JP6066158B2 - Epoxy resin, curable resin composition, cured product thereof, semiconductor sealing material, and semiconductor device - Google Patents
Epoxy resin, curable resin composition, cured product thereof, semiconductor sealing material, and semiconductor device Download PDFInfo
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- JP6066158B2 JP6066158B2 JP2012015225A JP2012015225A JP6066158B2 JP 6066158 B2 JP6066158 B2 JP 6066158B2 JP 2012015225 A JP2012015225 A JP 2012015225A JP 2012015225 A JP2012015225 A JP 2012015225A JP 6066158 B2 JP6066158 B2 JP 6066158B2
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- JP
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- Prior art keywords
- epoxy resin
- resin composition
- resin
- structural formula
- thermosetting resin
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims description 148
- 229920000647 polyepoxide Polymers 0.000 title claims description 148
- 239000011342 resin composition Substances 0.000 title claims description 59
- 239000004065 semiconductor Substances 0.000 title claims description 26
- 239000003566 sealing material Substances 0.000 title claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 39
- 238000002844 melting Methods 0.000 claims description 32
- 230000008018 melting Effects 0.000 claims description 32
- -1 phenol compound Chemical class 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 27
- 238000005259 measurement Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 47
- 239000011347 resin Substances 0.000 description 47
- 239000003063 flame retardant Substances 0.000 description 35
- 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 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 229920003986 novolac Polymers 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 22
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 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 18
- 239000005011 phenolic resin Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910000679 solder Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 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 6
- 238000005406 washing Methods 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 150000007973 cyanuric acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical group C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N C(C1OC1)Oc1ccccc1 Chemical compound C(C1OC1)Oc1ccccc1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 0 Cc1ccc(*)cc1 Chemical compound Cc1ccc(*)cc1 0.000 description 2
- 102100021202 Desmocollin-1 Human genes 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 2
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 2
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 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
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical group CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-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
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical class [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
本発明は得られる硬化物が、難燃性、耐湿信頼性に優れ、半導体封止材、プリント回路基板、塗料、注型用途等に好適に用いる事が出来る新規エポキシ樹脂、熱硬化性樹脂組成物、その硬化物、半導体封止材料、及び半導体装置に関する。 The cured product obtained in the present invention is excellent in flame retardancy and moisture resistance reliability, and is a novel epoxy resin and thermosetting resin composition that can be suitably used for semiconductor sealing materials, printed circuit boards, paints, casting applications, etc. The present invention relates to an object, a cured product thereof, a semiconductor sealing material, and a semiconductor device.
エポキシ樹脂及びその硬化剤を必須成分とする熱硬化性樹脂組成物は、高耐熱性、耐湿性、低粘性等の諸物性に優れる点から半導体封止材やプリント回路基板等の電子部品、電子部品分野、導電ペースト等の導電性接着剤、その他接着剤、複合材料用マトリックス、塗料、フォトレジスト材料、顕色材料等で広く用いられている。 Thermosetting resin compositions containing an epoxy resin and its curing agent as essential components are excellent in various physical properties such as high heat resistance, moisture resistance, and low viscosity. Electronic components such as semiconductor encapsulants and printed circuit boards, electronic Widely used in parts field, conductive adhesives such as conductive paste, other adhesives, matrix for composite materials, paints, photoresist materials, developer materials, etc.
近年、これら各種用途、とりわけ先端材料用途において、耐熱性、耐湿信頼性に代表される性能の一層の向上が求められている。例えば、半導体封止材料分野では、BGA、CSPといった表面実装パッケージへの移行、更に鉛フリー半田への対応により、リフロー処理温度が高温化するに至り、よって、これまでに増して耐湿耐半田性に優れる電子部品封止樹脂材料が求められている。 In recent years, in these various applications, particularly advanced material applications, further improvements in performance typified by heat resistance and moisture resistance reliability have been demanded. For example, in the field of semiconductor encapsulating materials, the transition to surface mount packages such as BGA and CSP, as well as support for lead-free solder, led to higher reflow processing temperatures, thus increasing moisture resistance and solder resistance. There is a demand for an electronic component encapsulating resin material that is excellent in performance.
その為、エポキシ樹脂の低溶融粘度化を図り、無機フィラーを高充填化して硬化物の低吸湿化を高め、耐湿耐半田性を改良する技術が知られており、例えば、低溶融粘度のエポキシ樹脂としては、結晶性エポキシ樹脂であるビフェニル型エポキシ樹脂が知られている(下記特許文献1参照)。
For this reason, techniques for reducing the melt viscosity of epoxy resins, increasing the filling of inorganic fillers to increase the moisture absorption of cured products, and improving moisture resistance and solder resistance are known. For example, epoxy resins with low melt viscosity As the resin, a biphenyl type epoxy resin which is a crystalline epoxy resin is known (see
然し乍ら、下記特許文献1記載の結晶性エポキシ樹脂は、溶融粘度低減の観点から分子量が低くなり、その為、樹脂中のエポキシ濃度が高くなって、難燃性に劣るものとなる他、硬化時に生成する2級水酸基の濃度が高まることから、結局、低吸湿化を図ることはできず、充分な耐湿耐半田性が得られないものであった。
However, the crystalline epoxy resin described in the following
他方、エポキシ樹脂硬化物の低吸湿化を図る技術として、下記構造式 On the other hand, as a technique for reducing moisture absorption of cured epoxy resin, the following structural formula
で表されるベンゾイルレゾルシノールとエピクロルヒドリンを主剤たるエポキシ樹脂として用いる技術が知られている(下記特許文献2参照)。また、同様の化学構造を持つエポキシ樹脂は下記特許文献3にも開示されている。
A technique using benzoylresorcinol and epichlorohydrin represented by the above formulas as epoxy resins as main ingredients is known (see
然し乍ら、特許文献2及び3に開示されたエポキシ樹脂は、何れも液状のエポキシ樹脂であって、ハンドリング性に劣る他、特に特許文献2記載のエポキシ樹脂は、不純物塩素原子を多く含むため、近年要求の高い難燃性能に劣る他、耐湿耐半田性に劣るものであった。また、特許文献3記載のエポキシ樹脂は、やはり硬化物の難燃性に劣るものであった。
However, the epoxy resins disclosed in
従って、本発明が解決しようとする課題は、硬化前においてはハンドリング性に優れると共に、硬化後は高い難燃性と耐湿耐半田性を発現するエポキシ樹脂、エポキシ樹脂組成物、半導体封止材料、高難燃性と耐湿耐半田性とを兼備したエポキシ樹脂組成物の硬化物、及び半導体装置を提供することにある。 Therefore, the problem to be solved by the present invention is an epoxy resin, an epoxy resin composition, a semiconductor encapsulating material, which is excellent in handling properties before curing and exhibits high flame resistance and moisture resistance after curing. An object of the present invention is to provide a cured product of an epoxy resin composition having both high flame resistance and moisture and solder resistance, and a semiconductor device.
本発明者らは、上記課題を解決するため、鋭意検討した結果、特定のベンゾイルジグリシジルオキシベンゼンを主たる成分とし、かつ、DSC測定において所定の融点領域を有するエポキシ樹脂を主剤として用いた場合に、硬化前のハンドリング性に優れると共に、硬化物においてハロゲンフリーで高い難燃性と耐湿耐半田性が飛躍的に向上することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a specific benzoyldiglycidyloxybenzene as a main component and an epoxy resin having a predetermined melting point region in a DSC measurement as a main agent. The present inventors have found that the handling property before curing is excellent, and that the cured product is drastically improved in halogen-free, high flame resistance and moisture and solder resistance.
即ち本発明は、下記構造式(1) That is, the present invention provides the following structural formula (1)
(式中、R1は水素原子又はメトキシ基を表す。)
で表される化合物を主たる成分とし、かつ、DSC装置を用いて毎分10℃の速度で昇温した際の融点が70℃〜100℃の範囲にあることを特徴とするエポキシ樹脂に関する。
(In the formula, R 1 represents a hydrogen atom or a methoxy group.)
And a melting point when the temperature is raised at a rate of 10 ° C. per minute using a DSC apparatus in a range of 70 ° C. to 100 ° C.
本発明は、更に、エポキシ樹脂(A)及び硬化剤(B)とを必須成分する硬化性樹脂組成物であって、前記エポキシ樹脂(A)として、下記構造式(1) The present invention is a curable resin composition further comprising an epoxy resin (A) and a curing agent (B) as essential components, and the epoxy resin (A) has the following structural formula (1):
(式中、R1は水素原子又はメトキシ基を表す。)
で表される化合物を主たる成分とし、かつ、DSC装置を用いて毎分10℃の速度で昇温した際の融点が70℃〜100℃の範囲にあるエポキシ樹脂(a)を用いることを特徴とする熱硬化性樹脂組成物に関する。
(In the formula, R 1 represents a hydrogen atom or a methoxy group.)
And the epoxy resin (a) having a melting point in the range of 70 ° C. to 100 ° C. when heated at a rate of 10 ° C. per minute using a DSC apparatus. It relates to a thermosetting resin composition.
本発明は、更に、前記熱硬化性樹脂組成物を硬化反応させてなることを特徴とする硬化物に関する。 The present invention further relates to a cured product obtained by curing the thermosetting resin composition.
本発明は、更に、前記エポキシ樹脂(A)及び前記硬化剤(B)に加え、更に無機質充填材を組成物中70〜95質量%となる割合で含有することを特徴とする熱硬化性樹脂組成物に関する。 In addition to the epoxy resin (A) and the curing agent (B), the present invention further contains an inorganic filler at a ratio of 70 to 95% by mass in the composition. Relates to the composition.
本発明は、更に、前記半導体封止材料を用いて、半導体チップを封止してなる半導体装置に関する。 The present invention further relates to a semiconductor device obtained by sealing a semiconductor chip using the semiconductor sealing material.
本発明によれば、硬化前においてはハンドリング性に優れると共に、硬化後は高い難燃性と耐湿耐半田性を発現するエポキシ樹脂、エポキシ樹脂組成物、半導体封止材料、高難燃性と耐湿耐半田性とを兼備したエポキシ樹脂組成物の硬化物、及び半導体装置を提供することにある。 According to the present invention, an epoxy resin, an epoxy resin composition, a semiconductor encapsulating material, a high flame retardance and moisture resistance which are excellent in handling properties before curing and exhibit high flame resistance and moisture resistance and solder resistance after curing. An object of the present invention is to provide a cured product of an epoxy resin composition having both solder resistance and a semiconductor device.
本発明のエポキシ樹脂は、前記した通り、下記構造式(1) As described above, the epoxy resin of the present invention has the following structural formula (1).
