TW201638175A - Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material - Google Patents
Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material Download PDFInfo
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- TW201638175A TW201638175A TW105110535A TW105110535A TW201638175A TW 201638175 A TW201638175 A TW 201638175A TW 105110535 A TW105110535 A TW 105110535A TW 105110535 A TW105110535 A TW 105110535A TW 201638175 A TW201638175 A TW 201638175A
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- epoxy resin
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- 239000000203 mixture Substances 0.000 title claims abstract description 196
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 111
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 111
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 49
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 48
- 239000011229 interlayer Substances 0.000 title claims description 10
- 239000004065 semiconductor Substances 0.000 title claims description 10
- 239000011810 insulating material Substances 0.000 title claims description 8
- -1 maleimide compound Chemical class 0.000 claims abstract description 123
- 239000000126 substance Substances 0.000 claims abstract description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 10
- 125000000732 arylene group Chemical group 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 8
- 239000000047 product Substances 0.000 claims description 39
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 29
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 7
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- 239000000155 melt Substances 0.000 claims description 7
- 229910005965 SO 2 Inorganic materials 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
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- 238000002156 mixing Methods 0.000 description 15
- 229910000420 cerium oxide Inorganic materials 0.000 description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 10
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
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- 239000000463 material Substances 0.000 description 4
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical group C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
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- 238000004806 packaging method and process Methods 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
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- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- DGRGLKZMKWPMOH-UHFFFAOYSA-N 4-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1 DGRGLKZMKWPMOH-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
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- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
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- 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 2
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- 239000001095 magnesium carbonate Substances 0.000 description 2
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
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- 125000006839 xylylene group Chemical group 0.000 description 2
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical group OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 description 1
- HEUDNCPBUYZJDR-UHFFFAOYSA-N 1,1-dimethyl-3-(2-methylphenyl)urea Chemical compound CN(C)C(=O)NC1=CC=CC=C1C HEUDNCPBUYZJDR-UHFFFAOYSA-N 0.000 description 1
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- WCZNKVPCIFMXEQ-UHFFFAOYSA-N 2,3,5,6-tetramethylbenzene-1,4-diamine Chemical compound CC1=C(C)C(N)=C(C)C(C)=C1N WCZNKVPCIFMXEQ-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
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- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 1
- PESXPUCWMKUMSI-UHFFFAOYSA-N 3-[2-(dimethylcarbamoylamino)phenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=CC=C1NC(=O)N(C)C PESXPUCWMKUMSI-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical group C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- ASNOFHCTUSIHOM-UHFFFAOYSA-N 4-[10-(4-aminophenyl)anthracen-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=C(N)C=C1 ASNOFHCTUSIHOM-UHFFFAOYSA-N 0.000 description 1
- GIGYUDLDUWARIU-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-methyl-5-prop-2-enylphenyl)propan-2-yl]-2-methyl-6-prop-2-enylphenol Chemical compound C=CCC1=C(O)C(C)=CC(C(C)(C)C=2C=C(CC=C)C(O)=C(C)C=2)=C1 GIGYUDLDUWARIU-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- PLQFLSNFGHYRJO-UHFFFAOYSA-J [O-]B([O-])[O-].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound [O-]B([O-])[O-].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 PLQFLSNFGHYRJO-UHFFFAOYSA-J 0.000 description 1
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- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
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- 238000004448 titration Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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Abstract
Description
本發明關於一種適於作為環氧樹脂的固化劑的成分或熱固性組合物的成分的組合物、含有該組合物的環氧樹脂固化劑、包含該環氧樹脂固化劑的環氧樹脂組合物、該環氧樹脂組合物的固化物、包含該組合物的熱固性組合物、該熱固性組合物的固化物、利用該環氧樹脂組合物或該熱固性組合物密封的半導體裝置、以及含有該環氧樹脂組合物或該熱固性組合物的層間絕緣材料。另外，本說明書中，「熱固性組合物」是指具有熱固性的組合物，「環氧樹脂組合物」是指含有具有環氧基的樹脂的組合物，且「熱固性組合物」的用語概念與「環氧樹脂組合物」的用語概念有重複部分。 The present invention relates to a composition suitable as a component of a curing agent for an epoxy resin or a composition of a thermosetting composition, an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, a cured product of the epoxy resin composition, a thermosetting composition containing the composition, a cured product of the thermosetting composition, a semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and a resin containing the epoxy resin composition A composition or an interlayer insulating material of the thermosetting composition. In the present specification, the term "thermosetting composition" means a composition having a thermosetting property, and the "epoxy resin composition" means a composition containing a resin having an epoxy group, and the term "thermosetting composition" is used. The terminology of epoxy resin compositions has a repeating part.
在環氧樹脂的固化劑中占較大一群的酚系固化劑除種類豐富以外，還因低成本等特徵而被用於各種產業。為了滿足伴隨產業技術進步所產生的各種要求性能，至今為止開發了多種該固化劑。 A large group of phenolic curing agents, which are a large group of curing agents for epoxy resins, are used in various industries because of their low cost and other characteristics. In order to satisfy various required performances accompanying advances in industrial technology, various curing agents have been developed to date.
在電子材料領域中，近年來，隨著半導體封裝的小型、薄型化以及形狀的複雜化，日益要求半導體密封材料用樹脂為低黏度。如果為低黏度，那麼通過樹脂的流動性提升，也能夠應對複雜形狀的封裝，例如BGA(Ball Grid Array，球柵陣列)等，而且，通過實現填料的高填充化，在所述用途所求的阻燃性、焊料耐熱性、耐濕可靠性的方面也變得有利。 In the field of electronic materials, in recent years, with the miniaturization, thinning, and complication of semiconductor packages, resins for semiconductor sealing materials have been increasingly required to have low viscosity. If it is low in viscosity, it can also cope with complicated shapes, such as BGA (Ball Grid Array), etc. by increasing the fluidity of the resin, and by achieving high filling of the filler, it is required for the use. The flame retardancy, solder heat resistance, and moisture resistance reliability are also advantageous.
另外，出於對地球環境的考慮，讓新穎的阻燃性環氧樹脂組合物代替至今為止所利用的含鹵素系化合物或銻化合物等阻燃劑的需求正在增長，對於從通用封裝到先進封裝用的用途中一直使用的苯酚芳烷基樹脂，也要求即便不使用鹵素系阻燃劑及銻化合物，也具有優異的阻燃性(例如專利文獻1等)。其中，已知導入有聯苯骨架的苯酚芳烷基樹脂為高阻燃性，且正被使用於先進封裝用途(例如專利文獻2等)。 In addition, in response to the global environment, the demand for flame retardant epoxy resin compositions to replace flame retardants such as halogen-containing compounds or antimony compounds that have been utilized so far is increasing, from general-purpose packaging to advanced packaging. The phenol aralkyl resin which has been used for the purpose of use is also required to have excellent flame retardancy (for example, Patent Document 1) even without using a halogen-based flame retardant and a ruthenium compound. Among them, a phenol aralkyl resin to which a biphenyl skeleton is introduced is known to have high flame retardancy and is being used for advanced packaging applications (for example, Patent Document 2).
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
專利文獻1：日本專利特開平5-97965號公報。 Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 5-97965.
專利文獻2：日本專利特開2000-129092號公報。 Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-129092.
然而，專利文獻2所記載的阻燃性環氧樹脂組合物有玻璃化轉變溫度(Tg)變低的傾向。Tg的下降通常會引起高溫可靠性與耐熱性的下降，因此期望提供能夠將所述方面改善的環氧樹脂固化劑。尤其是對於預想今後會越來越普及的電動汽車或混合動力車中所搭載的功率元件(power device)的密封材料，要求具有高耐熱性。此外，就近年來對密封材料的物性需求而言，與耐熱性相關聯地也要求具有高溫下的熱分解性低的特性(以下稱為「高溫下低分解特性」)。 However, the flame-retardant epoxy resin composition described in Patent Document 2 tends to have a low glass transition temperature (Tg). The drop in Tg generally causes a decrease in high temperature reliability and heat resistance, and therefore it is desirable to provide an epoxy resin curing agent capable of improving the aspect. In particular, a sealing material for a power device mounted in an electric vehicle or a hybrid vehicle that is expected to become more and more popular in the future is required to have high heat resistance. In addition, in recent years, in consideration of the physical properties of the sealing material, in addition to the heat resistance, it is required to have a low thermal decomposition property at a high temperature (hereinafter referred to as "low decomposition property at a high temperature").
