CN106084184B - 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
- Publication number
- CN106084184B CN106084184B CN201610245333.XA CN201610245333A CN106084184B CN 106084184 B CN106084184 B CN 106084184B CN 201610245333 A CN201610245333 A CN 201610245333A CN 106084184 B CN106084184 B CN 106084184B
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- China
- Prior art keywords
- epoxy resin
- compound
- composition
- composition according
- resin composition
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 186
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 116
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 116
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 49
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 49
- 239000004065 semiconductor Substances 0.000 title claims description 12
- 239000011229 interlayer Substances 0.000 title claims description 10
- 239000011810 insulating material Substances 0.000 title description 7
- -1 maleimide compound Chemical class 0.000 claims abstract description 120
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 125000000732 arylene group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 7
- 239000000047 product Substances 0.000 claims description 34
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 20
- 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 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 6
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 150000003672 ureas Chemical class 0.000 claims description 6
- 239000012803 melt mixture Substances 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 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
- 239000012774 insulation material Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 description 17
- 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 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 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
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
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- 238000000034 method Methods 0.000 description 6
- 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 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical group C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 229910002026 crystalline silica Inorganic materials 0.000 description 4
- 150000004714 phosphonium salts Chemical class 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 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
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 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
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 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
- 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
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- 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
- QTERLAXNZRFFMZ-UHFFFAOYSA-N 1,1-dimethyl-3-(4-methylphenyl)urea Chemical compound CN(C)C(=O)NC1=CC=C(C)C=C1 QTERLAXNZRFFMZ-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
- 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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- KDQTUCKOAOGTLT-UHFFFAOYSA-N 3-[3-(dimethylcarbamoylamino)-4-methylphenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=C(C)C(NC(=O)N(C)C)=C1 KDQTUCKOAOGTLT-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
- 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical group C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- XYQYGPLZIMRHFW-UHFFFAOYSA-N phenoxy(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)OC1=CC=CC=C1 XYQYGPLZIMRHFW-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 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
- 239000002966 varnish Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—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
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Abstract
The present invention provides a composition suitable as a curing agent for an epoxy resin composition which can satisfy high flame retardancy, high heat resistance and low decomposition property at high temperature. The composition contains a maleimide compound (A) represented by the following general formula (1), an aromatic amine compound (B) represented by the following general formula (2), and a phenol compound (C) represented by the following general formula (3): [ formula 1]
In the formula (1), Ar1Is an arylene group having 6 to 12 carbon atoms in which a substituent may be present, X1A C1-C6 divalent hydrocarbon group, O, S or SO2P is an integer of 0 to 2; [ chemical formula 2)]
In the formula (2), Ar2An arylene group having 6 to 12 carbon atoms containing 0 to 2 primary amino groups and optionally having a hydrocarbon substituent, X2A C1-C6 divalent hydrocarbon group, O, S or SO2Q is an integer of 0 to 2; [ chemical formula 3)]
In the formula (3), Ar3An arylene group having 6 to 24 carbon atoms which contains allyl groups such that the number of allyl groups in one molecule is in the range of 2 to 4 and which contains 0 to 2 hydroxyl groups, X3A C1-C6 divalent hydrocarbon group, O, S or SO2And r is an integer of 0 to 2.
Description
Technical Field
The present invention relates to a composition suitable as a component of a curing agent for an epoxy resin or a component 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 an interlayer insulating material containing the epoxy resin composition or the thermosetting composition. In the present specification, "thermosetting composition" refers to a composition having thermosetting properties, and "epoxy resin composition" refers to a composition containing a resin having an epoxy group, and the term concept of "thermosetting composition" and the term concept of "epoxy resin composition" have overlapping portions.
Background
Phenol-based curing agents, which are a large group of curing agents for epoxy resins, are used in various industries due to their characteristics such as low cost, in addition to their wide variety. Many of the curing agents have been developed so far in order to satisfy various required performances accompanying the progress of industrial technology.
In the field of electronic materials, in recent years, with the miniaturization, thinning and complication of the shape of semiconductor packages, resins for semiconductor encapsulating materials are increasingly required to have low viscosity. If the viscosity is low, the resin is improved in fluidity, and can be applied to a package having a complicated shape such as BGA (Ball Grid Array) and the like, and further, the filler is highly filled, which is advantageous in terms of flame retardancy, solder heat resistance and moisture resistance reliability required for the above-mentioned applications.
In addition, in consideration of global environment, there is an increasing demand for a novel flame-retardant epoxy resin composition to replace the conventionally used flame retardants such as halogen-containing compounds and antimony compounds, and there is a demand for a phenol aralkyl resin which is used in applications ranging from general encapsulation to advanced encapsulation and has excellent flame retardancy without using a halogen-containing flame retardant and an antimony compound (for example, patent document 1). Among them, phenol aralkyl resins having a biphenyl skeleton introduced therein are known to have high flame retardancy and are used for advanced sealing applications (for example, patent document 2).
