JP2008179733A - Epoxy resin composition and epoxy resin-based thin film - Google Patents
Epoxy resin composition and epoxy resin-based thin film Download PDFInfo
- Publication number
- JP2008179733A JP2008179733A JP2007015600A JP2007015600A JP2008179733A JP 2008179733 A JP2008179733 A JP 2008179733A JP 2007015600 A JP2007015600 A JP 2007015600A JP 2007015600 A JP2007015600 A JP 2007015600A JP 2008179733 A JP2008179733 A JP 2008179733A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- group
- thin film
- general formula
- polycarboxylic acid
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 116
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 116
- 239000000203 mixture Substances 0.000 title claims abstract description 103
- 239000010409 thin film Substances 0.000 title claims abstract description 72
- 239000002253 acid Substances 0.000 claims abstract description 87
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 80
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 42
- 238000004383 yellowing Methods 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000002723 alicyclic group Chemical group 0.000 claims description 75
- 150000001450 anions Chemical group 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 239000010408 film Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000003566 sealing material Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004018 acid anhydride group Chemical group 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 9
- QXBYUPMEYVDXIQ-UHFFFAOYSA-N 4-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound CC1CCCC2C(=O)OC(=O)C12 QXBYUPMEYVDXIQ-UHFFFAOYSA-N 0.000 claims description 7
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 claims description 7
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 claims description 7
- IVVOCRBADNIWDM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,3-dicarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)O)C1C2 IVVOCRBADNIWDM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- BFPKYGRZERDWLA-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(O)=O)C1(C)C2 BFPKYGRZERDWLA-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- OGRULRAOMCDCBO-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC1=CC=C2C=CC=CC2=C1OCC1CO1 OGRULRAOMCDCBO-UHFFFAOYSA-N 0.000 claims description 4
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- FEZWWDAFAFPTKZ-UHFFFAOYSA-L C12C(C(C(CC1)C2)C(=O)[O-])C(=O)[O-].C(CCC)[P+](CCCC)(CCCC)CCCC.C(CCC)[P+](CCCC)(CCCC)CCCC Chemical compound C12C(C(C(CC1)C2)C(=O)[O-])C(=O)[O-].C(CCC)[P+](CCCC)(CCCC)CCCC.C(CCC)[P+](CCCC)(CCCC)CCCC FEZWWDAFAFPTKZ-UHFFFAOYSA-L 0.000 claims description 2
- PHWLKYDFYXBKBN-UHFFFAOYSA-M COC(=O)C1C2CCC(C1C(=O)[O-])C2.C(CCC)[P+](CCCC)(CCCC)CCCC Chemical compound COC(=O)C1C2CCC(C1C(=O)[O-])C2.C(CCC)[P+](CCCC)(CCCC)CCCC PHWLKYDFYXBKBN-UHFFFAOYSA-M 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 6
- 125000000129 anionic group Chemical group 0.000 abstract description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 239000004065 semiconductor Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- -1 phosphonium organic acid salt Chemical class 0.000 description 13
- 239000008393 encapsulating agent Substances 0.000 description 8
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 4
- OZEHOHQZIRILDX-UHFFFAOYSA-N ctk1b7797 Chemical compound O=C1OC(=O)C2C1C1(C)CC2CC1 OZEHOHQZIRILDX-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 150000004714 phosphonium salts Chemical group 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LQOPXMZSGSTGMF-UHFFFAOYSA-N 6004-79-1 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C2 LQOPXMZSGSTGMF-UHFFFAOYSA-N 0.000 description 2
- MNMYUIQDDJHUNG-UHFFFAOYSA-N 8-methyl-4-oxatricyclo[5.2.1.02,6]decane-3,5-dione Chemical compound O=C1OC(=O)C2C1C1CC(C)C2C1 MNMYUIQDDJHUNG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 2
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- OIXUMCLBEXJAQZ-UHFFFAOYSA-N 1-methyl-4-oxatricyclo[5.2.1.02,6]dec-2(6)-ene-3,5-dione Chemical compound O=C1OC(=O)C2=C1C1(C)CC2CC1 OIXUMCLBEXJAQZ-UHFFFAOYSA-N 0.000 description 1
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 description 1
- DGBKTJIQJQNAIN-UHFFFAOYSA-N 2-butyl-3-methylbutanedioic acid Chemical compound CCCCC(C(O)=O)C(C)C(O)=O DGBKTJIQJQNAIN-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- JDBDDNFATWXGQZ-UHFFFAOYSA-N 5-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(C)CC2C(=O)OC(=O)C12 JDBDDNFATWXGQZ-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 0 CC(C(*)C(*)C1C(O)=O)C(*)C1C(O)=O Chemical compound CC(C(*)C(*)C1C(O)=O)C(*)C1C(O)=O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- XQVKVFCEFSKNKC-UHFFFAOYSA-M octanoate;tetrabutylphosphanium Chemical compound CCCCCCCC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC XQVKVFCEFSKNKC-UHFFFAOYSA-M 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- WQTXZYHEQMEIDJ-UHFFFAOYSA-L propanedioate;tetrabutylphosphanium Chemical compound [O-]C(=O)CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC WQTXZYHEQMEIDJ-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Landscapes
- Led Devices (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Led Device Packages (AREA)
Abstract
Description
本発明は、半導体パッケージや発光素子の薄膜封止材、液晶表示装置のような表示装置の表面コーティング等を形成するのに用いられるエポキシ樹脂系組成物、この組成物を硬化させてなるエポキシ樹脂系薄膜、この薄膜で封止された発光素子、エポキシ樹脂系薄膜の形成方法、及びエポキシ樹脂系薄膜の黄変防止方法に関する。 The present invention relates to a thin film encapsulant for semiconductor packages and light emitting elements, an epoxy resin composition used for forming a surface coating of a display device such as a liquid crystal display device, and an epoxy resin obtained by curing the composition. The present invention relates to a light-emitting element sealed with a thin film, a method for forming an epoxy resin thin film, and a method for preventing yellowing of an epoxy resin thin film.
近年、携帯電話、デジタルカメラ、ノート型パソコン等の携帯型電子機器の発展等に代表されるように、半導体素子（トランジスタ・電界効果トランジスタ（ＦＥＴ）、サイリスタ（ＳＣＲ）、ダイオード（整流器））、光半導体（フォトカプラ・発光ダイオード（ＬＥＤ）・フォトインタラプタ等）等の電子部品は、高密度化、高集積化に伴って、小型化、薄型化の傾向にある。半導体素子を組み合わせた半導体パッケージに関しては、実装面積をとらずに高集積できる手法として、ＢＧＡ（ボール・グリッド・アレー）、ＣＳＰ（チップ・サイズ・パッケージ）、ＣＯＧ（チップ・オン・グラス）、ＣＯＢ（チップ・オン・ボード）、ＭＣＭ（マルチ・チップ・モジュール）、ＬＧＡ（ランド・グリッド・アレイ）等の手法が開発されている。また、ＬＥＤ光半導体に関しても面実装が可能なチップタイプが開発されている。 In recent years, as represented by the development of portable electronic devices such as mobile phones, digital cameras, notebook computers, etc., semiconductor elements (transistors / field effect transistors (FETs), thyristors (SCRs), diodes (rectifiers)), Electronic components such as optical semiconductors (photocouplers, light-emitting diodes (LEDs), photointerrupters, etc.) tend to be smaller and thinner with higher density and higher integration. For semiconductor packages that combine semiconductor elements, BGA (Ball Grid Array), CSP (Chip Size Package), COG (Chip On Glass), COB are methods that can be highly integrated without taking up a mounting area. Techniques such as (chip on board), MCM (multi chip module), and LGA (land grid array) have been developed. Also, a chip type that can be surface-mounted has been developed for LED optical semiconductors.
これらの半導体素子は、それ自身の発熱が大きいため、樹脂封止材としては、作業性、硬化物の電気的特性、機械的特性、接着性、耐水性、耐溶剤性だけでなく、耐熱性にも優れている必要があり、通常、液状エポキシ樹脂が使用される。 Since these semiconductor elements generate a large amount of heat, the resin encapsulant has not only workability, electrical properties of cured products, mechanical properties, adhesiveness, water resistance, solvent resistance, but also heat resistance. In general, a liquid epoxy resin is used.
このような液状エポキシ樹脂の硬化剤としては、粘度が低いために作業性に優れ、多量の充填材が配合できるとともに、電気的特性、機械的特性、耐熱性に優れることから、液状の酸無水物が多用されており、用途に応じてその種類が適宜選択される。例えば、半導体パッケージのエポキシ樹脂封止材用の酸無水物硬化剤としては、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルノルボルネン−２，３−ジカルボン酸無水物、トリアルキル無水テトラヒドロ無水フタル酸等が使用される。また、チップタイプのＬＥＤ、光半導体の封止材は透明性が要求されることから、メチルヘキサヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸のような二重結合を持たない酸無水物が使用される。 As a curing agent for such a liquid epoxy resin, it is excellent in workability because of its low viscosity, and can be blended with a large amount of fillers, and also has excellent electrical characteristics, mechanical characteristics, and heat resistance. Many things are used, and the type is appropriately selected according to the application. For example, as an acid anhydride curing agent for an epoxy resin encapsulant of a semiconductor package, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnorbornene-2,3-dicarboxylic anhydride, Trialkyltetrahydrophthalic anhydride and the like are used. In addition, since chip-type LEDs and optical semiconductor encapsulants are required to be transparent, acid anhydrides having no double bonds such as methylhexahydrophthalic anhydride and hexahydrophthalic anhydride are used. .
封止材は、通常、素子が基板上にベア・チップ実装されたのち、ディスペンサー方式や、常圧スクリーン印刷又は真空スクリーン印刷方式で薄膜状(例えば２ｍｍ以下）に塗布されたり、ポッティングされたり、半導体素子と基板の隙間に含浸されたりする。さらに、通常は、封止材を塗布したもの、ポッティングしたもの又は含浸したものを所定期間貯蔵した後に、硬化炉にて硬化が行われる。 The sealing material is usually applied in a thin film (for example, 2 mm or less) or potted by a dispenser method, an atmospheric pressure screen printing method or a vacuum screen printing method after an element is mounted on a substrate on a bare chip. The gap between the semiconductor element and the substrate is impregnated. Further, usually, after applying a sealing material applied, potted or impregnated for a predetermined period of time, curing is performed in a curing furnace.
しかし、従来の酸無水物硬化剤を用いた液状エポキシ樹脂系組成物を硬化させて薄膜とする場合、硬化物のガラス転移温度（Ｔｇ）の低下や、クラック発生等の難点がある。また、無色透明性が求められる場合は、高温及び高エネルギーの光照射条件下での黄変（以下「黄変」又は「熱黄変」という）が問題となる。そのため、酸無水物硬化剤を用いたエポキシ樹脂系薄膜を使用できる用途は黄変ないし熱黄変が影響を与えない用途（赤色ＬＥＤ等）に限られており、黄変ないし熱黄変が品質に影響を及ぼす用途（青色や白色ＬＥＤ等）への使用は困難であった。 However, when a liquid epoxy resin composition using a conventional acid anhydride curing agent is cured to form a thin film, there are problems such as a decrease in the glass transition temperature (Tg) of the cured product and occurrence of cracks. In addition, when colorless transparency is required, yellowing under high temperature and high energy light irradiation conditions (hereinafter referred to as “yellowing” or “thermal yellowing”) becomes a problem. Therefore, the applications that can use epoxy resin thin films with acid anhydride curing agents are limited to applications that do not affect yellowing or thermal yellowing (red LEDs, etc.), and yellowing or thermal yellowing is quality. It was difficult to use for applications that affect the color (such as blue and white LEDs).
これらの問題を解決するために、不純物の量を特定量以下にしたメチルノルボルナン−２，３−ジカルボン酸無水物、又はメチルノルボルナン−２，３−ジカルボン酸無水物とノルボルナン−２，３−ジカルボン酸無水物の混合物を硬化剤とするエポキシ樹脂系組成物が提案されている（特許文献１）。しかし、このエポキシ樹脂系組成物は硬化促進剤がイミダゾール系であるためか、初期透明性（即ち、硬化直後のイエローインデックスの値が低く、無色透明であること）や耐熱黄変性（即ち、上記黄変ないし熱黄変を抑制する性質）の点で更に改善が求められている。 In order to solve these problems, methylnorbornane-2,3-dicarboxylic acid anhydride, or methylnorbornane-2,3-dicarboxylic acid anhydride and norbornane-2,3-dicarboxylic acid in which the amount of impurities is a specific amount or less is used. An epoxy resin-based composition using a mixture of acid anhydrides as a curing agent has been proposed (Patent Document 1). However, because this epoxy resin composition is an imidazole curing accelerator, initial transparency (that is, the yellow index value after curing is low and colorless and transparent) and heat yellowing (that is, the above-mentioned) Further improvement is required in terms of the property of suppressing yellowing or thermal yellowing.
