優れた硬化性を有するものの、耐熱変色性においては、十分なものではなかった。
また、特許文献2に記載の硬化性樹脂組成物においては、比較的良好な耐光変色性と機械的強度とを考慮した成形品を形成できるものの、かかる成形品は耐熱変色性の点で十分でない場合があった
However, the curable resin composition described in
Further, in the curable resin composition described in Patent Document 2, although a molded product considering relatively good light discoloration resistance and mechanical strength can be formed, such a molded product is not sufficient in terms of heat discoloration. There was a case
本発明が解決しようとする課題は、優れた耐熱性、耐熱変色性、及び透明性を有し、かつ、比較的低温環境下であっても硬化性に優れた封止材を提供することである。 The problem to be solved by the present invention is to provide a sealing material having excellent heat resistance, heat discoloration, and transparency, and excellent curability even in a relatively low temperature environment. is there.
(1)本発明の封止材は、下記一般式(I)で示される構造を有する(メタ)アクリロイル基含有ポリウレタン(A)とラジカル重合性不飽和単量体(B)とを含有することを特徴とする。 (1) The sealing material of the present invention contains a (meth) acryloyl group-containing polyurethane (A) having a structure represented by the following general formula (I) and a radical polymerizable unsaturated monomer (B). It is characterized by.
(2)本発明の封止材は、熱硬化剤又は光硬化剤(C)を更に含むことが好ましい。 (2) It is preferable that the sealing material of this invention further contains a thermosetting agent or a photocuring agent (C).
(3)本発明の封止材は、前記(メタ)アクリロイル基含有ポリウレタン(A)が、分子量100〜300の脂肪族環式構造含有ポリオール(a1)と、脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)と、活性水素原子含有(メタ)アクリレート(a3)とを反応させて得られるものであり、前記ラジカル重合性不飽和単量体(B)が、脂肪族環式構造、脂肪族鎖状構造又はイソシアヌル酸構造を有するものであることが好ましい。 (3) In the sealing material of the present invention, the (meth) acryloyl group-containing polyurethane (A) is an aliphatic cyclic structure-containing polyol (a1) having a molecular weight of 100 to 300, an alicyclic polyisocyanate, or an aliphatic poly It is obtained by reacting isocyanate (a2) with active hydrogen atom-containing (meth) acrylate (a3), and the radical polymerizable unsaturated monomer (B) has an aliphatic cyclic structure, an aliphatic group. It is preferable to have a chain structure or an isocyanuric acid structure.
(4)本発明の封止材は、前記脂肪族環式構造含有ポリオール(a1)がシクロヘキサンジメタノールであり、かつ前記脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)がイソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート及びノルボルネンジイソシアネートからなる群より選ばれる1種以上であることが好ましい。 (4) In the sealing material of the present invention, the aliphatic cyclic structure-containing polyol (a1) is cyclohexanedimethanol, and the alicyclic polyisocyanate or the aliphatic polyisocyanate (a2) is isophorone diisocyanate or dicyclohexylmethane. It is preferably at least one selected from the group consisting of diisocyanates and norbornene diisocyanates.
(5)本発明の封止材は、前記ラジカル重合性不飽和単量体(B)が、イソボルニル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、イソシアヌル酸エチレンオキシド変性ジ(メタ)アクリレート、及びイソシアヌル酸エチレンオキシド変性トリ(メタ)アクリレートからなる群より選ばれる1種以上であることが好ましい。 (5) In the sealing material of the present invention, the radical polymerizable unsaturated monomer (B) is isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, or isocyanuric acid ethylene oxide. It is preferably at least one selected from the group consisting of modified di (meth) acrylate and isocyanuric acid ethylene oxide modified tri (meth) acrylate.
(6)本発明の封止材は、前記活性水素原子含有(メタ)アクリレート(a3)が2−ヒドロキシエチル(メタ)アクリレート又はイソシアヌル酸構造を有する水酸基含有(メタ)アクリレートであることが好ましい。
(7)本発明の成形品は、前記封止材を用い封止して得られたことを特徴とする。
(8)本発明の光学部材は、前記封止材を用い封止して得られたことを特徴とする。
(9)本発明の発光ダイオードは、前記封止材を用い封止して得られたことを特徴とする。
(6) In the sealing material of the present invention, the active hydrogen atom-containing (meth) acrylate (a3) is preferably a hydroxyl group-containing (meth) acrylate having a 2-hydroxyethyl (meth) acrylate or an isocyanuric acid structure.
(7) The molded product of the present invention is obtained by sealing using the sealing material.
(8) The optical member of the present invention is obtained by sealing using the sealing material.
(9) The light emitting diode of the present invention is obtained by sealing using the sealing material.
本発明によれば、優れた耐熱性、耐熱変色性、及び透明性を有し、かつ、比較的低温環境下であっても硬化性に優れた封止材を提供することができる。 According to the present invention, it is possible to provide a sealing material having excellent heat resistance, heat discoloration, and transparency, and excellent curability even in a relatively low temperature environment.
本発明の封止材に用いられる(メタ)アクリロイル基含有ポリウレタン(A)(以下、(A)成分という。)は、下記一般式(I)で示される構造を有するものである。 The (meth) acryloyl group-containing polyurethane (A) (hereinafter referred to as component (A)) used for the sealing material of the present invention has a structure represented by the following general formula (I).
前記一般式(I)中のZは、脂肪族環式構造含有アルキレン基であり、脂肪族環式基と鎖状アルキレン基とから構成される。
脂肪族環式構造含有アルキレン基としては、脂肪族環式基(脂肪族炭化水素環から水素原子を2個除いた基)、該脂肪族環式基が鎖状アルキレン基の末端に結合するか又は鎖状アルキレン基の途中に介在する基などが挙げられる。
鎖状アルキレン基としては、直鎖状又は分岐鎖状のアルキレン基が挙げられる。
ここで、Zにおけるアルキレン基が、脂肪族環式基を有さず、鎖状アルキレン基や、芳香族環を有する炭化水素基である場合、(A)成分を含有する封止材の耐熱性が十分でないため、該封止材は、封止材硬化物の変形等を引き起こしやすく、また、熱や光の影響によって変色する場合がある。
Z in the general formula (I) is an aliphatic cyclic structure-containing alkylene group, and is composed of an aliphatic cyclic group and a chain alkylene group.
The aliphatic cyclic structure-containing alkylene group includes an aliphatic cyclic group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and whether the aliphatic cyclic group is bonded to the end of a chain alkylene group. Or the group which intervenes in the middle of a chain alkylene group etc. are mentioned.
Examples of the chain alkylene group include a linear or branched alkylene group.
Here, when the alkylene group in Z does not have an aliphatic cyclic group but is a chain alkylene group or a hydrocarbon group having an aromatic ring, the heat resistance of the sealing material containing the component (A) Therefore, the sealing material is likely to cause deformation of the cured sealing material, and may be discolored by the influence of heat or light.
Zにおける前記脂肪族環式構造含有アルキレン基の分子量は、65〜265であり、比較的小さいことが好ましい。
例えば、前記脂肪族環式構造含有アルキレン基は、後述する脂肪族環式構造含有ポリオール(a1)と、後述する脂肪族環式構造含有アルキレン基含有ポリイソシアネート(以下、脂環式ポリイソシアネート)又は鎖状アルキレン基含有ポリイソシアネート(以下、脂肪族ポリイソシアネート)(a2)とを反応させることによって式(I)中に導入される(a1)に由来する構造であることが好ましく、その分子量は後述する(a1)から2つの水酸基を除いた分子量に相当する。
例えば前記脂肪族環式構造含有ポリオール(a1)として分子量100〜300の範囲のものを使用した場合、前記脂肪族環式構造含有アルキレン基の分子量は、前記100〜300の範囲と、2つの水酸基の式量34.016との差分となる。
なお、Zにおける脂肪族環式構造含有アルキレン基の分子量は、脂肪族環式基を含むアルキレン基を構成する元素の式量に基づいて算出した値を示す。
The molecular weight of the aliphatic cyclic structure-containing alkylene group in Z is 65 to 265, and is preferably relatively small.
For example, the aliphatic cyclic structure-containing alkylene group includes an aliphatic cyclic structure-containing polyol (a1) described later and an aliphatic cyclic structure-containing alkylene group-containing polyisocyanate (hereinafter referred to as alicyclic polyisocyanate) or A structure derived from (a1) introduced into formula (I) by reacting with a chain alkylene group-containing polyisocyanate (hereinafter referred to as aliphatic polyisocyanate) (a2) is preferable, and the molecular weight thereof is described later. This corresponds to the molecular weight obtained by removing two hydroxyl groups from (a1).
For example, when the aliphatic cyclic structure-containing polyol (a1) has a molecular weight in the range of 100 to 300, the aliphatic cyclic structure-containing alkylene group has a molecular weight in the range of 100 to 300 and two hydroxyl groups. This is the difference from the formula amount 34.016.
In addition, the molecular weight of the aliphatic cyclic structure-containing alkylene group in Z is a value calculated based on the formula weight of the elements constituting the alkylene group containing the aliphatic cyclic group.
前記一般式(I)中のTは、脂肪族環式構造含有アルキレン基又は鎖状アルキレン基であり、例えば、後述する脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)由来の構造が挙げられる。
前記一般式(I)中のZが脂肪族環式構造含有アルキレン基であっても、前記Tが脂肪族環式構造含有アルキレン基又は鎖状アルキレン基でなく、例えば芳香族環を有する炭化水素基である場合には、封止材の耐熱変色性が低下する場合がある。
T in the general formula (I) is an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, and examples thereof include a structure derived from an alicyclic polyisocyanate or an aliphatic polyisocyanate (a2) described later. .
