JPH0525248A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH0525248A JPH0525248A JP18635691A JP18635691A JPH0525248A JP H0525248 A JPH0525248 A JP H0525248A JP 18635691 A JP18635691 A JP 18635691A JP 18635691 A JP18635691 A JP 18635691A JP H0525248 A JPH0525248 A JP H0525248A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- molecular weight
- xylenol
- average molecular
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 5
- 238000012935 Averaging Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000011342 resin composition Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 150000001299 aldehydes Chemical class 0.000 description 14
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 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
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 6
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-UHFFFAOYSA-N 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 229940015043 glyoxal Drugs 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 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
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- -1 Aliphatic aldehydes Chemical class 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 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 2
- 239000006229 carbon black Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 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
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-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
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- QMHAHUAQAJVBIW-UHFFFAOYSA-N [methyl(sulfamoyl)amino]methane Chemical compound CN(C)S(N)(=O)=O QMHAHUAQAJVBIW-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 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
- 150000001649 bromium compounds 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 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
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 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
- 150000003944 halohydrins Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid 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
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 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
- 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
- 238000007789 sealing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 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
- 230000008646 thermal stress Effects 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
- 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)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、エポキシ樹脂組成物に
関する。詳しくは、ガラス転移温度が高く、ハンダリフ
ロー温度での強度が大で、かつ吸湿性が少なく、パッケ
ージクラックの入りにくい半導体封止用エポキシ樹脂組
成物に関する。FIELD OF THE INVENTION The present invention relates to an epoxy resin composition. More specifically, the present invention relates to an epoxy resin composition for semiconductor encapsulation, which has a high glass transition temperature, high strength at a solder reflow temperature, low hygroscopicity, and is resistant to package cracks.
【0002】[0002]
【従来の技術】従来、半導体素子を外環境から守るた
め、エポキシ樹脂組成物で封止する方法が広く採用され
てきた。本組成物の一般的な構成は、エポキシ樹脂、硬
化剤、硬化促進剤、充填剤、その他配合剤からなり、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
とを反応したノボラック樹脂をエポキシ化したもの、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、硬化剤に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きた。2. Description of the Related Art Conventionally, a method of encapsulating a semiconductor element with an epoxy resin composition has been widely adopted in order to protect the semiconductor element from the external environment. The general constitution of this composition is composed of an epoxy resin, a curing agent, a curing accelerator, a filler, and other compounding agents, and as the epoxy resin, a novolac resin obtained by reacting phenols with formaldehyde is epoxidized, In particular, orthocresol novolac epoxy resin has been widely used, and phenol formaldehyde novolac resin has been adopted as a curing agent.
【0003】近年、半導体素子はますます高集積化大型
化し、多ピンのフラットパッケージが実用化され、封止
された素子にしめるエポキシ樹脂の割合が減少する傾向
にある。このため封止時に強い応力を受けやすく、実装
方式も表面実装方式がとられ、実装時に樹脂封止された
半導体を溶融ハンダ中に浸せきするため、強い熱ストレ
スを受けるとともに、樹脂内部に吸湿されている水が急
激に気化して体積膨張をおこす厳しい環境にさらされ
る。In recent years, semiconductor devices have become more highly integrated and larger in size, flat packages with a large number of pins have been put into practical use, and the proportion of epoxy resin used in the sealed devices tends to decrease. For this reason, strong stress is likely to occur during sealing, and the mounting method is also the surface mounting method.Since the resin-sealed semiconductor is immersed in molten solder during mounting, strong thermal stress is applied and moisture is absorbed inside the resin. The exposed water is exposed to the severe environment where it vaporizes rapidly and causes volume expansion.
【0004】前記エポキシ樹脂をもちいて、大容量半導
体を封止した場合、パッケージにクラックが発生する問
題が生じ、ボンディングワイヤが変形したり腐食による
断線が生じたり、素子パッシベーションのクラックなど
が発生しやすい問題がある。このため、高性能なエポキ
シ樹脂が種々提案されているが、未だ問題の解決には至
っていない。When a large-capacity semiconductor is encapsulated by using the epoxy resin, there arises a problem that cracks are generated in the package, the bonding wires are deformed or broken due to corrosion, and cracks in element passivation occur. There is an easy problem. Therefore, various high-performance epoxy resins have been proposed, but the problem has not been solved yet.