一方、ＤＢＵ（１，８−ジアザビシクロ（５．４．０）ウンデセン−７）類硬化促進剤やアンモニウム塩系硬化促進剤は硬化性が良い事からＬＥＤ用途等に広く使用されている。しかし、これらの硬化促進剤を用いたエポキシ樹脂硬化物は、初期無色透明性には比較的に優れるが、耐熱黄変性が悪いと言う難点がある（後述の比較例７及び８参照）。 On the other hand, DBU (1,8-diazabicyclo (5.4.0) undecene-7) type curing accelerators and ammonium salt-based curing accelerators are widely used for LED applications and the like because of their good curability. However, the cured epoxy resin using these curing accelerators is relatively excellent in initial colorless transparency, but has a problem that heat-resistant yellowing is poor (see Comparative Examples 7 and 8 described later).
硬化剤として酸無水物、硬化促進剤として４級ホスホニウム塩を含む積層板用エポキシ樹脂組成物は硬化速度が速く成形性に優れることが開示されている（特許文献２）。しかし、同文献はエポキシ樹脂組成物を硬化させて薄膜とする場合の硬化物のＴｇ低下や熱黄変の課題を解決する手段については何ら示唆していない。事実、同文献で開示されている４級ホスホニウムの鉱酸塩として一般に入手可能なテトラフェニルホスホニウムブロマイドやテトラブチルホスホニウムブロマイドを硬化促進剤として用いたエポキシ樹脂硬化物は、初期無色透明性には比較的に優れるが、薄膜硬化時のＴｇ低下が大きいと言う難点がある（後述の比較例５及び６参照）。 It has been disclosed that an epoxy resin composition for a laminated board containing an acid anhydride as a curing agent and a quaternary phosphonium salt as a curing accelerator has a high curing rate and excellent moldability (Patent Document 2). However, this document does not suggest any means for solving the problems of Tg reduction and thermal yellowing of the cured product when the epoxy resin composition is cured to form a thin film. In fact, epoxy resin cured products using tetraphenylphosphonium bromide and tetrabutylphosphonium bromide, which are generally available as quaternary phosphonium mineral salts disclosed in the same literature, are compared to the initial colorless and transparent properties. However, there is a drawback that the Tg reduction during thin film curing is large (see Comparative Examples 5 and 6 described later).
また、硬化剤として酸無水物を含み、硬化促進剤としてテトラブチルホスホニウムオクテートを含む液状エポキシ樹脂系組成物は、封止材として用いたときに透明性に優れることが開示されている（特許文献３）。しかし、この組成物を用いて得られる硬化物（特に薄膜）は、Ｔｇの低下が少ないが、耐熱黄変性の点で必ずしも満足できるものではない（後述の比較例１参照）。また、液状エポキシ樹脂組成物は、酸無水物系硬化剤に硬化促進剤をあらかじめ添加してなる混合物（以下「硬化剤液」という）と、エポキシ樹脂を主体とした主剤液との２液の形態で貯蔵、輸送され、使用直前に主剤液と硬化剤液を混合して使用されるため、硬化剤液は長期に亘って炭酸ガス発生による粘度増加を起こさないことが求められる。しかし、特許文献３の硬化促進剤を使用する場合、硬化剤液の粘度増加が大きいという問題もある（後述の比較例１参照）。 Further, it is disclosed that a liquid epoxy resin composition containing an acid anhydride as a curing agent and tetrabutylphosphonium octate as a curing accelerator is excellent in transparency when used as a sealing material (patent) Reference 3). However, a cured product (particularly a thin film) obtained using this composition has a small decrease in Tg, but is not necessarily satisfactory in terms of heat-resistant yellowing (see Comparative Example 1 described later). In addition, the liquid epoxy resin composition is a two-part solution consisting of a mixture obtained by adding a curing accelerator in advance to an acid anhydride curing agent (hereinafter referred to as “curing agent liquid”) and a main agent liquid mainly composed of an epoxy resin. Since it is stored and transported in the form and used by mixing the main agent solution and the curing agent solution immediately before use, the curing agent solution is required not to cause an increase in viscosity due to generation of carbon dioxide gas over a long period of time. However, when using the hardening accelerator of patent document 3, there also exists a problem that the viscosity increase of a hardening | curing agent liquid is large (refer the below-mentioned comparative example 1).
また、硬化剤として酸無水物を、硬化促進剤として４級ホスホニウムの有機酸塩を含む半導体封止用エポキシ樹脂組成物は、硬化時の着色がなく、経時熱変色が少ないことが開示されている（特許文献４）。しかし同文献は、エポキシ樹脂組成物を硬化させて薄膜とする場合の硬化物のＴｇ低下や薄膜での熱黄変の課題及びその課題を解決する手段については何ら示唆していない。特許文献４は、極めて広範な４級ホスホニウムの有機酸塩を開示しており、そこに記載されている４級ホスホニウムの有機酸塩が、(a)Ｔｇ低下抑制、(b)耐熱黄変性、及び(c)硬化剤液の粘度増加抑制の全てについて優れているかどうかについて全く記載がない。
本発明は、高いガラス転移温度（Ｔｇ）を有し、かつ耐熱黄変性に優れるエポキシ樹脂系薄膜、このような薄膜を形成できるエポキシ樹脂系組成物を提供することを主な課題とする。 The main object of the present invention is to provide an epoxy resin thin film having a high glass transition temperature (Tg) and excellent heat-resistant yellowing, and an epoxy resin composition capable of forming such a thin film.
本発明者らは、上記の課題を解決するために検討を重ねた結果、次の知見を得た。 The present inventors obtained the following knowledge as a result of repeated studies to solve the above-described problems.
(i)エポキシ樹脂系組成物による薄膜形成は通常高温で行われるところ、高温では硬化剤の酸無水物が揮発するため、硬化不良を生じて硬化物のガラス転移温度（Ｔｇ）が低くなる。実用上十分な耐劣化性及び耐湿性を備えるためには、薄膜のＴｇが高いことが必要である。高Ｔｇを得るために硬化促進剤の使用量を増やすと、使用時の熱で薄膜が黄変し易くなる。例えば、ディスプレイ表面のコーティング膜とする場合や、白色発光素子の薄膜封止材にする場合には、使用中に黄変しないことが重要である。しかし、高Ｔｇかつ耐熱黄変性に優れるエポキシ樹脂系薄膜は得られていないのが現状である。 (i) Thin film formation with an epoxy resin composition is usually carried out at a high temperature. However, since the acid anhydride of the curing agent volatilizes at a high temperature, poor curing occurs and the glass transition temperature (Tg) of the cured product is lowered. In order to provide practically sufficient deterioration resistance and moisture resistance, the thin film needs to have a high Tg. When the amount of the curing accelerator used is increased in order to obtain a high Tg, the thin film is easily yellowed by heat during use. For example, when it is used as a coating film on the display surface or when it is used as a thin film encapsulant for a white light emitting element, it is important that it does not turn yellow during use. However, at present, an epoxy resin thin film having a high Tg and excellent heat-resistant yellowing has not been obtained.
(ii)(a)エポキシ樹脂、(b)酸無水物系硬化剤及び(c)硬化促進剤を含むエポキシ樹脂系組成物であって、該硬化促進剤として、
(c-1)下記一般式（１-ｐ）
(ii) An epoxy resin composition comprising (a) an epoxy resin, (b) an acid anhydride curing agent and (c) a curing accelerator,
(c-1) The following general formula (1-p)
［式中、Ｒ１〜Ｒ４は、同一又は異なって、炭素数１〜１６の直鎖状若しくは分岐鎖状のアルキル基を示す。］で表されるホスホニウムカチオンと、
(c-2)下記一般式（２）で表される脂環族ポリカルボン酸及び一般式（３）で表される脂環族ポリカルボン酸からなる群から選ばれる少なくとも１種の脂環族ポリカルボン酸のアニオン残基
との塩を含むエポキシ樹脂系組成物が、厚さ１ｍｍ以下、特に０．４ｍｍ以下の薄膜を形成する場合にも、高いＴｇを有し、かつ耐熱黄変性に優れたものとなる。
[In formula, R < 1 > -R < 4 > is the same or different, and shows a C1-C16 linear or branched alkyl group. A phosphonium cation represented by
(c-2) At least one alicyclic selected from the group consisting of an alicyclic polycarboxylic acid represented by the following general formula (2) and an alicyclic polycarboxylic acid represented by the general formula (3) Even when an epoxy resin composition containing a salt with an anion residue of polycarboxylic acid forms a thin film having a thickness of 1 mm or less, particularly 0.4 mm or less, it has a high Tg and is excellent in heat-resistant yellowing It will be.
［式中、Ｒ５は、メチレン基又はエチレン基を示し、Ｒ６〜Ｒ９は、同一又は異なって、それぞれ水素原子、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、又はカルボキシル基を示す。］ [Wherein, R 5 represents a methylene group or an ethylene group, and R 6 to R 9 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or A carboxyl group is shown. ]
［式中、Ｒ１０〜Ｒ１３は、同一又は異なって、それぞれ水素原子、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、又はカルボキシル基を示す。］。 [Wherein, R 10 to R 13 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a carboxyl group. ].
本発明は上記知見に基づき完成されたものであり、下記のエポキシ樹脂系組成物などを提供するものである。 The present invention has been completed based on the above findings, and provides the following epoxy resin-based compositions and the like.
項１ (a)エポキシ樹脂、(b)酸無水物系硬化剤、及び(c)硬化促進剤を含有するエポキシ樹脂系組成物であって、該硬化促進剤(c)が、
(c-1)下記一般式（1-p）
Item 1 An epoxy resin composition comprising (a) an epoxy resin, (b) an acid anhydride curing agent, and (c) a curing accelerator, wherein the curing accelerator (c) is:
(c-1) The following general formula (1-p)
［式中、Ｒ１〜Ｒ４は、同一又は異なって、炭素数１〜１６の直鎖状若しくは分岐鎖状のアルキル基を示す。］
で表されるホスホニウムカチオンと、
(c-2)下記一般式（２）
[In formula, R < 1 > -R < 4 > is the same or different, and shows a C1-C16 linear or branched alkyl group. ]
A phosphonium cation represented by
(c-2) The following general formula (2)
（式中、Ｒ５は、メチレン基又はエチレン基を示し、Ｒ６〜Ｒ９は、同一又は異なって、それぞれ水素原子、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、又はカルボキシル基を示す。）で表される脂環族ポリカルボン酸及び一般式（３） (Wherein R 5 represents a methylene group or an ethylene group, and R 6 to R 9 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or An alicyclic polycarboxylic acid represented by the general formula (3)
（式中、Ｒ１０〜Ｒ１３は、同一又は異なって、それぞれ水素原子、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、又はカルボキシル基を示す。）で表される脂環族ポリカルボン酸からなる群から選ばれる少なくとも１種の脂環族ポリカルボン酸のアニオン残基
との塩であることを特徴とするエポキシ樹脂系組成物。
(Wherein R 10 to R 13 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a carboxyl group). An epoxy resin composition comprising a salt with an anion residue of at least one alicyclic polycarboxylic acid selected from the group consisting of aromatic polycarboxylic acids.
項２ 一般式（1-p）において、Ｒ１〜Ｒ４の全てがブチル基である上記項１に記載の組成物。 Item 2 The composition according to Item 1, wherein in General Formula (1-p), all of R 1 to R 4 are butyl groups.
項３ 上記少なくとも１種の脂環族ポリカルボン酸のアニオン残基が、（ア）一般式（２）において、Ｒ５がメチレン基であり、Ｒ６〜Ｒ９の全てが水素原子である脂環族ポリカルボン酸及び（イ）一般式（２）において、Ｒ５がメチレン基であり、Ｒ６〜Ｒ９の内いずれか１つがメチル基で残り３つが水素原子である脂環族ポリカルボン酸からなる群から選ばれる少なくとも１種の脂環族ポリカルボン酸のアニオン残基である上記項１又は２に記載の組成物。 Item 3 The anion residue of the at least one alicyclic polycarboxylic acid is (A) a fat in which R 5 is a methylene group and all of R 6 to R 9 are hydrogen atoms in the general formula (2) Cyclic polycarboxylic acid and (i) In general formula (2), R 5 is a methylene group, any one of R 6 to R 9 is a methyl group, and the remaining three are hydrogen atoms. Item 3. The composition according to Item 1 or 2, which is an anion residue of at least one alicyclic polycarboxylic acid selected from the group consisting of acids.