(式中、R1は水素原子又はメトキシ基を表す。)
で表される化合物を主たる成分とし、かつ、DSC装置を用いて毎分10℃の速度で昇温した際の融点が70℃以上にあることを特徴とするものである。
(In the formula, R 1 represents a hydrogen atom or a methoxy group.)
And a melting point when heated at a rate of 10 ° C. per minute using a DSC apparatus is 70 ° C. or more.
ここで、前記構造式(1)中、R1は水素原子又はメトキシ基であるが、本発明では、特に水素原子であることが難燃性の点から好ましい。また、前記化合物は、難燃性の点から下記構造式 Here, in the structural formula (1), R 1 is a hydrogen atom or a methoxy group. In the present invention, a hydrogen atom is particularly preferable from the viewpoint of flame retardancy. In addition, the compound has the following structural formula from the viewpoint of flame retardancy:
(式中、R1は水素原子又はメトキシ基を表す。)
で表されるものが好ましい。
(In the formula, R 1 represents a hydrogen atom or a methoxy group.)
The thing represented by these is preferable.
また、DSC装置の測定条件は、具体的には以下の条件が挙げられる。 Moreover, the measurement conditions of the DSC apparatus specifically include the following conditions.
[示差走査熱量測定(DSC)の測定条件]
以下の条件にて測定したDSC曲線における融解ピークの頂点を融点とする。
[Differential scanning calorimetry (DSC) measurement conditions]
Let the peak of the melting peak in the DSC curve measured under the following conditions be the melting point.
装置 ;メトラー・トレド株式会社製「DSC1」
サンプル量;約5mg
温度条件 ;10℃/min
Equipment: “DSC1” manufactured by METTLER TOLEDO
Sample amount; about 5mg
Temperature condition: 10 ° C / min
本発明では融点が70℃未満となる場合には、常温液状乃至低融点のエポキシ樹脂となって保存時のブロッキング化を招きやすくハンドリング性が低いものとなる他、エポキシ樹脂中に占める上記構造式(1)で表される化合物の含有量が少なくなり、硬化物の難燃性の低下を招くものとなる。 In the present invention, when the melting point is less than 70 ° C., it becomes a normal temperature liquid to low melting point epoxy resin, which tends to cause blocking at the time of storage and has low handling properties, and the above structural formula occupying in the epoxy resin The content of the compound represented by (1) is reduced, and the flame retardancy of the cured product is reduced.
また、本発明では、融点は、特に、70℃以上98℃以下の範囲に位置することが望ましい。融点が98℃以下の範囲となることにより、常温(25℃)にて結晶性に富み、ハンドリング性に優れ硬化剤等との混合時における均一性が良好なものとなる他、溶融混練時における流動性に優れ、トランスファー成形工程における成形性に優れたものとなる。 In the present invention, the melting point is particularly preferably in the range of 70 ° C. or higher and 98 ° C. or lower. When the melting point is in the range of 98 ° C. or less, it has excellent crystallinity at normal temperature (25 ° C.), excellent handling properties and good uniformity when mixed with a curing agent, etc. Excellent fluidity and excellent moldability in the transfer molding process.
前記したエポキシ樹脂は、上記構造式(1)で表されるものを主たる成分とするものであるが、その他の成分は例えば下記構造式(2) The above-mentioned epoxy resin is mainly composed of those represented by the above structural formula (1). Other components are, for example, the following structural formula (2)
(式中、n=0〜4の整数であり、Xは水素原子又はグリシジル基を、R1は水素原子又はメトキシ基を表す。)
であらわされる化合物、或いは、本発明のエポキシ樹脂を製造する際に、原料フェノール化合物とエピハロヒドリンとの反応において、クロロヒドリン構造からエポキシ基への閉環反応が進行できずに、樹脂構造中にα−グリコール又は加水分解性塩素として残存する樹脂成分が挙げられる。
(In the formula, n is an integer of 0 to 4, X represents a hydrogen atom or a glycidyl group, and R 1 represents a hydrogen atom or a methoxy group.)
In the reaction of the raw material phenol compound and epihalohydrin in the production of the epoxy resin of the present invention or the epoxy resin of the present invention, the ring closure reaction from the chlorohydrin structure to the epoxy group cannot proceed, and the α-glycol in the resin structure Or the resin component which remains as hydrolysable chlorine is mentioned.
前記α−グリコール量は、構造式(1)で表されるものを主たる成分とする本発明のエポキシ樹脂中、0.005〜0.025ミリ当量/gの範囲であることが、優れた貯蔵安定性を発現させることが出来る他、硬化物の吸湿性を低減でき、耐湿耐半田性を向上させることができる点から好ましい。 The amount of α-glycol in the epoxy resin of the present invention mainly comprising the component represented by the structural formula (1) is in the range of 0.005 to 0.025 meq / g, and excellent storage. It is preferable from the standpoint that stability can be expressed, moisture absorption of the cured product can be reduced, and moisture resistance and solder resistance can be improved.
また、加水分解性塩素は、構造式(1)で表されるものを主たる成分とする本発明のエポキシ樹脂中、200ppm以下の範囲であることが、硬化物の難燃性が飛躍的に優れる他、硬化性や耐熱性にも優れることから好ましい。 In addition, the hydrolyzable chlorine is in a range of 200 ppm or less in the epoxy resin of the present invention mainly composed of the compound represented by the structural formula (1), and the flame retardancy of the cured product is remarkably excellent. In addition, it is preferable because it is excellent in curability and heat resistance.
上記した本発明のエポキシ樹脂は、更に具体的には、下記構造式(1) More specifically, the epoxy resin of the present invention described above has the following structural formula (1).
(式中、R1は水素原子又はメトキシ基を表す。)
で表される化合物を、GPC測定における面積比率で70%以上となる割合で含有するものであることが硬化物の難燃性に優れる点から好ましい。
(In the formula, R 1 represents a hydrogen atom or a methoxy group.)
It is preferable from the point which is excellent in the flame retardance of hardened | cured material that it is what contains the compound represented by these by the ratio used as the area ratio in GPC measurement becoming 70% or more.
ここで、GPCの測定条件は、具体的には下記の条件を採用することができる。
測定装置 :
東ソー株式会社製「HLC−8220 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL−L」
+東ソー株式会社製「TSK−GEL G2000HXL」
+東ソー株式会社製「TSK−GEL G2000HXL」
+東ソー株式会社製「TSK−GEL G3000HXL」
+東ソー株式会社製「TSK−GEL G4000HXL」
検出器: RI(示差屈折径)
データ処理:東ソー株式会社製「GPC−8020モデルIIバージョン4.10」
測定条件: カラム温度 40℃ 展開溶媒 テトラヒドロフラン 流速 1.0ml/分
標準 : 前記「GPC−8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。 (使用ポリスチレン)
東ソー株式会社製「A−500」
東ソー株式会社製「A−1000」
東ソー株式会社製「A−2500」
東ソー株式会社製「A−5000」
東ソー株式会社製「F−1」
東ソー株式会社製「F−2」
東ソー株式会社製「F−4」
東ソー株式会社製「F−10」
東ソー株式会社製「F−20」
東ソー株式会社製「F−40」
東ソー株式会社製「F−80」
東ソー株式会社製「F−128」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)。
Here, specifically, the following conditions can be adopted as GPC measurement conditions.
measuring device :
"HLC-8220 GPC" manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions:
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
以上詳述した構造式(1)で表されるものを主たる成分とする本発明のエポキシ樹脂は、そのエポキシ当量が163〜200g/eq.の範囲にあることが難燃性、硬化性、耐熱性の点から好ましい。 The epoxy resin of the present invention, which mainly contains the component represented by the structural formula (1) detailed above, has an epoxy equivalent of 163 to 200 g / eq. It is preferable from the viewpoint of flame retardancy, curability, and heat resistance.
次に、上記した本発明のエポキシ樹脂は、例えば、下記構造式(1’) Next, the epoxy resin of the present invention described above has, for example, the following structural formula (1 ′)
で表されるフェノール化合物にエピクロルヒドリンを反応せしめることにより工業的に製造することができる。 It can manufacture industrially by making epichlorohydrin react with the phenol compound represented by these.
具体的には、
1)上記フェノール化合物の水酸基の1モルに対し、エピクロルヒドリンを0.7〜10モル添加し、塩基性触媒の存在下に20〜120℃で2〜7時間エポキシ化反応を行う方法、
2)上記フェノール化合物とエピクロルヒドリンとを4級アンモニウム塩の存在下に50〜150℃で1〜5時間反応させてクロルヒドリンエーテルを得、次いで、これに、アルカリ金属水酸化物の固体または水溶液を加え、再び20〜120℃で1〜10時間反応させ脱ハロゲン化水素(閉環)させる方法が挙げられる。
In particular,
1) A method in which 0.7 to 10 mol of epichlorohydrin is added to 1 mol of the hydroxyl group of the phenol compound, and an epoxidation reaction is performed at 20 to 120 ° C. for 2 to 7 hours in the presence of a basic catalyst,
2) The above phenol compound and epichlorohydrin are reacted in the presence of a quaternary ammonium salt at 50 to 150 ° C. for 1 to 5 hours to obtain a chlorohydrin ether, which is then added to a solid or aqueous solution of an alkali metal hydroxide. And dehydrohalogenation (ring closure) by reacting again at 20 to 120 ° C. for 1 to 10 hours.
上記方法1)で用いる塩基性触媒は、例えば、水酸化カリウム、水酸化ナトリウム、水酸化バリウム、酸化マグネシウム、炭酸ナトリウム、炭酸カリウム等が挙げられるが、中でも水酸化カリウム又は水酸化ナトリウムが好ましい。
また、上記方法2)で用いる4級アンモニウム塩は、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド等が挙げられる。
方法2)におけるアルカリ金属水酸化物は、具体的には、水酸化カリウム、水酸化ナトリウム、水酸化バリウム等が挙げられ、その使用量は粗エポキシ樹脂中に残存する加水分解性塩素1モルに対して、通常0.5〜10モル、好ましくは1.2〜5.0モルである。反応温度としては通常50〜120℃、反応時間としては通常0.5〜3時間である。反応速度の向上を目的として、4級アンモニウム塩やクラウンエーテル等の相関移動触媒を存在させてもよい。相関移動触媒を使用する場合のその使用量としては、粗エポキシ樹脂に対して0.1〜3.0質量%の範囲であることが好ましい。
Examples of the basic catalyst used in the above method 1) include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate and the like, among which potassium hydroxide or sodium hydroxide is preferable.
Examples of the quaternary ammonium salt used in the above method 2) include tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride.