[ Prior art documents ]
[ patent document ]
Patent document 1: japanese patent laid-open No. 5-97965.
Patent document 2: japanese patent laid-open No. 2000-129092.
Disclosure of Invention
[ problems to be solved by the invention ]
However, the flame-retardant epoxy resin composition described in patent document 2 tends to have a low glass transition temperature (Tg). A decrease 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 above aspects. In particular, high heat resistance is required for a sealing material for power devices (power devices) mounted in electric vehicles and hybrid vehicles, which are expected to become more and more popular in the future. In addition, in recent years, the physical properties of sealing materials have been required to have low thermal decomposition properties at high temperatures (hereinafter referred to as "low decomposition properties at high temperatures") in association with heat resistance.
The invention aims to provide a composition suitable as a component of a curing agent for an epoxy resin or a component of a thermosetting composition, which can satisfy high flame retardancy, high heat resistance and low decomposition property at high temperature. Further, an object of the present invention is to provide an epoxy resin curing agent containing the above composition, an epoxy resin composition containing the epoxy resin curing agent, a cured product of the epoxy resin composition, a thermosetting composition containing the above 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.
[ means for solving the problems ]
The present inventors have made extensive studies to solve the above-mentioned problems, and as a result, have found that a novel composition obtained by melt-mixing a specific phenol compound at a certain ratio in addition to a maleimide compound and an aromatic amine compound is suitable as a component of a thermosetting composition such as a component of an epoxy resin curing agent, and by using the composition, a thermosetting composition capable of forming a cured product having high flame retardancy, high heat resistance and low decomposition characteristics at high temperatures can be obtained.
One embodiment of the present invention provides a composition containing a maleimide compound (a) represented by the following general formula (1), an aromatic amine compound (B) represented by the following general formula (2), and the following general formula (3).
[ solution 1]
In the formula (1), Ar1Is an arylene group having 6 to 12 carbon atoms in which a substituent may be present, X1A C1-C6 divalent hydrocarbon group, O, S or SO2And p is an integer of 0 to 2.
[ solution 2]
In the formula (2), Ar2An arylene group having 6 to 12 carbon atoms containing 0 to 2 primary amino groups and optionally having a hydrocarbon substituent, X2A C1-C6 divalent hydrocarbon group, O, S or SO2And q is an integer of 0 to 2.
[ solution 3]
In the formula (3), Ar3Is based on the number of allyl groups in a moleculeAn arylene group having 6 to 24 carbon atoms including an allyl group and 0 to 2 hydroxyl groups, wherein X is in the range of 2 to 43A C1-C6 divalent hydrocarbon group, O, S or SO2And r is an integer of 0 to 2.
The composition preferably has a melt viscosity of 50 to 1000 mPas at 150 ℃ and a hydroxyl equivalent of 300 to 1500 g/eq.
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 (Michael) adduct of the maleimide compound (a) and the aromatic amine compound (B).
The composition may be a melt-blend of the composition comprising the maleimide compound (a), the aromatic amine compound (B), and the phenol compound (C).
In the composition, the total number of the partial structures based on the maleimide group derived from the maleimide compound (a) may be 1.5 times or more and 2.5 times or less the total number of the partial structures based on 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).
The phenol compound (C) preferably contains a bisphenol compound (C1) represented by the following general formula (4).
[ solution 4]
In the formula (4), R4And R5Each independently is a C1-4 alkyl group, R6And R7Each independently represents a hydrogen atom, a methyl group, a phenyl group, and c and d each independently represents an integer of 0 to 3.
The maleimide compound (A) is preferably such that p in the general formula (1) is 0 or 1. The aromatic amine compound (B) is preferably a phenylenediamine compound (B1) represented by the following general formula (5).
[ solution 5]
In the formula (5), R2Is a C1-4 hydrocarbon group, and b is an integer of 0-4.
Another embodiment of the present invention provides an epoxy resin curing agent comprising the composition of the present invention.
Still another embodiment of the present invention provides an epoxy resin composition comprising the epoxy resin curing agent of the present invention and an epoxy resin.
The epoxy resin composition of the present invention may further comprise a curing accelerator. In this case, the curing accelerator preferably includes one or more selected from the group consisting of imidazole compounds, urea compounds, and phosphonium salts, and more preferably includes imidazole compounds and urea compounds.
The epoxy resin composition of the present invention may further comprise an inorganic filler.
Still another aspect of the present invention provides a cured product of the epoxy resin composition of the present invention.
Yet 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.