項４ 上記少なくとも１種の脂環族ポリカルボン酸のアニオン残基が、(i)一般式（３）において、Ｒ１０〜Ｒ１３がすべて水素原子である脂環族ポリカルボン酸のアニオン残基であるか、又は、(ii)Ｒ１０〜Ｒ１３のうちの２つがカルボキシル基で残り２つが水素原子である脂環族ポリカルボン酸のアニオン残基である上記項１又は２に記載の組成物。 Item 4 The anion residue of the alicyclic polycarboxylic acid in which the anion residue of the at least one alicyclic polycarboxylic acid is (i) R 10 to R 13 are all hydrogen atoms in the general formula (3) Or (ii) the composition according to item 1 or 2 above, wherein two of R 10 to R 13 are anion residues of an alicyclic polycarboxylic acid in which two of the carboxyl groups and the remaining two are hydrogen atoms object.
項５ 上記少なくとも１種の脂環族ポリカルボン酸のアニオン残基が、ビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸、メチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸及び１，２，４，５−シクロヘキサンテトラカルボン酸からなる群より選ばれる少なくとも一種の脂環族ポリカルボン酸のアニオン残基である上記項１又は２に記載の組成物。 Item 5 The anion residue of the at least one alicyclic polycarboxylic acid is bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3. Item 3. The composition according to Item 1 or 2, which is an anion residue of at least one alicyclic polycarboxylic acid selected from the group consisting of dicarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid.
項６ エポキシ樹脂が、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ナフタレンジオールジグリシジルエーテル、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、及び水素化ビスフェノールＡジグリシジルエーテルからなる群より選ばれる少なくとも１種である上記項１〜５のいずれかに記載の組成物。 Item 6 The epoxy resin is bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, naphthalenediol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, and hydrogenated bisphenol A diglycidyl. Item 6. The composition according to any one of Items 1 to 5, which is at least one selected from the group consisting of ethers.
項７ 酸無水物系硬化剤が、３−メチルヘキサヒドロフタル酸無水物及び４−メチルヘキサヒドロフタル酸無水物からなる群より選ばれる少なくとも１種である上記項１〜６のいずれかに記載の組成物。 Item 7 The acid anhydride-based curing agent is at least one selected from the group consisting of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride. Composition.
項８ 酸無水物系硬化剤の含有量が、エポキシ樹脂中のエポキシ基に対する酸無水物系硬化剤中の酸無水物基の当量比が０．９〜１．２となる量である上記項１〜７のいずれかに記載の組成物。 Item 8: The above item, wherein the content of the acid anhydride curing agent is such that the equivalent ratio of the acid anhydride group in the acid anhydride curing agent to the epoxy group in the epoxy resin is 0.9 to 1.2. The composition in any one of 1-7.
項９ (a)エポキシ樹脂と、(b)３−メチルヘキサヒドロフタル酸無水物及び４−メチルヘキサヒドロフタル酸無水物からなる群より選ばれる少なくとも１種の酸無水物系硬化剤と、(c)テトラブチルホスホニウムのビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸塩、テトラブチルホスホニウムのメチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸塩及びテトラブチルホスホニウムの１，２，４，５−シクロヘキサンテトラカルボン酸塩からなる群より選ばれる少なくとも1種の化合物とを含み、酸無水物系硬化剤の含有量が、エポキシ樹脂中のエポキシ基に対する酸無水物系硬化剤中の酸無水物基の当量比が１〜１．１となる量であるエポキシ樹脂系組成物。 Item 9 (a) an epoxy resin, and (b) at least one acid anhydride curing agent selected from the group consisting of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride, c) Tetrabutylphosphonium bicyclo [2.2.1] heptane-2,3-dicarboxylate, tetrabutylphosphonium methylbicyclo [2.2.1] heptane-2,3-dicarboxylate and tetrabutylphosphonium And at least one compound selected from the group consisting of 1,2,4,5-cyclohexanetetracarboxylate, and the content of the acid anhydride curing agent is an acid anhydride for the epoxy group in the epoxy resin An epoxy resin composition in which the equivalent ratio of acid anhydride groups in the system curing agent is in an amount of 1 to 1.1.
項１０ (a)エポキシ樹脂、(b)酸無水物系硬化剤及び(c)硬化促進剤を含有する樹脂組成物から得られるエポキシ樹脂系薄膜の黄変を防止する方法であって、該硬化促進剤(c)として、
(c-1)下記一般式（１-ｐ）
Item 10 is a method for preventing yellowing of an epoxy resin-based thin film obtained from a resin composition containing (a) an epoxy resin, (b) an acid anhydride-based curing agent, and (c) a curing accelerator. As a promoter (c)
(c-1) The following general formula (1-p)
［式中、Ｒ１〜Ｒ４は、同一又は異なって、炭素数１〜１６の直鎖状若しくは分岐鎖状のアルキル基を示す。］で表されるホスホニウムカチオンと、
(c-2)下記一般式（２）
[In formula, R < 1 > -R < 4 > is the same or different, and shows a C1-C16 linear or branched alkyl group. A phosphonium cation represented by
(c-2) The following general formula (2)
（式中、Ｒ５は、メチレン基又はエチレン基を示し、Ｒ６〜Ｒ９は、同一又は異なって、それぞれ水素原子、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、又はカルボキシル基を示す。）で表される脂環族ポリカルボン酸及び一般式（３） (Wherein R 5 represents a methylene group or an ethylene group, and R 6 to R 9 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or An alicyclic polycarboxylic acid represented by the general formula (3)
（式中、Ｒ１０〜Ｒ１３は、同一又は異なって、それぞれ水素原子、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、又はカルボキシル基を示す。）で表される脂環族ポリカルボン酸からなる群から選ばれる少なくとも１種の脂環族ポリカルボン酸のアニオン残基との塩を用いる方法。 (Wherein R 10 to R 13 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a carboxyl group). Using a salt with an anion residue of at least one alicyclic polycarboxylic acid selected from the group consisting of aromatic polycarboxylic acids.
項１１ 上記項１〜９のいずれかに記載の組成物を基体上に塗布し、塗膜を硬化させて、厚さ１ｍｍ以下の薄膜を形成することを特徴とする、エポキシ樹脂系薄膜の形成方法。 Item 11: Forming an epoxy resin thin film, wherein the composition according to any one of Items 1 to 9 is applied on a substrate, and the coating film is cured to form a thin film having a thickness of 1 mm or less. Method.
項１２ 上記項１〜９のいずれかに記載の組成物を硬化してなる厚さ１ｍｍ以下の薄膜。 Item 12 A thin film having a thickness of 1 mm or less obtained by curing the composition according to any one of Items 1 to 9.
項１３ 薄膜が発光素子の封止材である上記項１２に記載の薄膜。 Item 13 The thin film according to Item 12, wherein the thin film is a sealing material for a light emitting device.
項１４ 薄膜がディスプレイ用コーティング材である上記項１２に記載の薄膜。 Item 14. The thin film according to Item 12, wherein the thin film is a display coating material.
項１５ 上記項１２に記載の薄膜で封止された発光素子。 Item 15 A light emitting device encapsulated with the thin film according to Item 12.
本発明の組成物は、エポキシ樹脂と酸無水物硬化剤と硬化促進剤とを含む組成物であって、硬化促進剤として上記一般式（１-ｐ）で表されるホスホニウムカチオンと特定の脂環族ポリカルボン酸のアニオン残基の塩を含む。これにより、この組成物を硬化させて得られる薄膜は、初期透明性に優れ、熱により黄変し難く、かつ高いＴｇを有するものとなる。 The composition of the present invention is a composition comprising an epoxy resin, an acid anhydride curing agent, and a curing accelerator, wherein the phosphonium cation represented by the general formula (1-p) and a specific fat are used as the curing accelerator. Includes salts of anionic residues of cyclic polycarboxylic acids. Thereby, the thin film obtained by curing this composition is excellent in initial transparency, hardly yellowed by heat, and has a high Tg.
発光素子の封止膜や表示装置の硬質コーティング膜には、発光素子、液晶バックライト、プラズマ発光などからもたらされる熱によって黄変し難いことが求められる。本発明のエポキシ樹脂系組成物を硬化させてなる薄膜は、このような用途に好適に使用できる。例えば、白色発光ダイオードはクリアな白色光を持続させるために封止材が黄変しないことが必要であることから、黄変し易い従来のエポキシ樹脂系組成物を用いて薄膜封止することはできなかった。本発明により、エポキシ樹脂系組成物で薄膜封止した白色発光ダイオードが実現した。 A sealing film of a light emitting element and a hard coating film of a display device are required to be hardly yellowed by heat generated from a light emitting element, a liquid crystal backlight, plasma emission, or the like. The thin film formed by curing the epoxy resin composition of the present invention can be suitably used for such applications. For example, white light-emitting diodes require that the encapsulant be non-yellowing in order to maintain clear white light, so thin-film sealing using a conventional epoxy resin-based composition that tends to yellow could not. According to the present invention, a white light emitting diode sealed with a thin film of an epoxy resin composition was realized.
また、既述のように、通常、液状エポキシ樹脂組成物は、酸無水物系硬化剤に硬化促進剤をあらかじめ添加してなる混合物（硬化剤液）と、エポキシ樹脂を主体とした主剤液との２液の形態で貯蔵、輸送され、使用直前に主剤液と硬化剤液を混合して使用されるため、硬化剤液は長期に亘って炭酸ガス発生による粘度増加を起こさないことが求められる。本発明の硬化促進剤は、硬化剤液の経時的な粘度変化が少なく保管安定性に優れているため、使用し易いものである。 Further, as described above, the liquid epoxy resin composition is usually composed of a mixture (curing agent liquid) obtained by adding a curing accelerator to an acid anhydride curing agent in advance, and a main agent liquid mainly composed of an epoxy resin. Since the two main liquids are stored and transported and mixed with the main agent liquid and the hardener liquid immediately before use, the hardener liquid is required not to increase in viscosity due to carbon dioxide generation over a long period of time. . The curing accelerator of the present invention is easy to use because it has little change in viscosity over time of the curing agent liquid and is excellent in storage stability.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のエポキシ樹脂系組成物は、基本的には、(a)エポキシ樹脂、(b)酸無水物系硬化剤及び(c)硬化促進剤たる上記塩を含む組成物である。 The epoxy resin-based composition of the present invention is basically a composition comprising (a) an epoxy resin, (b) an acid anhydride-based curing agent, and (c) the above-described salt that is a curing accelerator.
(a)エポキシ樹脂
エポキシ樹脂としては、公知のエポキシ樹脂を制限なく使用することができる。特に、エポキシ基を分子中に２個以上含有する液状のエポキシ樹脂が好ましく、例えば、ビスフェノールＡジグリシジルエーテル、ビスフェノールＡエチレンオキサイド付加物のジグリシジルエーテル、ビスフェノールＡプロピレンオキサイド付加物のジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ビスフェノールＡＤジグリシジルエーテル、ナフタレンジオールジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、水素化ビスフェノールＡのジグリシジルエーテル、水素化ビスフェノールＦのジグリシジルエーテルのようなグリシジルエーテル型エポキシ樹脂；ヘキサヒドロフタル酸ジグリシジルエステルのようなグリシジルエステル型エポキシ樹脂；３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、ビニルシクロヘキセンジエポキサイドのような脂環式エポキシ樹脂等が挙げられる。
(a) Epoxy resin As the epoxy resin, known epoxy resins can be used without limitation. In particular, a liquid epoxy resin containing two or more epoxy groups in the molecule is preferable. For example, bisphenol A diglycidyl ether, diglycidyl ether of bisphenol A ethylene oxide adduct, diglycidyl ether of bisphenol A propylene oxide adduct, Glycidyl ether type epoxy resins such as bisphenol F diglycidyl ether, bisphenol AD diglycidyl ether, naphthalenediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of hydrogenated bisphenol F Glycidyl ester type epoxy resin such as hexahydrophthalic acid diglycidyl ester; 3,4-epoxycyclohexylmethyl- ', 4'-epoxycyclohexane carboxylate, and alicyclic epoxy resins such as vinylcyclohexene diepoxide is.
