JPH07228663A - Epoxy resin and epoxy resin composition - Google Patents
Epoxy resin and epoxy resin compositionInfo
- Publication number
- JPH07228663A JPH07228663A JP4518994A JP4518994A JPH07228663A JP H07228663 A JPH07228663 A JP H07228663A JP 4518994 A JP4518994 A JP 4518994A JP 4518994 A JP4518994 A JP 4518994A JP H07228663 A JPH07228663 A JP H07228663A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- naphthol
- cocondensate
- allylnaphthol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 86
- 229920000647 polyepoxide Polymers 0.000 title claims description 86
- 239000000203 mixture Substances 0.000 title claims description 26
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 92
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 150000001299 aldehydes Chemical class 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 14
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 abstract description 49
- 150000004780 naphthols Chemical class 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 229910000679 solder Inorganic materials 0.000 abstract description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 31
- 230000008018 melting Effects 0.000 description 31
- 238000000034 method Methods 0.000 description 22
- 239000013256 coordination polymer Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- -1 allyl halide Chemical class 0.000 description 16
- 239000004593 Epoxy Substances 0.000 description 15
- 229930040373 Paraformaldehyde Natural products 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 229920002866 paraformaldehyde Polymers 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 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
- 239000000047 product Substances 0.000 description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 8
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 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
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000005406 washing Methods 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
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-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
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 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
- 238000005937 allylation reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 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
- 239000006229 carbon black Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 229940031826 phenolate Drugs 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000243 solution Substances 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
- 150000004786 2-naphthols Chemical class 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-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
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003377 acid catalyst 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
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 230000015572 biosynthetic process Effects 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction 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
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000004843 novolac epoxy resin Substances 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
- 238000011417 postcuring Methods 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-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
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、特定のアリルナフトー
ル共縮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含有するエポキ
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 allylnaphthol cocondensate and having excellent workability, and an epoxy resin composition containing this epoxy resin and a curing agent.
【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
を与える特定のアリルナフトール共縮合物をベースとし
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 allylnaphthol cocondensate 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化合物に、アリルナフトール類と
β−ナフトールとアルデヒド類が共縮合した重量平均分
子量が３００〜２０００のアリルナフトール・β−ナフ
トール共縮合物を用いることにより、この特定の共縮合
物とエピハロヒドリンを反応させて得られたエポキシ樹
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、かつ耐熱性及
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 polyhydroxy compounds, which are the base of epoxy resins, are co-condensed with allylnaphthols, β-naphthols and aldehydes. By using the allylnaphthol-β-naphthol cocondensate having a weight average molecular weight of 300 to 2000, the epoxy resin obtained by reacting this specific cocondensate with epihalohydrin has a low melting point and a low melt viscosity. The present invention was completed by discovering that it has excellent workability, exhibits a high glass transition temperature after curing, and has excellent heat resistance and moisture resistance.
【０００６】すなわち、下記一般式（Ｉ）又は（ＩＩ）
で示される重量平均分子量が３００〜２０００のアリル
ナフトール・β−ナフトール共縮合物とエピハロヒドリ
ンとの反応によって得られる多官能性エポキシ樹脂を提
供するものである。That is, the following general formula (I) or (II)
And a polyfunctional epoxy resin obtained by reacting an allylnaphthol / β-naphthol cocondensate having a weight average molecular weight of 300 to 2000 with epihalohydrin.
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】[0008]
【化４】 [Chemical 4]
【０００９】更に本発明は、前記アリルナフトール・β
−ナフトール共縮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 relates to the above-mentioned allylnaphthol.β.
Provided is an epoxy resin composition containing an epoxy resin based on a naphthol cocondensate and a curing agent.
【００１０】アリルナフトール・β−ナフトール共縮合
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 the epoxy resin based on the allylnaphthol / β-naphthol cocondensate preferably contains a curing accelerator, and in that case, it is particularly preferable as a semiconductor encapsulating composition. It is valid.
【００１１】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 include not only a resinous epoxy compound but also a low molecular weight epoxy compound unless otherwise specified.
【００１２】（手段を構成する要件）本発明の高性能エ
ポキシ樹脂を得るための必須要件は、前記一般式（Ｉ）
又は（ＩＩ）で示されるアリルナフトール類とβ−ナフ
トールとアルデヒド類が共縮合した分子構造を有する重
量平均分子量が３００〜２０００の化合物をエポキシ樹
脂のベースに用いることである。(Requirements Constituting Means) The essential requirements for obtaining the high performance epoxy resin of the present invention are the above-mentioned general formula (I).
Alternatively, the compound represented by (II), which has a molecular structure in which allylnaphthols, β-naphthol and aldehydes are co-condensed and has a weight average molecular weight of 300 to 2000, is used as the base of the epoxy resin.
【００１３】アリルナフトール類のアリル基は、ナフタ
レン核に１〜２個存在するが、縮合反応を促進させるた
めには１個であるのが好ましい。The allyl group of allylnaphthols is present in the naphthalene nucleus in an amount of 1 to 2 but is preferably 1 in order to accelerate the condensation reaction.
【００１４】アリルナフトール・β−ナフトール共縮合
物の重量平均分子量は３００〜２０００である。３００
未満であると、分子内のＯＨ基数が少なすぎエポキシ基
が少なくなり、その結果硬化時の硬化が不充分となり、
２０００を超えるとエポキシ樹脂の融点と粘度が高くな
り作業性に劣る。The weight average molecular weight of the allylnaphthol / β-naphthol cocondensate is 300 to 2000. 300
When it is less than 1, the number of OH groups in the molecule is too small and the number of epoxy groups becomes small, resulting in insufficient curing during curing,
If it exceeds 2000, the melting point and viscosity of the epoxy resin will be high and the workability will be poor.
【００１５】また、このβ−ナフトールの８０モル％以
下、好ましくは７０モル％以下をα−ナフトールで置き
換えた共縮合物も粘度が低く有用である。A cocondensate obtained by substituting 80 mol% or less, preferably 70 mol% or less of β-naphthol with α-naphthol is also useful because of its low viscosity.
