JPH07216052A - Epoxy resin and epoxy resin composition - Google Patents
Epoxy resin and epoxy resin compositionInfo
- Publication number
- JPH07216052A JPH07216052A JP2362294A JP2362294A JPH07216052A JP H07216052 A JPH07216052 A JP H07216052A JP 2362294 A JP2362294 A JP 2362294A JP 2362294 A JP2362294 A JP 2362294A JP H07216052 A JPH07216052 A JP H07216052A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- naphthol
- polyhydroxynaphthalene
- compound
- melting point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 82
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 46
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 21
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 38
- 238000009833 condensation Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 abstract description 35
- 230000008018 melting Effects 0.000 abstract description 35
- 239000004593 Epoxy Substances 0.000 abstract description 13
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 230000009477 glass transition Effects 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 238000005476 soldering Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 229950011260 betanaphthol Drugs 0.000 abstract 1
- 125000001624 naphthyl group Chemical group 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- -1 aldehyde compound Chemical class 0.000 description 14
- 239000000155 melt Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 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 4
- 238000005406 washing Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 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 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 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 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000009835 boiling Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- AXORVIZLPOGIRG-UHFFFAOYSA-N β-methylphenethylamine Chemical compound NCC(C)C1=CC=CC=C1 AXORVIZLPOGIRG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、特定のポリヒドロキシ
ナフタレン系化合物をベースとした作業性能に優れたエ
ポキシ樹脂、およびこのエポキシ樹脂と硬化剤を必須成
分とするエポキシ樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin based on a specific polyhydroxynaphthalene compound and having excellent workability, and an epoxy resin composition containing the epoxy resin and a curing agent as essential components.
【０００２】[0002]
【従来の技術】従来、半導体素子を外部環境から保護す
るため、エポキシ樹脂組成物で封止する方法が広く採用
されている。前記組成物は、通常、エポキシ樹脂，硬化
剤，硬化促進剤，充填剤，及びその他の添加剤で構成さ
れている。前記エポキシ樹脂としては、フェノール類と
ホルムアルデヒドとの反応により得られたノボラック樹
脂をエポキシ化した樹脂、特にオルトクレゾールノボラ
ックエポキシ樹脂が広く用いられ、硬化剤としては、フ
ェノールホルムアルデヒドノボラック樹脂が採用されて
いる。また、高性能なエポキシ樹脂としてα−ナフトー
ルとホルマリン水とを酸触媒を用いて反応させたノボラ
ック樹脂をベースとしたエポキシ樹脂が紹介されている
が、耐熱性，耐湿性等の性能は満足できるものの、融点
と溶融粘度が高く、成型等の作業性に劣るため実用化さ
れていないのが現状である。2. Description of the Related Art Conventionally, a method of encapsulating with a epoxy resin composition has been widely adopted in order to protect a semiconductor element from the external environment. The composition is usually composed of an epoxy resin, a curing agent, a curing accelerator, a filler, and other additives. As the epoxy resin, a resin obtained by epoxidizing a novolak resin obtained by the reaction of phenols and formaldehyde, particularly an orthocresol novolac epoxy resin is widely used, and a phenol-formaldehyde novolac resin is used as a curing agent. . Also, as a high-performance epoxy resin, an epoxy resin based on a novolac resin obtained by reacting α-naphthol with formalin water using an acid catalyst is introduced, but the performance such as heat resistance and moisture resistance is satisfactory. However, it has not been put to practical use because of its high melting point and melt viscosity and poor workability in molding and the like.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、融点
と溶融粘度が低いため作業性に優れ、かつ硬化剤との硬
化後に高いガラス転移温度，耐熱性及び耐湿性を有し、
パッケージにクラックが発生するのを防止できる硬化物
を与える特定のポリヒドロキシナフタレン系化合物をベ
ースとした多官能性エポキシ樹脂を提供することにあ
る。The object of the present invention is to have excellent workability due to its low melting point and melt viscosity, and to have a high glass transition temperature, heat resistance and humidity resistance after curing with a curing agent.
It is an object of the present invention to provide a polyfunctional epoxy resin based on a specific polyhydroxynaphthalene-based compound, which gives a cured product capable of preventing the package from cracking.
【０００４】本発明の他の目的は、ガラス転移温度が高
く耐熱性及び耐湿性に優れ、パッケージにクラックが発
生するのを防止できる半導体封止用材料として有用なエ
ポキシ樹脂組成物を提供することにある。Another object of the present invention is to provide an epoxy resin composition which has a high glass transition temperature, is excellent in heat resistance and moisture resistance, and is useful as a semiconductor encapsulating material capable of preventing cracks from being generated in a package. It is in.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記目的
を達成するため鋭意検討の結果、エポキシ樹脂のベース
となるポリヒドロキシナフタレン化合物において、
（１）β−ナフトール単独ではアルデヒド化合物との反
応が円滑に進行しないものの、α−ナフトールとβ−ナ
フトールとを併用し、更にパラホルムアルデヒドにより
共縮合反応が円滑に進行すること、（２）得られた共縮
合物において、ナフタレン核体数４以上のものの含有量
を特定量以下とすることによって融点と溶融粘度を低く
できることを見い出し、このことにより、（３）この特
定のポリヒドロキシナフタレン系化合物とエピハロヒド
リンを反応したエポキシ樹脂は融点と溶融粘度が低く、
それによって作業性が優れ、硬化後は高いガラス転移温
度を示し、耐熱性及び耐湿性に優れていることを見いだ
し本発明を完成した。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that in a polyhydroxynaphthalene compound which is a base of an epoxy resin,
(1) β-naphthol alone does not smoothly react with an aldehyde compound, but α-naphthol and β-naphthol are used in combination, and a co-condensation reaction smoothly proceeds with paraformaldehyde, (2) obtained In the obtained cocondensate, it was found that the melting point and the melt viscosity can be lowered by controlling the content of the naphthalene nuclide having a number of 4 or more to a specific amount or less, and as a result, (3) this specific polyhydroxynaphthalene compound The epoxy resin that reacted with epihalohydrin has a low melting point and melt viscosity,
As a result, they have found that they have excellent workability, exhibit a high glass transition temperature after curing, and have excellent heat resistance and moisture resistance, and completed the present invention.
【０００６】すなわち、本発明はα−ナフトールとβ−
ナフトールとパラホルムアルデヒドとの共縮合により得
られるポリヒドロキシナフタレン系化合物において、ナ
フタレン核体数が４以上の共縮合物の含有量が５０重量
％以下であるポリヒドロキシナフタレン系化合物とエピ
ハロヒドリンとから製造された多官能性エポキシ樹脂を
提供する。That is, the present invention is based on α-naphthol and β-naphthol.
A polyhydroxynaphthalene compound obtained by cocondensation of naphthol and paraformaldehyde, which is produced from a polyhydroxynaphthalene compound having a naphthalene nucleus number of 4 or more in a content of 50% by weight or less and epihalohydrin Provided are multifunctional epoxy resins.
【０００７】更に、前記ポリヒドロキシナフタレン系化
合物において、ナフタレン核体数が４以上の共縮合物の
含有量が３０重量％以下であるポリヒドロキシナフタレ
ン系化合物とエピハロヒドリンとから製造された多官能
性エポキシ樹脂を提供する。Further, in the above polyhydroxynaphthalene compound, a polyfunctional epoxy prepared from an epihalohydrin and a polyhydroxynaphthalene compound having a content of a cocondensate of 4 or more naphthalene nuclei of 30% by weight or less. Provide resin.