Even if Z in the general formula (I) is an aliphatic cyclic structure-containing alkylene group, the T is not an aliphatic cyclic structure-containing alkylene group or a chain alkylene group, for example, a hydrocarbon having an aromatic ring When it is a base, the heat discoloration of the sealing material may be lowered.
前記一般式(I)中のMは、(メタ)アクリロイル基を含む原子団である。例えば、後述する活性水素原子含有(メタ)アクリレート(a3)由来の構造が挙げられ、該構造は前記(A)成分の分子中に(メタ)アクリロイル基を付与する。前記(メタ)アクリロイル基は、前記(A)成分の分子末端にそれぞれ1〜10個存在することが好ましく、1〜3個存在することがより好ましい。 M in the general formula (I) is an atomic group containing a (meth) acryloyl group. For example, the structure derived from the active hydrogen atom containing (meth) acrylate (a3) mentioned later is mentioned, This structure provides a (meth) acryloyl group in the molecule | numerator of the said (A) component. The number of the (meth) acryloyl groups is preferably 1 to 10 and more preferably 1 to 3 at the molecular ends of the component (A).
前記(メタ)アクリロイル基含有ポリウレタン(A)としては、500〜1500の分子量を有するものを使用することが好ましく、500〜1200のものを使用することがより好ましい。なお、その分子量は、(メタ)アクリロイル基含有ポリウレタン(A)を構成する原子の式量に基づき、その合計量から求められる値を指す。 As said (meth) acryloyl group containing polyurethane (A), it is preferable to use what has a molecular weight of 500-1500, and it is more preferable to use the thing of 500-1200. In addition, the molecular weight points out the value calculated | required from the total amount based on the formula amount of the atom which comprises a (meth) acryloyl group containing polyurethane (A).
前記(メタ)アクリロイル基含有ポリウレタン(A)は、例えば、脂肪族環式構造含有ポリオール(a1)と、脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)と、活性水素原子含有(メタ)アクリレート(a3)とを用いて製造することができる。
より具体的には、例えば脂肪族環式構造含有ポリオール(a1)と、脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)とを反応させることによって分子末端にイソシアネート基を有するポリウレタン(A−1)を得、次いで前記ポリウレタン(A−1)と活性水素原子含有(メタ)アクリレート(a3)とを反応させることによって容易に製造することができる。
The (meth) acryloyl group-containing polyurethane (A) includes, for example, an aliphatic cyclic structure-containing polyol (a1), an alicyclic polyisocyanate or an aliphatic polyisocyanate (a2), and an active hydrogen atom-containing (meth) acrylate. (A3) and can be manufactured.
More specifically, for example, an aliphatic cyclic structure-containing polyol (a1) and an alicyclic polyisocyanate or an aliphatic polyisocyanate (a2) are reacted to form a polyurethane having an isocyanate group at the molecular terminal (A-1 And then reacting the polyurethane (A-1) with the active hydrogen atom-containing (meth) acrylate (a3).
脂肪族環式構造含有ポリオールとは、分子内に脂肪族環式基(脂肪族炭化水素環から水素原子を2個除いた基)を含有するポリオールをいう。
脂肪族環式構造含有ポリオール(a1)としては、例えば1,4−シクロヘキサンジメタノール、1,3−シクロヘキサンジオール、1,4−シクロヘキサンジオール、2−ビス(4−ヒドロキシシクロヘキシル)−プロパン等の脂環式ジオール等を使用することができる。
中でも分子量が100〜300の範囲である脂肪族環式構造含有ポリオールが好ましく、シクロヘキサンジメタノールがより好ましく、1,4−シクロヘキサンジメタノールが特に好ましい。
1,4−シクロヘキサンジメタノールは、後述するラジカル重合性組成物を製造する際の、(メタ)アクリロイル基含有ポリウレタン(A)のラジカル重合性不飽和単量体(B)に対する溶解性をより向上させるとともに、封止材を硬化して得られる成形物に、より一層優れた機械的強度を付与でき、かつ、封止材の硬化物の耐熱変色性を一層向上できる。
The aliphatic cyclic structure-containing polyol refers to a polyol containing an aliphatic cyclic group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) in the molecule.
Examples of the aliphatic cyclic structure-containing polyol (a1) include fats such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-bis (4-hydroxycyclohexyl) -propane, and the like. Cyclic diols and the like can be used.
Among them, an aliphatic cyclic structure-containing polyol having a molecular weight in the range of 100 to 300 is preferable, cyclohexanedimethanol is more preferable, and 1,4-cyclohexanedimethanol is particularly preferable.
1,4-cyclohexanedimethanol improves the solubility of the (meth) acryloyl group-containing polyurethane (A) in the radical polymerizable unsaturated monomer (B) when producing a radical polymerizable composition described later. In addition, the molded product obtained by curing the encapsulant can be given more excellent mechanical strength, and the heat discoloration of the cured encapsulant can be further improved.
脂環式ポリイソシアネートとは、分子内に脂肪族環式構造含有アルキレン基を含有するポリイソシアネートをいう。
脂肪族ポリイソシアネートとは、分子内に鎖状アルキレン基を含有するポリイソシアネートをいう。
本発明で使用する脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)としては、例えば1,6−ヘキサメチレンジイソシアネート、2,2,4−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ポリイソシアネート;イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、シクロヘキシルジイソシアネート、ビス(イソシアネートメチルシクロヘキサン)、ノルボルネンジイソシアネート等の脂環式ポリイソシアネート;これらのヌレートを、単独又は併用して使用することができる。
中でも、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ノルボルネンジイソシアネートが好ましい。
イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ノルボルネンジイソシアネートを使用することにより、ラジカル重合性組成物を製造する際の、(メタ)アクリロイル基含有ポリウレタン(A)のラジカル重合性不飽和単量体(B)に対する溶解性を一層向上するとともに、封止材を硬化して得られる成形物により一層優れた機械的強度や耐熱変色性を付与でき、各種部材に対する密着性にも優れる。
また、本発明の封止材は、前記一般式(I)における脂肪族環式構造を芳香族構造に置換した化合物を、本発明の性能を損なわない程度に、任意成分として、含有していてもよい。
The alicyclic polyisocyanate refers to a polyisocyanate containing an aliphatic cyclic structure-containing alkylene group in the molecule.
An aliphatic polyisocyanate refers to a polyisocyanate containing a chain alkylene group in the molecule.
Examples of the alicyclic polyisocyanate or aliphatic polyisocyanate (a2) used in the present invention include aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate; Cycloaliphatic polyisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate, bis (isocyanate methylcyclohexane), norbornene diisocyanate; these nurates can be used alone or in combination.
Of these, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and norbornene diisocyanate are preferable.
Dissolution of the (meth) acryloyl group-containing polyurethane (A) in the radically polymerizable unsaturated monomer (B) when producing a radically polymerizable composition by using isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate In addition, the molded product obtained by curing the encapsulant can be further improved in mechanical strength and heat discoloration, and has excellent adhesion to various members.
Moreover, the sealing material of this invention contains the compound which substituted the aliphatic cyclic structure in the said general formula (I) by the aromatic structure as an arbitrary component to such an extent that the performance of this invention is not impaired. Also good.
本発明で使用する活性水素原子含有(メタ)アクリレート(a3)としては、例えば、
2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、3−ヒドロキシブチル(メタ)アクリレート等が挙げられる。その他に、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の水酸基を2個有するアルコールのモノ(メタ)アクリレート類;α−オレフィンエポキシドと(メタ)アクリル酸の付加物;カルボン酸グリシジルエステルと(メタ)アクリル酸の付加物;トリス(ヒドロキシエチル)イソシアヌル酸のジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート;イソシアヌル酸エチレンオキシド変性モノ(メタ)アクリレート、イソシアヌル酸エチレンオキシド変性ジ(メタ)アクリレート等のイソシアヌル酸構造を有する水酸基含有(メタ)アクリレート;アミノメチル(メタ)アクリレート、2−アミノエチル(メタ)アクリレート、3−アミノプロピル(メタ)アクリレート;(メタ)アクリル酸;(メタ)アクリル酸のエチレンオキシド、プロピレンオキシド、テトラヒドロフランを含むブチレンオキシド付加物;上記水酸基含有(メタ)アクリレートの酸無水物付加物等が挙げられる。これらは単独で使用しても、発明の効果を妨げない範囲で併用して使用しても良い。
中でも、水酸基含有(メタ)アクリレートを使用することが好ましく、2−ヒドロキシエチル(メタ)アクリレート又はイソシアヌル酸構造を有する水酸基含有(メタ)アクリレートを使用することがより好ましい。
2−ヒドロキシエチル(メタ)アクリレートを使用することにより、前記封止材を用いて封止された成形品により優れた耐熱性と強度と付与でき、また、該封止材に一層の低温硬化性を付与することができる。
また、イソシアヌル酸構造を有する水酸基含有(メタ)アクリレートを使用することにより、前記封止材を用いて封止された成形品により優れた耐熱変色性を付与することができる。
As the active hydrogen atom-containing (meth) acrylate (a3) used in the present invention, for example,
Examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate. In addition, mono (meth) acrylates of alcohols having two hydroxyl groups such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; adducts of α-olefin epoxide and (meth) acrylic acid; carboxylic acid Addition of glycidyl ester and (meth) acrylic acid; di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate; isocyanuric acid ethylene oxide modified mono (meta) ) Acrylate, hydroxyl group-containing (meth) acrylate having an isocyanuric acid structure such as isocyanuric acid ethylene oxide modified di (meth) acrylate; aminomethyl (meth) acrylate, 2-aminoethyl (Meth) acrylate, 3-aminopropyl (meth) acrylate; (meth) acrylic acid; butylene oxide adducts of (meth) acrylic acid containing ethylene oxide, propylene oxide and tetrahydrofuran; acid anhydride of the above hydroxyl group-containing (meth) acrylate And adducts. These may be used alone or in combination as long as the effects of the invention are not impaired.