Specific examples of the alkali metal hydroxide in method 2) include potassium hydroxide, sodium hydroxide, barium hydroxide and the like, and the amount used is 1 mol of hydrolyzable chlorine remaining in the crude epoxy resin. On the other hand, it is 0.5-10 mol normally, Preferably it is 1.2-5.0 mol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the crude epoxy resin.
また、前記方法1)又は方法2)において、反応を円滑に進行させるためにメタノール、エタノール、イソプロピルアルコール、ブタノールなどのアルコール類;アセトン、メチルエチルケトンなどのケトン類;ジオキサンなどのエーテル類;ジメチルスルホン、ジメチルスルホキシド等の非プロトン性極性溶媒などを添加して反応を行うことが好ましい。溶媒を使用する場合のその使用量としては、エピクロルヒドリンの使用量に対し通常5〜50質量%、好ましくは10〜30質量%である。また非プロトン性極性溶媒を用いる場合はエピクロルヒドリンの量に対し通常5〜100質量%、好ましくは10〜60質量%である。 In the method 1) or method 2), alcohols such as methanol, ethanol, isopropyl alcohol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane; dimethyl sulfone; The reaction is preferably carried out by adding an aprotic polar solvent such as dimethyl sulfoxide. The amount of the solvent used is usually 5 to 50% by mass, preferably 10 to 30% by mass, based on the amount of epichlorohydrin used. Moreover, when using an aprotic polar solvent, it is 5-100 mass% normally with respect to the quantity of epichlorohydrin, Preferably it is 10-60 mass%.
また、上記1)又は2)の反応において、反応系内の水分量を低減させながら反応を行うことにより、エピクロルヒドリンのグリシドール化を防ぐと共に、生成したエポキシ基の加水分解を防止することができる。 Further, in the reaction 1) or 2), by performing the reaction while reducing the amount of water in the reaction system, epichlorohydrin can be prevented from being glycidolated and hydrolysis of the generated epoxy group can be prevented.
反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下トルエン、メチルイソブチルケトンなどの溶剤を留去することにより目的とする本発明のエポキシ樹脂を得ることができる。 After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and further, the target epoxy resin of the present invention can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.
また、本発明のエポキシ樹脂中の、前記構造式(1)で表される化合物のGPC測定による含有率を80〜98面積%の範囲に調節するには、フェノール化合物とエピハロヒドリンとの反応において、エピハロヒドリンのモル数の過剰率をできるだけ高くすることが好ましく、具体的には、前記構造式(1’)で表されるフェノール化合物1モルに対するエピクロルヒドリンのモル数を4〜10モルの範囲でエポキシ化反応を行うことが好ましい。 Moreover, in order to adjust the content rate by GPC measurement of the compound represented by the structural formula (1) in the epoxy resin of the present invention to a range of 80 to 98 area%, in the reaction of the phenol compound and epihalohydrin, It is preferable to make the excess of the number of moles of epihalohydrin as high as possible. Specifically, the number of moles of epichlorohydrin relative to 1 mole of the phenol compound represented by the structural formula (1 ′) is epoxidized in the range of 4 to 10 moles. It is preferable to carry out the reaction.
なお、工業生産を行う際、エポキシ樹脂生産の初バッチでは仕込みに用いるエピハロヒドリン類の全てが新しいものであるが、次バッチ以降は、粗反応生成物から回収されたエピハロヒドリン類と、反応で消費される分で消失する分に相当する新しいエピハロヒドリン類とを併用することが好ましい。この際、グリシドール等、エピクロルヒドリンと水、有機溶剤等との反応により誘導される不純物を含有していても良い。この時、使用するエピハロヒドリンは特に限定されないが、例えばエピクロルヒドリン、エピブロモヒドリン、β−メチルエピクロルヒドリン等が挙げられる。なかでも工業的入手が容易なことからエピクロルヒドリンが好ましい。 In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. Under the present circumstances, the impurity induced | guided | derived by reaction with epichlorohydrin, water, an organic solvent, etc. may be contained, such as glycidol. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.
前記1)又は2)の方法により、エポキシ化反応を行った後、反応生成物を水洗後、加熱減圧下、蒸留によって未反応のエピハロヒドリンや併用する有機溶媒を留去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、得られたエポキシ樹脂を再びトルエン、メチルイソブチルケトン、メチルエチルケトンなどの有機溶媒に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えてさらに反応を行うこともできる。この際、反応速度の向上を目的として、4級アンモニウム塩やクラウンエーテル等の相関移動触媒を存在させてもよい。相関移動触媒を使用する場合のその使用量としては、用いるエポキシ樹脂に対して0.1〜3.0質量%の範囲が好ましい。反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下トルエン、メチルイソブチルケトンなどの溶剤を留去することにより高純度のエポキシ樹脂を得ることができる。 After the epoxidation reaction is carried out by the method 1) or 2) above, the reaction product is washed with water, and then unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.
(結晶化の工程)
この様にして得られた該エポキシ樹脂は、次いで、溶剤を用いた再結晶により結晶性エポキシ樹脂とすることができる。溶剤種としては、メタノール、エタノール、イソプロピルアルコール等のアルコール系、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系、ヘプタン、ヘキサン、ベンゼン、トルエン、キシレン等の炭化水素系溶剤が挙げられる。これらの溶剤は単一でも、任意に混合して用いても良い。また、薄膜蒸留、種結晶添加と混錬等によっても結晶性エポキシ樹脂とすることが可能である。
(Crystallization process)
The epoxy resin thus obtained can then be converted into a crystalline epoxy resin by recrystallization using a solvent. Examples of the solvent species include alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and hydrocarbon solvents such as heptane, hexane, benzene, toluene and xylene. These solvents may be used singly or arbitrarily mixed. It is also possible to obtain a crystalline epoxy resin by thin film distillation, seed crystal addition and kneading.
本発明の熱硬化性樹脂組成物は、エポキシ樹脂(A)及び硬化剤(B)を必須成分とする熱硬化性樹脂組成物であって、前記エポキシ樹脂(A)が、前記した本発明のエポキシ樹脂であることを特徴とするものである。 The thermosetting resin composition of the present invention is a thermosetting resin composition containing an epoxy resin (A) and a curing agent (B) as essential components, and the epoxy resin (A) is the above-described one of the present invention. It is an epoxy resin.
本発明の熱硬化性樹脂組成物において、前記エポキシ樹脂(A)は単独で用いることができるが、本発明の効果を損なわない範囲で他のエポキシ樹脂(A’)を併用することができる。当該他のエポキシ樹脂(A’)を併用する場合、エポキシ樹脂成分全体に占める本発明のエポキシ樹脂(A’)の割合は30質量%以上となる割合であること、特に40質量%以上となる割合であることが好ましい。 In the thermosetting resin composition of the present invention, the epoxy resin (A) can be used alone, but other epoxy resins (A ′) can be used in combination as long as the effects of the present invention are not impaired. When the other epoxy resin (A ′) is used in combination, the ratio of the epoxy resin (A ′) of the present invention to the entire epoxy resin component is a ratio of 30% by mass or more, particularly 40% by mass or more. A ratio is preferred.
本発明のエポキシ樹脂(A)と併用されうる他のエポキシ樹脂(A’)としては、種々のエポキシ樹脂を用いることができるが、例えば、ジグリシジルオキシナフタレン、1,1−ビス(2,7−ジグリシジルオキシナフチル)メタン、1−(2,7−ジグリシジルオキシナフチル)−1−(2’−グリシジルオキシナフチル)メタン等のナフタレン型エポキシ樹脂;ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂等のビスフェノール型エポキシ樹脂;フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂;前記ノボラック型エポキシ樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂、前記ノボラック型エポキシ樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂;下記構造式B1 As another epoxy resin (A ′) that can be used in combination with the epoxy resin (A) of the present invention, various epoxy resins can be used. For example, diglycidyloxynaphthalene, 1,1-bis (2,7 -Naphthalene type epoxy resins such as -diglycidyloxynaphthyl) methane, 1- (2,7-diglycidyloxynaphthyl) -1- (2'-glycidyloxynaphthyl) methane; bisphenol A type epoxy resin, bisphenol F type epoxy resin Bisphenol type epoxy resin such as: phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthol novolak type epoxy resin, biphenyl novolac type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, na Novolak type epoxy resin such as tall-cresol co-condensed novolak type epoxy resin; epoxy resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the novolak type epoxy resin through a methylene group, aromatic nucleus of the novolak type epoxy resin An epoxy resin having a resin structure in which a methoxyphenyl skeleton is bonded to each other via a methylene group;
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるフェノールアラルキル型エポキシ樹脂、下記構造式B2
(In the formula, n is a repeating unit and is an integer of 0 or more.)
A phenol aralkyl type epoxy resin represented by the following structural formula B2
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるナフトールアラルキル型エポキシ樹脂、下記構造式B3
(In the formula, n is a repeating unit and is an integer of 0 or more.)
A naphthol aralkyl epoxy resin represented by the following structural formula B3
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるビフェニル型エポキシ樹脂、下記構造式B4
(In the formula, n is a repeating unit and is an integer of 0 or more.)
Biphenyl type epoxy resin represented by the following structural formula B4
(式中、Xは、フェニル基、ビフェニル基を表し、nは繰り返し単位であり、0以上の整数である。)
で表される芳香族メチレンを結節基とするノボラック型エポキシ樹脂;前記アラルキル型エポキシ樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂、前記アラルキル型エポキシ樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のエポキシ樹脂;その他テトラメチルビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、
ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂等が挙げられる。またこれらのエポキシ樹脂は単独で用いてもよく、2種以上を混合してもよい。
(In the formula, X represents a phenyl group or a biphenyl group, n is a repeating unit, and is an integer of 0 or more.)
A novolak-type epoxy resin having an aromatic methylene as a nodule group; an epoxy resin having a resin structure in which a methoxynaphthalene skeleton is bonded to an aromatic nucleus of the aralkyl-type epoxy resin via a methylene group; and the fragrance of the aralkyl-type epoxy resin Epoxy resin with a resin structure in which a methoxyphenyl skeleton is bonded to the nucleus via a methylene group; other tetramethylbiphenyl type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins,
Examples include dicyclopentadiene-phenol addition reaction type epoxy resin. Moreover, these epoxy resins may be used independently and may mix 2 or more types.
これらのなかでも特に、ナフタレン型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂、アルコキシ基含有ノボラック型エポキシ樹脂、又はアルコキシ基含有アラルキル型エポキシ樹脂が、難燃性や誘電特性に優れる点から特に好ましい。 Among these, in particular, naphthalene type epoxy resins, naphthol novolak type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, alkoxy group containing novolac type epoxy resins, or alkoxy group containing aralkyl type epoxy resins are flame retardant and This is particularly preferable from the viewpoint of excellent dielectric properties.