【０００８】更に本発明は、前記ポリヒドロキシナフタ
レン系化合物をベースとしたエポキシ樹脂と硬化剤とを
含むエポキシ樹脂組成物を提供する。The present invention further provides an epoxy resin composition containing an epoxy resin based on the polyhydroxynaphthalene compound and a curing agent.
【０００９】ポリヒドロキシナフタレン系化合物をベー
スとしたエポキシ樹脂を含む本発明のエポキシ樹脂組成
物は、硬化促進剤を含むのが好ましく、その場合には半
導体封止用組成物として特に有効である。The epoxy resin composition of the present invention containing an epoxy resin based on a polyhydroxynaphthalene compound preferably contains a curing accelerator, and in that case, it is particularly effective as a semiconductor encapsulating composition.
【００１０】なお、本明細書において、「エポキシ樹
脂」とは、特に断りがない限り、樹脂状のエポキシ化合
物のみならず低分子量のエポキシ化合物も含む意味に用
いる。In the present specification, the term "epoxy resin" is used to mean not only a resinous epoxy compound but also a low molecular weight epoxy compound unless otherwise specified.
【００１１】（手段を構成する要件）ポリヒドロキシナ
フタレン系化合物をベースとした作業性能に優れたエポ
キシ樹脂を得るための要件の１つは、ベースのポリヒド
ロキシナフタレン系化合物が、α−ナフトールとβ−ナ
フトールとパラホルムアルデヒドとの共縮合物である点
に存する。α−ナフトールは通常用いられるホルマリン
水（３０〜４０％水溶液）と反応させても円滑に反応が
進行しない。これは本反応が脱水反応であるためホルマ
リン水中の水が反応を阻害するためである。このためホ
ルマリン水を多量に入れるか、酸触媒を用いて反応する
ことになるが、これでは多核体が多くなり、このため分
子量が大きくなり、これをベースとしたエポキシ樹脂は
低融点，低粘度の作業性の優れた目的物とはならない。
一方β−ナフトールはアルデヒド化合物と反応させても
２量体で反応が停止し、縮合反応が進行せず、樹脂状化
合物が得られない。しかし、α−ナフトールの存在下、
β−ナフトールをパラホルムアルデヒドと反応させる
と、共縮合反応が円滑に進行し、目的のポリヒドロキシ
ナフタレン系化合物が生成する。(Requirements Constituting Means) One of the requirements for obtaining an epoxy resin having excellent workability based on a polyhydroxynaphthalene compound is that the base polyhydroxynaphthalene compound is α-naphthol and β. -It is a co-condensation product of naphthol and paraformaldehyde. The reaction of α-naphthol does not proceed smoothly even when it is reacted with normally used formalin water (30 to 40% aqueous solution). This is because this reaction is a dehydration reaction and water in formalin water inhibits the reaction. For this reason, a large amount of formalin water is added or the reaction is carried out using an acid catalyst, but this results in a large number of polynuclear bodies, which results in a large molecular weight, and the epoxy resin based on this has a low melting point and low viscosity. It is not an object with excellent workability.
On the other hand, when β-naphthol is reacted with an aldehyde compound, the reaction stops as a dimer, the condensation reaction does not proceed, and a resinous compound cannot be obtained. However, in the presence of α-naphthol,
When β-naphthol is reacted with paraformaldehyde, the cocondensation reaction proceeds smoothly and the target polyhydroxynaphthalene compound is produced.
【００１２】要件の２つ目は、ナフタレン核体数４以上
の共縮合物の含有量の限定であり、それを５０重量％以
下とすることである。本発明者はナフタレン核体数が４
以上の共縮合物の含有量に着目し、それと融点及び１５
０℃での溶融粘度との関係を調べた。その結果を図１に
示す。好ましい作業性能を有するエポキシ樹脂を得るた
めの、ポリヒドロキシナフタレン系化合物の物性である
融点が１２０℃以下、１５０℃での溶融粘度が２０ポイ
ズ以下とするためには、図１よりナフタレン核体数が４
以上の共縮合物の含有量を５０重量％以下とすればよい
ことが判明した。更にナフタレン核体数が４以上の共縮
合物の含有量を３０重量％以下とすれば、融点が１００
℃以下で１５０℃での溶融粘度が１０ポイズ以下になり
作業性能が更に良いエポキシ樹脂が得られる。The second requirement is the limitation of the content of the cocondensate having 4 or more naphthalene nuclides, which is 50% by weight or less. The present inventor has 4 naphthalene nuclides.
Focusing on the content of the above co-condensate, its melting point and 15
The relationship with the melt viscosity at 0 ° C was investigated. The result is shown in FIG. In order to obtain a polyhydroxynaphthalene-based compound having a melting point of 120 ° C. or lower and a melt viscosity at 150 ° C. of 20 poise or lower, which is a physical property for obtaining an epoxy resin having favorable workability, the number of naphthalene nuclides is determined from FIG. Is 4
It was found that the content of the above cocondensate should be 50% by weight or less. Further, when the content of the cocondensate having 4 or more naphthalene nuclei is 30% by weight or less, the melting point is 100.
The melt viscosity at 150 ° C below 10 ° C is 10 poise or less, and an epoxy resin having better workability can be obtained.
【００１３】又図１より、ナフタレン核体数が４以上の
縮合物の含有量が５０重量％を越えると、急激に融点と
溶融粘度が上がり、これをベースとしたエポキシ樹脂と
これを組成としたエポキシ樹脂組成物の融点と溶融粘度
が高くなり、精密な成形が実施できなくなり、作業性能
がきわめて悪くなることが判明した。Further, from FIG. 1, when the content of the condensate having 4 or more naphthalene nuclei exceeds 50% by weight, the melting point and the melt viscosity rapidly increase, and the epoxy resin based on this and the composition thereof are It was found that the melting point and melt viscosity of the above epoxy resin composition became high, precision molding could not be carried out, and the work performance was extremely deteriorated.
【００１４】目的とするポリヒドロキシナフタレン系化
合物を得るためのパラホルムアルデヒドの仕込量は、α
−ナフトールとβ−ナフトールの合計１モルに対して
０．５０〜０．８０モルの範囲である。パラホルムアル
デヒドの仕込量が、０．５０モル未満の場合は、未反応
ナフトールを多く含み、これをベースとしたエポキシ樹
脂を用いた硬化物の耐熱性が低下し、又０．８０モルを
こえるとナフタレン核体数４以上の共縮合物の含有量が
増え、融点が１２０℃をこえ、かつ１５０℃での溶融粘
度が２０ポイズをこえるようになり、これをベースとし
たエポキシ樹脂の作業性能が悪くなり、成型性に問題が
生じる。更に融点を１００℃以下、１５０℃での溶融粘
度を１０ポイズ以下とするには０．５５〜０．７０モル
とすればよい。The amount of paraformaldehyde charged to obtain the desired polyhydroxynaphthalene compound is α
-It is in the range of 0.50 to 0.80 mol per 1 mol of the total of naphthol and β-naphthol. When the charged amount of paraformaldehyde is less than 0.50 mol, the heat resistance of a cured product containing a large amount of unreacted naphthol and using an epoxy resin based on this decreases, and when it exceeds 0.80 mol. The content of the co-condensate containing 4 or more naphthalene nuclides increased, the melting point exceeded 120 ° C, and the melt viscosity at 150 ° C exceeded 20 poises. It deteriorates and causes problems in moldability. Further, in order to set the melting point to 100 ° C. or lower and the melt viscosity at 150 ° C. to 10 poise or lower, the amount may be 0.55 to 0.70 mol.