これらの中でも、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ナフタレンジオールジグリシジルエーテル、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、及び水素化ビスフェノールＡジグリシジルエーテルが好ましく、ビスフェノールＡジグリシジルエーテル、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、及び水素化ビスフェノールＡジグリシジルエーテルがより好ましい。これらのエポキシ樹脂を用いることにより、低粘度のエポキシ樹脂系組成物が得られ、良好な作業性が得られる。 Among these, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, naphthalene diol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, and hydrogenated bisphenol A diglycidyl ether Bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, and hydrogenated bisphenol A diglycidyl ether are more preferred. By using these epoxy resins, a low-viscosity epoxy resin composition can be obtained, and good workability can be obtained.
エポキシ樹脂は単独で、又は２種以上を混合して使用することができる。 An epoxy resin can be used individually or in mixture of 2 or more types.
(b)酸無水物系硬化剤
酸無水物系硬化剤としては、公知の酸無水物系硬化剤を制限なく使用することができる。例えば、ヘキサヒドロフタル酸無水物、３−メチルヘキサヒドロフタル酸無水物、４−メチルヘキサヒドロフタル酸無水物、１−メチルノルボルナン−２，３−ジカルボン酸無水物、５−メチルノルボルナン−２，３−ジカルボン酸無水物、ノルボルナン−２，３−ジカルボン酸無水物、１−メチルナジック酸無水物、５−メチルナジック酸無水物、ナジック酸無水物、フタル酸無水物、テトラヒドロフタル酸無水物、３−メチルテトラヒドロフタル酸無水物、４−メチルテトラヒドロフタル酸無水物、及びドデセニルコハク酸無水物等が挙げられる。
(b) Acid anhydride curing agent As the acid anhydride curing agent, a known acid anhydride curing agent can be used without limitation. For example, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 1-methylnorbornane-2,3-dicarboxylic anhydride, 5-methylnorbornane-2, 3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, 1-methylnadic acid anhydride, 5-methylnadic acid anhydride, nadic acid anhydride, phthalic acid anhydride, tetrahydrophthalic acid anhydride, Examples include 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, and the like.
中でも、化合物中に二重結合を持たず、揮発し難い酸無水物である、ヘキサヒドロフタル酸無水物、３−メチルヘキサヒドロフタル酸無水物、４−メチルヘキサヒドロフタル酸無水物、１−メチルノルボルナン−２，３−ジカルボン酸無水物、５−メチルノルボルナン−２，３−ジカルボン酸無水物、ノルボルナン−２，３−ジカルボン酸無水物が好ましく、３−メチルヘキサヒドロフタル酸無水物及び４−メチルヘキサヒドロフタル酸無水物からなる群から選ばれる少なくとも１種がより好ましい。二重結合を有さず、揮発し難い化合物を用いることにより、高Ｔｇを有し、かつ初期透明性、耐熱黄変性に一層優れたエポキシ樹脂系組成物が得られる。 Among them, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, which are acid anhydrides that do not have a double bond in the compound and hardly volatilize, 1- Methylnorbornane-2,3-dicarboxylic acid anhydride, 5-methylnorbornane-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride are preferred, and 3-methylhexahydrophthalic acid anhydride and 4 -At least one selected from the group consisting of methylhexahydrophthalic anhydride is more preferable. By using a compound which does not have a double bond and hardly volatilizes, an epoxy resin composition having a high Tg and further excellent in initial transparency and heat-resistant yellowing can be obtained.
酸無水物系硬化剤は、１種を単独で又は２種以上を組み合わせて使用することができる。 An acid anhydride type hardening | curing agent can be used individually by 1 type or in combination of 2 or more types.
酸無水物系硬化剤の含有量は、エポキシ樹脂中のエポキシ基に対する酸無水物系硬化剤中の酸無水物基の当量比が０．９〜１．２程度となる量が好ましく、１〜１．１程度となる量がより好ましい。上記範囲であれば硬化反応が十分に進行する。また、上記範囲であれば、透明性、耐熱黄変性に優れる硬化物が得られる。 The content of the acid anhydride curing agent is preferably such that the equivalent ratio of the acid anhydride group in the acid anhydride curing agent to the epoxy group in the epoxy resin is about 0.9 to 1.2, An amount of about 1.1 is more preferable. If it is the said range, hardening reaction will fully advance. Moreover, if it is the said range, the hardened | cured material which is excellent in transparency and heat-resistant yellowing will be obtained.
(c)硬化促進剤
本発明のエポキシ樹脂系組成物で使用する硬化促進剤(c)は、下記のホスホニウムカチオン(c-1)と下記の少なくとも１種の脂環族ポリカルボン酸のアニオン残基(c-2)との塩である。
(c) Curing accelerator The curing accelerator (c) used in the epoxy resin-based composition of the present invention comprises an anion residue of the following phosphonium cation (c-1) and at least one alicyclic polycarboxylic acid described below. A salt with group (c-2).
(c-1)：一般式（１-ｐ） (c-1): General formula (1-p)
［式中、Ｒ１〜Ｒ４は、同一又は異なって、炭素数１〜１６の直鎖状若しくは分岐鎖状のアルキル基を示す。］
で表されるホスホニウムカチオン。
[In formula, R < 1 > -R < 4 > is the same or different, and shows a C1-C16 linear or branched alkyl group. ]
A phosphonium cation represented by
(c-2)：下記一般式（２） (c-2): The following general formula (2)
［式中、Ｒ５は、メチレン基又はエチレン基を示し、Ｒ６〜Ｒ９は、同一又は異なって、それぞれ水素原子、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、又はカルボキシル基を示す。］
で表される脂環族ポリカルボン酸および一般式（３）
[Wherein, R 5 represents a methylene group or an ethylene group, and R 6 to R 9 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or A carboxyl group is shown. ]
And an alicyclic polycarboxylic acid represented by the general formula (3)
［式中、Ｒ１０〜Ｒ１３は、同一又は異なって、それぞれ水素原子、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、又はカルボキシル基を示す。］
で表される脂環族ポリカルボン酸からなる群から選ばれる少なくとも１種の脂環族ポリカルボン酸のアニオン残基。
[Wherein, R 10 to R 13 are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a carboxyl group. ]
An anion residue of at least one alicyclic polycarboxylic acid selected from the group consisting of alicyclic polycarboxylic acids represented by:
本明細書及び特許請求の範囲において、「脂環族ポリカルボン酸のアニオン残基」とは、脂環族ポリカルボン酸の１個又は２個以上（典型的には１個）のカルボキシル基の水素原子が外れて、１価又は２価以上（典型的には１価）のカルボキシルアニオンとなったものを指すものとする。 In the present specification and claims, the “anionic residue of an alicyclic polycarboxylic acid” refers to one or more (typically one) carboxyl group of the alicyclic polycarboxylic acid. The term “hydrogen atom” refers to a monovalent or divalent or higher (typically monovalent) carboxyl anion.
上記のホスホニウムカチオン(c-1)と少なくとも１種の脂環族ポリカルボン酸のアニオン残基(c-2)との塩は公知であるか、又は、公知の方法、例えば、特開昭６３−１９０８９３に記載の方法により容易に製造できる。例えば、テトラアルキルホスホニウムハライドの溶液（溶媒は、水、メタノール等）を、イオン交換することによりテトラアルキルホスホニウムヒドロキシドの溶液（溶媒は、水、メタノール等）とし、該溶液中で、そのテトラアルキルホスホニウムヒドロキシド１モルに対して上記一般式（２）で表される脂環族ポリカルボン酸及び一般式（３）で表される脂環族ポリカルボン酸からなる群から選ばれる少なくとも１種を０.５〜５モル、より好ましくは０.５〜２モル用いて中和することにより塩形成する方法などが挙げられる。得られた塩を含む反応混合物から、適当な方法、例えば、減圧蒸留等により溶媒を除去して、目的の塩を分離する。なお、上記テトラアルキルホスホニウムヒドロキシドは市販されているものを使用してもよい。 The salts of the phosphonium cation (c-1) and the anion residue (c-2) of at least one alicyclic polycarboxylic acid are known or known methods, for example, It can be easily produced by the method described in -190893. For example, a tetraalkylphosphonium halide solution (solvent is water, methanol, etc.) is ion-exchanged to obtain a tetraalkylphosphonium hydroxide solution (solvent is water, methanol, etc.). At least one selected from the group consisting of the alicyclic polycarboxylic acid represented by the general formula (2) and the alicyclic polycarboxylic acid represented by the general formula (3) with respect to 1 mol of phosphonium hydroxide. Examples include a method of forming a salt by neutralization using 0.5 to 5 mol, more preferably 0.5 to 2 mol. From the reaction mixture containing the obtained salt, the solvent is removed by an appropriate method such as distillation under reduced pressure to separate the target salt. In addition, the said tetraalkylphosphonium hydroxide may use what is marketed.
上記の方法により得られる塩は、通常は、ホスホニウムカチオン(c-1)１モルと少なくとも１種の脂環族ポリカルボン酸のアニオン残基(c-2)１モルとの１：１塩が主成分である。該１：１塩は、典型的には、次のような構造をしている。 The salt obtained by the above method is usually a 1: 1 salt of 1 mol of phosphonium cation (c-1) and 1 mol of anion residue (c-2) of at least one alicyclic polycarboxylic acid. The main component. The 1: 1 salt typically has the following structure:
上記一般式（１）において、Ｒ１〜Ｒ４は、同一又は異なって、炭素数１〜１６の直鎖状若しくは分岐鎖状のアルキル基を示す。 In the general formula (1), R 1 to R 4 are the same or different and represent a linear or branched alkyl group having 1 to 16 carbon atoms.
また、上記一般式（１）において、Ｘは、上記一般式（２）で表される脂環族ポリカルボン酸及び一般式（３）で表される脂環族ポリカルボン酸からなる群から選ばれる少なくとも１種の脂環族ポリカルボン酸のアニオン残基（１価のアニオン残基）を示す。即ち、上記式（１）において、Ｘは、一般式（２）で表される脂環族ポリカルボン酸及び一般式（３）で表される脂環族ポリカルボン酸からなる群から選ばれる少なくとも１種の脂環族ポリカルボン酸の複数のカルボキシル基のうちの一つがカルボキシルアニオン（−ＣＯＯ−）となったアニオン残基である。 In the general formula (1), X is selected from the group consisting of the alicyclic polycarboxylic acid represented by the general formula (2) and the alicyclic polycarboxylic acid represented by the general formula (3). An anion residue (monovalent anion residue) of at least one alicyclic polycarboxylic acid. That is, in the above formula (1), X is at least selected from the group consisting of an alicyclic polycarboxylic acid represented by the general formula (2) and an alicyclic polycarboxylic acid represented by the general formula (3). One of a plurality of carboxyl groups of one kind of alicyclic polycarboxylic acid is an anion residue which is a carboxyl anion (—COO − ).
上記製造法で得られる反応生成物中には、このような一般式（１）で表される１：１塩に加えて、他のタイプの塩（一般式(1-p)で表されるホスホニウムカチオンと上記少なくとも１種の脂環族ポリカルボン酸のアニオン残基との塩）が若干混在することもあるが、そのような反応生成物をそのまま本発明の硬化促進剤として使用することもできる。 In the reaction product obtained by the above production method, in addition to the 1: 1 salt represented by the general formula (1), other types of salts (represented by the general formula (1-p)) A salt of a phosphonium cation and an anion residue of at least one alicyclic polycarboxylic acid may be slightly mixed, but such a reaction product may be used as it is as a curing accelerator of the present invention. it can.
工業的に入手容易な一般式（２）で表される脂環族ポリカルボン酸は、通常、一般式（２）で表される酸の２種以上を含む混合物であることが多い。従って、一般式（２）で表される脂環族ポリカルボン酸の２種以上を含む混合物由来の混合アニオン残基と一般式(1-p)で表されるホスホニウムカチオンとの塩を使用してもよく、この場合も、後述の実施例１に示すように、優れた効果を示す。従って、上記一般式（１）において、Ｘは、一般式（２）で表される少なくとも２種の脂環族ポリカルボン酸のアニオン残基であってもよい。 The alicyclic polycarboxylic acid represented by the general formula (2) which is industrially easily available is usually a mixture containing two or more acids represented by the general formula (2). Accordingly, a salt of a mixed anion residue derived from a mixture containing two or more alicyclic polycarboxylic acids represented by the general formula (2) and a phosphonium cation represented by the general formula (1-p) is used. Also in this case, as shown in Example 1 described later, an excellent effect is exhibited. Therefore, in the general formula (1), X may be an anion residue of at least two alicyclic polycarboxylic acids represented by the general formula (2).