本発明の熱硬化性樹脂組成物に用いる硬化剤(B)としては、公知の各種エポキシ樹脂用硬化剤、例えばアミン系化合物、アミド系化合物、酸無水物系化合物、フェノ−ル系化合物などの硬化剤が使用できる。具体的には、アミン系化合物としてはジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾ−ル、BF3−アミン錯体、グアニジン誘導体等が挙げられ、アミド系化合物としては、ジシアンジアミド、リノレン酸の2量体とエチレンジアミンとより合成されるポリアミド樹脂等が挙げられ、酸無水物系化合物としては、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられ、フェノール系化合物としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、ナフトールノボラック樹脂、ナフトール−フェノール共縮ノボラック樹脂、ナフトール−クレゾール共縮ノボラック樹脂等のノボラック樹脂;前記ノボラック樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂、前記ノボラック樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂等のメトキシ芳香族構造含有フェノール樹脂;下記構造式 Examples of the curing agent (B) used in the thermosetting resin composition of the present invention include various known epoxy resin curing agents such as amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like. A curing agent can be used. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF 3 -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin A novolak resin such as a naphthol novolak resin, a naphthol-phenol co-condensed novolak resin, a naphthol-cresol co-condensed novolak resin, or the like; A phenol resin containing a methoxy aromatic structure such as a phenol resin having a methoxyphenyl skeleton bonded to the aromatic nucleus of the resin via a methylene group;
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるフェノールアラルキル樹脂、下記構造式
(In the formula, n is a repeating unit and is an integer of 0 or more.)
Phenol aralkyl resin represented by the following structural formula
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるナフトールアラルキル樹脂、下記構造式
(In the formula, n is a repeating unit and is an integer of 0 or more.)
Naphthol aralkyl resin represented by the following structural formula
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるビフェニル変性フェノール樹脂、下記構造式
(In the formula, n is a repeating unit and is an integer of 0 or more.)
Biphenyl modified phenolic resin represented by the following structural formula
(式中、nは繰り返し単位であり、0以上の整数である。)
で表されるビフェニル変性ナフトール樹脂等のアラルキル型フェノール樹脂;
前記アラルキル型フェノール樹脂の芳香核にメトキシナフタレン骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂、前記アラルキル型フェノール樹脂の芳香核にメトキシフェニル骨格がメチレン基を介して結合した樹脂構造のフェノール樹脂;下記構造式
(In the formula, n is a repeating unit and is an integer of 0 or more.)
Aralkyl type phenolic resins such as biphenyl-modified naphthol resins represented by:
A phenol resin having a resin structure in which a methoxynaphthalene skeleton is bonded to the aromatic nucleus of the aralkyl type phenol resin via a methylene group, and a phenol having a resin structure in which the methoxyphenyl skeleton is bonded to the aromatic nucleus of the aralkyl type phenol resin via a methylene group. Resin; following structural formula
(式中、Xは、フェニル基、ビフェニル基を表し、nは繰り返し単位であり、0以上の整数である。)で表される芳香族メチレンを結節基とするノボラック樹脂;トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ジシクロペンタジエンフェノール付加型フェノール樹脂、アミノトリアジン変性フェノール樹脂(メラミンやベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物)等の多価フェノール化合物が挙げられる。 (Wherein X represents a phenyl group or a biphenyl group, n is a repeating unit, and is an integer of 0 or more). A novolak resin having a nodule group represented by an aromatic methylene represented by: trimethylolmethane resin; Examples thereof include polyphenol compounds such as tetraphenylolethane resin, dicyclopentadiene phenol addition type phenol resin, aminotriazine-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.).
これらの中でも、特に芳香族骨格を分子構造内に多く含むものが難燃効果の点から好ましく、具体的には、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族メチレンを結節基とするノボラック樹脂、フェノールアラルキル樹脂、ナフトールアラルキル樹脂、ナフトールノボラック樹脂、ナフトール−フェノール共縮ノボラック樹脂、ナフトール−クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂、ビフェニル変性ナフトール樹脂、メトキシ芳香族構造含有フェノール樹脂、アミノトリアジン変性フェノール樹脂が難燃性に優れることから好ましい。また、流動性を向上させたい場合は、レゾルシン、カテコール、ハイドロキノン等のジヒドロキシフェノール類、ビスフェノールFやビスフェノールAなどのビスフェノール類、2,7−ジヒドロキシナフタレン、1,6−ジヒドロキシナフタレンなどのフェノール化合物を併用することが好ましい。 Among these, those containing a large amount of an aromatic skeleton in the molecular structure are particularly preferred from the viewpoint of the flame retardant effect. Specifically, phenol novolac resins, cresol novolak resins, novolak resins having aromatic methylene as a nodule, phenol Aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, methoxy aromatic structure-containing phenol resin, aminotriazine-modified phenol resin Is preferable because of its excellent flame retardancy. In order to improve fluidity, dihydroxyphenols such as resorcin, catechol and hydroquinone, bisphenols such as bisphenol F and bisphenol A, and phenol compounds such as 2,7-dihydroxynaphthalene and 1,6-dihydroxynaphthalene are used. It is preferable to use together.
本発明の熱硬化性樹脂組成物におけるエポキシ樹脂(A)と硬化剤(B)との配合量としては、特に制限されるものではないが、得られる硬化物の特性が良好である点から、前記エポキシ樹脂(A)を含むエポキシ樹脂中のエポキシ基の合計1当量に対して、硬化剤(B)中の活性基が0.7〜1.5当量となる量であることが好ましい。 The blending amount of the epoxy resin (A) and the curing agent (B) in the thermosetting resin composition of the present invention is not particularly limited, but from the point that the properties of the resulting cured product are good, It is preferable that the amount of active groups in the curing agent (B) is 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups in the epoxy resin containing the epoxy resin (A).
また、必要に応じて本発明の熱硬化性樹脂組成物には、更に硬化促進剤を適宜併用することもできる。前記硬化促進剤としては種々のものが使用できるが、例えば、リン系化合物、第3級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。特に半導体封止材料用途として使用する場合には、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、リン系化合物ではトリフェニルフォスフィン、第3級アミンでは1,8−ジアザビシクロ−[5.4.0]−ウンデセン(DBU)が好ましい。 Moreover, a curing accelerator can be used in combination with the thermosetting resin composition of the present invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.
以上詳述した本発明の熱硬化性樹脂組成物では、熱硬化性樹脂組成物におけるエポキシ樹脂(A)が優れた難燃性付与効果を有するものである為、従来用いられている難燃剤を配合しなくても、硬化物の難燃性が良好である。しかしながら、より高度な難燃性を発揮させるために、例えば半導体封止材料の分野においては、封止工程での成形性や半導体装置の信頼性を低下させない範囲で、実質的にハロゲン原子を含有しない非ハロゲン系難燃剤(C)を配合してもよい。 In the thermosetting resin composition of the present invention described in detail above, since the epoxy resin (A) in the thermosetting resin composition has an excellent flame retardancy imparting effect, a conventionally used flame retardant is used. Even if not blended, the flame retardancy of the cured product is good. However, in order to exert a higher degree of flame retardancy, for example, in the field of semiconductor sealing materials, it contains substantially halogen atoms in a range that does not reduce the moldability in the sealing process and the reliability of the semiconductor device. A non-halogen flame retardant (C) may be added.
かかる非ハロゲン系難燃剤(C)を配合した熱硬化性樹脂組成物は、実質的にハロゲン原子を含有しないものであるが、例えばエポキシ樹脂に含まれるエピハロヒドリン由来の5000ppm以下程度の微量の不純物によるハロゲン原子は含まれていても良い。 The thermosetting resin composition containing such a non-halogen flame retardant (C) is substantially free of halogen atoms. For example, due to a trace amount of impurities of about 5000 ppm or less derived from epihalohydrin contained in an epoxy resin. Halogen atoms may be included.
前記非ハロゲン系難燃剤(C)としては、例えば、リン系難燃剤、窒素系難燃剤、シリコーン系難燃剤、無機系難燃剤、有機金属塩系難燃剤等が挙げられ、それらの使用に際しても何等制限されるものではなく、単独で使用しても、同一系の難燃剤を複数用いても良く、また、異なる系の難燃剤を組み合わせて用いることも可能である。 Examples of the non-halogen flame retardant (C) include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. It is not limited at all, and it may be used alone, or a plurality of flame retardants of the same system may be used, or flame retardants of different systems may be used in combination.
前記リン系難燃剤としては、無機系、有機系のいずれも使用することができる。無機系化合物としては、例えば、赤リン、リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム、ポリリン酸アンモニウム等のリン酸アンモニウム類、リン酸アミド等の無機系含窒素リン化合物が挙げられる。 As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .
また、前記赤リンは、加水分解等の防止を目的として表面処理が施されていることが好ましく、表面処理方法としては、例えば、(i)水酸化マグネシウム、水酸化アルミニウム、水酸化亜鉛、水酸化チタン、酸化ビスマス、水酸化ビスマス、硝酸ビスマス又はこれらの混合物等の無機化合物で被覆処理する方法、(ii)水酸化マグネシウム、水酸化アルミニウム、水酸化亜鉛、水酸化チタン等の無機化合物、及びフェノール樹脂等の熱硬化性樹脂の混合物で被覆処理する方法、(iii)水酸化マグネシウム、水酸化アルミニウム、水酸化亜鉛、水酸化チタン等の無機化合物の被膜の上にフェノール樹脂等の熱硬化性樹脂で二重に被覆処理する方法等が挙げられる。 The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.
前記有機リン系化合物としては、例えば、リン酸エステル化合物、ホスホン酸化合物、ホスフィン酸化合物、ホスフィンオキシド化合物、ホスホラン化合物、有機系含窒素リン化合物等の汎用有機リン系化合物の他、9,10−ジヒドロ−9−オキサー10−ホスファフェナントレン=10−オキシド、10−(2,5−ジヒドロオキシフェニル)−10H−9−オキサ−10−ホスファフェナントレン=10−オキシド、10−(2,7−ジヒドロオキシナフチル)−10H−9−オキサ−10−ホスファフェナントレン=10−オキシド等の環状有機リン化合物、及びそれをエポキシ樹脂やフェノール樹脂等の化合物と反応させた誘導体等が挙げられる。 Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa 10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.