【００１５】前記エポキシ樹脂のベースのポリヒドロキ
シナフタレン系化合物を得るための縮合反応はナフタレ
ン核体数のコントロールを容易とするため、通常用いら
れる酸触媒や塩基性触媒を使わずに行い、α−ナフトー
ルとβ−ナフトーとパラホルムアルデヒドを高温に加熱
するだけの共縮合反応が行われる。この場合の反応温度
は、８０℃〜１５０℃が適し、特に８０℃〜１３０℃が
好ましい。反応は通常２〜１０時間程度で終了する。In order to easily control the number of naphthalene nuclides, the condensation reaction for obtaining the epoxy resin-based polyhydroxynaphthalene compound is carried out without using an acid catalyst or a basic catalyst which is usually used. A co-condensation reaction is carried out by simply heating naphthol, β-naphtho and paraformaldehyde to a high temperature. In this case, the reaction temperature is preferably 80 ° C to 150 ° C, particularly preferably 80 ° C to 130 ° C. The reaction is usually completed in about 2 to 10 hours.
【００１６】又反応の際の溶剤は用いずにも行えるが、
沸点が８０℃以上でかつ、水への溶解性の小さいトルエ
ン，キシレン，メチルイソブチルケトン等の溶剤を使用
するのが好ましい。The reaction can be carried out without using a solvent,
It is preferable to use a solvent such as toluene, xylene, or methyl isobutyl ketone, which has a boiling point of 80 ° C. or higher and has low solubility in water.
【００１７】なお反応終了後、必要により、不純物を水
洗などにより除去したり、溶剤洗浄や減圧脱気などの方
法で未反応モノマーを除去してもよい。After the reaction, if necessary, impurities may be removed by washing with water, or unreacted monomers may be removed by a method such as solvent washing or degassing under reduced pressure.
【００１８】このようにして得られたポリヒドロキシナ
フタレン系化合物のナフタレン核体数及びその含有量の
測定はゲルパーミエーションクロマトグラフィー（ＧＰ
Ｃ法）により行い、測定条件は下記に示すとおりであ
り、核体数の確定は、分子量既知のポリスチレンにより
行った。The number of naphthalene nuclei in the polyhydroxynaphthalene compound thus obtained and the content thereof are measured by gel permeation chromatography (GP).
Method C), the measurement conditions are as shown below, and the number of nuclides was determined by polystyrene having a known molecular weight.
【００１９】 溶媒：テトラヒドロフラン、流量：０．８ｍｌ／ｍｉｎ カラム：東ソー（株）製 Ｇ４０００Ｈ、Ｇ３０００
Ｈ、Ｇ２０００Ｈ（直列）であって、排除限界分子量が
それぞれ４０００００、６００００、１００００であ
る。 担体：スチレンジビニルベンゼン共重合体Solvent: Tetrahydrofuran, Flow rate: 0.8 ml / min Column: Tosoh Corp. G4000H, G3000
H and G2000H (series), and the exclusion limit molecular weights are 400000, 60000 and 10000, respectively. Carrier: Styrene divinylbenzene copolymer
【００２０】本発明のポリヒドロキシナフタレン系化合
物をベースにした多官能性エポキシ樹脂は、前記のα−
ナフトールとβ−ナフトーとパラホルムアルデヒドとの
共縮合物で４核体以上の共縮合物の含有量を限定したポ
リヒドロキシナフタレン系化合物とエピハロヒドリンを
反応させることにより得られるが、通常、反応は次の代
表的な二つの方法が利用できる。The polyfunctional epoxy resin based on the polyhydroxynaphthalene-based compound of the present invention comprises the above-mentioned α-
It can be obtained by reacting epihalohydrin with a polyhydroxynaphthalene-based compound in which the content of a tetranuclear or higher cocondensate of naphthol, β-naphtho, and paraformaldehyde is limited, and the reaction is usually as follows. Two typical methods are available.
【００２１】１）ポリヒドロキシナフタレン系化合物と
過剰のエピハロヒドリンとをアルカリ金属水酸化物の存
在下で付加反応とエポキシ環を形成する閉環反応を同時
に行なわせる一段法。1) A one-step method in which a polyhydroxynaphthalene compound and an excess of epihalohydrin are simultaneously subjected to an addition reaction in the presence of an alkali metal hydroxide and a ring-closing reaction to form an epoxy ring.
【００２２】２）ポリヒドロキシナフタレン系化合物と
過剰のエピハロヒドリンとを塩基性触媒の存在下で付加
反応させ、次いでアルカリ金属水酸化物を添加して閉環
反応させる二段法。2) A two-step method in which a polyhydroxynaphthalene compound and an excess of epihalohydrin are subjected to an addition reaction in the presence of a basic catalyst, and then an alkali metal hydroxide is added to carry out a ring-closing reaction.
【００２３】この反応におけるエピハロヒドリンとは、
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，β−メチルエピブロモヒドリン，
β−メチルエピヨードヒドリンなどがあげられるが、エ
ピクロルヒドリンが好ましい。Epihalohydrin in this reaction is
Epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, β-methylepibromohydrin,
Examples thereof include β-methylepiodohydrin, and epichlorohydrin is preferable.
【００２４】また、この反応におけるアルカリ金属水酸
化物としては、カセイソーダ，カセイカリが使用され、
これらは固体のままか、水溶液好ましくは４０〜５０％
水溶液で反応系に添加される。As the alkali metal hydroxide in this reaction, caustic soda and caustic potash are used.
These remain solid or aqueous solutions, preferably 40-50%
It is added to the reaction system as an aqueous solution.
【００２５】また、前記の反応における塩基性触媒とし
ては、テトラメチルアンモニウムクロリド，テトラメチ
ルアンモニウムブロミド，テトラエチルアンモニウムク
ロリド，テトラエチルアンモニウムブロミド，テトラブ
チルアンモニウムクロリド，テトラブチルアンモニウム
ブロミド，トリエチルメチルアンモニウムクロリド，ト
リメチルベンジルアンモニウムクロリド，トリエチルベ
ンジルアンモニウムクロリドなどの四級アンモニウム塩
が使用される。As the basic catalyst in the above reaction, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, triethylmethylammonium chloride, trimethylbenzyl. Quaternary ammonium salts such as ammonium chloride and triethylbenzylammonium chloride are used.
【００２６】前記の一段法においては、５０〜１５０
℃、好ましくは８０〜１２０℃の温度で反応する。アル
カリ水酸化物はポリヒドロキシナフタレン系化合物の水
酸基１当量あたり０．８〜１．５モル当量好ましくは
０．９〜１．１モル当量使用する。In the above one-step method, 50 to 150
The reaction is carried out at a temperature of 80 ° C, preferably 80 to 120 ° C. The alkali hydroxide is used in an amount of 0.8 to 1.5 molar equivalent, preferably 0.9 to 1.1 molar equivalent, per equivalent of hydroxyl group of the polyhydroxynaphthalene compound.