また、一般式(1-p)で表されるホスホニウムカチオンと一般式（３）で表される脂環族ポリカルボン酸のアニオン残基との塩を含む硬化促進剤に関しては、一般式（３）で表される脂環族ポリカルボン酸は実質上単品で工業上入手されることが多いので、通常は、１種類の一般式（３）で表される脂環族ポリカルボン酸を用いて得られる塩を使用するのが、工業的な入手容易性の観点からは、有利である。従って、一般式（３）で表される脂環族ポリカルボン酸を原料とする場合、典型的には、一般式（１）において、Ｘは、１種類の一般式（３）で表される脂環族ポリカルボン酸のアニオン残基である。勿論、Ｘは、２種以上の一般式（３）で表される脂環族ポリカルボン酸のアニオン残基であってもよい。 Further, regarding a curing accelerator including a salt of a phosphonium cation represented by the general formula (1-p) and an anion residue of an alicyclic polycarboxylic acid represented by the general formula (3), the general formula (3 The alicyclic polycarboxylic acid represented by) is substantially a single product and is often obtained industrially. Therefore, usually, the alicyclic polycarboxylic acid represented by one general formula (3) is used. Use of the resulting salt is advantageous from the viewpoint of industrial availability. Therefore, when the alicyclic polycarboxylic acid represented by the general formula (3) is used as a raw material, typically, in the general formula (1), X is represented by one type of the general formula (3). It is an anion residue of alicyclic polycarboxylic acid. Of course, X may be an anion residue of an alicyclic polycarboxylic acid represented by two or more general formulas (3).
本発明のエポキシ樹脂系組成物は、硬化促進剤が上記一般式（１）で表される塩に代表される、上記のホスホニウムカチオン(c-1)と少なくとも１種の脂環族ポリカルボン酸のアニオン残基(c-2)との塩であるため、高温で硬化させて薄膜を形成する場合でも、硬化剤が揮発し難く、硬化が十分に行われて高Ｔｇを有する硬化物が得られる。また、この組成物の硬化物は初期透明性に優れ、かつ耐熱黄変性に優れる。 The epoxy resin-based composition of the present invention includes the phosphonium cation (c-1) and at least one alicyclic polycarboxylic acid, the curing accelerator of which is represented by the salt represented by the general formula (1). Therefore, even when a thin film is formed by curing at a high temperature, the curing agent is difficult to volatilize and the cured product is sufficiently cured and has a high Tg. It is done. Further, the cured product of this composition is excellent in initial transparency and excellent in heat-resistant yellowing.
さらに、本発明で使用する上記塩は、酸無水物系硬化剤に溶解させた硬化剤液の経時粘度変化が少なく保管安定性に優れ、使用し易いものである。 Furthermore, the salt used in the present invention has little change in viscosity with time of a curing agent solution dissolved in an acid anhydride curing agent, is excellent in storage stability, and is easy to use.
上記(c-1)のホスホニウムカチオンに関して、一般式（1-p）におけるＲ１〜Ｒ４は、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、特にブチル基であることが好ましい。Ｒ１〜Ｒ４の全てが、炭素数１〜４の直鎖状若しくは分岐鎖状のアルキル基、特にブチル基であることがより好ましい。 Regarding the phosphonium cation of (c-1) above, R 1 to R 4 in the general formula (1-p) may be a linear or branched alkyl group having 1 to 4 carbon atoms, particularly a butyl group. preferable. It is more preferable that all of R 1 to R 4 are a linear or branched alkyl group having 1 to 4 carbon atoms, particularly a butyl group.
上記(c-2)の脂環族ポリカルボン酸のアニオン残基に関しては、次のアニオン残基が好ましいものとして例示できる。 With regard to the anion residue of the alicyclic polycarboxylic acid (c-2), the following anion residues can be exemplified as preferred examples.
一般式（２）において、Ｒ５がメチレン基であり、Ｒ６〜Ｒ９は全てが水素原子である脂環族ポリカルボン酸のアニオン残基（ア）であるか、又は、一般式（２）において、Ｒ５がメチレン基であり、Ｒ６〜Ｒ９の内いずれか１つがメチル基で残り３つが水素原子である脂環族ポリカルボン酸のアニオン残基（イ）であるか、又はこれら（ア）と（イ）との混合物であるのが好ましい。 In the general formula (2), R 5 is a methylene group, and R 6 to R 9 are all anion residues (a) of an alicyclic polycarboxylic acid which is a hydrogen atom, or the general formula (2) ) In which R 5 is a methylene group, and any one of R 6 to R 9 is a methyl group and the remaining three are hydrogen atoms, or an anionic residue (i) of an alicyclic polycarboxylic acid, or A mixture of (a) and (b) is preferred.
また、一般式（３）において、Ｒ１０〜Ｒ１３がすべて水素原子である脂環族ポリカルボン酸のアニオン残基であるか、又は、Ｒ１０〜Ｒ１３の内いずれか１つがメチル基で残り３つが水素原子である脂環族ポリカルボン酸のアニオン残基であるか、又は、Ｒ１０〜Ｒ１３のうちの２つが（特に、Ｒ１１及びＲ１２が）カルボキシル基で残り２つが水素原子である脂環族ポリカルボン酸のアニオン残基であるのが好ましい。 Moreover, in General formula (3), R < 10 > -R < 13 > is an anion residue of alicyclic polycarboxylic acid whose all are hydrogen atoms, or any one of R < 10 > -R < 13 > is a methyl group. The remaining three are anion residues of an alicyclic polycarboxylic acid which is a hydrogen atom, or two of R 10 to R 13 (particularly, R 11 and R 12 ) are carboxyl groups and the remaining two are hydrogen It is preferably an anion residue of an alicyclic polycarboxylic acid that is an atom.
特に、一般式（３）において、Ｒ１０〜Ｒ１３がすべて水素原子である脂環族ポリカルボン酸のアニオン残基であるか、又は、Ｒ１０〜Ｒ１３のうちの２つが（特に、Ｒ１１及びＲ１２が）カルボキシル基で残り２つが水素原子である脂環族ポリカルボン酸のアニオン残基であるのがより好ましい。 In particular, in the general formula (3), R 10 to R 13 are all anion residues of alicyclic polycarboxylic acid, which are all hydrogen atoms, or two of R 10 to R 13 are (especially, R More preferably, 11 and R 12 are anion residues of an alicyclic polycarboxylic acid wherein a carboxyl group and the remaining two are hydrogen atoms.
特に、一般式（１）のＸで表される脂環族ポリカルボン酸のアニオン残基としては、
(i)ビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸（一般式（２）において、Ｒ５がメチレン基、Ｒ６〜Ｒ９が水素原子）のアニオン残基、又は
(ii)メチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸（一般式（２）において、Ｒ５がメチレン基、Ｒ６〜Ｒ９の内いずれか１つがメチル基で残り３つが水素原子）のアニオン残基、又は
(iii)１，２，４，５−シクロヘキサンテトラカルボン酸（一般式（３）において、Ｒ１１及びＲ１２がカルボキシル基、Ｒ１０及びＲ１３が水素原子）のアニオン残基
であることが好ましい。これら(i)〜(iii)は単独で又は２種以上を組み合わせて使用することができる。
In particular, as an anion residue of the alicyclic polycarboxylic acid represented by X in the general formula (1),
(i) an anion residue of bicyclo [2.2.1] heptane-2,3-dicarboxylic acid (in the general formula (2), R 5 is a methylene group, and R 6 to R 9 are hydrogen atoms), or
(ii) methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid (in the general formula (2), R 5 is a methylene group and any one of R 6 to R 9 is a methyl group, and the remaining 3 An anion residue of one hydrogen atom), or
(iii) An anion residue of 1,2,4,5-cyclohexanetetracarboxylic acid (in formula (3), R 11 and R 12 are carboxyl groups, and R 10 and R 13 are hydrogen atoms) . These (i) to (iii) can be used alone or in combination of two or more.
上記ホスホニウムカチオン(c-1)と少なくとも１種の脂環族ポリカルボン酸のアニオン残基(c-2)との塩の含有量は、エポキシ樹脂１００重量部に対して、０.１〜５重量部程度が好ましく、０.５〜２重量部程度がより好ましい。上記範囲であれば、十分な硬化速度が得られ、初期透明性、耐熱黄変性に優れる硬化物が得られる。 The content of the salt of the phosphonium cation (c-1) and the anion residue (c-2) of at least one alicyclic polycarboxylic acid is 0.1 to 5 with respect to 100 parts by weight of the epoxy resin. About part by weight is preferable, and about 0.5 to 2 parts by weight is more preferable. If it is the said range, sufficient hardening speed will be obtained and the hardened | cured material which is excellent in initial transparency and heat-resistant yellowing will be obtained.
なお、上記一般式（２）及び（３）で表される脂環族ポリカルボン酸においては、隣接する炭素原子にそれぞれ結合した二つのカルボキシル基がシス配置である異性体と、該二つのカルボキシル基がトランス配置である異性体が存在する。上記シス配置は、該二つのカルボキシル基が結合する二つの炭素原子の間の一重結合に関して、該二つのカルボキシル基が同じ側に存在する場合を指す。また、トランス配置は、該二つのカルボキシル基が結合する二つの炭素原子の間の一重結合に関して、該二つのカルボキシル基のうちの一方が、他方とは異なる側に存在している場合を指す。 In the alicyclic polycarboxylic acid represented by the general formulas (2) and (3), an isomer in which two carboxyl groups bonded to adjacent carbon atoms are in cis configuration, and the two carboxyls There are isomers whose groups are in the trans configuration. The cis configuration refers to the case where the two carboxyl groups are on the same side with respect to a single bond between the two carbon atoms to which the two carboxyl groups are bonded. The trans configuration refers to a case where one of the two carboxyl groups is present on a different side from the other with respect to a single bond between the two carbon atoms to which the two carboxyl groups are bonded.
本発明においては、アニオン残基は、シス配置の脂環族ポリカルボン酸由来のもの及びトランス配置の脂環族ポリカルボン酸由来のものの何れであってもよく、また、両者の混合物であってもよい。原料とする該脂環族ポリカルボン酸がトランス−シス混合物であって、且つ隣接する炭素原子に結合した二つのカルボキシル基が１組である場合（換言すると一般式（２）においてＲ６〜Ｒ９がすべて水素原子である場合、又は、一般式（３）においてＲ１０〜Ｒ１３がすべて水素原子である場合）、シス配置の脂環族ポリカルボン酸由来のアニオン残基が、８０％以上（ＧＣ（ガスクロマトグラフィー）分析による面積基準）であるのが好ましい。基本的には、原料脂環族ポリカルボン酸の立体配置は、ホスホニウム塩の形成反応においても保存され、原料脂環族ポリカルボン酸のシス体含有量が、生成するホスホニウムと脂環族ポリカルボン酸アニオン残基との塩のシス体含有量とほぼ同一となるものと考えられる。 In the present invention, the anion residue may be derived from either a cis configuration alicyclic polycarboxylic acid or a trans configuration alicyclic polycarboxylic acid, or a mixture of both. Also good. When the alicyclic polycarboxylic acid used as a raw material is a trans-cis mixture, and two carboxyl groups bonded to adjacent carbon atoms are one set (in other words, in the general formula (2), R 6 to R 9 is a hydrogen atom, or R 10 to R 13 are all hydrogen atoms in the general formula (3)), the anion residue derived from the cis-configured alicyclic polycarboxylic acid is 80% or more. (Area standard based on GC (gas chromatography) analysis) is preferable. Basically, the steric configuration of the raw alicyclic polycarboxylic acid is preserved even in the formation reaction of the phosphonium salt, and the cis-form content of the raw alicyclic polycarboxylic acid is such that the phosphonium and alicyclic polycarboxylic acid to be produced are produced. It is considered that the cis-isomer content of the salt with the acid anion residue is almost the same.
その他の成分
本発明のエポキシ樹脂系組成物には、エポキシ樹脂系組成物に添加される公知の添加剤が含まれていてもよい。このような公知の添加剤として、フェノール系酸化防止剤やアミン系酸化防止剤のような酸化防止剤、ベンゾフェノン系紫外線吸収剤のような紫外線吸収剤、ヒンダードアミン系光安定剤のような光安定剤、炭化水素系滑剤、高級脂肪酸系滑剤のような離型剤などが挙げられる。また、エポキシ樹脂以外の樹脂を含むこともできる。
Other Components The epoxy resin composition of the present invention may contain known additives that are added to the epoxy resin composition. Examples of such known additives include antioxidants such as phenolic antioxidants and amine antioxidants, ultraviolet absorbers such as benzophenone ultraviolet absorbers, and light stabilizers such as hindered amine light stabilizers. And release agents such as hydrocarbon lubricants and higher fatty acid lubricants. Moreover, resin other than an epoxy resin can also be included.