それらの配合量としては、リン系難燃剤の種類、熱硬化性樹脂組成物の他の成分、所望の難燃性の程度によって適宜選択されるものであるが、例えば、エポキシ樹脂、硬化剤、非ハロゲン系難燃剤及びその他の充填材や添加剤等全てを配合した熱硬化性樹脂組成物100質量部中、赤リンを非ハロゲン系難燃剤として使用する場合は0.1〜2.0質量部の範囲で配合することが好ましく、有機リン化合物を使用する場合は同様に0.1〜10.0質量部の範囲で配合することが好ましく、特に0.5〜6.0質量部の範囲で配合することが好ましい。 The blending amount thereof is appropriately selected according to the type of the phosphorus-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, a curing agent, In 100 parts by mass of the thermosetting resin composition containing all of the non-halogen flame retardant and other fillers and additives, 0.1 to 2.0 mass when red phosphorus is used as the non-halogen flame retardant It is preferable to mix | blend in the range of 0.1 part, and when using an organophosphorus compound, it is preferable to mix | blend similarly in the range of 0.1-10.0 mass part, Especially the range of 0.5-6.0 mass part is preferable. It is preferable to mix with.
また前記リン系難燃剤を使用する場合、該リン系難燃剤にハイドロタルサイト、水酸化マグネシウム、ホウ化合物、酸化ジルコニウム、黒色染料、炭酸カルシウム、ゼオライト、モリブデン酸亜鉛、活性炭等を併用してもよい。 In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.
前記窒素系難燃剤としては、例えば、トリアジン化合物、シアヌル酸化合物、イソシアヌル酸化合物、フェノチアジン等が挙げられ、トリアジン化合物、シアヌル酸化合物、イソシアヌル酸化合物が好ましい。 Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.
前記トリアジン化合物としては、例えば、メラミン、アセトグアナミン、ベンゾグアナミン、メロン、メラム、サクシノグアナミン、エチレンジメラミン、ポリリン酸メラミン、トリグアナミン等の他、例えば、(i)硫酸グアニルメラミン、硫酸メレム、硫酸メラムなどの硫酸アミノトリアジン化合物、(ii)フェノール、クレゾール、キシレノール、ブチルフェノール、ノニルフェノール等のフェノール類と、メラミン、ベンゾグアナミン、アセトグアナミン、ホルムグアナミン等のメラミン類およびホルムアルデヒドとの共縮合物、(iii)前記(ii)の共縮合物とフェノールホルムアルデヒド縮合物等のフェノール樹脂類との混合物、(iv)前記(ii)、(iii)を更に桐油、異性化アマニ油等で変性したもの等が挙げられる。 Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is.
前記シアヌル酸化合物の具体例としては、例えば、シアヌル酸、シアヌル酸メラミン等を挙げることができる。 Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.
前記窒素系難燃剤の配合量としては、窒素系難燃剤の種類、熱硬化性樹脂組成物の他の成分、所望の難燃性の程度によって適宜選択されるものであるが、例えば、エポキシ樹脂、硬化剤、非ハロゲン系難燃剤及びその他の充填材や添加剤等全てを配合した熱硬化性樹脂組成物100質量部中、0.05〜10質量部の範囲で配合することが好ましく、特に0.1〜5質量部の範囲で配合することが好ましい。 The compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass in 100 parts by mass of the thermosetting resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in the range of 0.1-5 mass parts.
また前記窒素系難燃剤を使用する際、金属水酸化物、モリブデン化合物等を併用してもよい。 Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.
前記シリコーン系難燃剤としては、ケイ素原子を含有する有機化合物であれば特に制限がなく使用でき、例えば、シリコーンオイル、シリコーンゴム、シリコーン樹脂等が挙げられる。 The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.
前記シリコーン系難燃剤の配合量としては、シリコーン系難燃剤の種類、熱硬化性樹脂組成物の他の成分、所望の難燃性の程度によって適宜選択されるものであるが、例えば、エポキシ樹脂、硬化剤、非ハロゲン系難燃剤及びその他の充填材や添加剤等全てを配合した熱硬化性樹脂組成物100質量部中、0.05〜20質量部の範囲で配合することが好ましい。また前記シリコーン系難燃剤を使用する際、モリブデン化合物、アルミナ等を併用してもよい。 The amount of the silicone-based flame retardant is appropriately selected according to the type of the silicone-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the thermosetting resin composition in which all of the curing agent, non-halogen flame retardant and other fillers and additives are blended. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.
前記無機系難燃剤としては、例えば、金属水酸化物、金属酸化物、金属炭酸塩化合物、金属粉、ホウ素化合物、低融点ガラス等が挙げられる。 Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.
前記金属水酸化物の具体例としては、例えば、水酸化アルミニウム、水酸化マグネシウム、ドロマイト、ハイドロタルサイト、水酸化カルシウム、水酸化バリウム、水酸化ジルコニウム等を挙げることができる。 Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.
前記金属酸化物の具体例としては、例えば、モリブデン酸亜鉛、三酸化モリブデン、スズ酸亜鉛、酸化スズ、酸化アルミニウム、酸化鉄、酸化チタン、酸化マンガン、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化コバルト、酸化ビスマス、酸化クロム、酸化ニッケル、酸化銅、酸化タングステン等を挙げることができる。 Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.
前記金属炭酸塩化合物の具体例としては、例えば、炭酸亜鉛、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、塩基性炭酸マグネシウム、炭酸アルミニウム、炭酸鉄、炭酸コバルト、炭酸チタン等を挙げることができる。 Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.
前記金属粉の具体例としては、例えば、アルミニウム、鉄、チタン、マンガン、亜鉛、モリブデン、コバルト、ビスマス、クロム、ニッケル、銅、タングステン、スズ等を挙げることができる。 Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.
前記ホウ素化合物の具体例としては、例えば、ホウ酸亜鉛、メタホウ酸亜鉛、メタホウ酸バリウム、ホウ酸、ホウ砂等を挙げることができる。 Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.
前記低融点ガラスの具体例としては、例えば、シープリー(ボクスイ・ブラウン社)、水和ガラスSiO2−MgO−H2O、PbO−B2O3系、ZnO−P2O5−MgO系、P2O5−B2O3−PbO−MgO系、P−Sn−O−F系、PbO−V2O5−TeO2系、Al2O3−H2O系、ホウ珪酸鉛系等のガラス状化合物を挙げることができる。 Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO 2 —MgO—H 2 O, PbO—B 2 O 3 system, ZnO—P 2 O 5 —MgO system, P 2 O 5 —B 2 O 3 —PbO—MgO, P—Sn—O—F, PbO—V 2 O 5 —TeO 2 , Al 2 O 3 —H 2 O, lead borosilicate, etc. The glassy compound can be mentioned.
前記無機系難燃剤の配合量としては、無機系難燃剤の種類、熱硬化性樹脂組成物の他の成分、所望の難燃性の程度によって適宜選択されるものであるが、例えば、エポキシ樹脂、硬化剤、非ハロゲン系難燃剤及びその他の充填材や添加剤等全てを配合した熱硬化性樹脂組成物100質量部中、0.05〜20質量部の範囲で配合することが好ましく、特に0.5〜15質量部の範囲で配合することが好ましい。 The blending amount of the inorganic flame retardant is appropriately selected depending on the kind of the inorganic flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the thermosetting resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 0.5 to 15 parts by mass.
前記有機金属塩系難燃剤としては、例えば、フェロセン、アセチルアセトナート金属錯体、有機金属カルボニル化合物、有機コバルト塩化合物、有機スルホン酸金属塩、金属原子と芳香族化合物又は複素環化合物がイオン結合又は配位結合した化合物等が挙げられる。 Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.
前記有機金属塩系難燃剤の配合量としては、有機金属塩系難燃剤の種類、熱硬化性樹脂組成物の他の成分、所望の難燃性の程度によって適宜選択されるものであるが、例えば、エポキシ樹脂、硬化剤、非ハロゲン系難燃剤及びその他の充填材や添加剤等全てを配合した熱硬化性樹脂組成物100質量部中、0.005〜10質量部の範囲で配合することが好ましい。 The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of organometallic salt-based flame retardant, the other components of the thermosetting resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the thermosetting resin composition containing all of epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives, it is blended in the range of 0.005 to 10 parts by mass. Is preferred.
本発明の熱硬化性樹脂組成物には、必要に応じて無機質充填材を配合することができる。前記無機質充填材としては、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ等が挙げられる。前記無機充填材の配合量を特に大きくする場合は溶融シリカを用いることが好ましい。前記溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め且つ成形材料の溶融粘度の上昇を抑制するためには、球状のものを主に用いる方が好ましい。更に球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調整することが好ましい。その充填率は難燃性を考慮して、高い方が好ましく、熱硬化性樹脂組成物の全体量に対して65質量%以上が特に好ましい。また導電ペーストなどの用途に使用する場合は、銀粉や銅粉等の導電性充填剤を用いることができる。 An inorganic filler can be mix | blended with the thermosetting resin composition of this invention as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 65% by mass or more with respect to the total amount of the thermosetting resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.
本発明の熱硬化性樹脂組成物には、必要に応じて、シランカップリング剤、離型剤、顔料、乳化剤等の種々の配合剤を添加することができる。 Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the thermosetting resin composition of this invention as needed.
本発明の熱硬化性樹脂組成物は、上記した各成分を均一に混合することにより得られる。本発明の熱硬化性樹脂組成物は従来知られている方法と同様の方法で容易に硬化物とすることができる。該硬化物としては積層物、注型物、接着層、塗膜、フィルム等の成形硬化物が挙げられる。 The thermosetting resin composition of the present invention can be obtained by uniformly mixing the above-described components. The thermosetting resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.
本発明の熱硬化性樹脂組成物が用いられる用途としては、半導体封止材料、積層板や電子回路基板等に用いられる樹脂組成物、樹脂注型材料、接着剤、ビルドアップ基板用層間絶縁材料、絶縁塗料等のコーティング材料等が挙げられ、これらの中でも、半導体封止材料に好適に用いることができる。 Applications for which the thermosetting resin composition of the present invention is used include semiconductor sealing materials, resin compositions used for laminates and electronic circuit boards, resin casting materials, adhesives, and interlayer insulation materials for build-up substrates And coating materials such as insulating paints. Among these, among them, they can be suitably used for semiconductor sealing materials.