【００１６】アリルナフトール・β−ナフトール共縮合
物においては、１分子中のアリルナフトール類分子単位
とβ−ナフトール分子単位とのモル比が１０：９０〜５
０：５０（α−ナフトールを含む場合は６７：３３）で
あるのが好ましい。すなわちアリルナフトール類とβ−
ナフトールとアルデヒド類の共縮合した分子構造を有す
る共縮合物において、１分子中にアリルナフトール類分
子単位１０〜５０モル％とβ−ナフトール分子単位５０
〜９０モル％（アルデヒド類分子単位除外換算）を含有
するのが好ましい。この範囲からはずれると共縮合物が
得られにくく、アリルナフトールの単独縮合物が多量に
得られ好ましくない。In the allylnaphthol / β-naphthol cocondensate, the molar ratio of the allylnaphthols molecular unit to the β-naphthol molecular unit in one molecule is 10: 90-5.
It is preferably 0:50 (67:33 when α-naphthol is included). That is, allylnaphthols and β-
In a cocondensate having a molecular structure in which naphthol and an aldehyde are cocondensed, 10 to 50 mol% of allylnaphthol molecular units and 50 of β-naphthol molecular units are contained in one molecule.
It is preferable to contain ˜90 mol% (based on exclusion of aldehyde molecular units). If it deviates from this range, it is difficult to obtain a cocondensate, and a large amount of allylnaphthol monocondensate is obtained, which is not preferable.
【００１７】このアリルナフトール・β−ナフトール共
縮合物は、ナフトール共縮合物にアリル基が導入され分
子に立体障害効果が生じることにより粘度低下が生じ、
さらにβ−ナフトールの使用により２量体が多く生成
し、高分子量物が生じにくいために粘度が低くなる。こ
れら両効果により、極めて粘度の低い共縮合物が得られ
る。In this allylnaphthol / β-naphthol cocondensate, an allyl group is introduced into the naphthol cocondensate to cause a steric hindrance effect on the molecule, resulting in a decrease in viscosity.
Further, the use of β-naphthol produces a large amount of dimer, and a high molecular weight substance is less likely to be produced, resulting in a low viscosity. Due to both of these effects, a cocondensate having an extremely low viscosity can be obtained.
【００１８】このようなアリルナフトール・β−ナフト
ール共縮合物は、アリルナフトール類とβ−ナフトール
（必要によりα−ナフトールを含む）とアルデヒド類と
が共縮合した分子構造を有する化合物であれば良く、例
えば下記の２方法で製造することができる。Such an allylnaphthol / β-naphthol cocondensate may be any compound having a molecular structure in which allylnaphthols, β-naphthol (including α-naphthol if necessary) and aldehydes are cocondensed. For example, it can be manufactured by the following two methods.
【００１９】（Ａ法）予めナフトール類をアリル化して
アリルナフトール類を合成し、それにβ−ナフトール
（必要によりα−ナフトールを含む）とアルデヒド類を
加え、必要により酸や塩基を加えて通常のノボラックの
合成と同様に脱水反応する方法。(Method A) Allylnaphthols are preliminarily allylated to synthesize allylnaphthols, β-naphthol (including α-naphthol if necessary) and aldehydes are added thereto, and an acid or a base is added if necessary to obtain a usual naphthol. A method of dehydration similar to the synthesis of novolac.
【００２０】（Ｂ法）予めナフトール類とβ−ナフトー
ル（必要によりα−ナフトールを含む）とアルデヒド類
により縮合物を合成した後、ハロゲン化アリルと塩基と
必要により水や有機溶剤を加えて反応し、縮合物にアリ
ル基を導入する方法。(Method B) A condensate is previously synthesized from naphthols, β-naphthol (including α-naphthol if necessary) and aldehydes, and then the reaction is carried out by adding allyl halide, a base and optionally water or an organic solvent. And then introducing an allyl group into the condensate.
【００２１】Ａ法の場合、アリル化するナフトール類と
しては、アリル基を分子内に１個以上導入でき、かつア
ルデヒド類が付加できる位置が１個以上あるものが利用
でき、例えばα−ナフトールやジヒドロキシナフタレン
や一部アルキル基で置換されたα−ナフトールやジヒド
ロキシナフタレンなどが挙げられ、特にα−ナフトール
が好ましい。In the case of Method A, as the naphthol to be allylated, one having one or more allyl groups introduced into the molecule and one or more positions to which aldehydes can be added can be used. For example, α-naphthol or Examples thereof include dihydroxynaphthalene and α-naphthol and dihydroxynaphthalene partially substituted with an alkyl group, and α-naphthol is particularly preferable.
【００２２】ナフトール類をアリル化するには、（１）
水中にナフトール類と塩基を加えてフェノラート化した
後、ハロゲン化アリルを加えて反応し、不純物を水洗し
た後、加熱してクライゼン転位する方法、（２）前記
（１）の方法において、ハロゲン化アリルを長時間かけ
て滴下して加える方法、（３）ナフトール類とハロゲン
化アリルと必要により有機溶剤を加え、それに塩基水溶
液を滴下して反応させ、不純物を水洗した後、クライゼ
ン転位する方法など、いずれの方法によってもよい。To allylate naphthols, (1)
A method in which naphthols and a base are added to water to form a phenolate, and then an allyl halide is added to react with it, impurities are washed with water, and then Claisen rearrangement is carried out by heating, (2) In the method of (1) above, halogenation is performed. A method of adding allyl dropwise over a long period of time, (3) a method of adding naphthols and allyl halide and, if necessary, an organic solvent and adding an aqueous base solution to the reaction to wash the impurities, and then performing Claisen rearrangement. Any method may be used.