本發明的目的在於提供一種組合物，適於作為能夠滿足高阻燃性、高耐熱性以及高溫下低分解特性的環氧樹脂的固化劑的成分或熱固性組合物的成分。此外，本發明的目的在於提供一種含有該組合物的環氧樹脂固化劑、包含該環氧樹脂固化劑的環氧樹脂組合物、該環氧樹脂組合物的固化物、包含該組合物的熱固性組合物、該熱固性組合物的固化物、利用該環氧樹脂組合物或該熱固性組合物密封的半導體裝置、以及含有該環氧樹脂組合物或該熱固性組合物的層間絕緣材料。 An object of the present invention is to provide a composition suitable as a component of a curing agent or a component of a thermosetting composition of an epoxy resin capable of satisfying high flame retardancy, high heat resistance, and low decomposition property at a high temperature. Further, an object of the present invention is to provide an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, a cured product of the epoxy resin composition, and thermosetting properties comprising the composition. A composition, a cured product of the thermosetting composition, a semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and an interlayer insulating material containing the epoxy resin composition or the thermosetting composition.
本發明者們為瞭解決所述課題而進行了努力研究，結果發現，除馬來醯亞胺化合物以及芳香族胺化合物以外還以一定比率熔融混合特定的酚化合物所得的新穎的組合物 適於用作環氧樹脂固化劑的成分等熱固性組合物的成分，通過使用該組合物，可獲得能夠形成具有高阻燃性、高耐熱性以及高溫下低分解特性的固化物的熱固性組合物。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that a novel composition obtained by melt-mixing a specific phenol compound at a predetermined ratio in addition to a maleimide compound and an aromatic amine compound has been found. A thermosetting composition capable of forming a cured product having high flame retardancy, high heat resistance, and low decomposition property at high temperature by using the composition as a component of a thermosetting composition such as a component of an epoxy resin curing agent can be obtained by using the composition. .
本發明的一個技術方案提供一種組合物，含有下述化學式(1)所表示的馬來醯亞胺化合物(A)、下述化學式(2)所表示的芳香族胺化合物(B)、以及下述化學式(3)。 According to one aspect of the present invention, there is provided a composition comprising the maleic imine compound (A) represented by the following chemical formula (1), the aromatic amine compound (B) represented by the following chemical formula (2), and the lower Said chemical formula (3).
化學式(1)中，Ar1為可存在取代基的碳數6~12的亞芳基，X1為直接鍵結、碳數1~6的二價烴基、O、S或SO2，p為0~2的整數。 In the chemical formula (1), Ar 1 is an arylene group having 6 to 12 carbon atoms which may have a substituent, and X 1 is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S or SO 2 , and p is An integer from 0 to 2.
化學式(2)中，Ar2為包含0個~2個的範圍的一級氨 基且可存在烴的取代基的碳數6~12的亞芳基，X2為直接鍵結、碳數1~6的二價烴基、O、S或SO2，q為0~2的整數。 In the chemical formula (2), Ar 2 is an arylene group having 6 to 12 carbon atoms which may have a primary amino group in the range of 0 to 2 and may have a substituent of a hydrocarbon, and X 2 is a direct bond, and the carbon number is 1 to 6 The divalent hydrocarbon group, O, S or SO 2 , q is an integer of 0-2.
化學式(3)中，Ar3為以一分子內的烯丙基數成為2個~4個的範圍的方式包含烯丙基，並且包含0個~2個的範圍的羥基的碳數6~24的亞芳基，X3為直接鍵結、碳數1~6的二價烴基、O、S或SO2，r為0~2的整數。 In the chemical formula (3), Ar 3 includes an allyl group in such a range that the number of allyl groups in one molecule is from 2 to 4, and a carbon number of from 6 to 24 in a range of from 0 to 2 The arylene group, X 3 is a direct bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, O, S or SO 2 , and r is an integer of 0 to 2.
該組合物較佳150℃熔融黏度為50mPa‧s以上1000mPa‧s以下，且羥基當量為300g/eq以上1500g/eq以下。 The composition preferably has a melt viscosity at 150 ° C of 50 mPa ‧ or more and 1000 mPa ‧ s or less, and a hydroxyl equivalent of 300 g / eq or more and 1500 g / eq or less.
該組合物可還含有馬來醯亞胺化合物(A)與芳香族胺化合物(B)的反應產物。該反應產物可為該馬來醯亞胺化合物(A)與該芳香族胺化合物(B)的邁克爾(Michael)加成物。 The composition may further contain a reaction product of the maleimide compound (A) and the aromatic amine compound (B). The reaction product may be a Michael adduct of the maleimide compound (A) and the aromatic amine compound (B).
該組合物可為包含該馬來醯亞胺化合物(A)、該芳香族胺化合物(B)以及該酚化合物(C)的組合物的熔融混合體。 The composition may be a molten mixture of the composition comprising the maleimide compound (A), the aromatic amine compound (B), and the phenol compound (C).
該組合物中，基於源自該馬來醯亞胺化合物(A)的馬來 醯亞胺基的部分結構的總數可為基於源自該芳香族胺化合物(B)的一級氨基的部分結構與基於源自該酚化合物(C)的烯丙基的部分結構的總數的1.5倍以上2.5倍以下。 In the composition, based on Malay derived from the maleimide compound (A) The total number of partial structures of the fluorenylene group may be 1.5 times based on the partial structure of the primary amino group derived from the aromatic amine compound (B) and the partial structure based on the allyl group derived from the phenol compound (C). Above 2.5 times or less.
該酚化合物(C)較佳包含下述化學式(4)所表示的雙酚化合物(C1)。 The phenol compound (C) preferably contains the bisphenol compound (C1) represented by the following chemical formula (4).
化學式(4)中，R4及R5分別獨立為碳數1~4的烴基，R6及R7分別獨立為氫原子、甲基、苯基，c及d分別獨立為0~3的整數。 In the chemical formula (4), R 4 and R 5 are each independently a hydrocarbon group having 1 to 4 carbon atoms, and R 6 and R 7 are each independently a hydrogen atom, a methyl group and a phenyl group, and c and d are each independently an integer of 0 to 3. .
該馬來醯亞胺化合物(A)較佳為該化學式(1)中的p為0或1。而且，該芳香族胺化合物(B)較佳為下述化學式(5)所表示的苯二胺化合物(B1)。 The maleimide compound (A) is preferably such that p in the chemical formula (1) is 0 or 1. Further, the aromatic amine compound (B) is preferably a phenylenediamine compound (B1) represented by the following chemical formula (5).
化學式(5)中，R2為碳數1~4的烴基，b為0~4的整數。 In the chemical formula (5), R 2 is a hydrocarbon group having 1 to 4 carbon atoms, and b is an integer of 0 to 4.
本發明的另一個技術方案提供一種環氧樹脂固化劑，其包含所述本發明的組合物。 Another aspect of the present invention provides an epoxy resin curing agent comprising the composition of the present invention.
本發明的又另一個技術方案提供一種環氧樹脂組合物，其包含所述本發明的環氧樹脂固化劑與環氧樹脂。 Still another aspect of the present invention provides an epoxy resin composition comprising the epoxy resin curing agent of the present invention and an epoxy resin.
所述本發明的環氧樹脂組合物可還包含固化促進劑。這時，該固化促進劑較佳包含選自咪唑系化合物、脲系化合物、以及鏻鹽所組成的群中的一種或兩種以上，該固化促進劑更佳包含咪唑系化合物以及脲系化合物。 The epoxy resin composition of the present invention may further comprise a curing accelerator. In this case, the curing accelerator preferably contains one or more selected from the group consisting of an imidazole compound, a urea compound, and a phosphonium salt, and the curing accelerator more preferably contains an imidazole compound and a urea compound.
所述本發明的環氧樹脂組合物可還包含無機填充材料。 The epoxy resin composition of the present invention may further comprise an inorganic filler.
本發明的進而又另一個技術方案提供一種固化物，其為所述本發明的環氧樹脂組合物的固化物。 Still another aspect of the present invention provides a cured product which is a cured product of the epoxy resin composition of the present invention.