半導体封止材用に調製された熱硬化性樹脂組成物を作製するためには、充填剤を含む各成分を必要に応じて押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合して溶融混合型の熱硬化性樹脂組成物を得ればよい。その際、充填剤としては、通常シリカが用いられるが、その充填率は熱硬化性樹脂組成物100質量部当たり、充填剤を30〜95質量%の範囲が用いることが好ましく、中でも、難燃性や耐湿性や耐ハンダクラック性の向上、線膨張係数の低下を図るためには、70質量部以上が特に好ましく、それらの効果を格段に上げるためには、80質量部以上が一層その効果を高めることができる。 In order to produce a thermosetting resin composition prepared for a semiconductor encapsulant, each component including a filler is made uniform using an extruder, a kneader, a roll, or the like as necessary. It is sufficient to obtain a melt-mixing type thermosetting resin composition by sufficiently mixing the above. At that time, silica is usually used as the filler, and the filler is preferably used in a range of 30 to 95% by mass per 100 parts by mass of the thermosetting resin composition. 70 parts by mass or more is particularly preferable in order to improve the property, moisture resistance and solder crack resistance, and decrease the linear expansion coefficient, and 80 parts by mass or more is more effective in order to significantly increase these effects. Can be increased.
この様にして調整された熱硬化性樹脂組成物は、そのまま半導体封止材料として使用することができ、該組成物を注型、或いはトランスファー成形機、射出成形機などを用いて成形し、さらに50〜200℃で2〜10時間に加熱することにより成形物である半導体装置を得ることができる。 The thermosetting resin composition prepared in this manner can be used as a semiconductor sealing material as it is, and the composition is molded using a casting, transfer molding machine, injection molding machine, etc. A semiconductor device which is a molded product can be obtained by heating at 50 to 200 ° C. for 2 to 10 hours.
本発明の熱硬化性樹脂組成物をプリント回路基板用組成物に加工するには、例えばプリプレグ用樹脂組成物とすることができる。該熱硬化性樹脂組成物の粘度によっては無溶媒で用いることもできるが、有機溶剤を用いてワニス化することでプリプレグ用樹脂組成物とすることが好ましい。前記有機溶剤としては、メチルエチルケトン、アセトン、ジメチルホルムアミド等の沸点が160℃以下の極性溶剤を用いることが好ましく、単独でも2種以上の混合溶剤としても使用することができる。得られた該ワニスを、紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布などの各種補強基材に含浸し、用いた溶剤種に応じた加熱温度、好ましくは50〜170℃で加熱することによって、硬化物であるプリプレグを得ることができる。この時用いる樹脂組成物と補強基材の質量割合としては、特に限定されないが、通常、プリプレグ中の樹脂分が20〜60質量%となるように調製することが好ましい。また該熱硬化性樹脂組成物を用いて銅張り積層板を製造する場合は、上記のようにして得られたプリプレグを、常法により積層し、適宜銅箔を重ねて、1〜10MPaの加圧下に170〜250℃で10分〜3時間、加熱圧着させることにより、銅張り積層板を得ることができる。 In order to process the thermosetting resin composition of the present invention into a printed circuit board composition, for example, a prepreg resin composition can be used. Although it can be used without a solvent depending on the viscosity of the thermosetting resin composition, it is preferable to obtain a resin composition for prepreg by varnishing using an organic solvent. As the organic solvent, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more kinds. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this thermosetting resin composition, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and 1-10 MPa is added. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours under pressure.
本発明の熱硬化性樹脂組成物をレジストインキとして使用する場合には、例えば該熱硬化性樹脂組成物の硬化剤としてカチオン重合触媒を用い、更に、顔料、タルク、及びフィラーを加えてレジストインキ用組成物とした後、スクリーン印刷方式にてプリント基板上に塗布した後、レジストインキ硬化物とする方法が挙げられる。 When the thermosetting resin composition of the present invention is used as a resist ink, for example, a cationic polymerization catalyst is used as a curing agent for the thermosetting resin composition, and a pigment, talc, and filler are further added to form a resist ink. A method of forming a resist ink cured product after coating on a printed circuit board by a screen printing method after preparing the composition for use.
本発明の熱硬化性樹脂組成物を導電ペーストとして使用する場合には、例えば、微細導電性粒子を該熱硬化性樹脂組成物中に分散させ異方性導電膜用組成物とする方法、室温で液状である回路接続用ペースト樹脂組成物や異方性導電接着剤とする方法が挙げられる。 When using the thermosetting resin composition of the present invention as a conductive paste, for example, a method of dispersing fine conductive particles in the thermosetting resin composition to form a composition for an anisotropic conductive film, room temperature And a liquid paste resin composition for circuit connection and an anisotropic conductive adhesive.
本発明の熱硬化性樹脂組成物からビルドアップ基板用層間絶縁材料を得る方法としては例えば、ゴム、フィラーなどを適宜配合した当該硬化性樹脂組成物を、回路を形成した配線基板にスプレーコーティング法、カーテンコーティング法等を用いて塗布した後、硬化させる。その後、必要に応じて所定のスルーホール部等の穴あけを行った後、粗化剤により処理し、その表面を湯洗することによって、凹凸を形成させ、銅などの金属をめっき処理する。前記めっき方法としては、無電解めっき、電解めっき処理が好ましく、また前記粗化剤としては酸化剤、アルカリ、有機溶剤等が挙げられる。このような操作を所望に応じて順次繰り返し、樹脂絶縁層及び所定の回路パターンの導体層を交互にビルドアップして形成することにより、ビルドアップ基盤を得ることができる。但し、スルーホール部の穴あけは、最外層の樹脂絶縁層の形成後に行う。また、銅箔上で当該樹脂組成物を半硬化させた樹脂付き銅箔を、回路を形成した配線基板上に、170〜250℃で加熱圧着することで、粗化面を形成、メッキ処理の工程を省き、ビルドアップ基板を作製することも可能である。 As a method for obtaining an interlayer insulating material for a build-up substrate from the thermosetting resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler or the like is spray-coated on a wiring board on which a circuit is formed. After applying using a curtain coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.
本発明の硬化物を得る方法としては、一般的なエポキシ樹脂組成物の硬化方法に準拠すればよいが、例えば加熱温度条件は、組み合わせる硬化剤の種類や用途等によって、適宜選択すればよいが、上記方法によって得られた組成物を、20〜250℃程度の温度範囲で加熱すればよい。成形方法などもエポキシ樹脂組成物の一般的な方法が用いられ、特に本発明の熱硬化性樹脂組成物に特有の条件は不要である。 The method for obtaining the cured product of the present invention may be based on a general method for curing an epoxy resin composition. For example, the heating temperature condition may be appropriately selected depending on the type and use of the curing agent to be combined. What is necessary is just to heat the composition obtained by the said method in the temperature range about 20-250 degreeC. As the molding method and the like, a general method of the epoxy resin composition is used, and in particular, conditions specific to the thermosetting resin composition of the present invention are unnecessary.
従って、本発明では、ハロゲン系難燃剤を使用しなくても高度な難燃性が発現できる環境に安心なエポキシ樹脂材料を得ることができる。またその優れた誘電特性は、高周波デバイスの高速演算速度化を実現できる。また、前記フェノール樹脂(B)又はエポキシ樹脂(A)は、本発明の製造方法にて容易に効率よく製造する事が出来、目的とする前述の性能のレベルに応じた分子設計が可能となる。 Therefore, in the present invention, it is possible to obtain an epoxy resin material that is safe in an environment where high flame retardancy can be expressed without using a halogen-based flame retardant. In addition, its excellent dielectric characteristics can realize high-speed operation speed of high-frequency devices. In addition, the phenol resin (B) or the epoxy resin (A) can be easily and efficiently manufactured by the manufacturing method of the present invention, and a molecular design according to the target level of performance described above becomes possible. .
次に本発明を実施例、比較例により具体的に説明するが、以下において「部」及び「%」は特に断わりのない限り質量基準である。尚、融点測定、150℃における溶融粘度及びGPC測定、NMR、MSスペクトルは以下の条件にて測定した。
1)融点測定:下記の条件による示差走査熱量測定(DSC)により10℃/minで測定
(示差走査熱量測定(DSC))
以下の条件にて測定したDSC曲線における融解ピークの頂点を融点とした。
装置 ;メトラー・トレド株式会社製「DSC1」、
サンプル量;約5mg
温度条件 ;10℃/min
2)150℃における溶融粘度:ASTM D4287に準拠
3)GPC:
測定装置 :
東ソー株式会社製「HLC−8220 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL−L」
+東ソー株式会社製「TSK−GEL G2000HXL」
+東ソー株式会社製「TSK−GEL G2000HXL」
+東ソー株式会社製「TSK−GEL G3000HXL」
+東ソー株式会社製「TSK−GEL G4000HXL」
検出器: RI(示差屈折径)
データ処理:東ソー株式会社製「GPC−8020モデルIIバージョン4.10」
測定条件: カラム温度 40℃ 展開溶媒 テトラヒドロフラン 流速 1.0ml/分
標準 : 前記「GPC−8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。 (使用ポリスチレン)
東ソー株式会社製「A−500」
東ソー株式会社製「A−1000」
東ソー株式会社製「A−2500」
東ソー株式会社製「A−5000」
東ソー株式会社製「F−1」
東ソー株式会社製「F−2」
東ソー株式会社製「F−4」
東ソー株式会社製「F−10」
東ソー株式会社製「F−20」
東ソー株式会社製「F−40」
東ソー株式会社製「F−80」
東ソー株式会社製「F−128」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)。
4)NMR:日本電子株式会社製 NMR GSX270
5)MS :日本電子株式会社製 二重収束型質量分析装置 AX505H(FD505H)
Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. The melting point measurement, melt viscosity at 150 ° C., GPC measurement, NMR, and MS spectrum were measured under the following conditions.
1) Melting point measurement: measured at 10 ° C./min by differential scanning calorimetry (DSC) under the following conditions (differential scanning calorimetry (DSC))
The peak of the melting peak in the DSC curve measured under the following conditions was taken as the melting point.
Equipment: “DSC1” manufactured by METTLER TOLEDO CO., LTD.
Sample amount; about 5mg
Temperature condition: 10 ° C / min
2) Melt viscosity at 150 ° C .: according to ASTM D4287 3) GPC:
measuring device :
"HLC-8220 GPC" manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions:
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
4) NMR: NMR GSX270 manufactured by JEOL Ltd.
5) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.