【0005】[0005]
【発明が解決しようとする課題】本発明は、ガラス転移
温度が高く耐熱性に優れ、かつ耐湿性に優れたパッケー
ジにクラックが発生しにくい、新規な半導体封止用エポ
キシ樹脂組成物を提供することにある。DISCLOSURE OF THE INVENTION The present invention provides a novel epoxy resin composition for semiconductor encapsulation which has a high glass transition temperature, excellent heat resistance, and is resistant to cracks in a package having excellent moisture resistance. Especially.
【0006】[0006]
【課題を解決するための手段】すなわち、本発明は、第
一の発明としてジヒドロキシナフタレンとキシレノール
をアルデヒドで共縮合した平均分子量300〜2000
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
ンとから製造された多官能性エポキシ樹脂を含有するエ
ポキシ樹脂、硬化剤、硬化促進剤を必須成分とするエポ
キシ樹脂組成物であり、第二の発明としてジヒドロキシ
ナフタレンとキシレノールとアルデヒドの共縮合物にお
いて、1分子中にジヒドロキシナフタレン分子単位70
〜30モル%とキシレノール分子単位を30〜70モル
%(アルデヒド分子単位除外換算)含み、平均分子量が
400〜1500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とから製造された多官能性エポキシ
樹脂を含有するエポキシ樹脂、硬化剤、硬化促進剤を必
須成分とするエポキシ樹脂組成物である。That is, the present invention is, as the first invention, an average molecular weight of 300 to 2000 obtained by co-condensing dihydroxynaphthalene and xylenol with an aldehyde.
An epoxy resin composition containing a polyfunctional epoxy resin produced from a polyhydroxynaphthalene-based compound and epihalohydrin, a curing agent, and a curing accelerator as essential components, and dihydroxynaphthalene as the second invention. In the co-condensate of xylenol and aldehyde, dihydroxynaphthalene molecular unit 70 per molecule
Containing 30 to 70 mol% and 30 to 70 mol% of xylenol molecular units (calculated by excluding aldehyde molecular units), and containing a polyfunctional epoxy resin prepared from a polyhydroxynaphthalene compound having an average molecular weight of 400 to 1500 and epihalohydrin. It is an epoxy resin composition containing an epoxy resin, a curing agent, and a curing accelerator as essential components.
【0007】[手段を構成する要件]本発明に使用す
る、ジヒドロキシナフタレンとキシレノールとアルデヒ
ドの共縮合物において、ジヒドロキシナフタレンは、1
・5ジヒドロキシナフタレン、1・6ジヒドロキシナフ
タレン、1・7ジヒドロキシナフタレン、2・6ジヒド
ロキシナフタレン、2・7ジヒドロキシナフタレン、1
・4ジヒドロキシナフタレン、1・2ジヒドロキシナフ
タレン、1・3ジヒドロキシナフタレン、2・3ジヒド
ロキシナフタレンなどが挙げられる。中でも、共重合性
の高い1・6ジヒドロキシナフタレン、2・7ジヒドロ
キシナフタレン、1・4ジヒドロキシナフタレンが特に
好ましい。[Requirements Constituting Means] In the cocondensation product of dihydroxynaphthalene, xylenol and aldehyde used in the present invention, dihydroxynaphthalene is 1
* 5 dihydroxynaphthalene, 1.6 dihydroxynaphthalene, 1.7 dihydroxynaphthalene, 2.6 dihydroxynaphthalene, 2.7 dihydroxynaphthalene, 1
-4 dihydroxy naphthalene, 1.2 dihydroxy naphthalene, 1.3 dihydroxy naphthalene, 2.3 dihydroxy naphthalene etc. are mentioned. Among them, 1,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene, which have high copolymerizability, are particularly preferable.
【0008】キシレノールは、2・3キシレノール、2
・4キシレノール、2・5キシレノール、3・4キシレ
ノール、3・5キシレノールやそれらの混合物が用いら
れ、特に共縮合性の高い3・4キシレノールや3・5キ
シレノールが好ましい。Xylenol is 2.3 xylenol, 2
-4 xylenol, 2.5 xylenol, 3/4 xylenol, 3.5 xylenol, or a mixture thereof is used, and 3.4 xylenol and 3.5 xylenol having high cocondensability are particularly preferable.