Among these, it is preferable to use a hydroxyl group-containing (meth) acrylate, and it is more preferable to use 2-hydroxyethyl (meth) acrylate or a hydroxyl group-containing (meth) acrylate having an isocyanuric acid structure.
By using 2-hydroxyethyl (meth) acrylate, it is possible to impart excellent heat resistance and strength to the molded product sealed with the sealing material, and further low temperature curability to the sealing material. Can be granted.
Further, by using a hydroxyl group-containing (meth) acrylate having an isocyanuric acid structure, excellent heat discoloration can be imparted to a molded article sealed with the sealing material.
前記脂肪族環式構造含有ポリオール(a1)と前記脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)との反応は、例えば前記脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)のイソシアネート基と、前記脂肪族環式構造含有ポリオール(a1)の水酸基との当量比[(a2)のイソシアネート基/(a1)の水酸基]が1.3/1〜2.5/1の範囲になるような条件で行うことが好ましく、1.5/1〜2/1の範囲になるような条件で行うことがより好ましい。これにより、分子末端にイソシアネート基を有するポリウレタン(A−1)を容易に製造することができる。 The reaction between the aliphatic cyclic structure-containing polyol (a1) and the alicyclic polyisocyanate or the aliphatic polyisocyanate (a2) is, for example, an isocyanate group of the alicyclic polyisocyanate or the aliphatic polyisocyanate (a2). The equivalent ratio of the aliphatic cyclic structure-containing polyol (a1) to the hydroxyl group [isocyanate group of (a2) / hydroxyl group of (a1)] is in the range of 1.3 / 1 to 2.5 / 1. It is preferable to carry out under conditions, and it is more preferred to carry out under conditions that are in the range of 1.5 / 1 to 2/1. Thereby, the polyurethane (A-1) which has an isocyanate group in a molecular terminal can be manufactured easily.
前記脂肪族環式構造含有ポリオール(a1)と前記脂環式ポリイソシアネート又は脂肪族ポリイソシアネート(a2)との反応は、50〜110℃の温度範囲で行うことが好ましく、60〜90℃の温度範囲で行うことがより好ましい。
また、分子末端にイソシアネート基を有するポリウレタン(A−1)の数平均分子量は、400〜1300であることが好ましく、400〜1000であることがより好ましい。上記範囲内の数平均分子量とするための反応条件は適宜決定することができる。反応条件としては、例えば、上記反応温度範囲にて行い、必要に応じ反応触媒を併用することが好ましい。
また、前記分子末端にイソシアネート基を有するポリウレタン(A−1)を製造する際には、重合禁止剤を用いることができる。重合禁止剤としては、後述するものが挙げられ、例えば、ポリウレタン(A−1)に対して10〜1500ppmで用いることができる。
The reaction between the aliphatic cyclic structure-containing polyol (a1) and the alicyclic polyisocyanate or the aliphatic polyisocyanate (a2) is preferably performed in a temperature range of 50 to 110 ° C, and a temperature of 60 to 90 ° C. It is more preferable to carry out within a range.
Moreover, it is preferable that the number average molecular weights of the polyurethane (A-1) which has an isocyanate group in a molecular terminal are 400-1300, and it is more preferable that it is 400-1000. The reaction conditions for setting the number average molecular weight within the above range can be appropriately determined. As the reaction conditions, for example, it is preferable to carry out within the above reaction temperature range and use a reaction catalyst in combination as necessary.
Moreover, when manufacturing the polyurethane (A-1) which has an isocyanate group in the said molecular terminal, a polymerization inhibitor can be used. Examples of the polymerization inhibitor include those described later. For example, the polymerization inhibitor can be used at 10 to 1500 ppm with respect to the polyurethane (A-1).
また、(メタ)アクリロイル基含有ポリウレタン(A)の製造方法としては、前記分子末端にイソシアネート基を有するポリウレタン(A−1)と活性水素原子含有(メタ)アクリレート(a3)とを反応させる方法が好ましく挙げられる。
かかる反応は、前記活性水素原子含有(メタ)アクリレート(a3)が有する水酸基、アミノ基、又はカルボキシル基と、前記ポリウレタン(A−1)中に残存するイソシアネート基との当量割合が、活性水素当量/イソシアネート当量=1/1〜1.3/1となる条件で行うことが好ましい。
前記分子末端にイソシアネート基を有するポリウレタン(A−1)と活性水素原子含有(メタ)アクリレート(a3)との反応は、50〜100℃の温度範囲で行うことが好ましい。
前記(メタ)アクリロイル基含有ポリウレタン(A)を製造する際には、後述するようなオクチル錫系化合物などの公知の触媒を使用することができる。
また、前記(メタ)アクリロイル基含有ポリウレタン(A)を製造する際には、重合禁止剤を用いることができる。重合禁止剤としては、後述するものが挙げられ、例えば、(メタ)アクリロイル基含有ポリウレタン(A)に対して10〜1500ppmで用いることができる。
Moreover, as a manufacturing method of (meth) acryloyl group containing polyurethane (A), the method with which the polyurethane (A-1) which has an isocyanate group in the said molecular terminal, and active hydrogen atom containing (meth) acrylate (a3) is made to react. Preferably mentioned.
In this reaction, the equivalent ratio of the hydroxyl group, amino group, or carboxyl group of the active hydrogen atom-containing (meth) acrylate (a3) and the isocyanate group remaining in the polyurethane (A-1) is an active hydrogen equivalent. / Isocyanate equivalent = 1/1 to 1.3 / 1.
The reaction between the polyurethane (A-1) having an isocyanate group at the molecular terminal and the active hydrogen atom-containing (meth) acrylate (a3) is preferably performed in a temperature range of 50 to 100 ° C.
When manufacturing the said (meth) acryloyl group containing polyurethane (A), well-known catalysts, such as an octyl tin type compound which are mentioned later, can be used.
Moreover, when manufacturing the said (meth) acryloyl group containing polyurethane (A), a polymerization inhibitor can be used. Examples of the polymerization inhibitor include those described later. For example, the polymerization inhibitor can be used at 10 to 1500 ppm with respect to the (meth) acryloyl group-containing polyurethane (A).
前記触媒としては、例えば、テトラブチルチタネート、テトラプロピルチタネート、テトラエチルチタネート等の有機チタン化合物;オクチル酸錫、ジブチル錫オキシド、ジブチル錫ラウレート、ジブチル錫ジバーサテート等の有機錫化合物;ジルコニウム系化合物;鉄系化合物;さらには、塩化第一錫、臭化第一錫、ヨウ化第一錫等の酸やアルカリ等が挙げられる。これらの触媒の添加量は、全仕込み量に対して5〜10000ppmであることが好ましい。 Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; organotin compounds such as tin octylate, dibutyltin oxide, dibutyltin laurate, and dibutyltin diversate; zirconium compounds; iron-based compounds Compound; Furthermore, acids, alkalis, etc., such as stannous chloride, stannous bromide, stannous iodide, etc. are mentioned. The amount of these catalysts added is preferably 5 to 10,000 ppm with respect to the total charge.
本発明の封止材は、前記(メタ)アクリロイル基含有ポリウレタン(A)とともに、ラジカル重合性不飽和単量体(B)等を含有するものである。 The sealing material of this invention contains a radically polymerizable unsaturated monomer (B) etc. with the said (meth) acryloyl group containing polyurethane (A).