【００２３】アルデヒド類としては、例えば、ホルムア
ルデヒド、パラホルムアルデヒド、アセトアルデヒド、
プロピルアルデヒド、ブチルアルデヒド、グリオキサー
ルなどの脂肪族アルデヒド、ベンズアルデヒド、ｐ−ヒ
ドロキシベンズアルデヒド、サリチルアルデヒド、テレ
フタルアルデヒドなどの芳香族アルデヒドが利用でき、
中でもパラホルムアルデヒドや芳香族のベンズアルデヒ
ド、ｐ−ヒドロキシベンズアルデヒド、サリチルアルデ
ヒド、テレフタルアルデヒドが好ましい。これらのアル
デヒドは１種類を用いて反応させてもよく、２種類以上
を併用して反応させることも可能である。Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde,
Aliphatic aldehydes such as propylaldehyde, butyraldehyde and glyoxal, aromatic aldehydes such as benzaldehyde, p-hydroxybenzaldehyde, salicylaldehyde and terephthalaldehyde can be used,
Of these, paraformaldehyde, aromatic benzaldehyde, p-hydroxybenzaldehyde, salicylaldehyde, and terephthalaldehyde are preferable. One of these aldehydes may be used for the reaction, or two or more of them may be used in combination for the reaction.
【００２４】また、アルデヒドの使用量は、高核体の組
成があまり多くならないように、原料のアリルナフトー
ル類とβ−ナフトールの合計量の１モルに対して０．３
０〜０．８５モルとなるのが好ましい。このアルデヒド
の使用量が０．３０モル未満の場合は、共縮合物の分子
量が小さくなるため、エポキシ樹脂の硬化物の耐熱性が
低下する。また、０．８５モルを超えると、β−ナフト
ール単独使用の場合には反応に必要な量より過剰とな
り、不経済で臭気の問題が生じ、β−ナフトールとα−
ナフトールを併用する場合には高分子量物が生成してエ
ポキシ樹脂が高溶融粘度を生じ、作業性能が悪くなって
成形性に問題を生じる。特に、β−ナフトール単独使用
時は０．５０〜０．６０モル、β−ナフトールとα−ナ
フトールの併用時は０．５０〜０．７５モルが好まし
い。The amount of aldehyde used is 0.3 with respect to 1 mol of the total amount of allylnaphthols and β-naphthol as raw materials so that the composition of the high-nucleus body does not become too large.
It is preferably from 0 to 0.85 mol. When the amount of the aldehyde used is less than 0.30 mol, the molecular weight of the cocondensate becomes small, and thus the heat resistance of the cured product of the epoxy resin decreases. On the other hand, if it exceeds 0.85 mol, when β-naphthol is used alone, the amount exceeds the amount required for the reaction, which is uneconomical and causes an odor problem.
When naphthol is used in combination, a high molecular weight product is produced and the epoxy resin has a high melt viscosity, resulting in poor workability and a problem in moldability. Particularly, it is preferably 0.50 to 0.60 mol when β-naphthol is used alone and 0.50 to 0.75 mol when β-naphthol and α-naphthol are used in combination.
【００２５】縮合反応におけるアリルナフトール類とβ
−ナフトールとの使用モル比は、１０：９０〜５０：５
０（α−ナフトールを含む場合は６７：３３）の範囲が
好ましい。アリルナフトール類の使用モル比がこれより
小さいと、低粘度化や可撓性の効果が付与されず、大き
いと、共縮合反応が円滑に進行しなくなる。Allylnaphthols and β in the condensation reaction
-The molar ratio used with naphthol is 10:90 to 50: 5.
The range of 0 (67:33 when α-naphthol is included) is preferable. If the molar ratio of allylnaphthols used is smaller than this, the effect of lowering the viscosity and flexibility is not imparted, and if the molar ratio is large, the cocondensation reaction does not proceed smoothly.
【００２６】本発明で用いるアリルナフトール・β−ナ
フトール共縮合物を得るための共縮合反応は、ナフタレ
ン核体数のコントロールを容易にするため、高温に加熱
するだけで行なわれる。この場合の反応温度としては６
０〜１８０℃が適しており、特に８０〜１６０℃が好ま
しい。反応は通常１〜１０時間程度で終了する。なお、
必要により、酸や塩基などの触媒を用いてもよい。The cocondensation reaction for obtaining the allylnaphthol / β-naphthol cocondensate used in the present invention is carried out only by heating to a high temperature in order to facilitate control of the number of naphthalene nuclei. The reaction temperature in this case is 6
0 to 180 ° C. is suitable, and 80 to 160 ° C. is particularly preferable. The reaction is usually completed in about 1 to 10 hours. In addition,
If necessary, a catalyst such as an acid or a base may be used.
【００２７】また、反応は無溶剤でも行なえるが、沸点
が８０℃以上で、かつ水への溶解性の小さい溶剤、例え
ばトルエン、キシレン、メチルイソブチルケトンなどを
使用するのが好ましい。Although the reaction can be carried out without solvent, it is preferable to use a solvent having a boiling point of 80 ° C. or higher and a low solubility in water, such as toluene, xylene or methyl isobutyl ketone.
【００２８】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、溶媒および未反応物を減圧下にて除
去してもよい。After completion of the reaction, impurities may be removed by washing with water or the solvent and unreacted materials may be removed under reduced pressure, if necessary.
【００２９】なお、Ｂ法の場合、ナフトール類とβ−ナ
フトール（必要によりα−ナフトールを含む）と前記の
アルデヒド類を用いて、前記の縮合方法などにより予め
縮合物を合成した後、前記のアリル化法（１）、
（２）、（３）などを用いてアリル化すると、目的の分
子構造を有する共縮合物が得られる。In the case of Method B, naphthols, β-naphthol (including α-naphthol if necessary) and the above-mentioned aldehydes are used to synthesize a condensate in advance by the above-mentioned condensation method or the like, and then the above-mentioned Allylation method (1),
By allylation using (2), (3), etc., a cocondensate having a desired molecular structure can be obtained.