本發明的進而又另一個技術方案提供一種熱固性組合物，其包含所述本發明的組合物。該熱固性組合物可還包含無機填充材料。 Still another aspect of the present invention provides a thermosetting composition comprising the composition of the present invention. The thermosetting composition may further comprise an inorganic filler material.
本發明的進而又另一個技術方案提供一種固化物，其為所述本發明的熱固性組合物的固化物。 Still another aspect of the present invention provides a cured product which is a cured product of the thermosetting composition of the present invention.
本發明的進而又另一個技術方案提供一種半導體裝置以及層間絕緣材料，該半導體裝置是利用所述本發明的環氧樹脂組合物或所述本發明的熱固性組合物而密封，該層間絕緣材料含有所述本發明的環氧樹脂組合物或所述本發明的熱固性組合物。 Still another aspect of the present invention provides a semiconductor device and an interlayer insulating material which is sealed by using the epoxy resin composition of the present invention or the thermosetting composition of the present invention, the interlayer insulating material containing The epoxy resin composition of the present invention or the thermosetting composition of the present invention.
根據本發明，可提供一種組合物，適於作為滿足高阻燃性、高耐熱性以及高溫下低分解特性的環氧樹脂的固化劑的成分或熱固性組合物的成分。此外，根據本發明，可提供一種含有該組合物的環氧樹脂固化劑、包含該環氧樹脂固化劑的環氧樹脂組合物、該環氧樹脂組合物的環氧樹脂固化物、包含該組合物的熱固性組合物、該熱固性組合物的固化物、利用該環氧樹脂組合物或該熱固性組合物密封的半導體裝置、以及含有該環氧樹脂組合物或該熱固性組合物的層間絕緣材料。 According to the present invention, it is possible to provide a composition suitable as a component of a curing agent of an epoxy resin which satisfies high flame retardancy, high heat resistance, and low decomposition property at a high temperature, or a component of a thermosetting composition. Further, according to the present invention, there is provided an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, and an epoxy resin cured product of the epoxy resin composition, comprising the combination A thermosetting composition of the article, a cured product of the thermosetting composition, a semiconductor device sealed with the epoxy resin composition or the thermosetting composition, and an interlayer insulating material containing the epoxy resin composition or the thermosetting composition.
以下，對本發明的實施方式進行說明。 Hereinafter, embodiments of the present invention will be described.
本發明的一實施方式的組合物(以下，也將該組合物稱為「本組合物」)含有該化學式(1)所表示的馬來醯亞胺化合物(A)、該化學式(2)所表示的芳香族胺化合物(B)、以及 該化學式(3)所表示的酚化合物(C)。在一實施方式中，本組合物是包含該馬來醯亞胺化合物(A)、芳香族胺化合物(B)、以及酚化合物(C)的組合物的熔融混合體。 The composition of the embodiment of the present invention (hereinafter, the composition is also referred to as "the present composition") contains the maleimide compound (A) represented by the chemical formula (1), and the chemical formula (2) The aromatic amine compound (B) represented, and The phenol compound (C) represented by the chemical formula (3). In one embodiment, the present composition is a molten mixture of the composition comprising the maleimide compound (A), the aromatic amine compound (B), and the phenol compound (C).
馬來醯亞胺化合物(A)的較佳例能夠通過使馬來酸酐與二官能型芳香族胺類縮合而容易地獲得(例如參照日本專利特開昭60-260623號公報等)。本組合物所含有的馬來醯亞胺化合物(A)較佳具有熔點為100℃~250℃的物性。 A preferred example of the maleic imine compound (A) can be easily obtained by condensing maleic anhydride with a difunctional aromatic amine (for example, see JP-A-60-260623, etc.). The maleic imine compound (A) contained in the composition preferably has a physical property of a melting point of from 100 ° C to 250 ° C.
作為馬來醯亞胺化合物(A)的具體例，可列舉：N,N'-4,4'-二苯基甲烷雙馬來醯亞胺、N,N'-間亞苯基雙馬來醯亞胺、N,N'-4,4'-二苯基醚雙馬來醯亞胺、N,N'-間二甲苯雙馬來醯亞胺等。 Specific examples of the maleinimide compound (A) include N,N'-4,4'-diphenylmethane bismaleimide, and N,N'-m-phenylene bismale. Yttrium, N, N'-4, 4'-diphenyl ether, bismaleimide, N, N'-m-xylene, bismaleimide, and the like.
其中，就賦予耐熱性的觀點而言，馬來醯亞胺化合物(A)較佳為該化學式(1)中的p為0或1，更佳含有作為該化學式(1)中的p為1時的物質的一例的N,N'-4,4'-二苯基甲烷雙馬來醯亞胺，進一步較佳由該物質形成。另外，N,N'-4,4'-二苯基甲烷雙馬來醯亞胺在該化學式(1)中，Ar1為亞苯基，X1為亞甲基。 In the viewpoint of imparting heat resistance, the maleimide compound (A) preferably has a p of 0 or 1 in the chemical formula (1), and more preferably contains p as 1 in the chemical formula (1). Further, N,N'-4,4'-diphenylmethane bismaleimide, which is an example of the substance, is further preferably formed of the substance. Further, N,N'-4,4'-diphenylmethane bismaleimide In the chemical formula (1), Ar 1 is a phenylene group and X 1 is a methylene group.
作為芳香族胺化合物(B)的具體例，可列舉：鄰苯二胺、間苯二胺、對苯二胺、4-甲基-1,2-苯二胺、2,4-二氨基甲苯、2,3,5,6-四甲基-1,4-苯二胺、二(4-氨基苯基)碸、3,3'-二氨基聯苯胺、2,2'-亞甲基雙(4-甲基-1,5-苯二胺)等。其 中，就獲取的容易度而言，芳香族胺化合物(B)中的Ar2可包含的一級氨基的個數較佳為0。而且，就賦予耐熱性的觀點而言，芳香族胺化合物(B)較佳為該化學式(5)所表示的苯二胺化合物(B1)。作為苯二胺化合物(B1)的具體例，可列舉：鄰苯二胺、間苯二胺及對苯二胺、4-甲基-1,2-苯二胺等。 Specific examples of the aromatic amine compound (B) include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4-methyl-1,2-phenylenediamine, and 2,4-diaminotoluene. , 2,3,5,6-tetramethyl-1,4-phenylenediamine, bis(4-aminophenyl)anthracene, 3,3'-diaminobenzidine, 2,2 ' -methylene double (4-methyl-1,5-phenylenediamine) and the like. Among them, the number of primary amino groups which Ar 2 may contain in the aromatic amine compound (B) is preferably 0 in terms of ease of availability. In addition, the aromatic amine compound (B) is preferably the phenylenediamine compound (B1) represented by the chemical formula (5) from the viewpoint of imparting heat resistance. Specific examples of the phenylenediamine compound (B1) include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and 4-methyl-1,2-phenylenediamine.
作為酚化合物(C)，可例示：雙酚化合物的烯丙基化化合物、烯丙基化酚系酚醛清漆樹脂等。其中，酚化合物(C)較佳包含該化學式(4)所表示的雙酚化合物(C1)，更佳由雙酚化合物(C1)形成。雙酚化合物(C1)的具體結構並無限定。可例示：雙酚A結構、雙酚F結構、雙酚AP結構、雙酚BP結構等。通過具有所述結構，能夠確保成形時的適度流動性與成形品的適度耐熱性。作為雙酚化合物(C1)的具體例，可列舉：4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)苯酚]、4,4'-亞甲基雙[2-(2-丙烯基)苯酚]、4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)-6-甲基苯酚]等。在酚化合物(C)含有雙酚化合物(C1)時，雙酚化合物(C1)較佳含有4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)苯酚]，更較佳酚化合物(C)由4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)苯酚]形成。 The phenol compound (C) may, for example, be an allylate compound of a bisphenol compound or an allylated phenol novolak resin. Among them, the phenol compound (C) preferably contains the bisphenol compound (C1) represented by the chemical formula (4), and more preferably is formed of a bisphenol compound (C1). The specific structure of the bisphenol compound (C1) is not limited. A bisphenol A structure, a bisphenol F structure, a bisphenol AP structure, a bisphenol BP structure, etc. are illustrated. By having such a configuration, it is possible to ensure appropriate fluidity at the time of molding and moderate heat resistance of the molded article. Specific examples of the bisphenol compound (C1) include 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol], and 4,4'-methylene double [ 2-(2-propenyl)phenol], 4,4'-(dimethylmethylene)bis[2-(2-propenyl)-6-methylphenol], and the like. When the phenol compound (C) contains the bisphenol compound (C1), the bisphenol compound (C1) preferably contains 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol], More preferably, the phenol compound (C) is formed of 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol.