【0009】アルデヒドは、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などの芳香族アルデヒド、グリオキ
ザール、テレフタルアルデヒドなどの多価アルデヒドが
利用でき、中でもパラホルムアルデヒド、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、グリオキザール、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。Aldehydes are, for example, formaldehyde,
Aliphatic aldehydes such as paraformaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde,
Benzaldehyde, p-hydroxybenzaldehyde,
Aromatic aldehydes such as salicylaldehyde and polyhydric aldehydes such as glyoxal and terephthalaldehyde can be used. Among them, paraformaldehyde, benzaldehyde, p-hydroxybenzaldehyde, salicylaldehyde, glyoxal 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.
【0010】共縮合物を得るための、各成分の使用量
は、アルデヒド分子を除外した換算でジヒドロキシナフ
タレン70〜30モル%とキシレノール30〜70モル
%の配合物1モルに対しアルデヒド0.3〜0.95モ
ルが好ましく、この時の共縮合物の平均分子量は400
〜1500が望ましい。尚、アルデヒドの使用量を多く
し反応途中でそれらの一部を除去することもできる。The amount of each component used to obtain a cocondensate is 0.3 aldehyde based on 1 mol of a mixture of 70 to 30 mol% of dihydroxynaphthalene and 30 to 70 mol% of xylenol, excluding aldehyde molecules. Is preferably 0.95 mol, and the average molecular weight of the cocondensate at this time is 400.
-1500 is desirable. It is also possible to increase the amount of aldehyde used and remove some of them during the reaction.
【0011】分子中のキシレノール分子単位の含有量が
少ない場合はエポキシ樹脂組成物の耐湿性が悪くなり、
多すぎる場合は耐熱性に問題が生じる。また、アルデヒ
ドの使用量が少ない場合は共縮合物は適正な平均分子量
より小さくなるため耐熱性に劣り、多すぎると平均分子
量が高くなりすぎるため高粘度になり成形性に問題が生
じる。共縮合物の適正な平均分子量は300〜2000
であり、好ましくは400〜1500である。When the content of xylenol molecular units in the molecule is low, the epoxy resin composition has poor moisture resistance,
If it is too large, heat resistance will be a problem. Further, when the amount of aldehyde used is small, the cocondensate becomes smaller than the appropriate average molecular weight, resulting in poor heat resistance. When it is too large, the average molecular weight becomes too high, resulting in high viscosity and a problem in moldability. The proper average molecular weight of the co-condensate is 300 to 2000.
And preferably 400 to 1500.
【0012】共縮合反応は、通常、触媒として酸やアル
カリあるいは最初アルカリを次に酸を用いる2段階法な
どが利用されるが、酸を用いるのが一般的である。酸
は、硫酸、塩酸、硝酸、臭化水素酸などの鉱酸、パラト
ルエンスルホン酸、ベンゼンスルホン酸などのスルホン
酸類、シュウ酸、コハク酸、マロン酸などのカルボン酸
類が使用される。また触媒を用いなくても高温に加熱す
るだけで反応することも可能である。溶媒は必ずしも必
要とするものではないが、ベンゼン、トルエン、クロル
ベンゼン、ジクロルベンゼン、メチルエチルケトン、メ
チルイソブチルケトン、テトラヒドロフラン、ジメチル
スルフォオキシド、ジメチルスルフォアミドなどの溶媒
を用いて反応することができる。反応温度は50〜20
0℃好ましくは脂肪族アルデヒドの場合には60〜15
0℃、芳香族アルデヒドの場合は60〜190℃で、1
〜10時間反応させる。この後、必要により不純物を水
洗して除去したり、溶剤洗浄や減圧脱気で未反応モノマ
ーを除去する。In the co-condensation reaction, a two-step method using an acid or an alkali or a first alkali and then an acid as a catalyst is usually used, but an acid is generally used. As the acid, mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and hydrobromic acid, sulfonic acids such as paratoluenesulfonic acid and benzenesulfonic acid, and carboxylic acids such as oxalic acid, succinic acid and malonic acid are used. It is also possible to react by simply heating to a high temperature without using a catalyst. Although the solvent is not always necessary, it can be reacted using a solvent such as benzene, toluene, chlorobenzene, dichlorobenzene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethyl sulfamide. . Reaction temperature is 50 to 20
0 ° C., preferably 60 to 15 for aliphatic aldehydes
0 ℃, 60-190 ℃ for aromatic aldehyde, 1
Allow to react for 10 hours. Thereafter, if necessary, impurities are washed with water to remove, or unreacted monomers are removed by washing with a solvent or degassing under reduced pressure.