上記の添加剤、樹脂などの付加的成分を使用する場合、それらの含有量は、本発明の効果を損なわない範囲とすればよく、例えば、エポキシ樹脂と硬化剤と硬化促進剤との合計１００重量部に対して１０重量部以下の範囲であれば含まれていてもよい。 When using additional components, such as said additive and resin, those content should just be taken as the range which does not impair the effect of this invention, for example, the sum total of an epoxy resin, a hardening | curing agent, and a hardening accelerator is 100. If it is the range of 10 weight part or less with respect to a weight part, it may be contained.
エポキシ樹脂系組成物
本発明のエポキシ樹脂系組成物は、前記各成分を前記所定割合で混合することにより調製できる。好ましい調製方法として、硬化剤と硬化促進剤とを温度２０〜８０℃程度で撹拌混合し、得られた均質な硬化剤液に対してエポキシ樹脂を加えて温度２０℃〜８０℃程度で均一に攪拌、混合する方法を挙げることができる。
Epoxy resin-based composition The epoxy resin-based composition of the present invention can be prepared by mixing the respective components at the predetermined ratio. As a preferable preparation method, a curing agent and a curing accelerator are stirred and mixed at a temperature of about 20 to 80 ° C., and an epoxy resin is added to the obtained uniform curing agent solution to uniformly at a temperature of about 20 to 80 ° C. The method of stirring and mixing can be mentioned.
エポキシ樹脂、硬化剤、硬化促進剤の各成分は１度に添加してもよく、又は複数回に分けて少しずつ添加しても良い。酸化防止剤、紫外線吸収剤、光安定剤、離型剤などのその他の成分、及びエポキシ樹脂以外の樹脂は、硬化剤と硬化促進剤との混合時、エポキシ樹脂の添加前、エポキシ樹脂の添加時、又はその後など任意の時期に添加して混合することができる。 Each component of the epoxy resin, the curing agent, and the curing accelerator may be added at once, or may be added little by little in several times. Other components such as antioxidants, UV absorbers, light stabilizers, mold release agents, and resins other than epoxy resins are added before curing of epoxy resin before addition of epoxy resin when mixing curing agent and curing accelerator. It can be added and mixed at any time, such as at or after.
上記説明した本発明のエポキシ樹脂系組成物は、比較的高温で硬化させる場合にも、Ｔｇが高く、かつ初期透明性、耐熱黄変性に優れる硬化物が得られる。従って、比較的高温で硬化させる必要がある薄膜形成に特に適したものとなる。 The above-described epoxy resin-based composition of the present invention has a high Tg and a cured product excellent in initial transparency and heat-resistant yellowing even when cured at a relatively high temperature. Therefore, it is particularly suitable for forming a thin film that needs to be cured at a relatively high temperature.
エポキシ樹脂系薄膜
上記説明した本発明のエポキシ樹脂系組成物を、例えば、基体上に塗布し、塗膜を硬化させることにより、薄膜、特に、厚さ１ｍｍ以下の薄膜を形成することができる。薄膜の厚さは、好ましくは０．４ｍｍ以下程度である。また薄膜の厚さの下限値は通常０．０１ｍｍ程度である。
Epoxy resin-based thin film A thin film, particularly a thin film having a thickness of 1 mm or less, can be formed by applying the above-described epoxy resin-based composition of the present invention on a substrate and curing the coating film, for example. The thickness of the thin film is preferably about 0.4 mm or less. The lower limit of the thickness of the thin film is usually about 0.01 mm.
基体としては、特に限定されないが、例えばガラス、セラミック、アルミニウム、ＣＣＬ（銅張積層板）、耐熱性高分子フィルム等が挙げられる。 Although it does not specifically limit as a base | substrate, For example, glass, a ceramic, aluminum, CCL (copper clad laminated board), a heat resistant polymer film, etc. are mentioned.
本発明のエポキシ樹脂系組成物を基体上に塗布する方法としては、従来公知の方法が特に制限されることなく採用でき、例えば、スクリーン印刷やダイコーター、コンマコーター、ロールコーター、バーコーター、グラビアコーターカーテンコーター、スプレーコーターエアーナイフコーター、リバースコーター、ディップスクイズコーター等公知の方法が例示できる。 As a method for applying the epoxy resin-based composition of the present invention onto a substrate, a conventionally known method can be employed without any particular limitation. For example, screen printing, die coater, comma coater, roll coater, bar coater, gravure, etc. Known methods such as a coater curtain coater, a spray coater, an air knife coater, a reverse coater, and a dip squeeze coater can be exemplified.
塗膜の硬化方法は特に限定されず、公知の方法を採用できる。硬化には、密閉式硬化炉、連続硬化が可能なトンネル炉などの従来公知の硬化装置を使用することができる。加熱は、熱風循環、赤外線加熱、高周波加熱などの従来公知の方法で行うことができる。 The method for curing the coating film is not particularly limited, and a known method can be employed. For the curing, a conventionally known curing apparatus such as a closed curing furnace or a tunnel furnace capable of continuous curing can be used. Heating can be performed by a conventionally known method such as hot air circulation, infrared heating, and high frequency heating.
硬化温度及び硬化時間は、８０〜２５０℃程度で３０秒〜１５時間程度とすることができる。硬化物の内部応力を低減したい場合は、８０℃〜１３０℃程度で０．５時間〜５時間程度の条件で前硬化した後、１３０〜１８０℃程度で０．１時間〜１５時間程度の条件で後硬化することが好ましい。短時間硬化を目的とする場合は１５０〜２５０℃程度で３０秒〜３０分間程度の条件で硬化することが好ましい。 The curing temperature and curing time can be about 80 to 250 ° C. and about 30 seconds to 15 hours. To reduce the internal stress of the cured product, after pre-curing at about 80 ° C. to 130 ° C. for about 0.5 hours to about 5 hours, then at about 130 to 180 ° C. for about 0.1 hours to about 15 hours It is preferable to perform post-curing. When aiming at short-time curing, curing is preferably performed at about 150 to 250 ° C. for about 30 seconds to 30 minutes.
特に、０．０１〜１ｍｍ程度、特に０．０１〜０．４ｍｍ程度の薄膜を形成する場合の硬化温度及び硬化時間は、１００℃〜１３０℃程度で０．５〜２時間程度の条件で前硬化した後、１３０℃〜１８０℃程度で０．５〜５時間程度の条件で後硬化することが好ましい。 In particular, when forming a thin film of about 0.01 to 1 mm, particularly about 0.01 to 0.4 mm, the curing temperature and the curing time are about 100 ° C. to 130 ° C. and about 0.5 to 2 hours. After curing, post-curing is preferably performed at about 130 ° C. to 180 ° C. for about 0.5 to 5 hours.
なお、本発明のエポキシ樹脂系組成物は、薄膜硬化物の他、厚膜硬化物を形成するための材料として用いることもできる。例えば、本発明の組成物を封止材として使用する場合は、注型法、ポッティング法、ディッピング法、アンダーフィル法、印刷法などの公知の方法で封止することができる。例えば砲弾型ＬＥＤ封止材のような厚膜硬化物は、上記エポキシ樹脂系組成物を砲弾型枠に流し込み、上記方法にて硬化させることにより得ることができる。 In addition, the epoxy resin-type composition of this invention can also be used as a material for forming thick film hardened | cured material other than thin film hardened | cured material. For example, when using the composition of this invention as a sealing material, it can seal by well-known methods, such as a casting method, a potting method, a dipping method, an underfill method, and a printing method. For example, a thick film cured product such as a bullet-type LED encapsulant can be obtained by pouring the epoxy resin composition into a bullet mold and curing it by the above method.
また、例えば面実装型ＬＥＤ封止材のような薄膜は、スクリーン印刷やディスペンサー方式などの方法により塗布し、上記方法にて硬化させることにより得ることができる。 Further, for example, a thin film such as a surface mount type LED sealing material can be obtained by applying by a method such as screen printing or a dispenser method and curing by the above method.
また、例えば表面コーティング材を形成する場合は、上記本発明のエポキシ樹脂系組成物を基体に上記方法で塗布した後、上記方法で硬化させることにより得ることができる。こうして得られる表面コーティング材の厚さも、通常、０．０１〜１ｍｍ程度、特に０．０１〜０．４ｍｍ程度とすることが望ましい。 For example, when forming a surface coating material, it can be obtained by applying the epoxy resin composition of the present invention to a substrate by the above method and then curing it by the above method. The thickness of the surface coating material thus obtained is also preferably about 0.01 to 1 mm, particularly about 0.01 to 0.4 mm.
本発明のエポキシ樹脂系組成物を硬化させて得られる上記薄膜硬化物は、Ｔｇが高く、初期透明性に優れ、耐熱黄変性に優れる。この薄膜硬化物は、例えば１５０℃の高温で５日間熱履歴を与えた後でも黄変度が極めて軽微である（後述の実施例参照）。 The thin film cured product obtained by curing the epoxy resin composition of the present invention has a high Tg, excellent initial transparency, and excellent heat yellowing. This thin film cured product has a very slight degree of yellowing even after giving a heat history at a high temperature of, for example, 150 ° C. for 5 days (see Examples described later).
このため、特に面実装タイプの絶縁封止材料として最適であり、ＢＧＡ（ボール・グリッド・アレー）、ＣＳＰ（チップ・サイズ・パッケージ）、ＣＯＧ（チップ・オン・グラス）、ＣＯＢ（チップ・オン・ボード）、ＭＣＭ（マルチ・チップ・モジュール）又はＬＧＡ（ランド・グリッド・アレイ）等の面実装タイプの半導体装置の封止材料、チップタイプのＬＥＤのような発光素子又は光半導体等の封止材料等の絶縁材料を始めとして、工業的に広い分野において使用することができる。 For this reason, it is particularly suitable as an insulating sealing material of the surface mounting type, and BGA (ball grid array), CSP (chip size package), COG (chip on glass), COB (chip on glass). Board), MCM (multi-chip module) or LGA (land grid array) or other surface mounting type semiconductor device sealing material, chip type LED or other light emitting element or optical semiconductor sealing material It can be used in a wide range of industrial fields including insulating materials such as the above.
特に、発光素子の封止材は、発光素子自身からの発熱により黄変し難いことが重要であるため、本発明の組成物は発光素子の薄膜封止材として好適に使用できる。 In particular, since it is important that the sealing material of the light emitting element is not easily yellowed by heat generated from the light emitting element itself, the composition of the present invention can be suitably used as a thin film sealing material of the light emitting element.
本発明のエポキシ樹脂系組成物を硬化させてなる上記エポキシ樹脂系薄膜で封止された発光素子は、長期使用しても初期の色調が維持される。特に、本発明の薄膜で封止された白色発光素子は、長期使用によっても透明な白色光が維持される有用なものである。 The light emitting element sealed with the epoxy resin thin film obtained by curing the epoxy resin composition of the present invention maintains the initial color tone even after long-term use. In particular, the white light emitting device encapsulated with the thin film of the present invention is useful in that transparent white light is maintained even after long-term use.
また、この薄膜は、透明性、耐熱黄変性に優れることから、各種ガラス基板、自動車部品、液晶表示装置やプラズマディスプレイのような表示装置等の透明ハードコーティング材料としても好適に使用できる。特に、液晶表示装置はバックライトの高熱によって黄変し難いことが重要であるため、本発明の組成物は液晶表示装置のコーティング材として好適に使用できる。このように、本発明の薄膜は、ディスプレイ用のコーティング材としても有用である。 Moreover, since this thin film is excellent in transparency and heat-resistant yellowing, it can be suitably used as a transparent hard coating material for various glass substrates, automobile parts, display devices such as liquid crystal display devices and plasma displays. In particular, since it is important that the liquid crystal display device is not easily yellowed by the high heat of the backlight, the composition of the present invention can be suitably used as a coating material for the liquid crystal display device. Thus, the thin film of the present invention is also useful as a coating material for displays.