本組合物可還含有馬來醯亞胺化合物(A)與芳香族胺化合物(B)的反應產物。這時，反應產物可為馬來醯亞胺化合物(A)與芳香族胺化合物(B)的邁克爾加成物。 The composition may further contain a reaction product of the maleimide compound (A) and the aromatic amine compound (B). At this time, the reaction product may be a Michael adduct of the maleimide compound (A) and the aromatic amine compound (B).
就容易獲得該反應產物的觀點等而言，本組合物可為包含馬來醯亞胺化合物(A)、芳香族胺化合物(B)、以及酚化合物(C)的組合物的熔融混合體。 The present composition may be a molten mixture of a composition containing the maleimide compound (A), the aromatic amine compound (B), and the phenol compound (C) from the viewpoint of easily obtaining the reaction product.
本組合物存在如下情況：就使包含本組合物作為成分的熱固性組合物的固化物的耐熱特性提升的觀點而言，較佳基於源自馬來醯亞胺化合物(A)的馬來醯亞胺基的部分結構的總數為基於源自芳香族胺化合物(B)的一級氨基的部分結構與基於源自酚化合物(C)的烯丙基的部分結構的總數的1.5倍以上2.5倍以下。關於所述比(基於源自馬來醯亞胺化合物(A)的馬來醯亞胺基的部分結構的總數相對於基於源自芳香族胺化合物(B)的一級氨基的部分結構與基於源自酚化合物(C)的烯丙基的部分結構的總數的比)，存在更佳為1.8以上2.2以下的情況，且存在尤其較佳為1.9以上2.1以下的情況。 The present composition is preferably in the form of a Malayan derived from the maleic imine compound (A) from the viewpoint of improving the heat resistance of the cured product of the thermosetting composition containing the composition as a component. The total number of partial structures of the amine group is 1.5 times or more and 2.5 times or less based on the partial structure of the primary amino group derived from the aromatic amine compound (B) and the partial structure based on the allyl group derived from the phenol compound (C). Regarding the ratio (based on the total number of partial structures of the maleimine group derived from the maleimide compound (A) relative to the partial structure based on the primary amino group derived from the aromatic amine compound (B) and the source-based The ratio of the total number of partial structures of the allyl groups of the phenol compound (C) is more preferably 1.8 or more and 2.2 or less, and particularly preferably 1.9 or more and 2.1 or less.
在本組合物為該熔融混合體時，可利用使源自馬來醯亞胺化合物(A)的馬來醯亞胺基的總數成為源自芳香族胺化合物(B)的一級氨基與源自酚化合物(C)的烯丙基的總數的1.5倍以上2.5倍以下的成分混合比進行熔融混合。通過在這種條件下進行熔融混合，存在能夠使包含本組合物作為成分的熱固性組合物的固化物的耐熱特性提升的情況。所述成分混合比較佳為1.8以上2.2以下，更佳為1.9以上2.1以下。 When the composition is the molten mixture, the total number of maleimine groups derived from the maleimide compound (A) can be used as the primary amino group derived from the aromatic amine compound (B). The mixing ratio of the components of 1.5 to 2.5 times the total number of allyl groups of the phenol compound (C) is melt-mixed. By performing melt mixing under such conditions, there is a case where the heat resistance of the cured product of the thermosetting composition containing the composition as a component can be improved. The component mixture is preferably 1.8 or more and 2.2 or less, more preferably 1.9 or more and 2.1 or less.
該熔融混合的具體方法並無限定。能夠通過在加熱條件下且較佳在攪拌條件下，將馬來醯亞胺化合物(A)、芳香族胺化合物(B)以及酚化合物(C)等各成分在通常的混合容器中混合而獲得。作為將這些成分混合成組合物的方法，可例示：將馬來醯亞胺化合物(A)、芳香族胺化合物(B)以及酚化合物(C)一起熔融混合的方法；將芳香族胺化合物(B)與酚化合物(C)熔融混合之後混合馬來醯亞胺化合物(A)的方法等。就提升組合物的物性的穩定性的觀點而言，較佳首先將馬來醯亞胺化合物(A)以外的成分熔融混合，進一步在所得的混合物中混合馬來醯亞胺化合物(A)而製成熔融混合物。 The specific method of the melt mixing is not limited. It can be obtained by mixing the components of the maleimide compound (A), the aromatic amine compound (B), and the phenol compound (C) in a usual mixing container under heating and preferably under stirring. . As a method of mixing these components into a composition, a method in which a maleimide compound (A), an aromatic amine compound (B), and a phenol compound (C) are melt-mixed together can be exemplified; and an aromatic amine compound ( B) A method of mixing the maleic imine compound (A) after melt-mixing with the phenol compound (C). From the viewpoint of improving the stability of the physical properties of the composition, it is preferred to first melt-mix the components other than the maleimide compound (A), and further mix the maleimide compound (A) in the obtained mixture. A molten mixture is made.
該熔融混合的條件並無限定。如果進行並無限定的例示，那麼可列舉在100℃~200℃的溫度範圍攪拌混合15分鐘~60分鐘左右。本組合物的150℃熔融黏度較佳為50mPa‧s以上1000mPa‧s以下，更佳為10mPa‧s以上600mPa‧s以下。而且，本組合物的羥基當量較佳為300g/eq以上1500g/eq以下，更佳為600g/eq以上1200g/eq以下。 The conditions of the melt mixing are not limited. If not limited to the examples, the mixture may be stirred and mixed in a temperature range of 100 ° C to 200 ° C for about 15 minutes to 60 minutes. The 150 ° C melt viscosity of the composition is preferably 50 mPa ‧ or more and 1000 mPa ‧ or less, more preferably 10 mPa ‧ or more and 600 mPa ‧ s or less. Further, the hydroxyl equivalent of the present composition is preferably from 300 g/eq to 1,500 g/eq, more preferably from 600 g/eq to 1200 g/eq.
關於本發明的混合產物，推定混合成分是各成分以相溶狀態或成分彼此一部分已反應的狀態相溶而成。如所述那樣可包含邁克爾加成物。 In the mixed product of the present invention, the estimated mixed component is obtained by dissolving each component in a state of being dissolved or a state in which a part of the components have reacted with each other. A Michael adduct can be included as described.
在本發明的一實施方式中，本組合物被用作環氧樹脂固化物的成分。本發明的一實施方式的環氧樹脂固化物包含本組合物，較佳由本組合物形成。本發明的一實施方式的環氧樹脂固化劑的成形溫度區域內的熔融黏度低，加工性優異，且阻燃性、耐熱性優異，因此能夠用於成形材料、各種黏合劑、塗布材料、層疊材料等。 In one embodiment of the invention, the present composition is used as a component of a cured epoxy resin. The cured epoxy resin according to one embodiment of the present invention comprises the present composition, and is preferably formed from the present composition. The epoxy resin curing agent according to the embodiment of the present invention has low melt viscosity in the molding temperature region, is excellent in workability, and is excellent in flame retardancy and heat resistance. Therefore, it can be used for molding materials, various adhesives, coating materials, and laminates. Materials, etc.