前記ラジカル重合性不飽和単量体(B)としては、例えば、スチレン、α−メチルスチレン、クロルスチレン、ジクロルスチレン、ジビニルベンゼン、tert−ブチルスチレン、ビニルトルエン、酢酸ビニル;ジアリールフタレート;トリアリール(イソ)シアヌレート;メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert−ブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、ステアリル(メタ)アクリレート、トリデシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニロキシエチル(メタ)アクリレート、エチレングリコールモノメチルエーテル(メタ)アクリレート、エチレングリコールモノエチルエーテル(メタ)アクリレート、エチレングリコールモノブチルエーテル(メタ)アクリレート、エチレングリコールモノヘキシルエーテル(メタ)アクリレート、エチレングリコールモノ2−エチルヘキシルエーテル(メタ)アクリレート、ジエチレングリコールモノメチルエーテル(メタ)アクリレート、ジエチレングリコールモノエチルエーテル(メタ)アクリレート、ジエチレングリコールモノブチルエーテル(メタ)アクリレート、ジエチレングリコールモノヘキシルエーテル(メタ)アクリレート、ジエチレングリコールモノ2−エチルヘキシルエーテル(メタ)アクリレート、ジプロピレングリコールモノメチルエーテル(メタ)アクリレート、ジプロピレングリコールモノエチルエーテル(メタ)アクリレート、ジプロピレングリコールモノブチルエーテル(メタ)アクリレート、ジプロピレングリコールモノヘキシルエーテル(メタ)アクリレート、ジプロピレングリコールモノ2−エチルヘキシルエーテル(メタ)アクリレート等の(メタ)アクリル酸モノエステル;ジエチレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ポリテトラメチレンエーテルグリコール(PTMG)のジ(メタ)アクリレート、1,3−ブチレングリコールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、2−ヒドロキシ−1,3−ジメタクリロキシプロパン、2,2−ビス〔4−(メタクリロキシエトキシ)フェニル〕プロパン、2,2−ビス〔4−(メタクリロキシ・ジエトキシ)フェニル〕プロパン、2,2−ビス〔4−(メタクリロキシ・ポリエトキシ)フェニル〕プロパン、テトラエチレングリコールジ(メタ)アクリレート、ビスフェノールAのエチレンオキシド(EO)変性(n=2)ジ(メタ)アクリレート、イソシアヌル酸のエチレンオキシド(EO)変性(n=1〜3の単体又は混合物)ジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート等の(メタ)アクリル酸ジエステル;イソシアヌル酸のエチレンオキシド(EO)変性(n=1〜3の単体又は混合物)トリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート等の(メタ)アクリル酸トリエステル;ジペンタエリスリトールペンタ(メタ)アクリレート等の(メタ)アクリル酸ペンタエステル;2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、3−ヒドロキシブチル(メタ)アクリレート等の水酸基含有(メタ)アクリル酸エステル;(メタ)アクリル酸のエチレンオキシド又はプロピレンオキシド付加物等、樹脂と架橋可能な重合性不飽和化合物を使用することができる。
中でも、脂肪族環式構造、脂肪族鎖状構造又はイソシアヌル酸構造を含有するラジカル重合性不飽和単量体であることが好ましく、更には、イソボルニル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、イソシアヌル酸エチレンオキシド変性ジ(メタ)アクリレート、イソシアヌル酸エチレンオキシド変性トリ(メタ)アクリレート、或いは、これら単量体の混合物からなるラジカル重合性不飽和単量体を用いることが、封止材の耐熱変色性および低臭気に於いてより好ましい。
前記ラジカル重合性不飽和単量体(B)は、前記(メタ)アクリロイル基含有ポリウレタン(A)と前記ラジカル重合性不飽和単量体(B)との質量割合[(A)/(B)]が80/20〜20/80となる範囲で使用することが好ましい。
Examples of the radical polymerizable unsaturated monomer (B) include styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinyltoluene, vinyl acetate; diaryl phthalate; triaryl (Iso) cyanurate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) ) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) a Relate, dicyclopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate , Ethylene glycol mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2 -Ethylhexyl ether (meth) a Chryrate, dipropylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monobutyl ether (meth) acrylate, dipropylene glycol monohexyl ether (meth) acrylate, dipropylene glycol mono 2- (Meth) acrylic acid monoesters such as ethylhexyl ether (meth) acrylate; diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polytetramethylene ether glycol (PTMG) Di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) a Lilate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2 , 2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, tetraethylene glycol di (meth) acrylate, ethylene oxide (EO) modification of bisphenol A (n = 2) di (meth) acrylate, ethylene oxide of isocyanuric acid (EO) ) Modification (n = 1 to 3 simple substance or mixture) Di (meth) acrylate, (meth) acrylic diester such as pentaerythritol di (meth) acrylate; ethylene oxide (EO) modification of isocyanuric acid (n = 1 to 3) Simple substance or mixture) tri (meth) acrylate, (Meth) acrylic acid triesters such as intererythritol tri (meth) acrylate; (meth) acrylic acid pentaesters such as dipentaerythritol penta (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Use of a hydroxyl group-containing (meth) acrylic acid ester such as acrylate or 3-hydroxybutyl (meth) acrylate; a polymerizable unsaturated compound capable of crosslinking with a resin such as an ethylene oxide or propylene oxide adduct of (meth) acrylic acid Can do.
Among them, a radical polymerizable unsaturated monomer containing an aliphatic cyclic structure, an aliphatic chain structure or an isocyanuric acid structure is preferable, and isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, Use of radically polymerizable unsaturated monomers composed of dicyclopentanyl (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, or a mixture of these monomers Is more preferable in the heat discoloration resistance and low odor of the sealing material.
The radical polymerizable unsaturated monomer (B) is a mass ratio of the (meth) acryloyl group-containing polyurethane (A) and the radical polymerizable unsaturated monomer (B) [(A) / (B). ] Is preferably used within a range of 80/20 to 20/80.
本発明の封止材においては、加熱等によって(メタ)アクリロイル基含有ポリウレタン(A)が有する(メタ)アクリロイル基と、前記ラジカル重合性不飽和単量体(B)が有する不飽和基とのラジカル重合を進行させ、機械的強度や耐熱性等に優れた成形品を得るうえで、熱又は光によって硬化反応を進行させる熱硬化剤又は光硬化剤(C)を使用することが好ましい。
熱硬化剤は、熱により硬化反応に必要なラジカルを発生し、封止材を硬化させることができる。該熱硬化剤としては、各種分解温度の異なる過酸化物が市販されており、硬化温度条件と最適熱硬化剤を選択することにより、低温環境下であっても封止材を硬化させることができる。
In the sealing material of the present invention, the (meth) acryloyl group contained in the (meth) acryloyl group-containing polyurethane (A) by heating or the like and the unsaturated group contained in the radical polymerizable unsaturated monomer (B). In order to advance radical polymerization and obtain a molded article excellent in mechanical strength, heat resistance, etc., it is preferable to use a thermosetting agent or a photocuring agent (C) that allows a curing reaction to proceed by heat or light.
The thermosetting agent generates radicals necessary for the curing reaction by heat, and can cure the sealing material. As the thermosetting agent, various peroxides having different decomposition temperatures are commercially available. By selecting the curing temperature condition and the optimum thermosetting agent, the sealing material can be cured even in a low temperature environment. it can.
前記熱硬化剤としては、例えばジアシルパーオキシド系、パーオキシエステル系、ハイドロパーオキシド系、ジアルキルパーオキシド系、ケトンパーオキシド系、パーオキシケタール系、アルキルパーエステル系、パーカーボネート系等の公知のものを使用することができる。
前記熱硬化剤は、前記ラジカル重合性組成物を構成する(メタ)アクリロイル基含有ポリウレタン(A)と前記ラジカル重合性不飽和単量体(B)との合計100質量部に対して、0.1〜10質量部の範囲で使用することが好ましく、0.3〜3質量部の範囲で使用することがより好ましい。
前記光硬化剤としては、紫外線硬化剤が挙げられ、例えば、アシルホスフィンオキシド系、ベンゾインエーテル系、ベンゾフェノン系、アセトフェノン系、チオキサントン系化合物等を使用することができる。また、電子線硬化剤としては、例えば、ハロゲン化アルキルベンゼン、ジスルファイド系化合物等を使用することができる。
なお、光硬化剤として、電子線硬化剤等を、本発明の効果を損なわない範囲で併用してもよい。
Examples of the thermosetting agent include diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peresters, and carbonates. Things can be used.
The thermosetting agent is added in an amount of 0.1 to 100 parts by mass in total of the (meth) acryloyl group-containing polyurethane (A) and the radical polymerizable unsaturated monomer (B) constituting the radical polymerizable composition. It is preferably used in the range of 1 to 10 parts by mass, and more preferably in the range of 0.3 to 3 parts by mass.
Examples of the photocuring agent include an ultraviolet curing agent. For example, acylphosphine oxides, benzoin ethers, benzophenones, acetophenones, thioxanthones, and the like can be used. Moreover, as an electron beam hardening | curing agent, halogenated alkylbenzene, a disulfide type compound, etc. can be used, for example.
In addition, you may use an electron beam hardening agent etc. together as a photocuring agent in the range which does not impair the effect of this invention.
本発明の封止材は、例えば前記した方法で(メタ)アクリロイル基含有ポリウレタン(A)を製造し、次いで、該(メタ)アクリロイル基含有ポリウレタン(A)と前記ラジカル重合性不飽和単量体(B)とを混合、攪拌することによって製造することができる。前記熱硬化剤又は光硬化剤(C)は、前記(メタ)アクリロイル基含有ポリウレタン(A)と前記ラジカル重合性不飽和単量体(B)とを混合する際に使用してもよいが、予め(メタ)アクリロイル基含有ポリウレタン(A)と前記ラジカル重合性不飽和単量体(B)とを混合して得られたラジカル重合性組成物に対して、混合し使用することが好ましい。前記混合は、例えば攪拌機、ニーダー、ロールミル、スクリュー押出式混練機等の装置を使用して行ってもよい。 The sealing material of the present invention is produced by, for example, producing the (meth) acryloyl group-containing polyurethane (A) by the above-described method, and then the (meth) acryloyl group-containing polyurethane (A) and the radical polymerizable unsaturated monomer. (B) can be mixed and stirred. The thermosetting agent or photocuring agent (C) may be used when mixing the (meth) acryloyl group-containing polyurethane (A) and the radical polymerizable unsaturated monomer (B), It is preferable to mix and use a radical polymerizable composition obtained by previously mixing the (meth) acryloyl group-containing polyurethane (A) and the radical polymerizable unsaturated monomer (B). You may perform the said mixing using apparatuses, such as a stirrer, a kneader, a roll mill, a screw extrusion type kneader, for example.
本発明の封止材の粘度は、2.0〜800dPa・sの範囲にあることが好ましい。最適な粘度は、成形方法、用途によって異なる。即ち、ポッティング等による成形方法では、一定の粘度が必要で、粘度が低すぎる場合は、樹脂が成形とともに流れ出してしまい、所望の形状が得ることができない場合もあり、成形法に応じた最適な粘度に調整する必要がある。粘度を下げる場合、樹脂を予め加温し、最適な粘度に調整後、成形することができる。また、本発明の性能を損なわない範囲で、ラジカル重合性不飽和単量体を添加することにより、最適粘度を調整することが可能である。封止材の粘度は、JIS−K−6901に準じて、公知の装置等を用いて測定することができる。 The viscosity of the sealing material of the present invention is preferably in the range of 2.0 to 800 dPa · s. The optimum viscosity varies depending on the molding method and application. That is, in the molding method by potting or the like, a certain viscosity is required, and if the viscosity is too low, the resin may flow out together with the molding and a desired shape may not be obtained. It is necessary to adjust the viscosity. When the viscosity is lowered, the resin can be preheated and adjusted to an optimum viscosity, and then molded. Moreover, it is possible to adjust an optimal viscosity by adding a radically polymerizable unsaturated monomer in the range which does not impair the performance of this invention. The viscosity of the sealing material can be measured using a known device or the like according to JIS-K-6901.