Still another aspect of the present invention provides a cured product of the thermosetting composition of the present invention.
Still another aspect of the present invention provides a semiconductor device sealed with the epoxy resin composition of the present invention or the thermosetting composition of the present invention, and an interlayer insulating material containing the epoxy resin composition of the present invention or the thermosetting composition of the present invention.
[ Effect of the invention ]
According to the present invention, a composition suitable as a component of a curing agent for an epoxy resin or a component of a thermosetting composition which satisfies high flame retardancy, high heat resistance and low decomposition property at high temperature can be provided. Further, according to the present invention, there can be provided an epoxy resin curing agent containing the composition, an epoxy resin composition containing the epoxy resin curing agent, an epoxy resin 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 an interlayer insulating material containing the epoxy resin composition or the thermosetting composition.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
A composition according to an embodiment of the present invention (hereinafter, this composition is also referred to as "the present composition") contains the maleimide compound (a) represented by the general formula (1), the aromatic amine compound (B) represented by the general formula (2), and the phenol compound (C) represented by the general formula (3). In one embodiment, the present composition is a melt-mixture of a composition comprising the maleimide compound (a), the aromatic amine compound (B), and the phenol compound (C).
Preferred examples of the maleimide compound (A) can be easily obtained by condensing maleic anhydride with bifunctional aromatic amines (see, for example, Japanese patent laid-open No. Sho 60-260623). The maleimide compound (A) contained in the present composition preferably has a melting point of 100 to 250 ℃.
Specific examples of the maleimide compound (a) include: n, N '-4,4' -diphenylmethane bismaleimide, N '-m-phenylene bismaleimide, N' -4,4 '-diphenyl ether bismaleimide, N' -m-xylene bismaleimide, and the like.
Among these compounds, the maleimide compound (a) is preferably one in which p in the general formula (1) is 0 or 1, more preferably one containing N, N '-4,4' -diphenylmethane bismaleimide as an example of a substance in which p in the general formula (1) is 1, and even more preferably one formed from this substance, from the viewpoint of imparting heat resistance. In addition, N, N '-4,4' -diphenylmethane bismaleimideAmine in the general formula (1), Ar1Is phenylene, X1Is methylene.
Specific examples of the aromatic amine compound (B) include: o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4-methyl-1, 2-phenylenediamine, 2, 4-diaminotoluene, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, bis (4-aminophenyl) sulfone, 3 '-diaminobenzidine, 2' -methylenebis (4-methyl-1, 5-phenylenediamine), and the like. Among them, Ar in the aromatic amine compound (B) is Ar in the aspect of easiness of obtaining2The number of primary amino groups that can be contained is preferably 0. From the viewpoint of imparting heat resistance, the aromatic amine compound (B) is preferably a phenylenediamine compound (B1) represented by the above general formula (5). Specific examples of the phenylenediamine compound (B1) include: o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4-methyl-1, 2-phenylenediamine, etc.
Examples of the phenol compound (C) include: allylated compounds of bisphenol compounds, allylated phenol novolak resins, and the like. Among them, the phenol compound (C) preferably contains the bisphenol compound (C1) represented by the above general formula (4), and more preferably is formed of the bisphenol compound (C1). The specific structure of the bisphenol compound (C1) is not limited. Can exemplify: bisphenol A structure, bisphenol F structure, bisphenol AP structure, bisphenol BP structure, etc. By having such a structure, appropriate fluidity during molding and appropriate heat resistance of a molded article can be ensured. Specific examples of the bisphenol compound (C1) include: 4,4' - (dimethylmethylene) bis [2- (2-propenyl) phenol ], 4' -methylenebis [2- (2-propenyl) phenol ], 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 ], and more preferably the phenol compound (C) is formed from 4,4' - (dimethylmethylene) bis [2- (2-propenyl) phenol ].
The present composition may further contain a reaction product of the maleimide compound (a) and the aromatic amine compound (B). In this case, the reaction product may be a Michael adduct of the maleimide compound (A) and the aromatic amine compound (B).
From the viewpoint of easy availability of the reaction product, the present composition may be a melt-mixed body of a composition containing the maleimide compound (a), the aromatic amine compound (B), and the phenol compound (C).
The present compositions exist as follows: from the viewpoint of improving the heat resistance of a cured product of a thermosetting composition containing the present composition as a component, the total number of the partial structures based on the maleimide group derived from the maleimide compound (a) is preferably 1.5 times or more and 2.5 times or less the total number of the partial structures based on 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). The ratio (ratio of the total number of the partial structures based on the maleimide groups derived from the maleimide compound (a) to the total number of the partial structures based on the primary amino groups derived from the aromatic amine compound (B) and the allyl groups derived from the phenol compound (C)) is sometimes more preferably 1.8 to 2.2, and sometimes particularly preferably 1.9 to 2.1.