本發明的一實施方式的環氧樹脂組合物是包含所述本發明的一實施方式的環氧樹脂固化劑與環氧樹脂的環氧樹脂組合物。在環氧樹脂組合物中，作為能夠與本發明的一實施方式的環氧樹脂固化劑一起使用的環氧樹脂，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、苯酚聯苯芳烷基型環氧樹脂、通過苯酚、萘酚等與亞二甲苯基鍵結而成的芳烷基樹脂的環氧化物、二環戊二烯型環氧樹脂、二羥基萘型環氧樹脂、三苯酚甲烷型環氧樹脂等縮水甘油醚型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂等在一分子中具有兩個以上環氧基的環氧化合物。這些環氧樹脂可單獨使用，也可並用兩種以上。如果考慮耐濕性、熱時低彈性模量、阻燃性，那麼較佳使用雙酚F型環氧樹脂、聯苯型環氧樹脂等二官能型環氧樹脂、或者選自苯酚聯苯芳烷基型環氧樹脂、通過苯酚、萘酚等與亞二甲苯基鍵結而成的芳烷基樹脂的環氧化物等中的芳香環較多的多官能型環氧樹脂。 An epoxy resin composition according to an embodiment of the present invention is an epoxy resin composition containing the epoxy resin curing agent and the epoxy resin according to an embodiment of the present invention. In the epoxy resin composition, examples of the epoxy resin that can be used together with the epoxy resin curing agent according to one embodiment of the present invention include a bisphenol A epoxy resin and a bisphenol F epoxy resin. Cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, bonded with xylylene group by phenol, naphthol, etc. An aralkyl resin epoxide, a dicyclopentadiene type epoxy resin, a dihydroxy naphthalene type epoxy resin, a trisphenol methane type epoxy resin, etc., a glycidyl ether type epoxy resin, a glycidyl ester type epoxy An epoxy compound having two or more epoxy groups in one molecule, such as a resin or a glycidylamine type epoxy resin. These epoxy resins may be used singly or in combination of two or more. If moisture resistance, low modulus of elasticity, and flame retardancy are considered, it is preferred to use a difunctional epoxy resin such as a bisphenol F type epoxy resin or a biphenyl type epoxy resin, or a phenol biphenyl group. The alkyl type epoxy resin is a polyfunctional epoxy resin having a large number of aromatic rings in an epoxide such as an aralkyl resin bonded to a xylylene group such as phenol or naphthol.
在環氧樹脂的固化時，較佳並用固化促進劑。作為固化促進劑，可使用用於利用酚系固化劑使環氧樹脂固化的公知的固化促進劑，例如可列舉：三級胺化合物、四級銨鹽、咪唑類、脲系化合物、膦化合物、鏻鹽等。更具體而言，可列舉：三乙胺、三乙二胺、苄基二甲基胺、2,4,6-三(二甲基氨基甲基)苯酚、1,8-二氮雜雙環(5,4,0)十一烯-7等三級胺化合物；2-甲基咪唑、2,4-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑類；3-苯基-1,1-二甲基脲、3-(鄰甲基苯基)-1,1-二甲基脲、3-(對甲基苯基)-1,1-二甲基脲、1,1'-亞苯基雙(3,3-二甲基脲)、1,1'-(4-甲基-間亞苯基)-雙(3,3-二甲基脲)等脲系化合物；三苯基膦、三丁基膦、三(對甲基苯基)膦、三(壬基苯基)膦等膦化合物；三苯基鏻酚鹽、四苯基鏻四苯基硼酸鹽、四苯基鏻四萘甲酸硼酸鹽等鏻鹽等。較佳使用包含選自對環氧樹脂的固化與雙馬來醯亞胺的聚合的兩者均顯示高活性的咪唑類、脲系化合物、以及鏻鹽所組成的群中的一種或兩種以上的固化促進劑。固化促進劑更佳包含咪唑系化合物及脲系化合物的至少一者，尤其較佳包含咪唑系化合物及脲系化合物，即，並用咪唑系化合物與脲系化合物。 In the curing of the epoxy resin, a curing accelerator is preferably used in combination. As the curing accelerator, a known curing accelerator for curing the epoxy resin with a phenol-based curing agent can be used, and examples thereof include a tertiary amine compound, a quaternary ammonium salt, an imidazole, a urea compound, and a phosphine compound.鏻 salt and so on. More specifically, it may, for example, be triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo ( a tertiary amine compound such as 5,4,0) undecen-7; 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole; 3-phenyl-1,1-dimethylurea, 3-(o-methylphenyl)-1,1-dimethylurea, 3-(pair Methylphenyl)-1,1-dimethylurea, 1,1'-phenylenebis(3,3-dimethylurea), 1,1'-(4-methyl-m-phenylene) a urea compound such as bis(3,3-dimethylurea); a phosphine compound such as triphenylphosphine, tributylphosphine, tris(p-methylphenyl)phosphine or tris(nonylphenyl)phosphine; An antimony salt such as triphenylsulfonate, tetraphenylphosphonium tetraphenylborate or tetraphenylphosphonium tetranaphthalate borate. It is preferred to use one or more selected from the group consisting of imidazoles, urea compounds, and phosphonium salts which exhibit high activity from both curing of epoxy resin and polymerization of bismaleimide. Curing accelerator. The curing accelerator further preferably contains at least one of an imidazole compound and a urea compound, and particularly preferably contains an imidazole compound and a urea compound, that is, an imidazole compound and a urea compound are used in combination.
在本發明的一實施方式的環氧樹脂組合物中，可視需要添加或預先進行反應地使用無機填充劑、偶聯劑、脫模劑、著色劑、阻燃劑、低應力劑等。而且，也可並用其他 固化劑。作為所述其他固化劑的例子，可列舉：苯酚酚醛清漆樹脂、苯酚芳烷基樹脂、苯酚聯苯芳烷基樹脂、苯酚萘基芳烷基樹脂、萘酚芳烷基樹脂、三苯酚甲烷型酚醛清漆樹脂等。 In the epoxy resin composition of one embodiment of the present invention, an inorganic filler, a coupling agent, a releasing agent, a coloring agent, a flame retardant, a low stress agent, or the like may be added as needed or may be reacted in advance. Moreover, other types can also be used in combination Hardener. Examples of the other curing agent include a phenol novolak resin, a phenol aralkyl resin, a phenol biphenyl aralkyl resin, a phenol naphthyl aralkyl resin, a naphthol aralkyl resin, and a trisphenol methane type. Novolak resin, etc.
作為無機填充劑的例子，可列舉非晶性二氧化矽、結晶性二氧化矽、氧化鋁、玻璃、矽酸鈣、菱鎂礦、黏土、滑石、雲母、氧化鎂、硫酸鋇等，尤其較佳為非晶性二氧化矽、結晶性二氧化矽、硫酸鋇。而且，在想要維持優異的成形性且提高填充劑的調配量時，較佳使用如能細密填充的細微性分佈廣的球形填充劑。 Examples of the inorganic filler include amorphous cerium oxide, crystalline cerium oxide, aluminum oxide, glass, calcium silicate, magnesite, clay, talc, mica, magnesium oxide, barium sulfate, and the like. Preferably, it is amorphous cerium oxide, crystalline cerium oxide, and cerium sulfate. Further, when it is desired to maintain excellent formability and to increase the amount of the filler to be formulated, it is preferred to use a spherical filler which is finely distributed and can be finely packed.
作為偶聯劑的例子，可例示巰基矽烷系、乙烯基矽烷系、氨基矽烷系、環氧矽烷系等的矽烷偶聯劑或鈦偶聯劑；作為脫模劑的例子，可例示巴西棕櫚蠟、石蠟等，另外，著色劑可例示碳黑等。作為阻燃劑的例子，可列舉磷化合物、金屬氫氧化物等，作為低應力劑的例子，可列舉矽橡膠、改性腈橡膠、改性丁二烯橡膠、改性矽油等。 Examples of the coupling agent include a decane coupling agent such as a mercapto decane type, a vinyl decane type, an amino decane type, and an epoxy decane type, or a titanium coupling agent; and as an example of the releasing agent, carnauba wax can be exemplified. Further, the coloring agent may, for example, be carbon black or the like. Examples of the flame retardant include a phosphorus compound and a metal hydroxide. Examples of the low stress agent include a ruthenium rubber, a modified nitrile rubber, a modified butadiene rubber, and a modified eucalyptus oil.