本発明の封止材には、必要に応じて重合禁止剤や硬化促進剤等を使用することができる。
前記重合禁止剤としては、例えば、トルハイドロキノン、ハイドロキノン、ハイドロキノンモノメチルエーテル、1,4−ナフトキノン、パラベンゾキノン、トルハイドロノン、p−tert−ブチルカテコール、2,6−tert−ブチル−4−メチルフェノール等を使用することができる。重合禁止剤の使用量は、封止材中10〜1500ppmが好ましい。
A polymerization inhibitor, a curing accelerator, etc. can be used for the sealing material of this invention as needed.
Examples of the polymerization inhibitor include toluhydroquinone, hydroquinone, hydroquinone monomethyl ether, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert-butylcatechol, 2,6-tert-butyl-4-methylphenol. Etc. can be used. The amount of the polymerization inhibitor used is preferably 10 to 1500 ppm in the sealing material.
前記硬化促進剤としては、例えば、ナフテン酸コバルト、オクテン酸コバルト、オクテン酸バナジル、ナフテン酸銅、ナフテン酸バリウム等の金属石鹸類;バナジルアセチルアセテート、コバルトアセチルアセテート、鉄アセチルアセトネート等の金属キレート化合物;N,N−ジメチルアミノ−p−ベンズアルデヒド、N,N−ジメチルアニリン、N,N−ジエチルアニリン、N,N−ジメチル−p−トルイジン、N,N−ビス(2−ヒドロキシエチル)−p−トルイジン、4−N,N−ジメチルアミノベンズアルデヒド、4−N,N−ビス(2−ヒドロキシエチル)アミノベンズアルデヒド、4−メチルヒドロキシエチルアミノベンズアルデヒド、N,N−ビス(2−ヒドロキシプロピル)−p−トルイジン、N−エチル−m−トルイジン、トリエタノールアミン、m−トルイジン、ジエチレントリアミン、ピリジン、フェニルモルホリン、ピペリジン、ジエタノールアニリン等の化合物が挙げられる。本発明の封止材においては、これらを少量添加して用いることも可能である。 Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate; metal chelates such as vanadyl acetyl acetate, cobalt acetyl acetate, and iron acetylacetonate. Compound; N, N-dimethylamino-p-benzaldehyde, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p -Toluidine, 4-N, N-dimethylaminobenzaldehyde, 4-N, N-bis (2-hydroxyethyl) aminobenzaldehyde, 4-methylhydroxyethylaminobenzaldehyde, N, N-bis (2-hydroxypropyl) -p -Toluidine, N-ethyl-m-toluidine , Triethanolamine, m- toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, compounds such as diethanol aniline. In the sealing material of the present invention, a small amount of these can be added and used.
また、本発明の封止材には、必要に応じて従来から一般的に知られている不飽和ポリエステル樹脂、ビニルウレタン樹脂、ビニルエステル樹脂、ポリイソシアネート、ポリエポキシド、アクリル樹脂類、アルキッド樹脂類、尿素樹脂類、メラミン樹脂類、ポリ酢酸ビニル、酢酸ビニル系共重合体、ポリジエン系エラストマー、飽和ポリエステル類、飽和ポリエーテル類;ニトロセルローズ、セルローズアセテートブチレートなどのセルローズ誘導体;アマニ油、桐油、大豆油、ヒマシ油、エポキシ化油等の油脂類等、他の慣用の天然および合成高分子化合物を添加できる。
また、ガラス繊維、炭素繊維、アラミド繊維、ビニロン繊維、テトロン繊維等の有機繊維;金属繊維;ジュートやマニラ麻等の天然植物繊維;炭酸カルシウム、タルク、マイカ、クレー、シリカパウダー、コロイダルシリカ、硫酸バリウム、水酸化アルミニウム、ガラス粉、ガラスビーズ、砕砂等の充填剤を配合して用いることもできる。さらにステアリン酸亜鉛、チタン白、亜鉛華、その他各種顔料安定剤;難燃剤;消泡剤;内部離型剤;熱可塑性樹脂等の低収縮剤;低収縮剤がラジカル重合性樹脂と非相溶の場合は相溶化剤;老化防止剤、可塑剤、骨材、難燃剤、光安定剤、熱安定剤等の他の添加剤を使用することができる。
本発明の封止剤は、希釈溶媒としての有機溶媒を含んでもよく、これら有機溶剤は、前記封止剤を硬化せしめる前に、加熱により揮発除去されるものであり、用いる熱硬化剤に依存する硬化温度を考慮し用いることができる。例えば、トルエン、キシレンなどの芳香族系溶媒;ヘキサン、ヘプタン、オクタン、ミネラルスピリットなどの脂肪族系溶媒;メチルエチルケトン、アセトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶媒;ジエチルエーテル、イソプロピルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、アニソール、フェネトールなどのエーテル系溶媒;酢酸エチル、酢酸ブチル、酢酸イソプロピル、エチレングリコールジアセテートなどのエステル系溶媒;ジメチルホルムアミド、ジエチルホルムアミド、ジメチルスルホキシド、N−メチルピロリドンなどのアミド系溶媒;メチルセロソルブ、エチルセロソルブ、ブチルセロソルブなどのセロソルブ系溶媒;プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテートなどのエーテルエステル系溶媒;メタノール、エタノール、プロパノールなどのアルコール系溶媒等が挙げられる。これらの溶媒は単独で用いてもよく、また混合して用いてもよい。
In addition, the sealing material of the present invention includes conventionally known unsaturated polyester resins, vinyl urethane resins, vinyl ester resins, polyisocyanates, polyepoxides, acrylic resins, alkyd resins, if necessary, Urea resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers; cellulose derivatives such as nitrocellulose, cellulose acetate butyrate; linseed oil, tung oil, large Other conventional natural and synthetic polymer compounds such as bean oil, castor oil, and oils such as epoxidized oil can be added.
Organic fibers such as glass fiber, carbon fiber, aramid fiber, vinylon fiber, and tetron fiber; metal fiber; natural plant fiber such as jute and manila hemp; calcium carbonate, talc, mica, clay, silica powder, colloidal silica, barium sulfate Further, fillers such as aluminum hydroxide, glass powder, glass beads, and crushed sand can be blended and used. Furthermore, zinc stearate, titanium white, zinc white, and other various pigment stabilizers; flame retardants; antifoaming agents; internal mold release agents; low shrinkage agents such as thermoplastic resins; low shrinkage agents are incompatible with radical polymerizable resins In the case of, other additives such as a compatibilizing agent; an anti-aging agent, a plasticizer, an aggregate, a flame retardant, a light stabilizer, and a heat stabilizer can be used.
The sealing agent of the present invention may contain an organic solvent as a diluting solvent. These organic solvents are volatilized and removed by heating before the sealing agent is cured, and depend on the thermosetting agent used. It can be used in consideration of the curing temperature to be used. For example, aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane, octane and mineral spirit; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, Ether solvents such as dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate and ethylene glycol diacetate Dimethylformamide, diethylformamide, dimethylsulfoxy Amide solvents such as N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; ether ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; methanol, ethanol, propanol, etc. Examples include alcohol solvents. These solvents may be used alone or in combination.
本発明の封止材を透明性の求められる光学部材の封止に使用する場合は、透明性を損なわない封止材を使用する必要があるため、前記添加剤としても透明性の低下を引き起こしにくいものを使用することが好ましい。具体的には、シリカ、酸化チタン、酸化アルミニウム、酸化珪素、石英ガラス等を用いることができる。また、金属酸化物、窒化アルミニウム、窒化ボロン等の熱伝導性フィラーも用いることができる。 When the sealing material of the present invention is used for sealing an optical member that requires transparency, it is necessary to use a sealing material that does not impair the transparency, which causes a decrease in transparency as the additive. It is preferable to use a difficult one. Specifically, silica, titanium oxide, aluminum oxide, silicon oxide, quartz glass, or the like can be used. Further, a thermally conductive filler such as metal oxide, aluminum nitride, or boron nitride can also be used.
また、本発明の封止材を、例えばLED等の封止部材に使用する場合には、その回路パターン等を形成する金属材料等の無機材料に対する密着性を向上させる観点から、シランカップリング材を用いることが好ましい。例えば、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリエトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン、3−アクリロキシプロピルトリメトキシシラン、3−アクリロキシプロピルトリエトキシシラン、メタクリロキシメチルトリメトキシシラン、メタクリロキシメチルトリエトキシシラン、アクリロキシメチルトリメトキシシラン、アクリロキシメチルトリエトキシシラン等を用いることができる。 Moreover, when using the sealing material of this invention for sealing members, such as LED, for example, from a viewpoint of improving the adhesiveness with respect to inorganic materials, such as a metal material which forms the circuit pattern etc., a silane coupling material Is preferably used. For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxy Silane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, or the like can be used.