【００３０】なお、この共縮合物の分析・同定は、ゲル
パーミエーションクロマトグラフィー（ＧＰＣ法）、赤
外吸収スペクトル（ＩＲ）および核磁気共鳴スペクトル
（ＮＭＲ）により行なった。以下にＧＰＣとＮＭＲの測
定条件を示す。The analysis and identification of this cocondensate was carried out by gel permeation chromatography (GPC method), infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR). The measurement conditions of GPC and NMR are shown below.
【００３１】（ＧＰＣ分析） 溶 媒：テトラヒドロフラン 流 量：０．８ｍｌ／ｍｉｎ カラム：東ソー（株）製のＧ４０００Ｈ、Ｇ３０００
Ｈ、Ｇ２０００Ｈ（直列）であって、排除限界分子量が
それぞれ４００，０００、６０，０００、１０，０００
である。 担 体：スチレン・ジビニルベンゼン共重合体(GPC analysis) Solvent: Tetrahydrofuran Flow rate: 0.8 ml / min Column: G4000H and G3000 manufactured by Tosoh Corporation
H and G2000H (series) with exclusion limit molecular weights of 400,000, 60,000 and 10,000, respectively.
Is. Carrier: Styrene / divinylbenzene copolymer
【００３２】（ＮＭＲ）共縮合物のＮＭＲスペクトルは
以下に帰属されていることで確認を行なった。(NMR) The NMR spectrum of the co-condensate was confirmed as belonging to the following.
【００３３】[0033]
【化５】 [Chemical 5]
【００３４】本発明のアリルナフトール・β−ナフトー
ル共縮合物をベースにした多官能性エポキシ樹脂は、前
記のアリルナフトール・β−ナフトール（必要によりα
−ナフトールを含む）共縮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 allylnaphthol / β-naphthol cocondensation product of the present invention is the above-mentioned allylnaphthol / β-naphthol (if necessary α).
It can be obtained by reacting a co-condensate (including naphthol) with epihalohydrin, and the reaction can usually be performed by the following two typical methods.
【００３５】１）アリルナフトール・β−ナフトール共
縮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 an addition reaction of allylnaphthol / β-naphthol cocondensate and an excess of epihalohydrin are simultaneously carried out in the presence of an alkali metal hydroxide and a ring-closing reaction to form an epoxy ring.
【００３６】２）アリルナフトール・β−ナフトール共
縮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 an allylnaphthol / β-naphthol cocondensate and an excess 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.
【００３７】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.
【００３８】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.
【００３９】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.
【００４０】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
カリ水酸化物はアリルナフトール・β−ナフトール共縮
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 one-step method described above, 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 equivalents, preferably 0.9 to 1.1 molar equivalents, per equivalent of hydroxyl groups of the allylnaphthol / β-naphthol cocondensate.
【００４１】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アリルナフトー
ル・β−ナフトール共縮合物の水酸基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 based on 1 equivalent of the hydroxyl group of the allylnaphthol / β-naphthol cocondensate.
The amount is 1.3 to 20 molar equivalents, preferably 2 to 10 molar equivalents, and the excess epihalohydrin can be recovered and reused after the reaction.
【００４２】また、塩基性触媒は、アリルナフトール・
β−ナフトール共縮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、５
０〜１５０℃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 allylnaphthol.
0.002 to the hydroxyl group of the β-naphthol cocondensate
It is used in a proportion of ˜3.0 mol%. The latter reaction is 5
0 to 150 ° C., preferably 60 to 120 ° C. The alkali metal hydroxide is usually used in an amount of 1 to 1.1 mol based on the produced halohydrin.
【００４３】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 in the absence of a solvent or in the presence of an inert solvent such as methyl isobutyl ketone, 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.
【００４４】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、ベースのアリルナフトール・β
−ナフトール共縮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。ベースのアリルナフトール・β−ナフトール共
縮合物は、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４
０〜１００℃、１５０℃における粘度５〜２００ｃｐ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 workability is required. These are the base allylnaphthol β
-Depending on the melting point and melt viscosity of the naphthol co-condensate, if this is made as low as possible, an epoxy resin with good workability can be obtained. The base allylnaphthol / β-naphthol cocondensate has a melting point of 5 to 30 ° C. and a viscosity of about 1/5 to 4/5 when an epoxy resin is used.
An epoxy resin having a viscosity of 5 to 200 cp at 0 to 100 ° C. and 150 ° C. and excellent workability can be obtained.
【００４５】第２の発明は、硬化剤と前記アリルナフト
ール・β−ナフトール共縮合物をベースとしたエポキシ
樹脂を含有す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 second invention provides an epoxy resin composition containing a curing agent and an epoxy resin based on the allylnaphthol / β-naphthol cocondensation product. This composition preferably further contains a curing accelerator, and in this case, it is particularly useful as a resin composition for semiconductor encapsulation.
【００４６】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 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.
【００４７】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.
【００４８】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.
【００４９】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 compounding ratio of these curing agents is usually such that the equivalent ratio of the phenolic hydroxyl group of the curing agent to the epoxy group 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.
【００５０】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 a usual 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.
【００５１】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.
【００５２】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 can 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.
【００５３】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.
【００５４】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 blending 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.
【００５５】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 and the like, flame retardants include antimony trioxide, antimony pentoxide, phosphates and bromides, and release agents include 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.
【００５６】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.
【００５７】[0057]
【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.