本発明では、上述のように、エポキシ樹脂系薄膜の黄変を抑制乃至防止することができる。従って、本発明は、エポキシ樹脂系薄膜（より詳しくは、エポキシ樹脂、酸無水物系硬化剤、及び硬化促進剤を含む組成物を硬化して得られる薄膜）を製造する際に、エポキシ樹脂の硬化促進剤として上記のホスホニウムカチオン(c-1)と少なくとも１種の脂環族ポリカルボン酸のアニオン残基(c-2)との塩を用いることを特徴とするエポキシ樹脂系薄膜の黄変を防止する方法を提供するものでもある。 In the present invention, as described above, yellowing of the epoxy resin thin film can be suppressed or prevented. Therefore, the present invention provides an epoxy resin thin film (more specifically, a thin film obtained by curing a composition containing an epoxy resin, an acid anhydride curing agent, and a curing accelerator). Yellowing of an epoxy resin thin film characterized by using a salt of the above phosphonium cation (c-1) and an anion residue (c-2) of at least one alicyclic polycarboxylic acid as a curing accelerator It also provides a method for preventing this.
以下、実施例及び試験例を参照して本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples, but the present invention is not limited thereto.
物性評価方法
＜イエローインデックス（ＹＩ）＞
各硬化膜を熱処理する前のイエローインデックス（以下、「ＹＩ」という）、及び１５０℃で５日間熱処理した後のＹＩを測定し、両者の差をΔＹＩとした。ＹＩは硬化膜の黄色度を示し、この値が小さいほど無色透明性に優れ、値が大きくなるにつれ黄色度が増す。ΔＹＩは、熱履歴を受けた場合の黄変の程度、即ち耐熱黄変性を示し、この値が小さいほど硬化膜の耐熱黄変性が良好である。本発明においてＹＩは、ＡＳＴＭ Ｄ１９２５に準拠し、分光測色計を用いて反射率を測定し算出した値である。
Physical property evaluation method
<Yellow Index (YI)>
The yellow index (hereinafter referred to as “YI”) before heat treatment of each cured film and YI after heat treatment at 150 ° C. for 5 days were measured, and the difference between them was taken as ΔYI. YI indicates the yellowness of the cured film. The smaller this value, the better the colorless transparency, and the yellowness increases as the value increases. ΔYI indicates the degree of yellowing when subjected to heat history, that is, heat yellowing, and the smaller this value, the better the heat yellowing of the cured film. In the present invention, YI is a value calculated by measuring reflectance using a spectrocolorimeter in accordance with ASTM D1925.
具体的には、被験試料である液状エポキシ樹脂系組成物を、アルミ箔を敷いた直径６８ｍｍの金属製の皿に硬化後の厚みがそれぞれ５ｍｍ、１ｍｍ及び０．４ｍｍとなるように流し込み、１２０℃で１時間、更に１５０℃で３時間硬化した。この円板状硬化物について、片面に上記アルミ箔を接着した状態で、分光測色計（ミノルタ社製、ＣＭ−３５００ｄ）を用いて反射率を測定した。反射率からのＹＩの算出はＡＳＴＭ Ｄ１９２５の規定に準じて行った。 Specifically, a liquid epoxy resin composition as a test sample is poured into a metal dish with a diameter of 68 mm on which an aluminum foil is laid so that the thickness after curing is 5 mm, 1 mm, and 0.4 mm, and 120 The composition was cured at 1 ° C. for 1 hour and further at 150 ° C. for 3 hours. With respect to this disk-like cured product, the reflectance was measured using a spectrocolorimeter (manufactured by Minolta, CM-3500d) with the aluminum foil adhered to one side. YI was calculated from the reflectance according to ASTM D1925.
＜ガラス転移温度（Ｔｇ）＞
上記イエローインデックス（ＹＩ）の測定の項に記載の方法にて作成した厚み５ｍｍ及び０．４ｍｍの円盤状硬化物のガラス転移温度を、ＤＳＣ法を用いて、昇温速度２０℃／分で測定した。
<Glass transition temperature (Tg)>
The glass transition temperature of a disk-shaped cured product having a thickness of 5 mm and 0.4 mm prepared by the method described in the section of yellow index (YI) is measured using a DSC method at a heating rate of 20 ° C./min. did.
Ｔｇの値が大きいほど、劣化、特に熱による劣化が抑制され、耐湿性に優れた膜となる。 As the value of Tg is larger, deterioration, particularly deterioration due to heat is suppressed, and a film having excellent moisture resistance is obtained.
＜膜厚＞
硬化後の膜厚は、クーラントプルーフマイクロメータ（ミツトヨ社製）を用いて測定した。
<Film thickness>
The film thickness after curing was measured using a coolant proof micrometer (manufactured by Mitutoyo Corporation).
＜粘度＞
硬化剤液の粘度は、硬化剤液の温度を２５℃に保ち、ＪＩＳ Ｋ ７１１７に準じＢ型回転粘度計を使用して測定した。
<Viscosity>
The viscosity of the curing agent solution was measured using a B-type rotational viscometer according to JIS K 7117 while keeping the temperature of the curing agent solution at 25 ° C.
製造例１
(a)テトラブチルホスホニウムヒドロキシドの４０重量％水溶液１００重量部に、ビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸／メチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸（重量比１／４）混合物４２重量部を加えて中和し、得られた反応混合物から減圧蒸留法を用いて脱水することにより、硬化促進剤、即ち、テトラブチルホスホニウムカチオンとビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸／メチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸（重量比１／４）混合物由来の混合アニオン残基との塩８０重量部を得た。
Production Example 1
(a) Bicyclo [2.2.1] heptane-2,3-dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3- is added to 100 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide. 42 parts by weight of a dicarboxylic acid (1/4 weight ratio) mixture is added for neutralization, and the resulting reaction mixture is dehydrated using a vacuum distillation method, whereby a curing accelerator, that is, tetrabutylphosphonium cation and bicyclo [ 2.2.1] Salt 80 with a mixed anion residue derived from a mixture of heptane-2,3-dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid (1/4 by weight) Part by weight was obtained.
(b)ビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸及びメチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸は、シス体及びトランス体の異性体混合物であるが、シス体が９５重量％であることをＧＣ（ガスクロマトグラフィー）測定において確認した。 (b) Bicyclo [2.2.1] heptane-2,3-dicarboxylic acid and methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid are cis and trans isomer mixtures. However, it was confirmed by GC (gas chromatography) measurement that the cis-isomer was 95% by weight.
製造例２
テトラブチルホスホニウムヒドロキシドの４０重量％水溶液１００重量部に、１，２，４，５−シクロヘキサンテトラカルボン酸３８重量部を加えて中和し、得られた反応混合物から減圧蒸留法を用いて脱水することにより硬化促進剤、即ち、テトラブチルホスホニウムカチオンと１，２，４，５−シクロヘキサンテトラカルボン酸のアニオン残基との塩７６重量部を得た。
Production Example 2
Neutralizing by adding 38 parts by weight of 1,2,4,5-cyclohexanetetracarboxylic acid to 100 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide, and dehydrating the resulting reaction mixture by using a vacuum distillation method As a result, 76 parts by weight of a curing accelerator, that is, a salt of a tetrabutylphosphonium cation and an anion residue of 1,2,4,5-cyclohexanetetracarboxylic acid was obtained.
実施例１
硬化剤のリカシッドＭＨ-Ｔ（新日本理化（株）製；主成分は４−メチルヘキサヒドロフタル酸無水物）（酸無水物当量１６８）１００重量部（エポキシ樹脂中のエポキシ基に対して硬化剤中の酸無水物基の当量比が１．１となる量）に、製造例１で得た硬化促進剤、即ち、テトラブチルホスホニウムカチオンとビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸／メチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸（重量比１／４）混合物由来の混合アニオン残基との塩（以下「ＴＢＰ・ＨＮＡ塩」と略記する）を１重量部添加し、８０℃で３０分加熱後更に攪拌し溶解した後、室温まで冷却し常温で透明液状の硬化剤液を得た。これにエポキシ樹脂のビスフェノールＡジグリシジルエーテル（東都化成（株）製、エポトートＹＤ−１２８、エポキシ当量１８５）１００重量部を加え、さらに充分混合して真空脱泡後、常温で液状のエポキシ樹脂系組成物を得た。
Example 1
Curing agent Ricacid MH-T (manufactured by Shin Nippon Rika Co., Ltd .; main component is 4-methylhexahydrophthalic anhydride) (acid anhydride equivalent 168) 100 parts by weight (cured against epoxy group in epoxy resin) The amount of the acid anhydride group in the agent is 1.1), and the curing accelerator obtained in Production Example 1, that is, tetrabutylphosphonium cation and bicyclo [2.2.1] heptane-2,3 -Salt with a mixed anion residue derived from a dicarboxylic acid / methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid (weight ratio 1/4) mixture (hereinafter abbreviated as "TBP / HNA salt") 1 part by weight was added, heated at 80 ° C. for 30 minutes, further stirred and dissolved, then cooled to room temperature to obtain a transparent liquid curing agent liquid at room temperature. To this was added 100 parts by weight of epoxy resin bisphenol A diglycidyl ether (Etoto YD-128, epoxy equivalent 185, manufactured by Tohto Kasei Co., Ltd.). A composition was obtained.
実施例２
硬化促進剤のＴＢＰ・ＨＮＡ塩に代えて、製造例２で得たテトラブチルホスホニウムカチオンの１，２，４，５−シクロヘキサンテトラカルボン酸のアニオン残基との塩（以下「ＴＢＰ・ＨＰＭＡ塩」と略記する）を使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Example 2
Instead of the TBP / HNA salt of the curing accelerator, a salt of the tetrabutylphosphonium cation obtained in Production Example 2 with an anion residue of 1,2,4,5-cyclohexanetetracarboxylic acid (hereinafter referred to as “TBP / HPMA salt”). A curing agent solution and an epoxy resin-based composition were obtained in the same manner as in Example 1 except that the abbreviation was used.
比較例１
硬化促進剤のＴＢＰ・ＨＮＡ塩に代えて、テトラブチルホスホニウムオクタン酸塩（以下「ＴＢＰオクタン酸塩」と略記する）を使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Comparative Example 1
A curing agent solution and an epoxy resin system were used in the same manner as in Example 1 except that tetrabutylphosphonium octanoate (hereinafter abbreviated as “TBP octanoate”) was used in place of the TBP / HNA salt of the curing accelerator. A composition was obtained.
比較例２
硬化促進剤のＴＢＰ・ＨＮＡ塩に代えて、テトラブチルホスホニウムの１，４−シクロヘキサンジカルボン酸塩（以下「ＴＢＰ・ＣＨＤＡ塩」と略記する）を使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Comparative Example 2
Curing was carried out in the same manner as in Example 1 except that tetrabutylphosphonium 1,4-cyclohexanedicarboxylate (hereinafter abbreviated as “TBP / CHDA salt”) was used in place of the TBP / HNA salt of the curing accelerator. An agent solution and an epoxy resin composition were obtained.
比較例３
硬化促進剤のＴＢＰ・ＨＮＡ塩に代えて、テトラブチルホスホニウムのマロン酸塩（以下「ＴＢＰマロン酸塩」と略記する）を使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Comparative Example 3
A curing agent solution and an epoxy resin were used in the same manner as in Example 1 except that tetrabutylphosphonium malonate (hereinafter abbreviated as “TBP malonate”) was used in place of the TBP / HNA salt of the curing accelerator. A system composition was obtained.
比較例４
硬化促進剤のＴＢＰ・ＨＮＡ塩に代えて、テトラブチルホスホニウムのグルタル酸塩（以下「ＴＢＰグルタル酸塩」と略記する）を使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Comparative Example 4
A curing agent solution and an epoxy resin were used in the same manner as in Example 1 except that tetrabutylphosphonium glutarate (hereinafter abbreviated as “TBP glutarate”) was used instead of the TBP / HNA salt of the curing accelerator. A system composition was obtained.
比較例５
リカシッドＭＨ−Ｔの使用量を９１重量部（エポキシ樹脂中のエポキシ基に対して硬化剤中の酸無水物基の当量比が１．０となる量）に変更し、硬化促進剤のＴＢＰ・ＨＮＡ塩に代えてテトラブチルホスホニウムブロマイド（以下「ＴＢＰブロマイド」と略記する）を使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Comparative Example 5
The amount of Rikacid MH-T used was changed to 91 parts by weight (an amount in which the equivalent ratio of the acid anhydride group in the curing agent to the epoxy group in the epoxy resin was 1.0). A curing agent solution and an epoxy resin composition were obtained in the same manner as in Example 1 except that tetrabutylphosphonium bromide (hereinafter abbreviated as “TBP bromide”) was used instead of the HNA salt.