本発明の封止材においては、熱硬化剤の種類を選択することにより、その硬化温度を調整することができる。しかし、本発明の封止材を比較的熱に弱い部材の封止に使用する場合には、本発明の封止材を硬化させるために高温加熱することができないため、概ね50〜100℃の範囲で加熱することが好ましく、比較的低温の50℃〜80℃の範囲で加熱硬化することで封止された成形品を得ることがより好ましい。 In the sealing material of this invention, the curing temperature can be adjusted by selecting the kind of thermosetting agent. However, when the sealing material of the present invention is used for sealing a relatively heat-sensitive member, it cannot be heated at a high temperature in order to cure the sealing material of the present invention. It is preferable to heat in a range, and it is more preferable to obtain a molded product sealed by heat curing in a relatively low temperature range of 50 ° C to 80 ° C.
本発明の封止材は、例えばLED、レンズ、ディスプレー等の光学部材を製造する際の封止材として用いることができる。
前記LEDとしては、ランプ砲弾型、SMD型、チップ型等のいずれの種類に適用できる。封止硬化方法は、通常、エポキシ樹脂において用いられる手法が適用でき、発光素子が配置された部材に、型を用いた流し込み注型成形、ディスペンサーを用いた注型、型の中に樹脂を流し込み、発光素子をディップさせた後硬化させる等、で成形することが可能である。また、スクリーン印刷等による薄膜塗工後、硬化させ、薄膜耐熱変色性を有する特徴を活かした適用も可能である。
The sealing material of this invention can be used as a sealing material at the time of manufacturing optical members, such as LED, a lens, a display, for example.
The LED can be applied to any type such as a lamp shell type, an SMD type, and a chip type. Sealing and curing methods can be applied to the epoxy resin, and can be applied to the members where the light-emitting elements are placed. Pour casting using a mold, casting using a dispenser, and pouring the resin into the mold. The light emitting element can be formed by dipping and curing. In addition, it can be applied by utilizing the characteristics of thin film heat discoloration after being applied after thin film coating by screen printing or the like.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。なお、特に断りがない限り「部」は「質量部」、「%」は「質量%」である。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Unless otherwise specified, “part” is “part by mass” and “%” is “% by mass”.
(実施例1)
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた2リットルの四つ口フラスコに、1,4−シクロヘキサンジメタノール202部、イソホロンジイソシアネートを622部、トルハイドロキノンを50ppm仕込み、90℃で約2時間加熱攪拌して分子末端にイソシアネート基を有するポリウレタンを得た。その後、2−ヒドロキシエチルメタクリレート382部と錫系触媒50ppmを添加し、90℃で約7時間反応させることで、分子量848の(メタ)アクリロイル基含有ポリウレタン(以下、ポリウレタン(I))を得た(NCO%:0.3以下)。尚、前記分子量は、前記ポリウレタン(I)を構成する原子の式量に基づき計算して求めた値である。
次いで、得られた該ポリウレタン(I)とラジカル重合性不飽和単量体として2−ヒドロキシエチルメタクリレートとを混合することによって、下記表1記載の配合割合からなるラジカル重合性組成物を得た。得られた該ラジカル重合性組成物300部にラジカル硬化剤パーキュアーHO(N)(日油株式会社製;熱硬化剤)3部を添加して均一になる様混合し、実施例1の封止材を得た。
また、前記封止材を用い下記注型板作成法に従うことによって注型板を得た。
Example 1
A 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser was charged with 202 parts of 1,4-cyclohexanedimethanol, 622 parts of isophorone diisocyanate, and 50 ppm of toluhydroquinone, A polyurethane having an isocyanate group at the molecular end was obtained by heating and stirring at 90 ° C. for about 2 hours. Thereafter, 382 parts of 2-hydroxyethyl methacrylate and 50 ppm of tin-based catalyst were added and reacted at 90 ° C. for about 7 hours to obtain a (meth) acryloyl group-containing polyurethane (hereinafter, polyurethane (I)) having a molecular weight of 848. (NCO%: 0.3 or less). The molecular weight is a value obtained by calculation based on the formula weight of the atoms constituting the polyurethane (I).
Subsequently, the obtained polyurethane (I) and 2-hydroxyethyl methacrylate as a radical polymerizable unsaturated monomer were mixed to obtain a radical polymerizable composition having a blending ratio shown in Table 1 below. 3 parts of radical curing agent Percure HO (N) (manufactured by NOF Corporation; thermosetting agent) was added to 300 parts of the obtained radical polymerizable composition and mixed to be uniform. The material was obtained.
Moreover, the casting plate was obtained by using the said sealing material and following the casting plate preparation method below.
また、下記条件におけるIRスペクトルの測定により、実施例1にて得られたポリウレタン(I)を同定した。IRスペクトルを図1に示す。尚、図1中、横軸は波長(cm−1)を表し、スペクトル中のピークの帰属はそれぞれ以下のとおりである。
(IRスペクトル測定条件)
測定機器:赤外分光光度計FT/IR−460(日本分光(株)製)。
測定法:KBrプレート使用による透過法。
積算回数:16回。
Moreover, the polyurethane (I) obtained in Example 1 was identified by the measurement of IR spectrum on the following conditions. The IR spectrum is shown in FIG. In FIG. 1, the horizontal axis represents the wavelength (cm −1 ), and the peaks in the spectrum are as follows.
(IR spectrum measurement conditions)
Measuring instrument: Infrared spectrophotometer FT / IR-460 (manufactured by JASCO Corporation).
Measurement method: Transmission method using KBr plate.
Integration count: 16 times.
(ピークの帰属)
[シクロヘキサンジメタノール由来のピーク]
2920cm−1、2860cm−1、1450cm−1:C−H振動。
1030cm−1:C−O吸収。
[ウレタン結合生成確認のピーク]
1710cm−1:C=O基
1530cm−1:〜N(H)−C=O〜。
[イソシアネート基が消失していることを確認するピーク]
2260〜2270cm−1:NCO基。
(Peak attribution)
[Peak derived from cyclohexanedimethanol]
2920cm -1, 2860cm -1, 1450cm -1 : C-H vibrations.
1030 cm −1 : C—O absorption.
[Peak of confirmation of urethane bond formation]
1710cm -1: C = O group 1530cm -1: ~N (H) -C = O~.
[Peak confirming disappearance of isocyanate group]
2260-2270 cm < -1 >: NCO group.
(実施例2)
実施例1でポリウレタン(I)を希釈する際に使用した2−ヒドロキシエチルメタクリレートの代わりに、ラジカル重合性不飽和単量体として、イソボルニルメタアクリレートを使用すること以外は、実施例1と同様の方法によって、下記表1記載の配合割合からなる封止材を得た。また、実施例1で得た封止材の代わりに実施例2で得た封止材を使用すること以外は実施例1と同様の方法で注型板を作製した。
(Example 2)
Example 1 except that isobornyl methacrylate is used as a radical polymerizable unsaturated monomer instead of 2-hydroxyethyl methacrylate used in diluting polyurethane (I) in Example 1. By the same method, the sealing material which consists of a mixture ratio of the following Table 1 was obtained. A cast plate was produced in the same manner as in Example 1 except that the sealing material obtained in Example 2 was used instead of the sealing material obtained in Example 1.
(実施例3)
実施例1でポリウレタン(I)を希釈する際に使用した2−ヒドロキシエチルメタクリレートの代わりに、ラジカル重合性不飽和単量体として、ジシクロペンタニルメタアクリレートを使用すること以外は、実施例1と同様の方法によって、下記表1記載の配合割合からなる封止材を得た。また、また、実施例1で得た封止材の代わりに実施例3で得た封止材を使用すること以外は実施例1と同様の方法で注型板を作製した。
(Example 3)
Example 1 except that dicyclopentanyl methacrylate is used as a radically polymerizable unsaturated monomer instead of 2-hydroxyethyl methacrylate used in diluting polyurethane (I) in Example 1. By the same method, the sealing material which consists of a mixture ratio of the following Table 1 was obtained. Further, a cast plate was produced in the same manner as in Example 1 except that the sealing material obtained in Example 3 was used instead of the sealing material obtained in Example 1.
(実施例4)
実施例1でポリウレタン(I)を希釈する際に使用した2−ヒドロキシエチルメタクリレートの代わりに、ラジカル重合性不飽和単量体として、2−ヒドロキシエチルメタクリレートとイソシアヌル酸エチレンオキシド変性ジアクリレートとイソシアヌル酸エチレンオキシド変性トリアクリレートとを使用すること以外は、実施例1と同様の方法によって、下記表1記載の配合割合からなる封止材を得た。また、実施例1で得た封止材の代わりに実施例4で得た封止材を使用すること以外は実施例1と同様の方法で注型板を作製した。
Example 4
Instead of 2-hydroxyethyl methacrylate used in diluting polyurethane (I) in Example 1, 2-hydroxyethyl methacrylate, isocyanuric acid ethylene oxide-modified diacrylate, and isocyanuric acid ethylene oxide were used as radically polymerizable unsaturated monomers. A sealing material having a blending ratio shown in Table 1 below was obtained in the same manner as in Example 1 except that modified triacrylate was used. A cast plate was produced in the same manner as in Example 1 except that the sealing material obtained in Example 4 was used instead of the sealing material obtained in Example 1.