【００５８】実施例１ （アリルナフトール・β−ナフトール共縮合物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１４４ｇ（１モル）、水酸化ナ
トリウム１０％水溶液４４０ｇおよびメチルイソブチル
ケトン１４４ｇを仕込み、撹拌しながら８０℃に加熱し
て均一化させてフェノラート化させた。この反応液に塩
化アリル８４．２ｇ（１．１モル）を滴下ロートを用い
て３時間かけて滴下し、滴下終了後さらに１時間撹拌し
て反応させた。反応終了後、分離、水洗し、減圧下で溶
剤を完全に留去した。次いで、得られた反応生成物を反
応容器に移し、１４０℃に加熱して２時間撹拌して反応
させてアリルナフトール（ＯＨ基当量１８４）を得た。 Example 1 (Allylnaphthol / β-naphthol Cocondensate 1) In a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, 144 g (1 mol) of α-naphthol and hydroxylation were added. A 10% aqueous solution of sodium (440 g) and methyl isobutyl ketone (144 g) were charged, and the mixture was heated to 80 ° C. with stirring to homogenize it to obtain a phenolate. To this reaction solution, 84.2 g (1.1 mol) of allyl chloride was added dropwise using a dropping funnel over 3 hours, and after completion of the addition, the mixture was stirred for 1 hour to react. After the reaction was completed, the reaction mixture was separated and washed with water, and the solvent was completely distilled off under reduced pressure. Next, the obtained reaction product was transferred to a reaction vessel, heated to 140 ° C. and stirred for 2 hours to cause a reaction to obtain allylnaphthol (OH group equivalent 184).
【００５９】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、上記アリルナフトール９２ｇ
（０．５モル）、β−ナフトール７２ｇ（０．５モル）
およびパラホルムアルデヒド１６．５ｇ（アリルナフト
ールとβ−ナフトールの合計：パラホルムアルデヒド＝
１：０．５５（モル比、ホルムアルデヒド換算））を仕
込み、１４０℃に加熱して窒素気流下で３時間撹拌して
反応させた。次に、２００℃に加熱し、減圧下で未反応
物と水を除去し、下記式で示されるアリルナフトール共
縮合物を得た。この化合物の融点は６１℃、１５０℃の
溶融粘度は１０センチポイズ（以下ＣＰと記す）と低
く、作業性能に優れていた。（なお、以下の実施例およ
び比較例においても、粘度の測定はすべて１５０℃にお
いて行なった。）重量平均分子量（ＧＰＣ法で測定、以
下同様）は３８０で、ＯＨ基当量は１７８であった。92 g of the above-mentioned allylnaphthol was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet.
(0.5 mol), β-naphthol 72 g (0.5 mol)
And 16.5 g of paraformaldehyde (total of allylnaphthol and β-naphthol: paraformaldehyde =
1: 0.55 (molar ratio, converted to formaldehyde) was charged, heated to 140 ° C., and stirred for 3 hours under a nitrogen stream to react. Next, the mixture was heated to 200 ° C. and the unreacted material and water were removed under reduced pressure to obtain an allylnaphthol cocondensate represented by the following formula. The melting point of this compound was 61 ° C., and the melt viscosity at 150 ° C. was as low as 10 centipoise (hereinafter referred to as CP), and the workability was excellent. (In the following Examples and Comparative Examples, all viscosity measurements were also made at 150 ° C.) The weight average molecular weight (measured by GPC method, the same applies hereinafter) was 380 and the OH group equivalent was 178.
【００６０】[0060]
【化６】 [Chemical 6]
【００６１】（エポキシ樹脂１）前記共縮合物の全量と
エピクロルヒドリン４６０ｇ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１００〜１５０ｍｍＨｇ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た。得ら
れたエポキシ樹脂は、エポキシ当量は２６０で、融点は
４４℃、粘度は７ＣＰと低く作業性が優れていた。(Epoxy resin 1) The total amount of the co-condensate, 460 g of epichlorohydrin and 3 g of tetrabutylammonium bromide were charged and reacted under heating under reflux for 3 hours, and excess epichlorohydrin was removed under reduced pressure. The same amount of toluene as the contents was added, the mixture was cooled to 60 ° C., 41 g of sodium hydroxide was added with a water removing device, and the produced water was subjected to a ring-closing reaction while continuously removing the water at a reduced pressure of 100 to 150 mmHg. After washing with water to remove salts and unreacted alkali, toluene and water were removed under reduced pressure. The obtained epoxy resin had an epoxy equivalent of 260, a melting point of 44 ° C., and a viscosity of 7 CP and was low in workability.
【００６２】実施例２ （アリルナフトール・β−ナフトール共縮合物２）実施
例１の前段で合成したのと同じアリルナフトール６１．
６ｇ（０．３４モル）、β−ナフトール４８ｇ（０．３
３モル）、α−ナフトール４８ｇ（０．３３モル）、キ
シレン８６ｇおよびパラホルムアルデヒド１９．５ｇ
（アリルナフトールとβ−ナフトールとα−ナフトール
の合計：パラホルムアルデヒド＝１：０．６５（モル
比、ホルムアルデヒド換算））を仕込む以外は、実施例
１と同様にして共縮合物を製造した。キシレンは、反応
後に加熱減圧下で除去した。得られたアリルナフトール
共縮合物（下記式で示される）の融点は６５℃、粘度は
４０ＣＰと低く、作業性能に優れていた。重量平均分子
量は５５０で、ＯＨ基当量は１７０であった。 Example 2 (Allylnaphthol / β-naphthol cocondensate 2) The same allylnaphthol 61. as the one synthesized in the preceding stage of Example 1.
6 g (0.34 mol), β-naphthol 48 g (0.3
3 mol), 48 g (0.33 mol) of α-naphthol, 86 g of xylene and 19.5 g of paraformaldehyde.
A cocondensate was produced in the same manner as in Example 1 except that (total of allylnaphthol, β-naphthol, and α-naphthol: paraformaldehyde = 1: 0.65 (molar ratio, converted to formaldehyde)) was charged. Xylene was removed under heating and reduced pressure after the reaction. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 65 ° C. and a viscosity of 40 CP, which was excellent in work performance. The weight average molecular weight was 550 and the OH group equivalent was 170.
【００６３】[0063]
【化７】 [Chemical 7]
【００６４】（エポキシ樹脂２）前記２の縮合物全量を
用いて実施例１と同様にエポキシ樹脂を製造した。得ら
れたエポキシ樹脂は、エポキシ当量２６０で、融点４９
℃、粘度１５ＣＰ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 using the entire amount of the condensate obtained in the above 2. The obtained epoxy resin has an epoxy equivalent of 260 and a melting point of 49.