【００２７】また、前記の二段法においては、前段の反
応は６０〜１５０℃好ましくは１００〜１４０℃の温度
で行なう。エピハロヒドリンの使用量はポリヒドロキシ
ナフタレン系化合物の水酸基１当量に対して、１．３〜
２０モル当量好ましくは２〜１０モル当量であり、過剰
のエピハロヒドリンは反応後に回収して再使用できる。In the above two-step method, the reaction in the first step is carried out at a temperature of 60 to 150 ° C, preferably 100 to 140 ° C. The amount of epihalohydrin used is 1.3 to 1 equivalent of hydroxyl group of the polyhydroxynaphthalene compound.
20 molar equivalents, preferably 2 to 10 molar equivalents, excess epihalohydrin can be recovered and reused after the reaction.
【００２８】また、塩基性触媒は、ポリヒドロキシナフ
タレン系化合物の水酸基に対して、０．００２〜３．０
モル％の割合で使用される。後段の反応は、５０〜１５
０℃好ましくは、６０〜１２０℃で行なう。アルカリ金
属水酸化物は生成したハロヒドリンに対して通常、１〜
１．１モル量用いられる。The basic catalyst is 0.002 to 3.0 based on the hydroxyl group of the polyhydroxynaphthalene compound.
Used in a molar percentage. The latter reaction is 50 to 15
0 degreeC Preferably it carries out at 60-120 degreeC. Alkali metal hydroxide is usually 1 to 1 to the halohydrin formed.
1.1 molar amount is used.
【００２９】これらの前段および後段の反応は、無溶媒
下でもよく、メチルイソブチルケトン，シクロヘキサ
ン，トルエンなどの不活性溶媒の存在下で行なってもよ
い。これらは、反応終了後に、水洗や溶媒洗浄で精製し
たり、蒸発脱気を行なって本発明の多官能性エポキシ樹
脂を得る。These first-stage and second-stage reactions may be carried out without solvent or in the presence of an inert solvent such as methylisobutylketone, cyclohexane or toluene. After completion of the reaction, these are purified by washing with water or solvent, or evaporated and degassed to obtain the polyfunctional epoxy resin of the present invention.
【００３０】本発明の多官能性エポキシ樹脂の作業性
は、その融点や溶融粘度と関係があり、より低いものが
求められる。これらは、ベースのポリヒドロキシナフタ
レン系化合物の融点や溶融粘度に依存し、これを極力低
くしておけば、作業性のよいエポキシ樹脂が得られる。
ベースのポリヒドロキシナフタレン系化合物は、エポキ
シ樹脂にすると融点は５〜３０℃低下し、粘度は１／５
〜４／５程度に低下するので、融点５０〜１００℃、１
５０℃における粘度０．０２〜１６ポイズの作業性に優
れたエポキシ樹脂が得られる。The workability of the polyfunctional epoxy resin of the present invention is related to its melting point and melt viscosity, and a lower one is required. These depend on the melting point and the melt viscosity of the base polyhydroxynaphthalene compound, and if these are kept as low as possible, an epoxy resin with good workability can be obtained.
When the epoxy resin is used as the base polyhydroxynaphthalene compound, the melting point is lowered by 5 to 30 ° C and the viscosity is 1/5.
Since it decreases to about 4/5, the melting point is 50 to 100 ° C., 1
An epoxy resin having a viscosity of 0.02 to 16 poise at 50 ° C. and excellent workability can be obtained.
【００３１】第３の発明は、硬化剤と前記ポリヒドロキ
シナフタレン系化合物をベースとしたエポキシ樹脂から
なるエポキシ樹脂組成物を提供する。この組成物は、さ
らに硬化促進剤を含むのが好ましく、この場合には、特
に半導体封止用樹脂組成物として有用である。The third invention provides an epoxy resin composition comprising a curing agent and an epoxy resin based on the polyhydroxynaphthalene compound. This composition preferably further contains a curing accelerator, and in this case, it is particularly useful as a resin composition for semiconductor encapsulation.
【００３２】本発明の多官能性エポキシ樹脂は、単独で
用いてもよいし、７０重量％以下好ましくは５０重量％
以下の一般のエポキシ樹脂、たとえばオルトクレゾール
レジンエポキシ樹脂，ビスフェノール系エポキシ樹脂，
フェノールレジンエポキシ樹脂と併用して用いることも
できる。The polyfunctional epoxy resin of the present invention may be used alone or may be 70% by weight or less, preferably 50% by weight.
The following general epoxy resins such as ortho-cresol resin epoxy resin, bisphenol epoxy resin,
It can also be used in combination with a phenol resin epoxy resin.
【００３３】次に、本発明に用いる硬化剤は、分子中に
２個以上好ましくは３個以上のフェノール性水酸基を有
するものである。具体的には、フェノールや置換フェノ
ール、例えば、ｏ−クレゾール，ｐ−クレゾール，ｔ−
ブチルフェノール，クミルフェノール，フェニルフェノ
ールとホルムアルデヒドを酸やアルカリで反応したもの
が挙げられる。ホルムアルデヒドの替わりに、ほかのア
ルデヒド、例えば、ベンズアルデヒド，クロトンアルデ
ヒド，サリチルアルデヒド，ヒドロキシベンズアルデヒ
ド，グリオキザール，テレフタルアルデヒドを用いた物
も利用できる。レゾルシンとアルデヒドの反応物やポリ
ビニルフェノールも本発明の硬化剤として用いることが
できる。Next, the curing agent used in the present invention has two or more, preferably three or more phenolic hydroxyl groups in the molecule. Specifically, phenol and substituted phenols such as o-cresol, p-cresol, t-
Examples include butylphenol, cumylphenol, phenylphenol and formaldehyde reacted with an acid or alkali. Instead of formaldehyde, other aldehydes such as benzaldehyde, crotonaldehyde, salicylaldehyde, hydroxybenzaldehyde, glyoxal, and terephthalaldehyde can be used. A reaction product of resorcin and an aldehyde and polyvinylphenol can also be used as the curing agent of the present invention.
【００３４】また、ポリヒドロキシナフタレン系化合
物、例えば、α−ナフトールホルマリン縮合物，α−ナ
フトールアルデヒド縮合物，β−ナフトールアルデヒド
縮合物，α−ナフトール・β−ナフトールアルデヒド共
縮合物，ナフトール・フェノールアルデヒド共縮合物，
ナフトール・クレゾールアルデヒド共縮合物，ナフトー
ルキシレノールアルデヒド共縮合物，ナフトール・アル
キル（Ｃ3 以上）フェノール・アルデヒド共縮合物，ジ
ヒドロキシナフタレンアルデヒド縮合物，ジヒドロキシ
ナフタレン・ナフトールアルデヒド共縮合物，ジヒドロ
キシナフタレン・フェノール・アルデヒド共縮合物，ジ
ヒドロキシナフタレン・クレゾール・アルデヒド共縮合
物，ジヒドロキシナフタレン・キシレノール・アルデヒ
ド共縮合物，ジヒドロキシナフタレンアルキル（Ｃ3 以
上）フェノール・アルデヒド共縮合物等も硬化剤として
有用である。Further, polyhydroxynaphthalene compounds such as α-naphthol formalin condensate, α-naphthol aldehyde condensate, β-naphthol aldehyde condensate, α-naphthol / β-naphthol aldehyde co-condensate, naphthol / phenol aldehyde Cocondensate,
Naphthol-cresol aldehyde co-condensate, naphthol xylenol aldehyde co-condensate, naphthol-alkyl (C 3 or more) phenol-aldehyde co-condensate, dihydroxynaphthalene aldehyde condensate, dihydroxynaphthalene-naphthol aldehyde co-condensate, dihydroxynaphthalene-phenol Aldehyde cocondensates, dihydroxynaphthalene / cresol / aldehyde cocondensates, dihydroxynaphthalene / xylenol / aldehyde cocondensates, dihydroxynaphthalenealkyl (C 3 or more) phenol / aldehyde cocondensates, etc. are also useful as curing agents.