In the case where the present composition is the melt-blended composition, the melt-blending may be carried out at a component mixing ratio such that the total number of maleimide groups derived from the maleimide compound (a) becomes 1.5 times or more and 2.5 times or less the total number of primary amino groups derived from the aromatic amine compound (B) and allyl groups derived from the phenol compound (C). By performing melt-mixing under such conditions, the heat resistance of a cured product of a thermosetting composition containing the present composition as a component may be improved. The mixing ratio of the components is preferably 1.8 to 2.2, more preferably 1.9 to 2.1.
The specific method of melt mixing is not limited. Can be obtained by mixing each component such as the maleimide compound (a), the aromatic amine compound (B) and the phenol compound (C) in a usual mixing vessel under heating conditions and preferably under stirring conditions. Examples of a method for mixing these components into a composition include: a method of melt-mixing the maleimide compound (a), the aromatic amine compound (B), and the phenol compound (C) together; a method in which the aromatic amine compound (B) and the phenol compound (C) are melt-mixed and then the maleimide compound (A) is mixed. From the viewpoint of improving the stability of the physical properties of the composition, it is preferable that the components other than the maleimide compound (a) are first melt-mixed, and the maleimide compound (a) is further mixed with the resulting mixture to prepare a melt mixture.
The conditions for the melt mixing are not limited. The mixing may be carried out, for example, without limitation, by stirring and mixing at a temperature of 100 to 200 ℃ for about 15 to 60 minutes. The melt viscosity at 150 ℃ of the present composition is preferably 50 to 1000 mPas, more preferably 10 to 600 mPas. The hydroxyl group equivalent of the present composition is preferably 300g/eq to 1500g/eq, more preferably 600g/eq to 1200 g/eq.
In the mixed product of the present invention, it is assumed that the mixed components are obtained by mixing the components in a compatible state or in a state where the components are partially reacted with each other. Which as stated may comprise michael adducts.
In one embodiment of the present invention, the present composition is used as a component of a cured epoxy resin. The epoxy resin cured product according to an embodiment of the present invention contains the present composition, and is preferably formed from the present composition. The epoxy resin curing agent according to an embodiment of the present invention has a low melt viscosity in a molding temperature range, is excellent in processability, and is excellent in flame retardancy and heat resistance, and therefore can be used for molding materials, various adhesives, coating materials, laminating materials, and the like.
The epoxy resin composition according to an embodiment of the present invention is an epoxy resin composition containing the epoxy resin curing agent according to an embodiment of the present invention and an epoxy resin. Examples of the epoxy resin that can be used together with the epoxy resin curing agent according to one embodiment of the present invention in the epoxy resin composition include: epoxy compounds having two or more epoxy groups in one molecule, such as bisphenol a type epoxy resins, bisphenol F type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, biphenyl type epoxy resins, phenol biphenyl aralkyl type epoxy resins, epoxy compounds of aralkyl resins obtained by bonding a xylylene group with phenol, naphthol, or the like, dicyclopentadiene type epoxy resins, dihydroxynaphthalene type epoxy resins, glycidyl ether type epoxy resins such as trisphenol methane type epoxy resins, glycidyl ester type epoxy resins, and glycidyl amine type epoxy resins. These epoxy resins may be used alone or in combination of two or more. In consideration of moisture resistance, low elastic modulus at heat, and flame retardancy, it is preferable to use a bifunctional epoxy resin such as a bisphenol F type epoxy resin and a biphenyl type epoxy resin, or a polyfunctional epoxy resin having a large number of aromatic rings selected from an epoxy compound of a phenol biphenyl aralkyl type epoxy resin, an aralkyl resin formed by bonding a xylylene group with phenol, naphthol, or the like.
In curing the epoxy resin, a curing accelerator is preferably used in combination. As the curing accelerator, a known curing accelerator for curing an epoxy resin with a phenol-based curing agent can be used, and examples thereof include: tertiary amine compounds, quaternary ammonium salts, imidazoles, urea compounds, phosphine compounds, phosphonium salts, and the like. More specifically, there may be mentioned: tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5,4,0) undecene-7 and the like; imidazoles such as 2-methylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole; urea compounds such as 3-phenyl-1, 1-dimethylurea, 3- (o-methylphenyl) -1, 1-dimethylurea, 3- (p-methylphenyl) -1, 1-dimethylurea, 1 '-phenylenebis (3, 3-dimethylurea), and 1,1' - (4-methyl-m-phenylene) -bis (3, 3-dimethylurea); phosphine compounds such as triphenylphosphine, tributylphosphine, tris (p-methylphenyl) phosphine, and tris (nonylphenyl) phosphine; phosphonium salts such as triphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, and tetraphenylphosphonium tetranaphthoate borate. It is preferable to use one or more curing accelerators selected from the group consisting of imidazoles, urea compounds, and phosphonium salts, which exhibit high activity for both curing of epoxy resins and polymerization of bismaleimides. The curing accelerator more 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.