It had a low workability of as low as 15 ° C. and a viscosity of 15 CP.
【００６５】実施例３ （アリルナフトール・β−ナフトール共縮合物３）実施
例１の前段で合成したのと同じアリルナフトール９２ｇ
（０．５モル）、β−ナフトール７２ｇ（０．５モ
ル）、トルエン１８４ｇおよびベンズアルデヒド５８．
３ｇ（アリルナフトールとβ−ナフトールの合計：ベン
ズアルデヒド＝１：０．５５（モル比））を仕込む以外
は、実施例１と同様にして共縮合物を製造した。トルエ
ンは、反応後に加熱減圧下で除去した。得られたアリル
ナフトール共縮合物（下記式で示される）の融点は７５
℃、粘度は２０ＣＰと低く、作業性能に優れていた。重
量平均分子量は４３０で、ＯＨ基当量は２１２であっ
た。 Example 3 (Allylnaphthol / β-naphthol cocondensate 3) 92 g of the same allylnaphthol as synthesized in the previous stage of Example 1
(0.5 mol), β-naphthol 72 g (0.5 mol), toluene 184 g and benzaldehyde 58.
A cocondensate was produced in the same manner as in Example 1 except that 3 g (total of allylnaphthol and β-naphthol: benzaldehyde = 1: 0.55 (molar ratio)) was charged. Toluene was removed under heating and reduced pressure after the reaction. The melting point of the obtained allylnaphthol cocondensate (shown by the following formula) is 75.
It had a low working temperature and low viscosity of 20 CP, and was excellent in work performance. The weight average molecular weight was 430 and the OH group equivalent was 212.
【００６６】[0066]
【化８】 [Chemical 8]
【００６７】（エポキシ樹脂３）前記３の縮合物全量を
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は、エポキシ当量３１０で、融点６
５℃、粘度１２ＣＰ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 using the whole amount of the condensate obtained in the above 3. The obtained epoxy resin has an epoxy equivalent of 310 and a melting point of 6
The workability was excellent at a low temperature of 5 ° C and a viscosity of 12 CP.
【００６８】実施例４ （アリルナフトール・β−ナフトール共縮合物４）パラ
ホルムアルデヒドの代わりにベンズアルデヒド７４．２
ｇを用いる以外は、実施例２と同様にして共縮合物を製
造した。得られたアリルナフトール共縮合物（下記式で
示される）の融点は８２℃、粘度は５０ＣＰと低く、作
業性能に優れていた。重量平均分子量は６８０で、ＯＨ
基当量は２２２であった。 Example 4 (Allylnaphthol / β-naphthol Cocondensate 4) Benzaldehyde 74.2 in place of paraformaldehyde
A cocondensate was produced in the same manner as in Example 2 except that g was used. The obtained allylnaphthol co-condensate (shown by the following formula) had a melting point of 82 ° C. and a viscosity of 50 CP, which was low and was excellent in workability. Weight average molecular weight is 680, OH
The base equivalent was 222.
【００６９】[0069]
【化９】 [Chemical 9]
【００７０】（エポキシ樹脂４）前記４の縮合物全量を
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は、エポキシ当量３２０で、融点７
３℃、粘度１８ＣＰと低く、作業性が優れていた。(Epoxy resin 4) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the condensate obtained in 4 above. The obtained epoxy resin has an epoxy equivalent of 320 and a melting point of 7
It had a low workability of 3 ° C and a viscosity of 18 CP, and was excellent in workability.
【００７１】実施例５ （アリルナフトール・β−ナフトール共縮合物５）パラ
ホルムアルデヒドの代わりにｐ−ヒドロキシベンズアル
デヒド６７．１ｇを用いる以外は、実施例１と同様にし
て共縮合物を製造した。得られたアリルナフトール共縮
合物（下記式で示される）の融点は９５℃、粘度は２０
ＣＰと低く、作業性能に優れていた。重量平均分子量は
４５５で、ＯＨ基当量は１５０であった。 Example 5 (Allylnaphthol / β-naphthol cocondensate 5) A cocondensate was produced in the same manner as in Example 1 except that 67.1 g of p-hydroxybenzaldehyde was used instead of paraformaldehyde. The obtained allylnaphthol cocondensate (shown by the following formula) has a melting point of 95 ° C. and a viscosity of 20.
It had a low CP and excellent workability. The weight average molecular weight was 455 and the OH group equivalent was 150.
【００７２】[0072]
【化１０】 [Chemical 10]
【００７３】（エポキシ樹脂５）前記５の縮合物全量を
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は、エポキシ当量２３０で、融点８
３℃、粘度１６ＣＰと低く作業性が優れていた。(Epoxy resin 5) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the condensate obtained in 5 above. The obtained epoxy resin has an epoxy equivalent of 230 and a melting point of 8
It had a low workability of 3 ° C and a viscosity of 16 CP.
【００７４】実施例６ （アリルナフトール・β−ナフトール共縮合物６）パラ
ホルムアルデヒドの代わりにホルマリン水（３７％）４
４．６ｇを用いる以外は、実施例１と同様にして共縮合
物を製造した。得られたアリルナフトール共縮合物（下
記式で示される）の融点は７０℃、粘度は４０ＣＰと低
く、作業性能に優れていた。重量平均分子量は３９０
で、ＯＨ基当量は１８０であった。 Example 6 (Allylnaphthol / β-naphthol cocondensate 6) Formalin water (37%) 4 in place of paraformaldehyde
A cocondensate was produced in the same manner as in Example 1 except that 4.6 g was used. The obtained allylnaphthol cocondensate (represented by the following formula) had a melting point as low as 70 ° C. and a viscosity as low as 40 CP, and was excellent in work performance. Weight average molecular weight is 390
The OH group equivalent was 180.