【００３５】これらの硬化剤の配合割合は、エポキシ樹
脂のエポキシ基に対する硬化剤のフェノール性水酸基の
当量比（エポキシ基／フェノール性水酸基）が通常、１
／０．８〜１／１．２、好ましくは１／０．９〜１／
１．１の範囲が耐熱性，耐湿性の点から選ばれる。The mixing ratio of these curing agents is usually such that the equivalent ratio of the phenolic hydroxyl groups of the curing agent to the epoxy groups of the epoxy resin (epoxy group / phenolic hydroxyl group) is 1.
/0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 /
The range of 1.1 is selected from the viewpoint of heat resistance and moisture resistance.
【００３６】前記硬化促進剤は通常の触媒であり、特に
限定されない。硬化促進剤の具体例としては、たとえば
トリフェニルフォスフィン、トリス−２，６ジメトキシ
フェニルフォスフィン、トリ−ｐトリルフォスフィン、
亜リン酸トリフェニルなどのリン化合物、２−メチルイ
ミダゾール、２−フェニルイミダゾール、２−ウンデシ
ルイミダゾール、２−ヘプタデシルイミダゾール、２−
エチル−４−メチルイミダゾールなどのイミダゾール
類、２−ジメチルアミノメチルフェノール、ベンジルジ
メチルアミン、α−メチルベンジルメチルアミンなどの
第三アミン類、１，８−ジアザビシクロ（５，４，０）
ウンデセン−７、１，８−ジアザビシクロ（５，４，
０）ウンデセン−７の有機酸塩類などがあげられる。The curing accelerator is an ordinary catalyst and is not particularly limited. Specific examples of the curing accelerator include, for example, triphenylphosphine, tris-2,6dimethoxyphenylphosphine, tri-p-tolylphosphine,
Phosphorus compounds such as triphenyl phosphite, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-
Imidazoles such as ethyl-4-methylimidazole, tertiary amines such as 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzylmethylamine, 1,8-diazabicyclo (5,4,0)
Undecene-7,1,8-diazabicyclo (5,4,
0) Organic acid salts of undecene-7 and the like.
【００３７】硬化促進剤の配合量は、本発明の組成物中
０．１〜３．０重量％であるのが耐熱性と耐湿性の点か
ら好ましい。From the viewpoint of heat resistance and moisture resistance, it is preferable that the amount of the curing accelerator is 0.1 to 3.0% by weight in the composition of the present invention.
【００３８】本発明では、前記の各成分のほかに、必要
に応じてさらに種々のものを配合することができる。例
えば、充填剤や充填剤の表面を処理するための表面処理
剤や難燃剤や離型剤や着色剤や可撓性付与剤である。In the present invention, in addition to the above-mentioned components, various compounds may be blended as required. For example, it is a surface treatment agent for treating the surface of the filler or the filler, a flame retardant, a release agent, a coloring agent, and a flexibility imparting agent.
【００３９】充填剤としてはとくに限定はなく、例え
ば、結晶性シリカ粉，溶融性シリカ粉，石英ガラス粉，
タルク，ケイ酸カルシュウム粉，ケイ酸ジルコニュウム
粉，アルミナ粉，炭酸カルシウム粉などがあげられる
が、シリカ系のものが好ましい。The filler is not particularly limited, and examples thereof include crystalline silica powder, fusible silica powder, quartz glass powder,
Examples thereof include talc, calcium silicate powder, zirconium silicate powder, alumina powder, and calcium carbonate powder, with silica-based powders being preferred.
【００４０】充填剤の配合割合は、全組成物に対して６
０〜９０重量％好ましくは７０〜８５重量％である。充
填剤の配合量が９０重量％をこえると、組成物の流動性
が低くなって成形がむつかしく、６０重量％未満では熱
膨張が大きくなる傾向がある。The compounding ratio of the filler is 6 with respect to the total composition.
0 to 90% by weight, preferably 70 to 85% by weight. If the compounding amount of the filler exceeds 90% by weight, the fluidity of the composition will be low and molding will be difficult. If it is less than 60% by weight, the thermal expansion tends to be large.
【００４１】表面処理剤としては、公知のシランカップ
リング剤などがあげられ、難燃剤としては三酸化アンチ
モン，五酸化アンチモン，リン酸塩，臭素化物があげら
れ、離型剤としては各種ワックス類を、着色剤にはカー
ボンブラックなどを、可撓性付与剤としてはシリコーン
樹脂，ブタジエン−アクリルニトリルゴムなどが用いら
れる。但し、これらに限定されるものではない。Examples of the surface treatment agent include known silane coupling agents, flame retardants such as antimony trioxide, antimony pentoxide, phosphates and bromides, and release agents including various waxes. Carbon black or the like is used as the colorant, and silicone resin, butadiene-acrylonitrile rubber or the like is used as the flexibility-imparting agent. However, it is not limited to these.
【００４２】本発明のエポキシ樹脂組成物の調製方法は
とくに限定されず、常法によって行なえる。また、本発
明の樹脂組成物を用いて半導体を封止する際の条件にも
とくに限定はなく、通常、１７５℃、成形圧１００ｋｇ
／ｃｍ2 、３分間の成形と１８０℃、６時間の後硬化の
ごとき条件が採用される。The method for preparing the epoxy resin composition of the present invention is not particularly limited and can be carried out by a conventional method. The conditions for encapsulating a semiconductor using the resin composition of the present invention are not particularly limited, and are usually 175 ° C. and a molding pressure of 100 kg.
/ Cm 2 , conditions such as molding for 3 minutes and post-curing at 180 ° C. for 6 hours are adopted.
【００４３】[0043]
【実施例】以下、実施例を挙げて、本発明の実施の態様
を具体的に例示して説明する。本発明はこれらの実施例
に限定されるものではない。EXAMPLES Hereinafter, the embodiments of the present invention will be specifically illustrated and described with reference to Examples. The invention is not limited to these examples.
【００４４】〔実施例１〕 （ポリヒドロキシナフタレン系化合物１）撹拌装置，還
流冷却管，温度計，窒素吹込口を備えた反応容器内に、
α−ナフトール９６ｇ、β−ナフトール４８ｇ、パラホ
ルムアルデヒド２０ｇ（α−ナフトール：β−ナフトー
ル：パラホルムアルデヒド＝０．６７：０．３３：０．
６７（モル比、ホルマリン換算、以下同様））を仕込
み、１１０℃に加熱して窒素気流下で８時間撹拌して反
応させた。この後、２００℃に加熱し、５ｍｍＨｇで未
反応物と水を除去し、ポリヒドロキシナフタレン系化合
物１を得た。得られたポリヒドロキシナフタレン系化合
物１のナフタレン核体数を測定した。そのＧＰＣチャー
トを図２に示す。この時の４核体以上の共縮合物の含有
量は２８．１重量％であった。また、融点は８１℃、１
５０℃における溶融粘度は１．５ポイズ（以下Ｐと記
す）と低く、作業性能がすぐれていた。なお、以下の実
施例においても、粘度の測定はすべて１５０℃において
行った。Example 1 (Polyhydroxynaphthalene Compound 1) In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet,
96 g of α-naphthol, 48 g of β-naphthol, 20 g of paraformaldehyde (α-naphthol: β-naphthol: paraformaldehyde = 0.67: 0.33: 0.