In the epoxy resin composition according to one embodiment of the present invention, an inorganic filler, a coupling agent, a mold release agent, a colorant, a flame retardant, a low stress agent, and the like may be added or previously reacted as necessary. Further, other curing agents may be used in combination. Examples of the other curing agents include: phenol novolac resins, phenol aralkyl resins, phenol biphenyl aralkyl resins, phenol naphthyl aralkyl resins, naphthol aralkyl resins, trisphenolmethane type novolac resins, and the like.
Examples of the inorganic filler include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesium oxide, and barium sulfate, and amorphous silica, crystalline silica, and barium sulfate are particularly preferable. In addition, when the amount of the filler to be blended is increased while maintaining excellent moldability, it is preferable to use, for example, a spherical filler having a broad particle size distribution which can be packed finely.
Examples of the coupling agent include silane coupling agents such as mercaptosilane coupling agents, vinylsilane coupling agents, aminosilane coupling agents, and epoxysilane coupling agents, and titanium coupling agents; examples of the release agent include carnauba wax and paraffin wax, and examples of the colorant include carbon black. Examples of the flame retardant include phosphorus compounds and metal hydroxides, and examples of the low-stress agent include silicone rubber, modified nitrile rubber, modified butadiene rubber, modified silicone oil, and the like.
Regarding the blending ratio of the epoxy resin curing agent and the epoxy resin according to one embodiment of the present invention, the equivalent ratio of epoxy group/hydroxyl group is preferably in the range of 0.5 to 1.5, particularly 0.8 to 1.2, in consideration of heat resistance, mechanical properties, and the like. When the epoxy resin composition is used in combination with another curing agent, the ratio of epoxy groups to hydroxyl groups is preferably set to the above ratio. The curing accelerator is preferably used in a range of 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin, in consideration of curing characteristics and physical properties. When a plurality of curing accelerators are used in combination, it is also preferable that the mass part per 100 parts by weight of the epoxy resin is in the above range. The blending ratio of the inorganic filler varies depending on the kind, but if solder heat resistance, moldability (melt viscosity, fluidity), low stress property, low water absorption property, and the like are taken into consideration, it is preferable to blend the inorganic filler at a ratio of, for example, 60 to 93% by weight based on the entire composition.
The thermosetting composition according to an embodiment of the present invention contains the present composition. The present composition can be used not only as a curing agent as described above but also as a curable material by itself. In this case, a cured product can be obtained by self-polymerization of the present composition contained in the thermosetting composition of one embodiment of the present invention. In this case, the thermosetting composition according to one embodiment of the present invention may contain other curable substances in addition to the present composition.
In the thermosetting composition according to one embodiment of the present invention, an inorganic filler, a coupling agent, a mold release agent, a colorant, a flame retardant, a low stress agent, and the like may be added or previously reacted as necessary.
Examples of the inorganic filler include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesium oxide, and barium sulfate, and amorphous silica, crystalline silica, and barium sulfate are particularly preferable. In addition, when the amount of the filler to be blended is increased while maintaining excellent moldability, it is preferable to use, for example, a spherical filler having a broad particle size distribution which can be packed finely.
As a general method for producing the epoxy resin composition according to one embodiment of the present invention or the thermosetting composition according to one embodiment of the present invention as a molding material, the following methods can be mentioned: the raw materials are thoroughly mixed at a predetermined ratio by, for example, a mixer, kneaded by a heat roll, a kneader, or the like, further cooled and solidified, pulverized into an appropriate size, and optionally formed into a sheet. The molding material thus obtained can be used for sealing a semiconductor by, for example, low-pressure transfer molding to produce a semiconductor device.
As a general method for producing 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, a varnish for interlayer insulation for coating a circuit board with the obtained solution can be prepared by dissolving each raw material in a solvent at a predetermined ratio; a prepreg for the above-mentioned use can be produced by impregnating the solution with glass fibers and subjecting the impregnated solution to a heat treatment; alternatively, the solution may be heat-treated on a support film to form an adhesive sheet for the above-mentioned application in the form of a film. The interlayer insulating layer can be formed in any of the above forms.
The curing of the epoxy resin composition containing the present composition or the curing of the thermosetting composition containing the present article is carried out at a temperature ranging from 100 ℃ to 250 ℃ for example, regardless of the form of the article.
The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment also includes a concept of all design modifications and equivalents that fall within the technical scope of the present invention.