【００７５】[0075]
【化１１】 [Chemical 11]
【００７６】（エポキシ樹脂６）前記の縮合物全量を用
いて、実施例１と同様にエポキシ樹脂を製造した。得ら
れたエポキシ樹脂は、エポキシ当量２７０で、融点５５
℃、粘度３０ＣＰと低く作業性が優れていた。(Epoxy resin 6) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the above condensate. The obtained epoxy resin has an epoxy equivalent of 270 and a melting point of 55.
It had a low workability of 30 ° C. and a viscosity of 30 CP.
【００７７】実施例７ （アリルナフトール・β−ナフトール共縮合物７）パラ
ホルムアルデヒドの代わりにサリチルアルデヒド６７ｇ
を用いる以外は、実施例１と同様にして共縮合物を製造
した。得られたアリルナフトール共縮合物（下記式で示
される）の融点は７８℃、粘度は５０ＣＰと低く、作業
性能に優れていた。重量平均分子量は６４０で、ＯＨ基
当量は１１２であった。 Example 7 (Allylnaphthol / β-naphthol cocondensation product 7) 67 g of salicylaldehyde instead of paraformaldehyde
A cocondensate was produced in the same manner as in Example 1 except that The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point of 78 ° C. and a low viscosity of 50 CP, and was excellent in workability. The weight average molecular weight was 640 and the OH group equivalent was 112.
【００７８】[0078]
【化１２】 [Chemical 12]
【００７９】（エポキシ樹脂７）前記の縮合物全量を用
いて、実施例１と同様にエポキシ樹脂を製造した。得ら
れたエポキシ樹脂は、エポキシ当量２１０で、融点６３
℃、粘度１５ＣＰと低く作業性が優れていた。(Epoxy resin 7) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the above condensate. The obtained epoxy resin has an epoxy equivalent of 210 and a melting point of 63.
It had a low workability of as low as 15 ° C. and a viscosity of 15 CP.
【００８０】実施例８ （アリルナフトール・β−ナフトール共縮合物８）パラ
ホルムアルデヒドの代わりにテレフタルアルデヒド４９
ｇを用いる以外は、実施例１と同様にして共縮合物を製
造した。得られたアリルナフトール共縮合物（下記式で
示される）の融点は８８℃、粘度は８０ＣＰと低く、作
業性能に優れていた。重量平均分子量は７８０で、ＯＨ
基当量は１８５であった。 Example 8 (Allylnaphthol / β-naphthol Cocondensate 8) Terephthalaldehyde 49 instead of paraformaldehyde
A cocondensate was produced in the same manner as in Example 1 except that g was used. The obtained allylnaphthol cocondensate (shown by the following formula) had a melting point as low as 88 ° C. and a viscosity of 80 CP and was excellent in workability. Weight average molecular weight is 780, OH
The base equivalent was 185.
【００８１】[0081]
【化１３】 [Chemical 13]
【００８２】（エポキシ樹脂８）前記の縮合物全量を用
いて、実施例１と同様にエポキシ樹脂を製造した。得ら
れたエポキシ樹脂は、エポキシ当量２７０で、融点７７
℃、粘度３０ＣＰと低く作業性が優れていた。(Epoxy resin 8) An epoxy resin was produced in the same manner as in Example 1 using the entire amount of the above condensate. The obtained epoxy resin has an epoxy equivalent of 270 and a melting point of 77.
It had a low workability of 30 ° C. and a viscosity of 30 CP.
【００８３】比較例１ （縮合物９）実施例１において、まったくアリルナフト
ールを用いず、α−ナフトールを１４４ｇ（１．０モ
ル）とする以外は同様にして縮合物を得た。水酸基当量
は１６８、融点は１３５℃、１５０℃の溶融粘度は３２
００ＣＰと高く、きわめて流動性が劣るため作業性が悪
かった。 Comparative Example 1 (Condensate 9) A condensate was obtained in the same manner as in Example 1, except that no allylnaphthol was used and the amount of α-naphthol was changed to 144 g (1.0 mol). Hydroxyl equivalent is 168, melting point is 135 ° C, melt viscosity at 150 ° C is 32.
It was as high as 00 CP, and the workability was poor because the fluidity was extremely poor.
【００８４】（エポキシ樹脂９）前記縮合物９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９は、エポキシ当量２５０で、融点
１２１℃、粘度２４００ＣＰ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 9) An epoxy resin was produced in the same manner as in Example 1 except that the whole amount of the condensate 9 was used. The obtained epoxy resin 9 had a high epoxy equivalent of 250, a melting point of 121 ° C. and a viscosity of 2400 CP, and was extremely inferior in fluidity, resulting in poor workability.
【００８５】比較例２ （縮合物１０）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用いる以外は比較例１と同様にし
て、縮合物１０を製造した。水酸基当量は１７２、融点
は１３５℃、粘度は３２００ＣＰ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 (Condensate 10) Condensate 10 was prepared in the same manner as in Comparative 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. Manufactured. The hydroxyl group equivalent was 172, the melting point was 135 ° C., the viscosity was as high as 3200 CP, and the fluidity was extremely poor, resulting in poor workability.
【００８６】（エポキシ樹脂１０）前記縮合物１０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１０は、エポキシ当量２５０
で、融点１１９℃、粘度２６００ＣＰ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 10) An epoxy resin was produced in the same manner as in Example 1 except that the whole amount of the condensate 10 was used. The obtained epoxy resin 10 has an epoxy equivalent of 250.
The melting point was 119 ° C. and the viscosity was as high as 2600 CP, and the workability was poor because the fluidity was extremely poor.