67 (molar ratio, converted to formalin, the same applies below) was charged, heated to 110 ° C., and stirred for 8 hours under a nitrogen stream to react. Then, the mixture was heated to 200 ° C. and the unreacted material and water were removed at 5 mmHg to obtain polyhydroxynaphthalene compound 1. The number of naphthalene nuclei in the obtained polyhydroxynaphthalene compound 1 was measured. The GPC chart is shown in FIG. At this time, the content of the co-condensation product having 4 or more nuclides was 28.1% by weight. Also, the melting point is 81 ° C., 1
The melt viscosity at 50 ° C. was as low as 1.5 poise (hereinafter referred to as P), and the work performance was excellent. In addition, also in the following Examples, all the viscosity measurements were performed at 150 ° C.
【００４５】（エポキシ樹脂１）前記ポリヒドロキシナ
フタレン系化合物１の全量とエピクロルヒドリン２００
０ｇとテトラブチルアンモニウムブロマイド３ｇを仕込
み加熱還流下で３時間反応させ、減圧下で過剰のエピク
ロルヒドリンを除去した。内容物と同量のトルエンを加
え６０℃に冷却し、水分除去装置をつけて水酸化ナトリ
ウム４１ｇを加え、生成する水を減圧度１００〜１５０
ｍｍＨｇで連続的に除去しながら閉環反応させた。水洗
して塩類や未反応アルカリを除去した後減圧下でトルエ
ンと水などを除去しエポキシ樹脂１を得た。得られたエ
ポキシ樹脂１はエポキシ当量は２４５で、融点は６５
℃、粘度は０．３Ｐと低く作業性が優れていた。(Epoxy resin 1) The total amount of the polyhydroxynaphthalene compound 1 and epichlorohydrin 200
0 g and tetrabutylammonium bromide 3 g were charged and reacted under heating and reflux for 3 hours, and excess epichlorohydrin was removed under reduced pressure. Toluene in the same amount as the contents is added, cooled to 60 ° C., equipped with a water removing device, 41 g of sodium hydroxide is added, and the produced water is decompressed at a degree of 100 to 150.
The ring-closing reaction was carried out while continuously removing it with mmHg. After washing with water to remove salts and unreacted alkali, toluene and water were removed under reduced pressure to obtain an epoxy resin 1. The obtained epoxy resin 1 has an epoxy equivalent of 245 and a melting point of 65.
The workability was excellent as the temperature was low and the viscosity was 0.3P.
【００４６】〔実施例２〕 （ポリヒドロキシナフタレン系化合物２）α−ナフトー
ル７２ｇ、β−ナフトール７２ｇ、キシレン７２ｇ、パ
ラホルムアルデヒドを１８．２ｇ（α−ナフトール：β
−ナフトール：パラホルムアルデヒド＝０．５：０．
５：０．６１（モル比））とする以外、実施例１と同様
にして、ポリヒドロキシナフタレン系化合物２を製造し
た。キシレンは縮合後、加熱減圧下で除去した。得られ
たポリヒドロキシナフタレン系化合物２のナフタレン核
体数４以上の共縮合物の含有量は１７重量％であった。
融点は７３℃、粘度は０．３Ｐと低く、作業性能がすぐ
れていた。Example 2 (Polyhydroxynaphthalene Compound 2) 72 g of α-naphthol, 72 g of β-naphthol, 72 g of xylene and 18.2 g of paraformaldehyde (α-naphthol: β)
-Naphthol: paraformaldehyde = 0.5: 0.
A polyhydroxynaphthalene compound 2 was produced in the same manner as in Example 1 except that the ratio was 5: 0.61 (molar ratio). After condensation, xylene was removed under reduced pressure with heating. The content of the copolycondensate of the obtained polyhydroxynaphthalene compound 2 having 4 or more naphthalene nuclei was 17% by weight.
The melting point was 73 ° C and the viscosity was as low as 0.3P, and the work performance was excellent.
【００４７】（エポキシ樹脂２）前記ポリヒドロキシナ
フタレン系化合物２の全量を用いて実施例１と同様にエ
ポキシ樹脂を製造した。得られたエポキシ樹脂２は、エ
ポキシ当量２４５で、融点５８℃、粘度０．１Ｐと低く
作業性が優れていた。(Epoxy resin 2) An epoxy resin was produced in the same manner as in Example 1 except that the total amount of the polyhydroxynaphthalene compound 2 was used. The obtained epoxy resin 2 had an epoxy equivalent of 245, a melting point of 58 ° C., and a viscosity of 0.1 P, and was low in workability.
【００４８】〔実施例３〕 （ポリヒドロキシナフタレン系化合物３）α−ナフトー
ル４８ｇ、β−ナフトール９６ｇ、トルエン１４４ｇ、
パラホルムアルデヒドを１９ｇ（α−ナフトール：β−
ナフトール：パラホルムアルデヒド＝０．３３：０．６
７：０．６３（モル比））とする以外、実施例１と同様
にして、ポリヒドロキシナフタレン系化合物３を製造し
た。トルエンは縮合後、加熱減圧下で除去した。得られ
たポリヒドロキシナフタレン系化合物３のナフタレン核
体数４以上の共縮合物の含有量は２０重量％であった。
融点は７８℃、粘度は０．９Ｐと低く、作業性能がすぐ
れていた。Example 3 (Polyhydroxynaphthalene Compound 3) 48 g of α-naphthol, 96 g of β-naphthol, 144 g of toluene,
19 g of paraformaldehyde (α-naphthol: β-
Naphthol: paraformaldehyde = 0.33: 0.6
Polyhydroxynaphthalene compound 3 was produced in the same manner as in Example 1 except that the ratio was 7: 0.63 (molar ratio). After condensation, toluene was removed under reduced pressure with heating. The polyhydroxynaphthalene compound 3 thus obtained contained 20% by weight of a cocondensate having 4 or more naphthalene nuclides.
The melting point was 78 ° C and the viscosity was 0.9P, which was low, and the work performance was excellent.
【００４９】（エポキシ樹脂３）前記ポリヒドロキシナ
フタレン系化合物３の全量を用いて、実施例１と同様に
エポキシ樹脂を製造した。得られたエポキシ樹脂３は、
エポキシ当量２４５で、融点６５℃、粘度０．２Ｐと低
く作業性が優れていた。(Epoxy resin 3) An epoxy resin was produced in the same manner as in Example 1 except that the total amount of the polyhydroxynaphthalene compound 3 was used. The obtained epoxy resin 3 is
The epoxy equivalent was 245, the melting point was 65 ° C., and the viscosity was 0.2P, which was low and workability was excellent.