[ examples ]
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
[ example 1]
30.8g (0.10 mol) of 4,4'- (dimethylmethylene) bis [2- (2-propenyl) phenol ] (DABPA, hydroxyl equivalent: 159g/eq, manufactured by DABPA chemical industries Co., Ltd.), 10.8g (0.10 mol) of 1, 3-phenylenediamine, and 143.2g (0.40 mol) of 4,4' -diphenylmethane bismaleimide were stirred at 150 ℃ for 20 minutes and then cooled at room temperature to obtain 184.5g (mixed product 1) of a homogeneous reddish brown glassy melt as a mixed product.
The melt viscosity of the mixed product 1 at 150 ℃ measured by an ICI melt viscometer was 480 mPas. Then, the hydroxyl equivalent of the mixed product 1 was calculated to be 924g/eq based on the hydroxyl equivalent of DABPA and the concentrations of the components thereof. The mixed product 1 obtained in example 1 is referred to as composition 1, and when used as a curing agent, it may be referred to as "curing agent 1".
[ example 2]
Will be downAn epoxy resin represented by the following general formula (6) (NC 3000 manufactured by japan chemical company, phenol biphenyl aralkyl type, epoxy equivalent weight 275g/eq), the curing agent 1 obtained in example 1, fused silica, and a curing accelerator containing an imidazole curing accelerator (Curezol C11Z-a manufactured by four chemical company) were mixed and sufficiently mixed at a ratio shown in table 2 (numerical values in table 2 are parts by mass, the same applies hereinafter), and then kneaded for 3 minutes by two rolls at 85 ℃ ± 3 ℃, cooled, and pulverized, thereby obtaining a molding composition as an epoxy resin composition. The epoxy resin composition was molded by a transfer molding machine under a pressure of 100kgf/cm2After molding at 175 ℃ for 2 minutes, post baking (postcure) was carried out at 230 ℃ for 6 hours to prepare test pieces for measuring glass transition temperature, weight loss at 350 ℃ and flame retardancy, and the evaluation thereof was carried out. The results are shown in Table 2.
[ solution 6]
Wherein G is a glycidyl group, and n is a natural number of 1 to 10.
[ example 3]
Molding compositions were prepared and obtained as epoxy resin compositions in the same manner as in example 2, except that curing accelerators including an imidazole curing accelerator ("Curezol C11Z-a" manufactured by four chemical companies) and a urea curing accelerator ("U-CAT 3513N" manufactured by thatprobo (San-Apro)) were used at the formulation ratios shown in table 2. The results of the evaluation are shown in table 2.
[ example 4]
A molding composition was prepared and obtained as an epoxy resin composition in the same manner as in example 2 except that a urea-based curing accelerator ("U-CAT 3512T" manufactured by San-Apro) was used in place of the imidazole-based curing accelerator at the blending ratio shown in table 2, and the results of the evaluation thereof are shown in table 2.
[ example 5]
Molding compositions were prepared at the compounding ratios shown in table 2 in the same manner as in example 1, and obtained as thermosetting compositions having composition 1 (cured product 1) as the main curing component. The results of the evaluation are shown in table 2. In table 2, the thermosetting composition produced in example 5 is shown as an epoxy resin composition for convenience of illustration, but does not contain a component having an epoxy group.
Comparative example 1
18.8g (HE 910C-10 manufactured by Evoret (Air Water) Corp., hydroxyl equivalent 100g/eq) of phenol novolac-modified triphenylmethane resin and 9.6g (0.06 mol) of 2, 7-dihydroxynaphthalene were melt-mixed at 150 ℃ for 30 minutes, and then the liquid temperature was lowered to 120 ℃ and 71.6g (0.20 mol) of 4,4' -diphenylmethane bismaleimide was added. This was stirred at this temperature for 30 minutes and then cooled at room temperature, whereby 100.0g of a homogeneous dark brown glassy melt was obtained as a mixed product 2.
The melt viscosity of the mixed product 2 at 150 ℃ measured by an ICI melt viscometer was 80 mPas. The hydroxyl equivalent weight of the mixed product 2 was 295g/eq as measured by acetylation back titration. The mixed product 2 obtained in comparative example 1 was referred to as a curing agent 2.
Table 1 shows physical properties of the curing agent 1 prepared in example 1 and the curing agent 2 prepared in comparative example 1.
[ Table 1]
Comparative example 2
An epoxy resin represented by the general formula (6), the curing agent 2 obtained in comparative example 1, fused silica, and an imidazole-based curing accelerator ("Curezol C11Z-a" manufactured by four chemical companies) were mixed at the ratios shown in table 2, and then a molding composition was prepared and obtained as an epoxy resin composition in the same manner as in example 2. The results of the evaluation are shown in table 2.