關於本發明的一實施方式的環氧樹脂固化劑與環氧樹脂的調配比，如果考慮耐熱性、機械特性等，那麼環氧基/羥基的當量比較佳處於0.5~1.5的範圍，尤其是0.8~1.2的範圍。而且，在與其他固化劑並用時，也較佳使環氧基/羥基的當量比成為該比率。關於固化促進劑，如果考慮固 化特性及各物性，那麼較佳在相對於環氧樹脂100重量份而為0.1重量份~10重量份的範圍內使用。在並用多種固化促進劑時，也較佳使相對於環氧樹脂100重量份的品質份成為所述範圍。無機填充劑的調配率雖也因種類而不同，但如果考慮焊料耐熱性、成形性(熔融黏度、流動性)、低應力性、低吸水性等，那麼較佳以如占組合物整體的60重量%~93重量%的比率調配無機填充劑。 When the ratio of the epoxy resin curing agent to the epoxy resin according to the embodiment of the present invention is considered to be heat resistance, mechanical properties, etc., the epoxy group/hydroxy group equivalent ratio is preferably in the range of 0.5 to 1.5, especially 0.8. The range of ~1.2. Further, when used in combination with other curing agents, it is also preferred to make the equivalent ratio of the epoxy group/hydroxy group to this ratio. Regarding the curing accelerator, if considering solid The chemical properties and the physical properties are preferably in the range of 0.1 part by weight to 10 parts by weight based on 100 parts by weight of the epoxy resin. When a plurality of curing accelerators are used in combination, it is also preferred to set the mass portion with respect to 100 parts by weight of the epoxy resin in the above range. The blending ratio of the inorganic filler varies depending on the type. However, in consideration of solder heat resistance, moldability (melt viscosity, fluidity), low stress property, low water absorbability, etc., it is preferable to use 60% of the entire composition. The inorganic filler is formulated in a ratio of % by weight to 93% by weight.
本發明的一實施方式的熱固性組合物包含本組合物。本組合物不僅能夠如所述那樣作為固化劑使用，且自身能作為固化性物質發揮功能。這時，可通過使本發明的一實施方式的熱固性組合物中所含的本組合物自聚而獲得固化物。在該情況下，本發明的一實施方式的熱固性組合物除了本組合物以外可以還含有其他固化性物質。 The thermosetting composition of one embodiment of the present invention comprises the present composition. The present composition can be used not only as a curing agent as described above, but also as a curable substance. In this case, the cured product can be obtained by self-polymerizing the present composition contained in the thermosetting composition of one embodiment of the present invention. In this case, the thermosetting composition of one embodiment of the present invention may further contain other curable substances in addition to the composition.
在本發明的一實施方式的熱固性組合物中，可視需要添加或預先進行反應地使用無機填充劑、偶聯劑、脫模劑、著色劑、阻燃劑、低應力劑等。 In the thermosetting composition of one embodiment of the present invention, an inorganic filler, a coupling agent, a releasing agent, a coloring agent, a flame retardant, a low stress agent, or the like may be used as needed or may be reacted in advance.
作為無機填充劑的例子，可列舉非晶性二氧化矽、結晶性二氧化矽、氧化鋁、玻璃、矽酸鈣、菱鎂礦、黏土、滑石、雲母、氧化鎂、硫酸鋇等，尤其較佳為非晶性二氧化矽、結晶性二氧化矽、硫酸鋇。而且，在想要維持優異的成形性且提高填充劑的調配量時，較佳使用如能細密填 充的細微性分佈廣的球形填充劑。 Examples of the inorganic filler include amorphous cerium oxide, crystalline cerium oxide, aluminum oxide, glass, calcium silicate, magnesite, clay, talc, mica, magnesium oxide, barium sulfate, and the like. Preferably, it is amorphous cerium oxide, crystalline cerium oxide, and cerium sulfate. Moreover, when it is desired to maintain excellent formability and to increase the amount of the filler to be formulated, it is preferred to use a fine filling. A spherical filler with a wide distribution of fineness.
作為將本發明的一實施方式的環氧樹脂組合物或本發明的一實施方式的熱固性組合物作為成形材料製備時的一般方法，可列舉如下等方法：利用例如混合器將規定比率的各原料充分混合後，利用熱輥或捏合機等施予混煉處理，進一步進行冷卻固化後，粉碎成適當大小，且視需要進行片狀化。如此所得的成形材料可通過例如低壓轉移成形等密封半導體而製造半導體裝置。 As a general method for preparing an epoxy resin composition according to an embodiment of the present invention or a thermosetting composition according to an embodiment of the present invention as a molding material, a method in which a predetermined ratio of each raw material is used by, for example, a mixer, is exemplified. After sufficiently mixing, the mixture is subjected to a kneading treatment by a hot roll or a kneader, and further cooled and solidified, then pulverized to an appropriate size, and flaky as necessary. The molding material thus obtained can be manufactured by sealing a semiconductor by, for example, low-pressure transfer molding.
作為將本發明的一實施方式的環氧樹脂組合物或本發明的一實施方式的熱固性組合物作為絕緣層材料製備時的一般方法，可使規定比率的各原料溶解至溶劑中，製成用於將所得的溶液塗布在電路基板上的層間絕緣用清漆；可通過使玻璃纖維含浸該溶液並進行加熱處理而製成所述用途的預浸體；或者可在支撐膜上將該溶液加熱處理而製成膜狀的所述用途的黏接片。所述各者以任一形態使用均可製成層間絕緣層。 As a general method for preparing an epoxy resin composition according to an embodiment of the present invention or a thermosetting composition according to an embodiment of the present invention as an insulating layer material, each raw material having a predetermined ratio can be dissolved in a solvent to be used. a varnish for interlayer insulation coated on the circuit substrate; the prepreg of the use may be prepared by impregnating the glass fiber with a heat treatment; or the solution may be heat treated on the support film The adhesive sheet for the use of the film is formed. Each of the above may be used in any form to form an interlayer insulating layer.
關於包含本組合物的環氧樹脂組合物的固化或包含本製品的熱固性組合物的固化，不論為所述哪一製品形態均在例如100℃~250℃的溫度範圍內進行。 The curing of the epoxy resin composition containing the present composition or the curing of the thermosetting composition containing the product is carried out in a temperature range of, for example, 100 ° C to 250 ° C regardless of the product form.
以上所說明的實施方式是為了易於理解本發明而記載 的，並非為了限定本發明而記載的。因此，所述實施方式所公開的各要素也包括屬於本發明的技術範圍的所有設計變更及均等物的概念。 The embodiments described above are described for easy understanding of the present invention. It is not described in order to limit the invention. Therefore, each element disclosed in the above embodiments also includes all the design changes and the concept of the equivalent of the technical scope of the present invention.
[實施例] [Examples]
以下，利用實施例及比較例對本發明更具體地進行說明，但本發明並不受這些例子任何的限制。 Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited by these examples.
[實施例1] [Example 1]
將4,4'-(二甲基亞甲基)雙[2-(2-丙烯基)苯酚]30.8g(0.10莫耳)(大和化成工業公司製造，DABPA，羥基當量為159g/eq)、1,3-苯二胺10.8g(0.10莫耳)、以及4,4'-二苯基甲烷雙馬來醯亞胺143.2g(0.40莫耳)在150℃攪拌20分鐘後進行常溫冷卻，由此獲得作為混合產物的均質的紅褐色的玻璃狀熔融物184.5g(混合產物1)。 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol] 30.8 g (0.10 mol) (manufactured by Daiwa Kasei Kogyo Co., Ltd., DABPA, hydroxyl equivalent weight: 159 g/eq), 11.8 g (0.10 mol) of 1,3-phenylenediamine and 143.2 g (0.40 mol) of 4,4'-diphenylmethane bismaleimide were stirred at 150 ° C for 20 minutes and then cooled at room temperature. This gave 184.5 g (mixed product 1) of a homogeneous reddish brown glassy melt as a mixed product.
利用ICI熔融黏度計測定出的150℃下的混合產物1的熔融黏度為480mPa‧s。而且，根據DABPA的羥基當量及其成分濃度而算出混合產物1的羥基當量為924g/eq。將本實施例1中所得的混合產物1設為組合物1，在作為固化劑使用時有稱為「固化劑1」的情況。 The melt viscosity of the mixed product 1 at 150 ° C measured by an ICI melt viscosity meter was 480 mPa ‧ s. Further, the hydroxyl equivalent of the mixed product 1 was calculated to be 924 g/eq from the hydroxyl equivalent of DABPA and the component concentration thereof. The mixed product 1 obtained in the first embodiment is referred to as the composition 1 and may be referred to as "curing agent 1" when used as a curing agent.