【００５０】〔実施例４〕 （ポリヒドロキシナフタレン系化合物４）α−ナフトー
ル７２ｇ、β−ナフトール７２ｇ、メチルイソブチルケ
トン７２ｇ、パラホルムアルデヒド２１．９ｇ（α−ナ
フトール：β−ナフトール：パラホルムアルデヒド＝
０．５：０．５：０．７３（モル比））とする以外、実
施例１と同様にして、ポリヒドロキシナフタレン系化合
物４を製造した。メチルイソブチルケトンは縮合後加熱
減圧下で除去した。得られたポリヒドロキシナフタレン
系化合物４のナフタレン核体数４以上の共縮合物の含有
量は４７重量％であった。融点は１０５℃、粘度は１
９．１Ｐと低く、作業性能がすぐれていた。Example 4 (Polyhydroxynaphthalene Compound 4) 72 g of α-naphthol, 72 g of β-naphthol, 72 g of methyl isobutyl ketone, 21.9 g of paraformaldehyde (α-naphthol: β-naphthol: paraformaldehyde =
Polyhydroxynaphthalene compound 4 was produced in the same manner as in Example 1 except that the ratio was 0.5: 0.5: 0.73 (molar ratio). Methyl isobutyl ketone was removed under heat and reduced pressure after condensation. The content of the obtained polyhydroxynaphthalene compound 4 cocondensate having 4 or more naphthalene nuclides was 47% by weight. Melting point is 105 ° C, viscosity is 1
It had a low workability of 9.1P.
【００５１】（エポキシ樹脂４）前記ポリヒドロキシナ
フタレン系化合物４の全量を用いて、実施例１と同様に
エポキシ樹脂を製造した。得られたエポキシ樹脂４は、
エポキシ当量２５０で、融点９３℃、粘度５．５Ｐと低
く、作業性がすぐれていた。(Epoxy resin 4) An epoxy resin was produced in the same manner as in Example 1 except that the total amount of the polyhydroxynaphthalene compound 4 was used. The obtained epoxy resin 4 is
The epoxy equivalent was 250, the melting point was 93 ° C., and the viscosity was 5.5 P, which was low and the workability was excellent.
【００５２】〔比較例１〕 （ポリヒドロキシナフタレン系化合物５）パラホルムア
ルデヒド２０ｇを２８ｇ（α−ナフトール：β−ナフト
ール：パラホルムアルデヒド＝０．６７：０．３３：
０．９３（モル比））とする以外、実施例１と同様にし
て、ポリヒドロキシナフタレン系化合物５を製造した。
得られたポリヒドロキシナフタレン系化合物５のナフタ
レン核体数４以上の共縮合物の含有量は５８重量％であ
った。融点は１３５℃、粘度は３２Ｐと高く、きわめて
流動性が劣るため作業性能が悪かった。Comparative Example 1 (Polyhydroxynaphthalene Compound 5) 28 g of 20 g of paraformaldehyde (α-naphthol: β-naphthol: paraformaldehyde = 0.67: 0.33:
Polyhydroxynaphthalene compound 5 was produced in the same manner as in Example 1 except that the amount was 0.93 (molar ratio).
The content of the obtained polyhydroxynaphthalene compound 5, a cocondensate having 4 or more naphthalene nuclides, was 58% by weight. The melting point was as high as 135 ° C and the viscosity was as high as 32P, and the workability was poor because the fluidity was extremely poor.
【００５３】（エポキシ樹脂５）前記ポリヒドロキシナ
フタレン系化合物５の全量を用いて、実施例１と同様に
エポキシ樹脂を製造した。得られたエポキシ樹脂５は、
エポキシ当量２５０で、融点１２１℃、粘度２４Ｐと高
く、きわめて流動性が劣るため作業性能が悪かった。(Epoxy Resin 5) An epoxy resin was produced in the same manner as in Example 1 except that the total amount of the polyhydroxynaphthalene compound 5 was used. The obtained epoxy resin 5 is
The epoxy equivalent was 250, the melting point was 121 ° C., the viscosity was 24P, and the workability was poor because the fluidity was extremely poor.
【００５４】〔比較例２〕 （ポリヒドロキシナフタレン系化合物６）触媒としてパ
ラトルエンスルホン酸を０．５ｇ、パラホルムアルデヒ
ドの代わりにホルマリン水（３５％）を６０ｇ用いる以
外は実施例１と同様にして、ポリヒドロキシナフタレン
系化合物６を製造した。得られたポリヒドロキシナフタ
レン系化合物６のナフタレン核体数４以上の共縮合物の
含有量は５８重量％であった。融点は１３５℃、粘度は
３２Ｐと高く、きわめて流動性が劣ることで、作業性能
が悪かった。Comparative Example 2 (Polyhydroxynaphthalene Compound 6) The same as Example 1 except that 0.5 g of paratoluenesulfonic acid was used as a catalyst and 60 g of formalin water (35%) was used instead of paraformaldehyde. , A polyhydroxynaphthalene compound 6 was produced. The content of the obtained copolycondensate of polyhydroxynaphthalene compound 6 having 4 or more naphthalene nuclides was 58% by weight. The melting point was as high as 135 ° C and the viscosity was as high as 32P, and the fluidity was extremely poor, resulting in poor workability.
【００５５】（エポキシ樹脂６）前記ポリヒドロキシナ
フタレン系化合物６の全量を用いて、実施例１と同様に
エポキシ樹脂を製造した。得られたエポキシ樹脂６は、
エポキシ当量２５０で、融点１１９℃、粘度２６Ｐと高
く、きわめて流動性が劣るため作業性能が悪かった。(Epoxy resin 6) An epoxy resin was produced in the same manner as in Example 1 except that the total amount of the polyhydroxynaphthalene compound 6 was used. The obtained epoxy resin 6 is
The epoxy equivalent was 250, the melting point was 119 ° C., the viscosity was 26P, and the workability was poor because the fluidity was extremely poor.
【００５６】実施例５〜８及び比較例３ 下記に示すエポキシ樹脂，硬化剤，硬化促進剤，充填
剤，及び三酸化アンチモン，シランカップリング剤，ワ
ックス，カーボンブラックを、表１に示す割合で配合し
て、二本ロールで７０〜１１０℃の温度にて混練したの
ち冷却し、粉砕して半導体封止用エポキシ樹脂組成物を
調製した。Examples 5 to 8 and Comparative Example 3 The following epoxy resin, curing agent, curing accelerator, filler, antimony trioxide, silane coupling agent, wax and carbon black were added in the proportions shown in Table 1. The mixture was mixed, kneaded with a two-roll mill at a temperature of 70 to 110 ° C., cooled, and pulverized to prepare an epoxy resin composition for semiconductor encapsulation.
【００５７】 エポキシ樹脂：実施例１〜４で得られたエポキシ樹脂 ｏ−クレゾールノボラック型エポキシ樹脂 エポキシ当量 １９５ 融点 ８５℃ 臭素化フェノールノボラック型エポキシ樹脂 エポキシ当量 ２８０ 融点 ８３℃ 硬化剤：フェノールノボラック樹脂 水酸基当量 １０６ 融点 ８０℃ 硬化促進剤：トリフェニルフォスフィン 充填剤：球状シリカ（三菱金属（株）のＢＦ１００）Epoxy resin: Epoxy resin obtained in Examples 1 to 4 o-cresol novolac type epoxy resin Epoxy equivalent 195 melting point 85 ° C. Brominated phenol novolac type epoxy resin epoxy equivalent 280 melting point 83 ° C. Curing agent: phenol novolac resin hydroxyl group Equivalent 106 Melting point 80 ° C Curing accelerator: Triphenylphosphine Filler: Spherical silica (BF100 from Mitsubishi Metals)
【００５８】得られた組成物を、１７５℃、１００ｋｇ
／ｃｍ2 、３分間の硬化条件で成型し、ついで１８０
℃、６時間の条件でポストキュアーさせ成型試験片を作
製した。このパッケージは８０ピン四方向フラットパッ
ケージ（８０ピンＱＦＰ、サイズ；２０×１４×２ｍ
ｍ）であり、ダイパッドサイズ８×８ｍｍである。The composition obtained was treated at 175 ° C. and 100 kg.