【００８７】実施例９〜１６および比較例３ 下記に示すエポキシ樹脂、硬化剤、硬化促進剤、充填
剤、三酸化アンチモン、シランカップリング剤、ワック
スおよびカーボンブラックを、表１と表２に示す割合
（重量部）で配合して、二本ロールで７０〜１１０℃の
温度にて混練した後に冷却し、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 9 to 16 and Comparative Example 3 Tables 1 and 2 show the epoxy resin, curing agent, curing accelerator, filler, antimony trioxide, silane coupling agent, wax and carbon black shown below. The epoxy resin composition for semiconductor encapsulation was prepared by mixing in a ratio (parts by weight), kneading with a two-roll mill at a temperature of 70 to 110 ° C., then cooling and pulverizing.
【００８８】 エポキシ樹脂：実施例１〜８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 8 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 of Mitsubishi Metals Co., Ltd.)
【００８９】得られた組成物を、１７５℃、１００ｋｇ
／ｃｍ2 、３分間の硬化条件で成形し、次いで、１８０
℃、６時間の条件でポストキュアーさせて成形試験片を
作製した。この試験片は、８０ピン四方向フラットパッ
ケージ（８０ピンＱＦＰ、サイズ２０×１４×２ｍｍ）
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 , molded under curing conditions of 3 minutes, then 180
A post-cure was performed under the conditions of ° C and 6 hours to prepare a molded test piece. This test piece is an 80-pin four-way flat package (80-pin QFP, size 20 x 14 x 2 mm)
And the die pad size is 8 × 8 mm.
【００９０】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 flowability and workability, and good test pieces could not be obtained. It was impossible.
【００９１】[0091]
【表１】 [Table 1]
【００９２】[0092]
【表２】 [Table 2]
【００９３】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
行ないクラック発生数を調べた。また、前記試験片を、
８５℃／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秒間浸漬し
て耐クラック性試験を行なった。結果を表３と表４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 crack resistance test was performed by allowing the sample to stand in a constant temperature bath having a relative humidity of 85 ° C./85% RH to absorb moisture, and then immersing it in a solder melt at 260 ° C. for 10 seconds. The results are shown in Tables 3 and 4.
【００９４】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。結果を表５と表６に示す。The bending strength (high temperature strength) of the obtained test piece at 200 ° C., the glass transition temperature, the coefficient of thermal expansion,
The water absorption was examined after a humidification test at 85 ° C./85% RH for 500 hours. The results are shown in Tables 5 and 6.
【００９５】[0095]
【表３】 [Table 3]
【００９６】[0096]
【表４】 [Table 4]
【００９７】[0097]
【表５】 [Table 5]
【００９８】[0098]
【表６】 [Table 6]
【００９９】[0099]
【発明の効果】本発明のアリルナフトール・β−ナフト
ール共縮合物をベースとしたエポキシ樹脂は、融点およ
び溶融粘度が低く、作業性能に優れている。また、硬化
剤と併用して使用すると、得られるエポキシ樹脂硬化物
が、高いガラス転移温度、耐熱性および耐湿性を有す
る。すなわち、このエポキシ樹脂組成物の硬化物は、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、しかも吸水率が小さく耐湿性に優れ、半田処理に
おいてもクラックの発生が極めて少ない。そのため、本
発明のエポキシ樹脂組成物は、半導体封止用組成物とし
て有用である。The epoxy resin based on the allylnaphthol / β-naphthol cocondensate of the present invention has a low melting point and melt viscosity and is excellent in workability. Further, when used in combination with a curing agent, the obtained epoxy resin cured product has a high glass transition temperature, heat resistance and moisture resistance. That is, the cured product of this epoxy resin composition has a high glass transition temperature, excellent heat resistance, high mechanical strength, low water absorption rate, and excellent moisture resistance, and very few cracks are generated during soldering. Therefore, the epoxy resin composition of the present invention is useful as a semiconductor encapsulating composition.
Claims (4)
子量が３００〜２０００のアリルナフトール共縮合物と
エピハロヒドリンとの反応によって得られる多官能性エ
ポキシ樹脂。 【化１】 1. A polyfunctional epoxy resin obtained by reacting an allylnaphthol cocondensate having a weight average molecular weight of 300 to 2000 represented by the following general formula (I) with epihalohydrin. [Chemical 1]
分子量が３００〜２０００のアリルナフトール共縮合物
とエピハロヒドリンとの反応によって得られる多官能性
エポキシ樹脂。 【化２】 2. A polyfunctional epoxy resin obtained by reacting an allylnaphthol cocondensate having a weight average molecular weight of 300 to 2000, which is represented by the following general formula (II), with epihalohydrin. [Chemical 2]
アルデヒド類とを共縮合させて得られた重量平均分子量
が３００〜２０００のアリルナフトール共縮合物とエピ
ハロヒドリンとの反応によって得られる多官能性エポキ
シ樹脂。3. A polyfunctional epoxy resin obtained by the reaction of an allylnaphthol cocondensate having a weight average molecular weight of 300 to 2000 obtained by cocondensing allylnaphthols, β-naphthol and aldehydes with epihalohydrin. .
ポキシ樹脂と硬化剤を含有してなるエポキシ樹脂組成
物。4. An epoxy resin composition containing the epoxy resin according to claim 1 and a curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04518994A JP3325694B2 (en) | 1994-02-17 | 1994-02-17 | Epoxy resin and epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04518994A JP3325694B2 (en) | 1994-02-17 | 1994-02-17 | Epoxy resin and epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07228663A true JPH07228663A (en) | 1995-08-29 |
| JP3325694B2 JP3325694B2 (en) | 2002-09-17 |
Family
ID=12712327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04518994A Expired - Fee Related JP3325694B2 (en) | 1994-02-17 | 1994-02-17 | Epoxy resin and epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3325694B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020129249A1 (en) * | 2018-12-21 | 2020-06-25 | 日立化成株式会社 | Resin composition for sealing and electronic component device |
-
1994
- 1994-02-17 JP JP04518994A patent/JP3325694B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020129249A1 (en) * | 2018-12-21 | 2020-06-25 | 日立化成株式会社 | Resin composition for sealing and electronic component device |
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| Publication number | Publication date |
|---|---|
| JP3325694B2 (en) | 2002-09-17 |
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