[實施例2] [Embodiment 2]
將下述化學式(6)所表示的環氧樹脂(日本化藥公司製造的「NC3000」，苯酚聯苯芳烷基型，環氧當量為275 g/eq)、實施例1中所得的固化劑1、熔融二氧化矽、以及包含咪唑系固化促進劑(四國化成公司製造的「Curezol C11Z-A」)的固化促進劑以表2所示的比率(表2中的數值為品質份，以下相同)調配且充分混合後，利用85℃±3℃的兩根輥混煉3分鐘，且進行冷卻、粉碎，由此獲得成形用組合物作為環氧樹脂組合物。利用轉移成形機將該環氧樹脂組合物以壓力100kgf/cm2在175℃成形2分鐘後，在230℃進行6小時的後烘焙(post cure)，而製備玻璃化轉變溫度測定用、350℃重量減少率測定用、以及阻燃性試驗用的試片且進行其評價。將其結果示於表2。 An epoxy resin represented by the following chemical formula (6) ("NC3000" manufactured by Nippon Kayaku Co., Ltd., phenol biphenyl aralkyl type, epoxy equivalent: 275 g/eq), the curing agent 1 obtained in Example 1, molten cerium oxide, and a curing accelerator containing an imidazole-based curing accelerator ("Curezol C11Z-A" manufactured by Shikoku Kasei Co., Ltd.) are shown in Table 2. The ratio (the values in Table 2 are the mass parts, the same applies hereinafter), and the mixture is thoroughly mixed, and then kneaded by two rolls at 85 ° C ± 3 ° C for 3 minutes, and cooled and pulverized to obtain a molding composition. Epoxy resin composition. The epoxy resin composition was molded at 175 ° C for 2 minutes at a pressure of 100 kgf/cm 2 by a transfer molding machine, and post-cured at 230 ° C for 6 hours to prepare a glass transition temperature for measurement, and a weight of 350 ° C was used. The test piece for the reduction rate measurement and the flame retardancy test was evaluated and evaluated. The results are shown in Table 2.
化學式(6)中，G為縮水甘油基，n為1~10的自然數。 In the chemical formula (6), G is a glycidyl group, and n is a natural number of 1 to 10.
[實施例3] [Example 3]
以表2所示的調配比率使用包含咪唑系固化促進劑(四國化成公司製造的「Curezol C11Z-A」)以及脲系固化促進劑(三亞普羅(San-Apro)公司製造的「U-CAT 3513N」)的固化促進劑，除此以外，以與實施例2同樣的方式製備成形用組合物且作為環氧樹脂組合物獲得。將進行其評價所 得的結果示於表2。 The imidazole-based curing accelerator ("Curezol C11Z-A" manufactured by Shikoku Chemicals Co., Ltd.) and the urea-based curing accelerator ("U-CAT" manufactured by San-Apro Co., Ltd.) were used at the mixing ratio shown in Table 2. A molding composition was prepared in the same manner as in Example 2 except that a curing accelerator of 3513 N) was used, and it was obtained as an epoxy resin composition. Will conduct its evaluation office The results obtained are shown in Table 2.
[實施例4] [Example 4]
代替咪唑系固化促進劑而以表2所示的調配比率使用脲系固化促進劑(三亞普羅(San-Apro)公司製造的「U-CAT 3512T」)，除此以外，以與實施例2同樣的方式製備成形用組合物且作為環氧樹脂組合物獲得，將進行其評價所得的結果示於表2。 In the same manner as in Example 2 except that the urea-based curing accelerator ("U-CAT 3512T" manufactured by San-Apro Co., Ltd.) was used in the formulation ratio shown in Table 2 instead of the imidazole-based curing accelerator. The composition for molding was prepared and obtained as an epoxy resin composition, and the results obtained by the evaluation thereof are shown in Table 2.
[實施例5] [Example 5]
以表2所示的調配比率且以與實施例1同樣的方式製備成形用組合物，且作為將組合物1(固化物1)作為主固化成分的熱固性組合物獲得。將進行其評價所得的結果示於表2。另外，在表2中，為了便於顯示，將利用實施例5所製造的熱固性組合物顯示為環氧樹脂組合物，但並不含有具有環氧基的成分。 The molding composition was prepared in the same manner as in Example 1 at the blending ratio shown in Table 2, and was obtained as a thermosetting composition in which the composition 1 (cured product 1) was used as a main curing component. The results obtained by the evaluation thereof are shown in Table 2. Further, in Table 2, the thermosetting composition produced in Example 5 was shown as an epoxy resin composition for the sake of convenience of display, but did not contain a component having an epoxy group.
[比較例1] [Comparative Example 1]
將苯酚酚醛清漆改性三苯酚甲烷樹脂18.8g(愛沃特(Air Water)公司製造的「HE910C-10」，羥基當量為100g/eq)、2,7-二羥基萘9.6g(0.06莫耳)在150℃熔融混合30分鐘後，使液體溫度下降至120℃且添加4,4'-二苯基甲烷雙馬來醯亞胺71.6g(0.20莫耳)。將其在該溫度下攪拌30分鐘後進行常溫冷卻，由此獲得作為混合產物2的均質的 黑褐色的玻璃狀熔融物100.0g。 The phenol novolac modified 18.7 g of trisphenol methane resin ("HE910C-10" manufactured by Air Water Co., Ltd., hydroxyl equivalent: 100 g/eq), and 9.6 g (0.06 mol) of 2,7-dihydroxynaphthalene After melt-mixing at 150 ° C for 30 minutes, the liquid temperature was lowered to 120 ° C and 71.6 g (0.20 mol) of 4,4'-diphenylmethane bismaleimide was added. After stirring at this temperature for 30 minutes, it was cooled at room temperature, thereby obtaining a homogeneous product as the mixed product 2. Dark brown glassy melt 100.0 g.
利用ICI熔融黏度計測定出的150℃下的混合產物2的熔融黏度為80mPa‧s。而且，關於混合產物2的羥基當量，利用乙醯化返滴定法測定的結果為295g/eq。將本比較例1中所得的混合產物2設為固化劑2。 The melt viscosity of the mixed product 2 at 150 ° C measured by an ICI melt viscosity meter was 80 mPa ‧ s. Further, the hydroxyl equivalent of the mixed product 2 was 295 g/eq as measured by an acetamidine back titration method. The mixed product 2 obtained in Comparative Example 1 was used as the curing agent 2.
將利用實施例1所製作的固化劑1以及利用比較例1所製作的固化劑2的物性示於表1。 The physical properties of the curing agent 1 produced in Example 1 and the curing agent 2 produced in Comparative Example 1 are shown in Table 1.
[比較例2] [Comparative Example 2]
將該化學式(6)所表示的環氧樹脂、比較例1中所得的固化劑2、熔融二氧化矽、以及咪唑系固化促進劑(四國化成公司製造的「Curezol C11Z-A」)以表2所示的比率調配，以下，以與實施例2同樣的方式製備成形用組合物且作為環氧樹脂組合物獲得。將進行其評價所得的結果示於表2。 The epoxy resin represented by the chemical formula (6), the curing agent 2 obtained in Comparative Example 1, the molten cerium oxide, and the imidazole-based curing accelerator ("Curezol C11Z-A" manufactured by Shikoku Kasei Co., Ltd.) are listed. In the ratio formulation shown in 2, a molding composition was prepared in the same manner as in Example 2 and obtained as an epoxy resin composition. The results obtained by the evaluation thereof are shown in Table 2.
通過以下的方法測定利用實施例以及比較例所製作的環氧樹脂組合物以及熱固性組合物(以下，將它們統稱為「環氧樹脂組合物等」)的物性。 The physical properties of the epoxy resin composition and the thermosetting composition produced by the examples and the comparative examples (hereinafter, collectively referred to as "epoxy resin composition" or the like) were measured by the following methods.
(1)組合物的熔融黏度 (1) Melt viscosity of the composition
將環氧樹脂組合物等2.5g製成片狀，利用高化式流動試驗儀(flow tester)(溫度為175℃，孔徑為1mm，長度為1mm)進行測定。 2.5 g of an epoxy resin composition or the like was formed into a sheet shape, and the measurement was carried out by a flow tester (temperature: 175 ° C, pore diameter: 1 mm, length: 1 mm).