The physical properties of the epoxy resin compositions and thermosetting compositions (hereinafter, these are collectively referred to as "epoxy resin compositions and the like") prepared in examples and comparative examples were measured by the following methods.
(1) Melt viscosity of the composition
2.5g of the epoxy resin composition and the like were formed into a sheet shape, and measured by a flow tester (flow tester) (temperature 175 ℃, pore diameter 1mm, length 1 mm).
(2) Glass transition temperature
The linear expansion coefficient of a test piece such as an epoxy resin composition was measured at a temperature rise rate of 10 ℃/min using TMA (thermo mechanical Analyzer), and the inflection point of the linear expansion coefficient was set to the glass transition temperature.
(3) Weight loss rate at 350 ℃ (measurement of thermal decomposition degree)
A test piece of an epoxy resin composition or the like was heated at a temperature rising rate of 10 ℃/min using TGA (Thermogravimetric Analyzer), and the weight loss rate at 350 ℃ was measured. It can be said that the lower the weight loss rate, the more excellent the low-decomposition property at high temperatures.
(4) Flame retardancy
Using a sample (5 pieces in each case) of an epoxy resin composition or the like having a thickness of 1.6mm, a width of 10mm and a length of 135mm, the time to ignition was measured in accordance with UL-94V and evaluated. The maximum time of the afterflame times measured by performing the contact flame twice for each sample was Fmax (unit: second), and the total of the afterflame times obtained by performing the test on 5 samples was Ftotal (unit: second). The evaluation results are shown in table 2.
[ Table 2]
As is clear from table 2, the epoxy resin composition containing the curing agent 1 of the present invention has a higher glass transition temperature and excellent low decomposition characteristics at high temperatures, and can provide a cured product having excellent heat resistance, as compared with an epoxy resin composition using a known curing agent (curing agent 2), and the flame retardancy of the cured product is also equivalent to that of a cured product produced from an epoxy resin composition using a known curing agent (curing agent 2). Further, the glass transition temperature can be particularly raised while maintaining other properties by using various curing accelerators in the table. Further, as shown in example 5, it was confirmed that the present composition can obtain a cured product as a thermosetting composition even when the composition does not contain a substance having an epoxy group, and the cured product does not contain a component derived from a substance having an epoxy group, and therefore, the composition is particularly excellent in heat resistance and flame retardancy.
[ industrial applicability ]
The composition provided by the present invention can be suitably used as a curing component of an epoxy resin curing agent or a thermosetting composition which satisfies high flame retardancy, high heat resistance, and low thermal decomposition properties at high temperatures.
The present invention also provides an epoxy resin composition using a novel epoxy resin curing agent satisfying high flame retardancy, high heat resistance, and low thermal decomposition at high temperatures, and a cured product thereof, and a thermosetting composition and a cured product thereof.
The present invention provides a composition capable of forming an epoxy resin composition, a composition capable of forming a thermosetting composition, and a thermosetting composition, which are useful particularly as an epoxy resin curing agent and are excellent in flame retardancy, curability, and higher heat resistance particularly when used for semiconductor sealing, power element sealing, and interlayer insulating material.
Claims (20)
1. A composition comprising a maleimide compound (A) represented by the following general formula (1), a phenylenediamine compound (B1) represented by the following general formula (2), and a phenol compound (C) represented by the following general formula (3), wherein the total number of partial structures based on maleimide groups derived from the maleimide compound (A) is 1.5-fold or more and 2.5-fold or less of the total number of partial structures based on primary amino groups derived from the phenylenediamine compound (B1) and partial structures based on allyl groups derived from the phenol compound (C):
[ solution 1]
In the formula (1), Ar1Is an arylene group having 6 to 12 carbon atoms in which a substituent may be present, X1A C1-C6 divalent hydrocarbon group, O, S or SO2P is an integer of 0 to 2;
[ solution 2]
In the formula (2), R2A C1-4 hydrocarbon group, b is an integer of 0-4;
[ solution 3]
In the formula (3), Ar3An arylene group having 6 to 24 carbon atoms which contains allyl groups such that the number of allyl groups in one molecule is in the range of 2 to 4 and which contains 0 to 2 hydroxyl groups, X3A C1-C6 divalent hydrocarbon group, O, S or SO2And r is an integer of 0 to 2.
2. The composition according to claim 1, wherein the melt viscosity at 150 ℃ is 50 to 1000 mPas and the hydroxyl equivalent weight is 300 to 1500 g/eq.
3. The composition according to claim 1 or 2, further comprising a reaction product of the maleimide compound (a) and the phenylenediamine compound (B1).
4. The composition of claim 3, wherein the reaction product is a Michael adduct of the maleimide compound (A) and the phenylenediamine compound (B1).