実施例1 〔結晶性エポキシ樹脂(E−1)の合成〕
温度計、滴下ロート、冷却管、撹拌機を取り付けたフラスコに、窒素ガスパージを施しながら、2,4−ジヒドロキシベンゾフェノンを54g(水酸基0.5当量)、エピクロルヒドリン463g(5.0モル)、n−ブタノール139g、テトラエチルベンジルアンモニウムクロライド2gを仕込み溶解させた。65℃に昇温した後、共沸する圧力まで減圧して、49%水酸化ナトリウム水溶液90g(1.1モル)を5時間かけて滴下した。その後、同条件で0.5時間撹拌を続けた。この間、共沸によって留出してきた留出分をディーンスタークトラップで分離し、水層を除去し、油層を反応系内に戻しながら、反応を行った。その後、未反応のエピクロルヒドリンを減圧蒸留によって留去させた。それで得られた粗エポキシ樹脂にメチルイソブチルケトン590gとn−ブタノール177gとを加え溶解した。更にこの溶液に10%水酸化ナトリウム水溶液10gを添加して80℃で2時間反応させた後に洗浄液のPHが中性となるまで水150gで水洗を3回繰り返した。次いで共沸によって系内を脱水し、精密濾過を経た後に、溶媒を減圧下で留去し、淡黄色液状エポキシ樹脂74gを得た。得られた液状樹脂をナウター型混合機に投入し、そこに別途調製した2,4−ジヒドロキシベンゾフェノンのジグリシジルエーテルの結晶5gを入れて混合し、白色の結晶性エポキシ樹脂(E−1)を得た。得られたエポキシ樹脂の溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.07dPa・s、エポキシ当量は183g/eq.であった。
Example 1 [Synthesis of Crystalline Epoxy Resin (E-1)]
While a nitrogen gas purge was applied to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 54 g of 2,4-dihydroxybenzophenone (hydroxyl group 0.5 equivalent), 463 g of epichlorohydrin (5.0 mol), n- 139 g of butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 590 g of methyl isobutyl ketone and 177 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 74 g of a pale yellow liquid epoxy resin. The obtained liquid resin was put into a Nauter type mixer, and 5 g of diglycidyl ether crystal of 2,4-dihydroxybenzophenone prepared separately was added and mixed, and white crystalline epoxy resin (E-1) was mixed. Obtained. The resulting epoxy resin has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.07 dPa · s, and an epoxy equivalent of 183 g / eq. Met.
得られたエポキシ樹脂(E−1)のGPCチャートを図1に、C13 NMRチャートを図2に、MSスペクトルを図3、示差走査熱量測定(DSC)のチャートを図4に示す。
示差走査熱量測定(DSC)のチャートより融点は83℃、GPCチャートより下記構造式
The GPC chart of the obtained epoxy resin (E-1) is shown in FIG. 1, the C13 NMR chart is shown in FIG. 2, the MS spectrum is shown in FIG. 3, and the differential scanning calorimetry (DSC) chart is shown in FIG.
The melting point is 83 ° C from the differential scanning calorimetry (DSC) chart, and the following structural formula from the GPC chart
で表される化合物(以下、これを「化合物a」と略記する。)のピーク面積比が全体の80%であった。なお、図4中のaは融点を示す溶融ピークである。 The peak area ratio of the compound represented by (hereinafter abbreviated as “compound a”) was 80% of the total. In FIG. 4, a is a melting peak indicating the melting point.
実施例2〔結晶性エポキシ樹脂(E−2)の合成〕
実施例1で得た淡黄色液状エポキシ樹脂に、トルエンとメタノールを95:5の重量比で混合した溶剤を、重量パーセント濃度95%となるように加え、加熱溶解した。その樹脂溶液に、別途調製した2,4−ジヒドロキシベンゾフェノンのジグリシジルエーテルの微粉末結晶を入れて30℃で静置して樹脂の結晶化を行い、白色の結晶性エポキシ樹脂(E−2)を得た。得られたエポキシ樹脂の溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.05dPa・s、エポキシ当量は180g/eq.であった。
Example 2 [Synthesis of Crystalline Epoxy Resin (E-2)]
A solvent in which toluene and methanol were mixed at a weight ratio of 95: 5 was added to the light yellow liquid epoxy resin obtained in Example 1 so as to have a weight percent concentration of 95% and dissolved by heating. Into the resin solution, separately prepared fine powder crystals of 2,4-dihydroxybenzophenone diglycidyl ether and allowed to stand at 30 ° C. to crystallize the resin, white crystalline epoxy resin (E- 2 ) Got. The resulting epoxy resin has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.05 dPa · s and an epoxy equivalent of 180 g / eq. Met.
得られたエポキシ樹脂(E−2)のGPCチャートを図5、示差走査熱量測定(DSC)のチャートを図6に示す。示差走査熱量測定(DSC)のチャートより融点は89℃、GPCチャートより化合物aのピーク面積比が全体の85%であった。なお、図6中のbは融点を示す溶融ピークである。 The GPC chart of the obtained epoxy resin (E-2) is shown in FIG. 5, and the differential scanning calorimetry (DSC) chart is shown in FIG. The melting point was 89 ° C. from the differential scanning calorimetry (DSC) chart, and the peak area ratio of compound a was 85% from the GPC chart. Note that b in FIG. 6 is a melting peak indicating the melting point.
実施例3〔エポキシ樹脂(E−3)の合成〕
実施例1で得た淡黄色液状エポキシ樹脂に、トルエンとメタノールを95:5の重量比で混合した溶剤を、重量パーセント濃度90%となるように加え、加熱溶解した。その樹脂溶液に、別途調製した2,4−ジヒドロキシベンゾフェノンのジグリシジルエーテルの微粉末結晶を入れて30℃で静置して樹脂の結晶化を行い、白色の結晶性エポキシ樹脂(E−3)を得た。得られたエポキシ樹脂の溶融粘度(測定法:ICI粘度計法、測定温度:150℃)は0.04dPa・s、エポキシ当量は173g/eq.であった。
得られたエポキシ樹脂(E−3)のGPCチャートを図7、示差走査熱量測定(DSC)のチャートを図8に示す。示差走査熱量測定(DSC)のチャートより融点は93℃、GPCチャートより、化合物aのピーク面積比が全体の92%であった。なお、図4中のcは融点を示す溶融ピークである。
Example 3 [Synthesis of Epoxy Resin (E-3)]
To the light yellow liquid epoxy resin obtained in Example 1, a solvent prepared by mixing toluene and methanol at a weight ratio of 95: 5 was added so as to have a weight percent concentration of 90% and dissolved by heating. Into the resin solution, separately prepared fine powder crystals of diglycidyl ether of 2,4-dihydroxybenzophenone were allowed to stand at 30 ° C. to crystallize the resin, and a white crystalline epoxy resin (E-3) Got. The resulting epoxy resin has a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 0.04 dPa · s, and an epoxy equivalent of 173 g / eq. Met.
The GPC chart of the obtained epoxy resin (E-3) is shown in FIG. 7, and the differential scanning calorimetry (DSC) chart is shown in FIG. The melting point was 93 ° C. from the differential scanning calorimetry (DSC) chart, and the peak area ratio of compound a was 92% from the GPC chart. In FIG. 4, c is a melting peak indicating the melting point.
比較例1〔エポキシ樹脂(E−4)の合成:特許文献3記載のエポキシ樹脂〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、2,4−ジヒドロキシベンゾフェノンを240.8g(1.125モル)、エピクロルヒドリン1041g(11.25モル)を仕込み115℃まで加熱昇温した。これに、50%水酸化ナトリウム水溶液183g(2.29モル)を1.5時間かけて滴下した。滴下中、反応温度は100℃以上に保ち、共沸されてくるエピクロルヒドリンはディーンスターク水分離器を通じて系内に戻し、水は系外へ除去した。苛性ソーダ水溶液の滴下終了後、水の留出がなくなった時点を反応の終点とした。反応終了後、過剰のエピクロルヒドリンを減圧留去した。アセトン1200mLを加え、15分間還流して樹脂を溶解させた。樹脂溶液中で析出した副生無機塩等を濾別し、濾液よりアセトンを減圧留去することにより淡黄色液状のエポキシげん樹脂(E−4)を得た。得られたエポキシ樹脂の粘度(測定法:ICI粘度計法、測定温度:50℃)は40dPa・s、エポキシ当量は180g/eq.であった。GPCチャートより、化合物aのピーク面積比が全体の74%であった。
Comparative Example 1 [Synthesis of Epoxy Resin (E-4): Epoxy Resin described in Patent Document 3 ]
240.8 g (1.125 mol) of 2,4-dihydroxybenzophenone and 1041 g of epichlorohydrin were added to a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer while performing a nitrogen gas purge. .25 mol) was added and heated to 115 ° C. To this, 183 g (2.29 mol) of 50% aqueous sodium hydroxide solution was added dropwise over 1.5 hours. During the dropping, the reaction temperature was kept at 100 ° C. or higher, and the azeotropic epichlorohydrin was returned to the system through a Dean-Stark water separator, and water was removed out of the system. The end point of the reaction was defined as the point at which the distillation of water ceased after completion of the dropwise addition of the aqueous sodium hydroxide solution. After completion of the reaction, excess epichlorohydrin was distilled off under reduced pressure. Acetone 1200 mL was added and refluxed for 15 minutes to dissolve the resin. By-product inorganic salts precipitated in the resin solution were filtered off, and acetone was distilled off from the filtrate under reduced pressure to obtain a light yellow liquid epoxy resin (E-4). The resulting epoxy resin had a viscosity (measurement method: ICI viscometer method, measurement temperature: 50 ° C.) of 40 dPa · s and an epoxy equivalent of 180 g / eq. Met. From the GPC chart, the peak area ratio of Compound a was 74% of the total.
比較例2〔エポキシ樹脂(E−5)の合成:特許文献2記載のエポキシ樹脂〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、窒素ガスパージを施しながら、2,4−ジヒドロキシベンゾフェノンを214g(1モル)、エピクロルヒドリン1110g(12モル)を仕込み、滴下装置中に48%水酸化ナトリウム水溶液(2モル)を2時間かけて滴下した。滴下中は反応温度70℃、100Torrで還流させ、共沸されてくるエピクロルヒドリンはディーンスターク水分離器を通じて系内に戻し、水は系外へ除去した。滴下終了後、さらに2時間反応させた後、脱エピクロルヒドリン、水洗、脱溶剤及びろ過を行い、液状のエポキシ樹脂(E−5)を得た。得られたエポキシ樹脂の粘度(測定法:ICI粘度計法、測定温度:50℃)は50dPa・s、エポキシ当量は185g/eq.であった。GPCチャートより、化合物aのピーク面積比が全体の75%であった。
比較例3〔エポキシ樹脂(E−6)の合成〕
エポキシ化反応は、実施例1において2,4−ジヒドロキシベンゾフェノン54g(水酸基0.5当量)を、2,4−ジヒドロキシベンゾフェノン107g(水酸基1当量)に変更した以外は実施例1と同様にして行い、結晶化は行わなかった。得られた淡黄色液状エポキシ樹脂(E−6)のエポキシ当量は199g/eq.であった。GPCチャートより、化合物aのピーク面積比が全体の67%であった。
Comparative Example 2 [Synthesis of Epoxy Resin (E-5): Epoxy Resin described in Patent Document 2]
A flask equipped with a thermometer, cooling tube, fractionating tube, nitrogen gas inlet tube, and stirrer was charged with 214 g (1 mol) of 2,4-dihydroxybenzophenone and 1110 g (12 mol) of epichlorohydrin while purging with nitrogen gas. A 48% aqueous sodium hydroxide solution (2 mol) was dropped into the dropping apparatus over 2 hours. During the dropping, the mixture was refluxed at a reaction temperature of 70 ° C. and 100 Torr. Epichlorohydrin azeotroped was returned to the system through a Dean-Stark water separator, and water was removed out of the system. After completion of the dropwise addition, the reaction was further continued for 2 hours, followed by deepichlorohydrin, water washing, solvent removal and filtration to obtain a liquid epoxy resin (E-5). The resulting epoxy resin had a viscosity (measurement method: ICI viscometer method, measurement temperature: 50 ° C.) of 50 dPa · s, and an epoxy equivalent of 185 g / eq. Met. From the GPC chart, the peak area ratio of Compound a was 75% of the whole.