(2)玻璃化轉變溫度 (2) Glass transition temperature
使用TMA(Thermomechanical Analyzer，熱機械分析裝置)，以升溫速度10℃/分鐘測定環氧樹脂組合物等的試片的線膨脹係數，將線膨脹係數的反曲點設為玻璃化轉變溫度。 The coefficient of linear expansion of the test piece of the epoxy resin composition or the like was measured at a temperature increase rate of 10 ° C/min using a TMA (Thermomechanical Analyzer), and the inflection point of the linear expansion coefficient was defined as the glass transition temperature.
(3)350℃重量減少率(熱分解度測定) (3) 350 ° C weight reduction rate (thermal decomposition measurement)
使用TGA(Thermogravimetric Analyzer，熱重量分析裝置)，以升溫速度10℃/分鐘加熱環氧樹脂組合物等的試片，測定到達350℃時的重量減少率。可以說該重量減少率越低高溫下低分解特性越優異。 A test piece such as an epoxy resin composition was heated at a temperature increase rate of 10 ° C /min using a TGA (Thermogravimetric Analyzer), and the weight loss rate at 350 ° C was measured. It can be said that the lower the weight reduction rate, the more excellent the low decomposition property at high temperatures.
(4)阻燃性 (4) Flame retardancy
使用厚度1.6mm×寬度10mm×長度135mm的環氧樹脂組合物等的樣品(每一例為5片)，依照UL-94V測定續燃時間並進行評價。將對各樣品進行兩次接觸火焰所測定的續燃時間中的最長時間設為Fmax(單位：秒)，將對5片樣品進行試驗所得的續燃時間的合計設為Ftotal(單位：秒)。將它們的評價結果示於表2。 A sample such as an epoxy resin composition having a thickness of 1.6 mm × a width of 10 mm × a length of 135 mm (for each case, five sheets) was used, and the after-burning time was measured in accordance with UL-94 V and evaluated. The maximum time in the after-burning time measured by performing two contact flames on each sample was Fmax (unit: second), and the total of the after-burning time obtained by testing five samples was Ftotal (unit: second). . The evaluation results of these are shown in Table 2.
由表2瞭解到包含本發明的固化劑1的環氧樹脂組合物相比於使用公知的固化劑(固化劑2)的環氧樹脂組合物，玻璃化轉變溫度高，高溫下低分解特性也優異，能夠提供耐熱性優異的固化物，且該固化物的阻燃性也與由使用公知的固化劑(固化劑2)的環氧樹脂組合物所製作的固化物同等。而且，也能夠通過使用多種表中的固化促進劑，而在維持其他性能的狀況下使玻璃化轉變溫度特別地提升。此外，如實施例5所示，確認到本組合物即便在不含有具有環氧基的物質時，作為熱固性組合物也能夠獲得固 化物，且該固化物因為不含有源自具有環氧基的物質的成分，所以耐熱性以及阻燃性尤其優異。 It is understood from Table 2 that the epoxy resin composition containing the curing agent 1 of the present invention has a high glass transition temperature and a low decomposition property at a high temperature as compared with an epoxy resin composition using a known curing agent (curing agent 2). It is excellent in that it can provide a cured product excellent in heat resistance, and the flame retardancy of the cured product is also equivalent to a cured product produced by using an epoxy resin composition of a known curing agent (curing agent 2). Moreover, it is also possible to particularly increase the glass transition temperature while maintaining other properties by using a curing accelerator in various tables. Further, as shown in Example 5, it was confirmed that the present composition can be obtained as a thermosetting composition even when it does not contain a substance having an epoxy group. Since the cured product does not contain a component derived from a substance having an epoxy group, the cured product is particularly excellent in heat resistance and flame retardancy.
[產業利用性] [Industry Utilization]
由本發明提供的組合物可適於用作滿足高阻燃性、高耐熱性、以及高溫下低熱分解特性的環氧樹脂固化劑或熱固性組合物的固化性成分。 The composition provided by the present invention can be suitably used as a curable component of an epoxy resin curing agent or a thermosetting composition which satisfies high flame retardancy, high heat resistance, and low thermal decomposition characteristics at high temperatures.
而且，利用本發明，可提供使用滿足高阻燃性、高耐熱性、以及高溫下的低熱分解性的新穎的環氧樹脂固化劑的環氧樹脂組合物及其固化物、以及熱固性組合物及其固化物。 Moreover, according to the present invention, it is possible to provide an epoxy resin composition using a novel epoxy resin curing agent which satisfies high flame retardancy, high heat resistance, and low thermal decomposition property at a high temperature, and a cured product thereof, and a thermosetting composition and Its cured product.
利用本發明，可提供能夠形成環氧樹脂組合物的組合物及該環氧樹脂組合物、以及能夠形成熱固性組合物的組合物及該熱固性組合物，其尤其作為環氧樹脂固化劑有用，且尤其在用於半導體密封、用於功率元件密封、用作層間絕緣材料时，阻燃性、固化性、更高耐熱性優異。 According to the present invention, it is possible to provide a composition capable of forming an epoxy resin composition, the epoxy resin composition, and a composition capable of forming a thermosetting composition, and the thermosetting composition, which is particularly useful as an epoxy resin curing agent, and In particular, when used for semiconductor sealing, for power element sealing, and as an interlayer insulating material, it is excellent in flame retardancy, curability, and higher heat resistance.
Claims (21)
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| JP2015255473A JP6546527B2 (en) | 2015-04-27 | 2015-12-26 | Composition, epoxy resin curing agent, epoxy resin composition, thermosetting composition, cured product, semiconductor device, and interlayer insulating material |
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| KR101955754B1 (en) * | 2016-02-16 | 2019-03-07 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
| JP6724817B2 (en) * | 2017-02-24 | 2020-07-15 | 信越化学工業株式会社 | Thermosetting epoxy resin composition for optical semiconductor and semiconductor device |
| JP6867894B2 (en) * | 2017-06-22 | 2021-05-12 | エア・ウォーター株式会社 | Compositions, epoxy resin curing agents, epoxy resin compositions, thermosetting compositions, cured products, semiconductor devices, and interlayer insulating materials |
| JP6988588B2 (en) * | 2018-03-08 | 2022-01-05 | 味の素株式会社 | Resin composition, sheet-like laminated material, printed wiring board and semiconductor device |
| JP7272405B2 (en) * | 2018-03-08 | 2023-05-12 | 味の素株式会社 | Resin composition, sheet laminate material, printed wiring board and semiconductor device |
| KR20210056996A (en) * | 2018-09-12 | 2021-05-20 | 니폰 가야꾸 가부시끼가이샤 | Maleimide resin, curable resin composition and cured product thereof |
| WO2024064047A1 (en) * | 2022-09-19 | 2024-03-28 | Henkel Ag & Co. Kgaa | Resin composition for die attach film with excellent performance with large die applications |
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| US5037689A (en) * | 1989-02-17 | 1991-08-06 | Basf Aktiengesellschaft | Toughened thermosetting structural materials |
| JPH0597965A (en) | 1991-10-04 | 1993-04-20 | Mitsui Toatsu Chem Inc | Epoxy resin composition |
| JPH07268074A (en) * | 1994-03-31 | 1995-10-17 | Toagosei Co Ltd | Thermosetting resin composition |
| JP3349963B2 (en) | 1998-10-21 | 2002-11-25 | 日本電気株式会社 | Flame-retardant epoxy resin composition and semiconductor device using the same |
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| CN102167825B (en) * | 2011-03-11 | 2012-09-05 | 南京航空航天大学 | Bismaleimide resin for microdiameter pultrusion process and preparation method thereof |
| JP6060541B2 (en) * | 2012-02-23 | 2017-01-18 | 日立化成株式会社 | Thermosetting resin composition for semiconductor encapsulation and semiconductor device using the same |
| JP6192523B2 (en) * | 2013-03-05 | 2017-09-06 | エア・ウォーター株式会社 | Epoxy resin curing agent, production method, and use thereof |
| CN104530430B (en) * | 2015-01-09 | 2017-02-01 | 西北工业大学 | High-tenacity flame-retardant bismaleimide resin and preparation method thereof |
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