5. The composition according to claim 1 or 2, characterized by being a melt-mixture of a composition comprising the maleimide compound (a), the phenylenediamine compound (B1), and the phenol compound (C).
6. The composition according to claim 1 or 2, characterized in that the total number of partial structures based on maleimide groups derived from the maleimide compound (a) is 1.8 times or more and 2.2 times or less the total number of partial structures based on primary amino groups derived from the phenylenediamine compound (B1) and partial structures based on allyl groups derived from the phenol compound (C).
7. The composition according to claim 1 or 2, wherein the phenol compound (C) comprises a bisphenol compound (C1) represented by the following general formula (4):
[ solution 4]
In the formula (4), R4And R5Each independently is a C1-4 alkyl group, R6And R7Each independently represents a hydrogen atom, a methyl group, a phenyl group, and c and d each independently represents an integer of 0 to 3.
8. The composition according to claim 1 or 2, characterized in that p in the general formula (1) of the maleimide compound (a) is 0 or 1.
9. An epoxy resin curing agent comprising the composition according to any one of claims 1 to 8.
10. An epoxy resin composition comprising the epoxy resin curing agent according to claim 9 and an epoxy resin.
11. The epoxy resin composition according to claim 10, further comprising a curing accelerator.
12. The epoxy resin composition according to claim 11, wherein the curing accelerator comprises one or more selected from the group consisting of imidazole compounds and urea compounds.
13. The epoxy resin composition according to claim 12, wherein the curing accelerator comprises an imidazole compound and a urea compound.
14. The epoxy resin composition according to any one of claims 10 to 13, further comprising an inorganic filler.
15. A cured product of the epoxy resin composition according to any one of claims 10 to 14.
16. Thermosetting composition, characterized in that it comprises a composition according to any one of claims 1 to 8 and is free from substances having epoxy groups.
17. The thermosetting composition of claim 16, further comprising an inorganic filler material.
18. A cured product of the thermosetting composition according to claim 16 or 17.
19. A semiconductor device sealed with the epoxy resin composition according to any one of claims 10 to 14 or the thermosetting composition according to claim 16 or 17.
20. An interlayer insulation material comprising the epoxy resin composition according to any one of claims 10 to 14 or the thermosetting composition according to claim 16 or 17.
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| JP2015090428 | 2015-04-27 | ||
| JP2015-090428 | 2015-04-27 | ||
| JP2015-255473 | 2015-12-26 | ||
| 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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| CN106084184B true CN106084184B (en) | 2020-05-01 |
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| JP (1) | JP6546527B2 (en) |
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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 |
| TW202424095A (en) * | 2022-09-19 | 2024-06-16 | 德商漢高股份有限及兩合公司 | Resin composition for die attach film with excellent performance with large die applications |
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| JP2009001783A (en) * | 2007-05-18 | 2009-01-08 | Nippon Kayaku Co Ltd | Resin composition for laminate, prepreg and laminate |
| CN102167825A (en) * | 2011-03-11 | 2011-08-31 | 南京航空航天大学 | Bismaleimide resin for microdiameter pultrusion process and preparation method thereof |
| CN104530430A (en) * | 2015-01-09 | 2015-04-22 | 西北工业大学 | High-tenacity flame-retardant bismaleimide resin and preparation method thereof |
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| CH647249A5 (en) * | 1981-12-23 | 1985-01-15 | Ciba Geigy Ag | STORAGE-STABLE, HEAT-CURABLE, POLYIMIDE-BASED MIXTURES CONTAINING A POLYMERIZATION CATALYST. |
| 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 |
| 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 |
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- 2015-12-26 JP JP2015255473A patent/JP6546527B2/en active Active
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- 2016-04-01 TW TW105110535A patent/TWI693250B/en not_active IP Right Cessation
- 2016-04-19 CN CN201610245333.XA patent/CN106084184B/en not_active Expired - Fee Related
- 2016-04-25 KR KR1020160049928A patent/KR20160127665A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009001783A (en) * | 2007-05-18 | 2009-01-08 | Nippon Kayaku Co Ltd | Resin composition for laminate, prepreg and laminate |
| CN102167825A (en) * | 2011-03-11 | 2011-08-31 | 南京航空航天大学 | Bismaleimide resin for microdiameter pultrusion process and preparation method thereof |
| CN104530430A (en) * | 2015-01-09 | 2015-04-22 | 西北工业大学 | High-tenacity flame-retardant bismaleimide resin and preparation method thereof |
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| KR20160127665A (en) | 2016-11-04 |
| CN106084184A (en) | 2016-11-09 |
| TW201638175A (en) | 2016-11-01 |
| JP6546527B2 (en) | 2019-07-17 |
| TWI693250B (en) | 2020-05-11 |
| JP2016204626A (en) | 2016-12-08 |
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