本比較例５において、リカシッドＭＨ−Ｔの使用量を９１重量部（エポキシ樹脂中のエポキシ基に対して硬化剤中の酸無水物基の当量比が１．０となる量）に変更した理由は、この使用量の場合に、最も高いTgとなり、かつ透明性が良好であることが予備実験で確認されたためである。リカシッドＭＨ−Ｔの使用量を実施例１と同じ量（当量比が１．１となる量）にした場合は、本比較例５に比べて、Tg及び透明性が劣る。 In this Comparative Example 5, the amount of Ricacid MH-T used was changed to 91 parts by weight (an amount in which the equivalent ratio of the acid anhydride group in the curing agent to the epoxy group in the epoxy resin was 1.0). This is because preliminary experiments confirmed that the Tg was the highest and the transparency was good for this amount. When the amount of Rikacid MH-T used is the same amount as in Example 1 (amount at which the equivalent ratio is 1.1), Tg and transparency are inferior compared to Comparative Example 5.
比較例６
リカシッドＭＨ−Ｔ８２重量部（エポキシ樹脂中のエポキシ基に対して硬化剤中の酸無水物基の当量比が０．９となる量）に変更し、硬化促進剤のＴＢＰ・ＨＮＡ塩に代えてテトラフェニルホスホニウムブロマイドを使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Comparative Example 6
Changed to 82 parts by weight of Ricacid MH-T (amount in which the equivalent ratio of acid anhydride groups in the curing agent to the epoxy groups in the epoxy resin is 0.9), and instead of the TBP / HNA salt of the curing accelerator A curing agent solution and an epoxy resin composition were obtained in the same manner as in Example 1 except that tetraphenylphosphonium bromide was used.
本比較例６において、リカシッドＭＨ−Ｔの使用量を８２重量部（エポキシ樹脂中のエポキシ基に対して硬化剤中の酸無水物基の当量比が０．９となる量）に変更した理由は、この使用量の場合に、最も高いTgとなり、かつ透明性が良好であることが予備実験で確認されたためである。リカシッドＭＨ−Ｔの使用量を実施例１と同じ量（当量比が１．１となる量）にした場合は、本比較例６に比べて、Tg及び透明性が劣る。 In this Comparative Example 6, the amount of Ricacid MH-T used was changed to 82 parts by weight (the amount of the equivalent ratio of acid anhydride groups in the curing agent to the epoxy groups in the epoxy resin was 0.9). This is because preliminary experiments confirmed that the amount of Tg was the highest and the transparency was good for this amount. When the amount of Rikacid MH-T used is the same amount as in Example 1 (amount at which the equivalent ratio is 1.1), Tg and transparency are inferior compared to Comparative Example 6.
比較例７
硬化促進剤のＴＢＰ・ＨＮＡ塩に代えて、１，８−ジアザビシクロ（５．４．０）ウンデセン−７・オクチル酸塩（Ｕ−ＣＡＴ ＳＡ１０２，サンアプロ社製）を使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Comparative Example 7
Example 1 except that 1,8-diazabicyclo (5.4.0) undecene-7.octylate (U-CAT SA102, manufactured by San Apro) was used in place of the TBP / HNA salt of the curing accelerator. In the same manner as above, a curing agent liquid and an epoxy resin composition were obtained.
なお、表１及び２において、１，８−ジアザビシクロ（５．４．０）ウンデセン−７・オクチル酸塩を「ＤＢＵオクチル酸塩」と略記する。 In Tables 1 and 2, 1,8-diazabicyclo (5.4.0) undecene-7.octylate is abbreviated as “DBU octylate”.
比較例８
硬化促進剤のＴＢＰ・ＨＮＡ塩に代えて、テトラブチルアンモニウムブロマイドを使用した以外は、実施例１と同様にして硬化剤液及びエポキシ樹脂系組成物を得た。
Comparative Example 8
A curing agent solution and an epoxy resin composition were obtained in the same manner as in Example 1 except that tetrabutylammonium bromide was used in place of the TBP / HNA salt of the curing accelerator.
実施例１及び２、比較例１〜８のエポキシ樹脂系組成物について、硬化物のＴｇ（５ｍｍ厚、０．４ｍｍ厚）、硬化直後のイエローインデックス（５ｍｍ厚、１ｍｍ厚、０．４ｍｍ厚）、１５０℃で５日間熱処理（エージング）後のイエローインデックス（５ｍｍ厚、１ｍｍ厚、０．４ｍｍ厚）を評価し、硬化剤液については、６０℃で７日保管後の粘度変化を評価した。 For the epoxy resin compositions of Examples 1 and 2 and Comparative Examples 1 to 8, the Tg of the cured product (5 mm thickness, 0.4 mm thickness), the yellow index immediately after curing (5 mm thickness, 1 mm thickness, 0.4 mm thickness) The yellow index (5 mm thickness, 1 mm thickness, 0.4 mm thickness) after heat treatment (aging) at 150 ° C. for 5 days was evaluated, and the curing agent liquid was evaluated for viscosity change after storage at 60 ° C. for 7 days.
結果を表１及び２に示す。 The results are shown in Tables 1 and 2.
上記表１及び２の結果から、次のことが分かる。 From the results of Tables 1 and 2, the following can be understood.
(a)０．４ｍｍ厚さの薄膜において、熱処理後のＹＩが５以下であり、かつ熱処理前後のΔＹＩが５以下であれば発光素子や液晶バックライトの発熱によっても黄変せず、これらの用途にも十分使用できるものとなる。 (a) In a thin film having a thickness of 0.4 mm, if YI after heat treatment is 5 or less and ΔYI before and after heat treatment is 5 or less, yellowing does not occur due to heat generation of the light emitting element or the liquid crystal backlight. It can also be used for applications.
この点、比較例１〜５、７及び８は、熱処理後のＹＩが５より大きく、かつ熱処理前後のΔＹＩが５より大きく、熱黄変の点から上記用途への使用は難しい。これに対して、硬化促進剤がテトラブチルホスホニウムカチオンと特定化学構造の脂環族ポリカルボン酸のアニオン残基との塩である実施例１及び２のエポキシ樹脂系組成物は、熱処理後のＹＩ及びΔＹＩが上記範囲であり実用可能な薄膜を形成できることが分かる。 In this respect, Comparative Examples 1 to 5, 7, and 8 have YI after heat treatment larger than 5, and ΔYI before and after heat treatment is larger than 5, and are difficult to use in the above applications from the viewpoint of thermal yellowing. In contrast, the epoxy resin compositions of Examples 1 and 2 in which the curing accelerator is a salt of a tetrabutylphosphonium cation and an anion residue of an alicyclic polycarboxylic acid having a specific chemical structure, the YI after heat treatment And ΔYI is in the above range, and it can be seen that a practical thin film can be formed.
(b)また、Ｔｇが高いほど劣化、特に熱による劣化が抑制され、耐湿性に優れた膜となる。薄膜封止材や表示装置のコーティング材として使用する場合は熱劣化し難いことや耐湿性が重要であり、０．４ｍｍ厚の膜のＴｇが１４０℃以上であり、かつ５ｍｍ厚膜のＴｇと０．４ｍｍ厚膜のＴｇの差（Ｔｇ差）が１０℃より小さければ、これらの用途にも実用できるものとなる。 (b) Further, the higher the Tg, the more the deterioration, particularly the deterioration due to heat, is suppressed, and the film has excellent moisture resistance. When used as a thin film encapsulant or a coating material for a display device, it is difficult to be thermally deteriorated and moisture resistance is important. The Tg of a 0.4 mm-thick film is 140 ° C. or higher, and If the Tg difference (Tg difference) of the 0.4 mm thick film is smaller than 10 ° C., it can be used for these applications.
この点、比較例５及び６（市販のホスホニウム塩系硬化促進剤を使用）では、０．４ｍｍ厚の膜のＴｇが１４０℃より低く、かつＴｇ差が１０℃以上あり、耐熱性の点から上記用途への使用は難しい。また、比較例１〜４、７及び８は、Ｔｇ及びＴｇ差の点では良好な結果を示しているが、前記(a)のように、熱処理後のＹＩが５より大きく、かつ熱処理前後のΔＹＩが５より大きく、熱黄変の点から上記用途への使用は難しい。 In this respect, in Comparative Examples 5 and 6 (using a commercially available phosphonium salt-based curing accelerator), the Tg of the 0.4 mm-thick film is lower than 140 ° C., and the Tg difference is 10 ° C. or higher. It is difficult to use for the above purposes. Comparative Examples 1 to 4, 7 and 8 show good results in terms of Tg and Tg difference, but as described in (a) above, YI after heat treatment is greater than 5, and before and after heat treatment. ΔYI is larger than 5 and it is difficult to use for the above-mentioned purposes from the viewpoint of thermal yellowing.
これに対して、硬化促進剤がテトラブチルホスホニウムカチオンと特定化学構造の脂環族ポリカルボン酸のアニオン残基との塩である実施例１及び２のエポキシ樹脂系組成物は、０．４ｍｍ厚の硬化膜のＴｇ及びＴｇ差が上記範囲であり、実用可能な薄膜を形成できることが分かる。 On the other hand, the epoxy resin compositions of Examples 1 and 2 in which the curing accelerator is a salt of a tetrabutylphosphonium cation and an anion residue of an alicyclic polycarboxylic acid having a specific chemical structure has a thickness of 0.4 mm. It can be seen that the Tg and Tg difference of the cured film is in the above range, and a practical thin film can be formed.
(c)また、硬化剤液は、使用直前にエポキシ樹脂と混合されるが、通常、予め酸無水物と硬化促進剤を混合したものを貯蔵及び輸送し、その間、炭酸ガス発生による粘度増加が極力低く抑えられていることが好ましい。 (c) In addition, the curing agent liquid is mixed with the epoxy resin immediately before use, but usually stores and transports a mixture of an acid anhydride and a curing accelerator in advance, during which the viscosity increases due to the generation of carbon dioxide gas. It is preferable to keep it as low as possible.
この点、比較例１〜４、７及び８で得た硬化剤液は粘度変化が大きいが、実施例１及び２の硬化剤液は粘度変化が少なく、保管安定性に優れた使用し易いものである。 In this respect, the curing agent liquids obtained in Comparative Examples 1 to 4, 7 and 8 have a large viscosity change, but the curing agent liquids of Examples 1 and 2 have a small viscosity change and are excellent in storage stability and easy to use. It is.
本発明のエポキシ樹脂系組成物を硬化させてなる薄膜は、Ｔｇが高く、初期透明性に優れ、高温で熱履歴を与えた後でも黄変の程度が軽微である。このような優れた性能を併せ持つため、工業上の広い分野で使用することができる。特に面実装タイプの絶縁封止材料として最適であり、ＢＧＡ（ボール・グリッド・アレー）、ＣＳＰ（チップ・サイズ・パッケージ）、ＣＯＧ（チップ・オン・グラス）、ＣＯＢ（チップ・オン・ボード）、ＭＣＭ（マルチ・チップ・モジュール）又はＬＧＡ（ランド・グリッド・アレイ）等の面実装タイプの半導体装置の封止材料、チップタイプのＬＥＤ又は光半導体等の発光素子の封止材料等の絶縁材料として好適に使用できる。 The thin film obtained by curing the epoxy resin composition of the present invention has a high Tg, excellent initial transparency, and a slight degree of yellowing even after giving a thermal history at a high temperature. Since it has such excellent performance, it can be used in a wide range of industrial fields. It is particularly suitable as a surface mount type insulation sealing material, and is BGA (ball grid array), CSP (chip size package), COG (chip on glass), COB (chip on board), As an insulating material such as a sealing material for a surface mount type semiconductor device such as MCM (multi-chip module) or LGA (land grid array), or a sealing material for a light emitting element such as a chip type LED or optical semiconductor. It can be used suitably.
また、その硬化薄膜は、各種ガラス基板、自動車部品、表示装置等の透明ハードコーティング材料としても好適に使用できる。 The cured thin film can also be suitably used as a transparent hard coating material for various glass substrates, automobile parts, display devices and the like.
Claims (15)
(c-1)下記一般式（1-p）
で表されるホスホニウムカチオンと、
(c-2)下記一般式（２）
との塩であることを特徴とするエポキシ樹脂系組成物。 An epoxy resin composition containing (a) an epoxy resin, (b) an acid anhydride-based curing agent, and (c) a curing accelerator, wherein the curing accelerator (c) is:
(c-1) The following general formula (1-p)
A phosphonium cation represented by
(c-2) The following general formula (2)
(c-1)下記一般式(1-p)
(c-2)下記一般式（２）
(c-1) The following general formula (1-p)
(c-2) The following general formula (2)
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