(実施例5)
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた2リットルの四つ口フラスコに、1,4−シクロヘキサンジメタノール202部、イソホロンジイソシアネートを622部、トルハイドロキノンを50ppm仕込み、90℃で約2時間加熱攪拌して分子末端にイソシアネート基を有するポリウレタンを得た。その後、イソシアヌル酸エチレンオキシド変性ジアクリレート1567部とイソシアヌル酸エチレンオキシド変性トリアクリレート930部と錫系触媒50ppmを添加し、90℃で約7時間反応させることで、分子量1326の(メタ)アクリロイル基含有ポリウレタン(以下、ポリウレタン(II))と、未反応のイソシアヌル酸エチレンオキシド変性ジアクリレートとイソシアヌル酸エチレンオキシド変性トリアクリレートとの混合物を得た(NCO%:0.3以下)。なお、前記分子量は、前記ポリウレタン(II)を構成する原子の式量に基づき計算して求めた値である。
次いで、前記で得たポリウレタン(II)を含む上記混合物と、イソボルニルメタアクリレートとを混合することによって、下記表1記載の配合割合からなるラジカル重合性組成物を得た。
得られた該ラジカル重合性組成物300部にラジカル硬化剤パーキュアーHO(N)(日油株式会社製;熱硬化剤)3部を添加して均一になるよう混合することによって、実施例5の封止材を得た。また、実施例1で得た封止材の代わりに実施例5で得た封止材を使用すること以外は実施例1と同様の方法で注型板を作製した。
(Example 5)
A 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser was charged with 202 parts of 1,4-cyclohexanedimethanol, 622 parts of isophorone diisocyanate, and 50 ppm of toluhydroquinone, A polyurethane having an isocyanate group at the molecular end was obtained by heating and stirring at 90 ° C. for about 2 hours. Thereafter, 1567 parts of isocyanuric acid ethylene oxide-modified diacrylate, 930 parts of isocyanuric acid ethylene oxide-modified triacrylate, and 50 ppm of a tin-based catalyst were added and reacted at 90 ° C. for about 7 hours, whereby a (meth) acryloyl group-containing polyurethane having a molecular weight of 1326 ( Hereinafter, a mixture of polyurethane (II)), unreacted isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate was obtained (NCO%: 0.3 or less). The molecular weight is a value obtained by calculation based on the formula weight of the atoms constituting the polyurethane (II).
Subsequently, the said mixture containing polyurethane (II) obtained above and the isobornyl methacrylate were mixed, and the radically polymerizable composition which consists of a mixture ratio of following Table 1 was obtained.
By adding 3 parts of radical curing agent Percure HO (N) (manufactured by NOF Corporation; thermosetting agent) to 300 parts of the obtained radical polymerizable composition, mixing to be uniform, Example 5 A sealing material was obtained. A cast plate was produced in the same manner as in Example 1 except that the sealing material obtained in Example 5 was used instead of the sealing material obtained in Example 1.
(比較例1)
適当な大きさの容器に、脂環式エポキシ樹脂YX8000(ジャパンエポキシレジン株式会社製)を160部、脂環式酸無水物リカシッドMH−700G(新日本理化株式会社製)を140部、硬化触媒ニッサンカチオンM2−100R(日油株式会社製)を2.4部添加して混合し、比較例1の封止材(エポキシ樹脂混合物)を得た。得られた該エポキシ樹脂を30cm×30cm大の2枚のガラス板に離型剤を塗布し、合成ゴム製チューブをガラス板の間に挟み、スペーサーを用い隙間3mmとなる様調整した型に流し込み、80℃で3時間加熱した。
前記加熱後、封止材は未だ十分に硬化していなかったため、更に、100℃で2時間加熱し、更に120℃で5時間加熱させることで注型板を得た。
(Comparative Example 1)
In an appropriately sized container, 160 parts of alicyclic epoxy resin YX8000 (manufactured by Japan Epoxy Resin Co., Ltd.), 140 parts of alicyclic acid anhydride Rikacid MH-700G (manufactured by Shin Nippon Rika Co., Ltd.), curing catalyst 2.4 parts of Nissan Cation M2-100R (manufactured by NOF Corporation) was added and mixed to obtain a sealing material (epoxy resin mixture) of Comparative Example 1. The obtained epoxy resin was applied to two glass plates of 30 cm × 30 cm in size, a release agent was applied, a synthetic rubber tube was sandwiched between the glass plates, and poured into a mold adjusted to have a gap of 3 mm using a spacer. Heat at 3 ° C. for 3 hours.
After the heating, the encapsulant was not yet fully cured, and further heated at 100 ° C. for 2 hours and further heated at 120 ° C. for 5 hours to obtain a cast plate.
(比較例2)
実施例1と全く同一の反応装置に、ビスフェノールA系エポキシ樹脂(エポキシ当量187)830部、メタクリル酸365部、ジブチルヒドロキシトルエン350ppm、2−メチルイミダゾールを1000ppm添加し、110℃で約5時間反応させ、酸価が4に達したところで反応を終了し、エポキシメタクリレート樹脂を得た。更に、得られた該樹脂とスチレンモノマーとを混合することによって、下記表2に記載の配合割合からなる比較例2の封止材を得た。また、実施例1で得た封止材の代わりに比較例2で得た封止材を使用すること以外は実施例1と同様の方法で注型板を作製した。
(Comparative Example 2)
830 parts of bisphenol A epoxy resin (epoxy equivalent 187), 365 parts of methacrylic acid, 350 ppm of dibutylhydroxytoluene and 1000 ppm of 2-methylimidazole were added to the same reactor as in Example 1, and the reaction was carried out at 110 ° C. for about 5 hours. The reaction was terminated when the acid value reached 4 to obtain an epoxy methacrylate resin. Furthermore, the sealing material of the comparative example 2 which consists of a mixture ratio of the following Table 2 was obtained by mixing this obtained resin and styrene monomer. In addition, a cast plate was produced in the same manner as in Example 1 except that the sealing material obtained in Comparative Example 2 was used instead of the sealing material obtained in Example 1.
(比較例3)
実施例1と全く同一の反応装置に、脂環式系エポキシ樹脂(デナコールEX−252、エポキシ当量215、ナガセケムテック(株)社製)946部、メタクリル酸360部、2−メチルイミダゾールを1000ppm添加し、110℃で約10時間反応させ、酸価が10以下に達したところで反応を終了し、脂環式系エポキシメタクリレート樹脂を得た。更に、得られた該樹脂とイソボルニルメタアクリレートとを混合することによって、下記表2に記載の配合割合からなる比較例3の封止材を得た。また、実施例1で得た封止材の代わりに比較例3で得た封止材を使用すること以外は実施例1と同様の方法で注型板を作製した。
(Comparative Example 3)
In the same reactor as in Example 1, 946 parts of alicyclic epoxy resin (Denacol EX-252, epoxy equivalent 215, manufactured by Nagase Chemtech Co., Ltd.), 360 parts of methacrylic acid, 1000 ppm of 2-methylimidazole The mixture was added and reacted at 110 ° C. for about 10 hours. When the acid value reached 10 or less, the reaction was terminated to obtain an alicyclic epoxy methacrylate resin. Furthermore, the sealing material of the comparative example 3 which consists of a mixture ratio of following Table 2 was obtained by mixing this obtained resin and isobornyl methacrylate. Further, a cast plate was produced in the same manner as in Example 1 except that the sealing material obtained in Comparative Example 3 was used instead of the sealing material obtained in Example 1.
(比較例4)
実施例1と全く同一の反応装置に、ポリプロピレングリコール(数平均分子量700)を701部、トリレンジイソシアネートを296部、イソホロンジイソシアネートを67部仕込み、80℃で約5時間後加熱攪拌して分子末端にイソシアネート基を有するポリウレタン(イソシアネート当量532)を得た。その後、2−ヒドロキシエチルメタクリレート273部を仕込み、80℃で約4時間反応し、(メタ)アクリロイル基含有ポリウレタン(以下、ポリウレタン(III))を得た(NCO%:0.3以下)。更に、得られた該ポリウレタン(III)とラジカル重合性不飽和単量体としてメチルメタクリレートとを混合することによって、下記表2に記載の配合割合からなる比較例4の封止材を得た。また、実施例1で得た封止材の代わりに比較例4で得た封止材を使用すること以外は実施例1と同様の方法で注型板を作製した。
(Comparative Example 4)
701 parts of polypropylene glycol (number average molecular weight 700), 296 parts of tolylene diisocyanate, and 67 parts of isophorone diisocyanate are charged in the same reaction apparatus as in Example 1, and heated at 80 ° C. for about 5 hours, followed by heating and stirring to obtain molecular terminals. To obtain an isocyanate group-containing polyurethane (isocyanate equivalent 532). Thereafter, 273 parts of 2-hydroxyethyl methacrylate was added and reacted at 80 ° C. for about 4 hours to obtain a (meth) acryloyl group-containing polyurethane (hereinafter, polyurethane (III)) (NCO%: 0.3 or less). Furthermore, the obtained polyurethane (III) and methyl methacrylate as a radical polymerizable unsaturated monomer were mixed to obtain a sealing material of Comparative Example 4 having a blending ratio shown in Table 2 below. A cast plate was produced in the same manner as in Example 1 except that the sealing material obtained in Comparative Example 4 was used instead of the sealing material obtained in Example 1.
(比較例5)
比較例4でポリウレタン(III)を希釈する際に使用したメチルメタクリレートの代わりに、ラジカル重合性不飽和単量体として、イソボルニルメタアクリレートを使用すること以外は、実施例1と同様の方法によって、下記表1記載の配合割合からなる封止材を得た。また、実施例1で得た封止材の代わりに比較例5で得た封止材を使用すること以外は実施例1と同様の方法で注型板を作製した。
(Comparative Example 5)
The same method as in Example 1 except that isobornyl methacrylate is used as a radical polymerizable unsaturated monomer in place of methyl methacrylate used in diluting polyurethane (III) in Comparative Example 4. The sealing material which consists of a mixture ratio of the following Table 1 was obtained. A cast plate was produced in the same manner as in Example 1 except that the sealing material obtained in Comparative Example 5 was used instead of the sealing material obtained in Example 1.