/ Cm 2 , molding under curing conditions for 3 minutes, then 180
Post-cure was performed under the conditions of ° C and 6 hours to prepare a molded test piece. This package is an 80-pin 4-way flat package (80-pin QFP, size: 20 x 14 x 2 m)
m) and the die pad size is 8 × 8 mm.
【００５９】尚、比較例１，２のエポキシ樹脂を用いた
場合はエポキシ樹脂組成物の粘度が高く流動性と作業性
が悪く、良好な試験片を得ることができなかったため以
下の評価は実施不可能であった。When the epoxy resins of Comparative Examples 1 and 2 were used, the epoxy resin compositions had high viscosity and poor fluidity and workability, and good test pieces could not be obtained. It was impossible.
【００６０】このようにして得られた半導体装置につい
て、−５０℃／５分〜１５０℃／５分のＴＣＴテストを
行いクラック発生数を調べた。また、前記試験片を、８
５℃／８５％ＲＨの相対湿度の恒温槽中に放置して吸湿
させた後に、２６０℃の半田溶融液に１０秒間浸漬する
試験を行った。結果を下記の表２に示す。The semiconductor device thus obtained was subjected to a TCT test of -50 ° C./5 minutes to 150 ° C./5 minutes to check the number of cracks. In addition, the test piece
A test was conducted in which the sample was left in a constant temperature bath having a relative humidity of 5 ° C./85% RH to absorb moisture, and then immersed in a solder melt at 260 ° C. for 10 seconds. The results are shown in Table 2 below.
【００６１】また、得られた試験片の２００℃における
曲げ強度（高温強度）、ガラス転移温度，熱膨張係数，
８５℃，８５％ＲＨで５００時間の加湿試験後の吸水率
を調べた。結果を下記の表３に示す。The bending strength (high temperature strength) of the obtained test piece at 200 ° C., the glass transition temperature, the thermal expansion coefficient,
The water absorption was examined after a humidity test at 85 ° C. and 85% RH for 500 hours. The results are shown in Table 3 below.
【００６２】[0062]
【表１】 [Table 1]
【００６３】[0063]
【表２】 [Table 2]
【００６４】[0064]
【表３】 [Table 3]
【００６５】[0065]
【発明の効果】本発明の特定のポリヒドロキシナフタレ
ン系化合物をベースとしたエポキシ樹脂は、融点及び溶
融粘度が低く、作業性能に優れている。又本発明のエポ
キシ樹脂は、高いガラス転移温度，耐熱性及び耐湿性を
有し、ハンダ処理においてもパッケージにクラックが発
生するのを防止できる硬化物を与える。The epoxy resin based on the specific polyhydroxynaphthalene compound of the present invention has a low melting point and melt viscosity and is excellent in workability. Further, the epoxy resin of the present invention has a high glass transition temperature, heat resistance and moisture resistance, and provides a cured product capable of preventing cracks from occurring in the package even during soldering.
【００６６】ポリヒドロキシナフタレン系化合物をベー
スとしたエポキシ樹脂を含む本発明のエポキシ樹脂組成
物は、硬化樹脂のガラス転移温度が高く耐熱性に優れ、
また機械的強度も大きく、しかも吸水率が少なく耐湿性
に優れ、ハンダ処理においてもクラックの発生が極めて
少ない。そのため、半導体封止用組成物として有用であ
る。また前記エポキシ樹脂組成物は硬化促進剤を含むの
が好ましく、その場合には半導体封止用として特に有用
である。The epoxy resin composition of the present invention containing an epoxy resin based on a polyhydroxynaphthalene compound has a high glass transition temperature of the cured resin and excellent heat resistance,
It also has high mechanical strength, low water absorption and excellent moisture resistance, and cracks are extremely few even during soldering. Therefore, it is useful as a composition for semiconductor encapsulation. Further, the epoxy resin composition preferably contains a curing accelerator, and in that case, it is particularly useful for encapsulating a semiconductor.
【図１】ポリヒドロキシナフタレン系化合物のナフタレ
ン核体数が４以上の共縮合物の含有量と融点又は１５０
℃での溶融粘度との関係図である。FIG. 1 shows the content and melting point of a co-condensate of a polyhydroxynaphthalene compound having 4 or more naphthalene nuclei and a melting point of 150.
It is a relationship diagram with a melt viscosity in ° C.
【図２】実施例１におけるポリヒドロキシナフタレン系
化合物１のＧＰＣチャートである。2 is a GPC chart of polyhydroxynaphthalene compound 1 in Example 1. FIG.
Claims (3)
ホルムアルデヒドとの共縮合により得られ、かつナフタ
レン核体数が４以上の縮合物の含有量が５０重量％以下
であるポリヒドロキシナフタレン系化合物と、エピハロ
ヒドリンとから製造された多官能性エポキシ樹脂。1. A polyhydroxynaphthalene compound obtained by co-condensation of α-naphthol, β-naphthol and paraformaldehyde, and having a content of a condensate having 4 or more naphthalene nuclides of 50% by weight or less. , A polyfunctional epoxy resin produced from epihalohydrin.
におけるナフタレン核体数が４以上の縮合物の含有量が
３０重量％以下である請求項１記載のエポキシ樹脂。2. The epoxy resin according to claim 1, wherein the content of the condensate having 4 or more naphthalene nuclei in the polyhydroxynaphthalene compound is 30% by weight or less.
化剤を必須成分とするエポキシ樹脂組成物。3. An epoxy resin composition containing the epoxy resin according to claim 1 and a curing agent as essential components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2362294A JPH07216052A (en) | 1994-01-25 | 1994-01-25 | Epoxy resin and epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2362294A JPH07216052A (en) | 1994-01-25 | 1994-01-25 | Epoxy resin and epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07216052A true JPH07216052A (en) | 1995-08-15 |
Family
ID=12115706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2362294A Pending JPH07216052A (en) | 1994-01-25 | 1994-01-25 | Epoxy resin and epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07216052A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013067697A (en) * | 2011-09-21 | 2013-04-18 | Dic Corp | Naphthol resin, curable resin composition, its cured product, and printed circuit board |
| JP2013185081A (en) * | 2012-03-08 | 2013-09-19 | Dic Corp | Curable resin composition, cured product and printed wiring board |
| KR20140071357A (en) * | 2011-09-08 | 2014-06-11 | 닛뽄 가야쿠 가부시키가이샤 | Epoxy resin, epoxy resin composition, and cured product thereof |
-
1994
- 1994-01-25 JP JP2362294A patent/JPH07216052A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140071357A (en) * | 2011-09-08 | 2014-06-11 | 닛뽄 가야쿠 가부시키가이샤 | Epoxy resin, epoxy resin composition, and cured product thereof |
| JP2013067697A (en) * | 2011-09-21 | 2013-04-18 | Dic Corp | Naphthol resin, curable resin composition, its cured product, and printed circuit board |
| JP2013185081A (en) * | 2012-03-08 | 2013-09-19 | Dic Corp | Curable resin composition, cured product and printed wiring board |
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