Comparative Example 3 [Synthesis of Epoxy Resin (E-6)]
The epoxidation reaction was performed in the same manner as in Example 1 except that 54 g of 2,4-dihydroxybenzophenone (0.5 equivalent of hydroxyl group) in Example 1 was changed to 107 g of 2,4-dihydroxybenzophenone (1 equivalent of hydroxyl group). No crystallization was performed. The obtained light yellow liquid epoxy resin (E-6) has an epoxy equivalent of 199 g / eq. Met. From the GPC chart, the peak area ratio of Compound a was 67% of the whole.
実施例4〜6及び比較例4〜7
エポキシ樹脂として上記(E−1)〜(E−6)、及び三菱化学株式会社製「YX−4000H」(ビフェニル型エポキシ樹脂、エポキシ当量:195g/eq.)、フェノール樹脂として三井化学株式会社製XLC−3L(フェノールアラルキル樹脂、水酸基当量:172g/eq.)、硬化促進剤としてトリフェニルホスフィン(TPP)、無機充填材として球状シリカ(電気化学株式会社製FB−560)、シランカップリング剤としてγ−グリシドキシトリエトキシキシシラン(信越化学工業株式会社製「KBM−403」)、カルナウバワックス(株式会社セラリカ野田製「PEARL WAX No.1−P」)、カーボンブラックを用いて表1に示した組成(表中の配合比率は質量基準)で配合し、2本ロールを用いて90℃の温度で5分間溶融混練して目的の組成物を作成した。得られた組成物を粉砕したものを、トランスファー成形機にて、圧力70kg/cm2、カラム速度5cm/秒、温度175℃、時間180秒でφ50mm×3(t)mmの円板状に成形したもの、または幅12.7mm、長さ127mm、厚み1.6mmの長方形に成形したものを180℃で5時間さらに硬化せしめた。硬化物の物性は、前記トランスファー成形により得られた硬化物を用い下記の方法で試験片を作成し、耐熱性、線膨張係数、吸湿率、耐湿耐ハンダ性、難燃性を下記の方法で測定し結果を表1に示した。
<流動性>
半導体封止材用樹脂組成物を試験用金型に注入し、175℃、70kg/cm2、120秒の条件でスパイラルフロー値を測定した。
<硬化性>
エポキシ樹脂組成物0.15gを175℃に加熱したキュアプレート(THERMO ELECTRIC社製)上に載せ、ストップウォッチで計時を開始する。棒の先端にて試料を均一に攪拌し、糸状に試料が切れてプレートに残るようになった時、ストップウォッチを止める。この試料が切れてプレートに残るようになるまでの時間をゲルタイムとした。
<耐熱性>
ガラス転移温度:粘弾性測定装置(レオメトリック社製 固体粘弾性測定装置RSAII、二重カレンチレバー法;周波数1Hz、昇温速度3℃/min)を用いて測定した。
<線膨張係数>
硬化物を幅約5mm長さ約5mmの試験片とし、熱機械分析装置(TMA:セイコーインスツルメント社製SS−6100)を用いて、圧縮モードで熱機械分析を行った。(測定架重:30mN、昇温速度:3℃/分で2回、測定温度範囲:−50℃から250℃)2回目の測定における、50℃における線膨張係数を評価した。
<吸湿率>
前記φ50mm×3(t)mmの円板状の試験片を用い85℃/85%RHの恒温恒湿装置中で300時間処理した前後の重量変化(wt%)を吸湿率として測定した。
<耐湿耐半田性>
前記φ50mm×3(t)mmの円板状の試験片を用い85℃/85%RHの雰囲気下168時間放置し、吸湿処理を行った後、これを260℃のハンダ浴に10秒間浸漬させた際、クラックの発生の有無を調べた。
<難燃性>
幅12.7mm、長さ127mm、厚み1.6mmの評価用試験片を用いUL−94試験法に準拠し、厚さ1.6mmの試験片5本を用いて、燃焼試験を行った。
*1:試験片5本の合計燃焼時間(秒)
*2:1回の接炎における最大燃焼時間(秒)
Examples 4-6 and Comparative Examples 4-7
The above (E-1) to (E-6) as an epoxy resin, and “YX-4000H” (biphenyl type epoxy resin, epoxy equivalent: 195 g / eq.) Manufactured by Mitsubishi Chemical Corporation, and Mitsui Chemicals, Inc. as a phenol resin. XLC-3L (phenol aralkyl resin, hydroxyl equivalent: 172 g / eq.), Triphenylphosphine (TPP) as a curing accelerator, spherical silica (FB-560 manufactured by Electrochemical Co., Ltd.) as an inorganic filler, and silane coupling agent Table 1 using γ-glycidoxytriethoxyxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (“PEARL WAX No. 1-P” manufactured by Celerica Noda Co., Ltd.), and carbon black Blended with the indicated composition (the blending ratio in the table is based on mass) and heated at 90 ° C. using two rolls. The desired composition was prepared by melt-kneading for 5 minutes. The obtained composition was pulverized and formed into a disk shape of φ50 mm × 3 (t) mm with a transfer molding machine at a pressure of 70 kg / cm 2 , a column speed of 5 cm / sec, a temperature of 175 ° C., and a time of 180 seconds. The one formed into a rectangle having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm was further cured at 180 ° C. for 5 hours. For the physical properties of the cured product, a test piece was prepared by the following method using the cured product obtained by the transfer molding, and the heat resistance, linear expansion coefficient, moisture absorption rate, moisture resistance solder resistance, and flame resistance were determined by the following method. The measurement results are shown in Table 1.
<Fluidity>
The resin composition for a semiconductor sealing material was poured into a test mold, and the spiral flow value was measured under the conditions of 175 ° C., 70 kg / cm 2 , and 120 seconds.
<Curing property>
0.15 g of the epoxy resin composition is placed on a cure plate (made by THERMO ELECTRIC) heated to 175 ° C., and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.
<Heat resistance>
Glass transition temperature: measured using a viscoelasticity measuring device (solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Ltd., double currant lever method;
<Linear expansion coefficient>
The cured product was used as a test piece having a width of about 5 mm and a length of about 5 mm, and thermomechanical analysis was performed in a compression mode using a thermomechanical analyzer (TMA: SS-6100 manufactured by Seiko Instruments Inc.). (Measurement weight: 30 mN, temperature increase rate: twice at 3 ° C./min, measurement temperature range: −50 ° C. to 250 ° C.) The linear expansion coefficient at 50 ° C. in the second measurement was evaluated.
<Hygroscopic rate>
The weight change (wt%) before and after being treated for 300 hours in a constant temperature and humidity apparatus at 85 ° C./85% RH using the disk-shaped test piece of φ50 mm × 3 (t) mm was measured as the moisture absorption rate.
<Moisture resistance and solder resistance>
The disk-shaped test piece of φ50 mm × 3 (t) mm was left standing in an atmosphere of 85 ° C./85% 168 hours for 168 hours to absorb moisture, and then immersed in a 260 ° C. solder bath for 10 seconds. The presence or absence of cracks was examined.
<Flame retardance>
Using a test piece for evaluation having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm, a combustion test was performed using five test pieces having a thickness of 1.6 mm in accordance with the UL-94 test method.
* 1: Total burning time of 5 specimens (seconds)
* 2: Maximum burning time (seconds) in one flame contact
a・・・融点を示す溶融ピーク。
b・・・融点を示す溶融ピーク。
c・・・融点を示す溶融ピーク。
a: Melting peak indicating melting point.
b: Melting peak indicating melting point.
c: Melting peak indicating melting point.
Claims (11)
で表される化合物を、GPC測定における面積比率で70%以上となる割合で含有し、かつ、示差走査熱量測定(DSC)にて毎分10℃の速度で昇温した際の融点が70℃以上98℃以下の範囲にあることを特徴とする結晶性エポキシ樹脂。 The following structural formula (1)
A compound represented by in, in a proportion to be 70% or more by area ratio in GPC measurement, and a melting point of 70 ° C. when the temperature was raised at a rate of 10 ° C. by a differential scanning calorimetry (DSC) A crystalline epoxy resin having a temperature range of 98 ° C. or lower .
である請求項1記載の結晶性エポキシ樹脂。The crystalline epoxy resin according to claim 1.
で表される化合物とエピハロヒドリンとを反応させる工程と、
溶剤を用いた再結晶、薄膜蒸留又は種結晶添加との混練の何れかの工程
を必須とする結晶性エポキシ樹脂の製造方法。 The following structural formula (1 ')
A step of reacting a compound represented by: and an epihalohydrin ;
Any process of recrystallization using solvent, thin-film distillation or kneading with seed crystal addition
Is a method for producing a crystalline epoxy resin .
で表される化合物を、GPC測定における面積比率で70%以上となる割合で含有し、かつ、示差走査熱量測定(DSC)にて毎分10℃の速度で昇温した際の融点が70℃以上98℃以下の範囲にある結晶性エポキシ樹脂(a)を用いることを特徴とする熱硬化性樹脂組成物。 A curable resin composition containing an epoxy resin (A) and a curing agent (B) as essential components, the epoxy resin (A) having the following structural formula (1)
A compound represented by in, in a proportion to be 70% or more by area ratio in GPC measurement, and a melting point of 70 ° C. when the temperature was raised at a rate of 10 ° C. by a differential scanning calorimetry (DSC) A thermosetting resin composition characterized by using a crystalline epoxy resin (a) in a range of 98 ° C. or lower .
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