(注型板作成法)
実施例1〜5及び比較例2〜5の封止材から得られた注型板の作製は以下のように行った。
すなわち、30cm×30cm大の2枚のガラス板に離型剤を塗布し、合成ゴム製チューブをガラス板の間に挟み、スペーサーを用い隙間3mmとなる様調整し、実施例1〜5及び比較例2〜5で示された各樹脂組成物を流し込み、湯浴にて常温から80℃まで4時間掛けて昇温、硬化させ、硬化後、ガラス板ごと乾燥機に入れ、120℃、1時間で完全硬化を行い、冷却後、ガラス板を外して、平滑な厚さ3mmの注型板を得た。
(Casting plate making method)
The casting plates obtained from the sealing materials of Examples 1 to 5 and Comparative Examples 2 to 5 were produced as follows.
That is, a release agent was applied to two glass plates of 30 cm × 30 cm, a synthetic rubber tube was sandwiched between the glass plates, and a spacer was used to adjust the gap to 3 mm. Examples 1 to 5 and Comparative Example 2 Each resin composition indicated by ~ 5 was poured, heated and cured in a hot water bath from room temperature to 80 ° C over 4 hours, cured, and put into a dryer together with the glass plate, completely at 120 ° C for 1 hour. After curing and cooling, the glass plate was removed to obtain a smooth cast plate having a thickness of 3 mm.
(評価方法1.粘度)
上記実施例1〜5及び比較例1〜5における封止材の硬化前の粘度を、JIS−K−6901に順じて測定した。
(
The viscosity before hardening of the sealing materials in Examples 1 to 5 and Comparative Examples 1 to 5 was measured according to JIS-K-6901.
(評価方法2.硬化性評価)
上記実施例1〜5及び比較例1〜5における封止材において、80℃での、JIS−K−6901に順じ、ゲル化時間を測定し、30分以内にゲル化したものを良好(○)と判定し、それ以上の時間がかかるものを不良(×)と判定した。
(Evaluation method 2. Curability evaluation)
In the sealing materials in Examples 1 to 5 and Comparative Examples 1 to 5, the gelation time was measured in accordance with JIS-K-6901 at 80 ° C., and gelled within 30 minutes was good ( ○), and those that took more time were judged as defective (x).
(評価方法3.臭気)
上記実施例1〜5及び比較例1〜5における封止材の臭気について、官能試験により、臭気が強い(×)、臭気がやや強い(△)、臭気が少ない(○)として評価した。
(Evaluation method 3. Odor)
About the odor of the sealing material in the said Examples 1-5 and Comparative Examples 1-5, it evaluated by the sensory test as a strong odor (x), a slightly strong odor ((triangle | delta)), and a little odor ((circle)).
(評価方法4.注型板外観)
実施例1〜5及び比較例1〜5の封止材から得られた該注型板の外観を目視にて評価した。
(Evaluation method 4. Cast plate appearance)
The appearance of the cast plates obtained from the sealing materials of Examples 1 to 5 and Comparative Examples 1 to 5 was visually evaluated.
(評価方法5.熱変形温度)
実施例1〜5及び比較例1〜5の封止材から得られた注型板の熱変形温度を、JIS−K−7207に順じて測定した。100℃以上の値を有するものを耐熱性が優れ、良好(○)と判断した。100℃以下のものを、不良(×)として評価した。
(Evaluation method 5. Thermal deformation temperature)
The thermal deformation temperature of the casting plate obtained from the sealing materials of Examples 1 to 5 and Comparative Examples 1 to 5 was measured according to JIS-K-7207. Those having a value of 100 ° C. or higher were judged to have excellent heat resistance and good (◯). The thing below 100 degreeC was evaluated as a defect (x).
(評価方法6.透明性評価)
実施例1〜5及び比較例1〜5の封止材から得られた注型板から約4cm×4cmの試験片を切削した。測定機器として紫外可視分光光度計試験機器を用い、該試験片の光線透過率(%)(589nm波長)を測定し、透明性の評価を行った。85%以上有するものを優(○)、それ以下のものを不良(×)として評価した。
(Evaluation method 6. Transparency evaluation)
A test piece of about 4 cm × 4 cm was cut from the cast plate obtained from the sealing materials of Examples 1 to 5 and Comparative Examples 1 to 5. Transparency was evaluated by measuring the light transmittance (%) (589 nm wavelength) of the test piece using an ultraviolet-visible spectrophotometer test device as a measuring device. Those having 85% or more were evaluated as excellent (◯), and those having less than 85% were evaluated as defective (×).
(評価方法7.耐熱変色性評価:色差および透明性の評価)
実施例1〜5及び比較例1〜5の封止材から得られた該注型板から約4cm×4cmの試験片を切削した。試験機器として高温恒温機(エスペック株式会社製)を使用し、180℃にて試験片を加熱し、100時間経過後の試験片の着色の度合いを紫外可視分光光度計を使用して評価した。初期値との色変化の指標として色差:ΔEを下記により算出した。
(Evaluation method 7. Evaluation of heat discoloration: Evaluation of color difference and transparency)
A test piece of about 4 cm × 4 cm was cut from the cast plate obtained from the sealing materials of Examples 1 to 5 and Comparative Examples 1 to 5. A high-temperature thermostat (manufactured by Espec Co., Ltd.) was used as a test device, the test piece was heated at 180 ° C., and the degree of coloring of the test piece after 100 hours was evaluated using an ultraviolet-visible spectrophotometer. The color difference: ΔE was calculated as follows as an index of color change from the initial value.
判定評価基準: 優 (○):ΔE=40未満
不良 (×):ΔE=40以上
上記、180℃、100時間熱処理後の該試験片の光線透過率(589nm波長)を紫外可視分光光度計試験機器を用い、測定した。80%以上有するものを優(○)、それ以下のものを不良(×)として、熱処理後の透明性の評価をした。
Judgment evaluation criteria: Excellent (○): ΔE = less than 40
Defect (x): ΔE = 40 or more
The light transmittance (589 nm wavelength) of the test piece after heat treatment at 180 ° C. for 100 hours was measured using a UV-visible spectrophotometer test instrument. Transparency after heat treatment was evaluated with 80% or more being excellent (◯) and less than that being poor (x).
表1中、HEMAは、2−ヒドロキシエチルメタクリレートを示し、IBXMAは、イソボルニルメタアクリレートを示す。IBXAは、イソボルニルアクリレートを示す。イソシアヌル酸EO変性ジアクリレートはイソシアヌル酸エチレンオキシド変性ジアクリレートを示す。イソシアヌル酸EO変性トリアクリレートはイソシアヌル酸エチレンオキシド変性トリアクリレートを示す。 In Table 1, HEMA represents 2-hydroxyethyl methacrylate, and IBXMA represents isobornyl methacrylate. IBXA represents isobornyl acrylate. Isocyanuric acid EO-modified diacrylate refers to isocyanuric acid ethylene oxide-modified diacrylate. Isocyanuric acid EO-modified triacrylate refers to isocyanuric acid ethylene oxide-modified triacrylate.
表2中、SMは、スチレンを示し、IBXMAは、イソボルニルメタアクリレートを示し、MMAは、メチルメタクリレートを示す。 In Table 2, SM represents styrene, IBXMA represents isobornyl methacrylate, and MMA represents methyl methacrylate.
表1に示されるように、実施例1〜5の封止材は、優れた耐熱性、耐熱変色性、透明性を有し、80℃といった低温環境下であっても硬化性に優れていることが確認された。また、実施例1〜5の封止材は、臭気が少ないものであることが確認された。
一方、比較例1〜3の封止材は、(メタ)アクリロイル基含有ポリウレタンを含まないものであるため、耐熱変色性に劣っていた。また、脂環式エポキシを含有する比較例1の封止材は、硬化性の点でも劣っていた。
比較例4〜5の封止材は、芳香族イソシアネートを用いたものであるため、耐熱性、耐熱変色性の点で劣っていた。
As shown in Table 1, the sealing materials of Examples 1 to 5 have excellent heat resistance, heat discoloration, and transparency, and are excellent in curability even in a low temperature environment such as 80 ° C. It was confirmed. Moreover, it was confirmed that the sealing material of Examples 1-5 has few odors.
On the other hand, since the sealing materials of Comparative Examples 1 to 3 did not contain (meth) acryloyl group-containing polyurethane, they were inferior in heat discoloration. Moreover, the sealing material of the comparative example 1 containing an alicyclic epoxy was inferior also in the sclerosis | hardenability point.
Since the sealing materials of Comparative Examples 4 to 5 used aromatic isocyanate, they were inferior in terms of heat resistance and heat discoloration.
本発明は、ラジカル重合性組成物からなる封止材およびそれを用いた成形品として、特に低温での硬化性、透明性、耐熱変色性に優れる封止材およびそれからなる成形品が要求される医療分野、電気電子分野、機械分野、土木建築等幅広い分野で利用可能である。 The present invention requires a sealing material composed of a radically polymerizable composition and a molded product using the same, particularly a sealing material excellent in curability at low temperatures, transparency and heat discoloration, and a molded product composed thereof. It can be used in a wide range of fields such as the medical field, electrical and electronic field, mechanical field, civil engineering and architecture.
Claims (9)
A light-emitting diode obtained by sealing using the sealing material according to claim 1.
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WO2016043239A1 (en) * | 2014-09-16 | 2016-03-24 | 株式会社巴川製紙所 | Protective film, film laminate, and polarizing plate |
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WO2006120887A1 (en) * | 2005-05-12 | 2006-11-16 | Nippon Kayaku Kabushiki Kaisha | Photosensitive resin compositions, cured articles of the compositions, and films containing the compositions |
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