【0013】本発明の共縮合物をベースにした多官能性
エポキシ樹脂は、前記のジヒドロキシナフタレンとキシ
レノールをアルデヒドで共縮合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 cocondensate of the present invention is obtained by reacting the above-mentioned polyhydroxynaphthalene compound obtained by cocondensing dihydroxynaphthalene and xylenol with an aldehyde, and epihalohydrin. The following two typical methods can be used for the reaction.
【0014】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.
【0015】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.
【0016】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.
【0017】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、40〜50%水溶液で反応系に
添加される。Further, as the alkali metal hydroxide in this reaction, caustic soda and caustic potash are used,
These remain as solids or are added to the reaction system as 40-50% aqueous solutions.
【0018】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, triethylbenzylammonium chloride are used.
【0019】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-mentioned 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.
【0020】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.
【0021】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1〜1.1
モル量用いられる。The basic catalyst is used in an amount of 0.002 to 3.0 with respect to 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. The alkali metal hydroxide is 1 to 1.1 with respect to the produced halohydrin.
Used in molar amounts.
【0022】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.
【0023】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、70wt%以下好ましくは50wt%
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Aベースエポキシ
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.
It can also be used in combination with the following general epoxy resins such as ortho-cresol resin epoxy resin, bisphenol A base epoxy resin, and phenol resin epoxy resin.
【0024】次に、本発明の硬化剤は、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 of the present invention has two or more, preferably three or more phenolic hydroxyl groups in the molecule. Specifically, phenol and substituted phenols,
For example, o-cresol, p-cresol, t-butylphenol, cumylphenol, phenylphenol and formaldehyde are reacted with an acid or an alkali. Instead of formaldehyde, other aldehydes such as benzaldehyde, crotonaldehyde,
Those using salicylaldehyde, hydroxybenzaldehyde, glyoxal, and terephthalaldehyde can also be used. A reaction product of resorcin and an aldehyde and polyvinylphenol can also be used as the curing agent of the present invention.
【0025】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 the curing agent is 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 usually 1/0.
The range of 8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1 is selected from the viewpoint of heat resistance and moisture resistance.
【0026】本発明に用いる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 used in the present invention is an ordinary catalyst and is not particularly limited. Specific examples of the curing accelerator include, for example, triphenylphosphine, tris-2,
Phosphorus compounds such as 6-dimethoxyphenylphosphine, tri-p-tolylphosphine, and triphenylphosphite;
2-methylimidazole, 2-phenylimidazole,
2-undecylimidazole, 2-heptadecylimidazole, imidazoles such as 2-ethyl-4-methylimidazole, 2-dimethylaminomethylphenol,
Tertiary amines such as benzyldimethylamine and α-methylbenzylmethylamine, organic of 1,8-diazabicyclo (5,4,0) undecene-7,1,8-diazabicyclo (5,4,0) undecene-7 Examples thereof include acid salts.
【0027】硬化促進剤の配合量は、本発明の組成物中
0.1〜3.0%であるのが耐熱性と耐湿性の点から好
ましい。The compounding amount of the curing accelerator is preferably 0.1 to 3.0% in the composition of the present invention from the viewpoint of heat resistance and moisture resistance.
【0028】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、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, a filler, a surface treatment agent for treating the surface of the filler, a flame retardant, a release agent, a coloring agent, and a flexibility imparting agent.
【0029】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、炭酸カルシュ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, calcium carbonate powder and the like, with silica-based powders being preferred.
【0030】充填剤の配合割合は、全組成物に対して6
0〜90wt%、好ましくは70〜85wt%である。
充填剤の配合量が90wt%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、60wt%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.
It is 0 to 90 wt%, preferably 70 to 85 wt%.
If the blending amount of the filler exceeds 90 wt%, the fluidity of the composition will be low and molding will be difficult. If it is less than 60 wt%, the thermal expansion tends to be large.
【0031】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.
【0032】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.
【0033】[0033]
【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.
【0034】エポキシ樹脂製造例1
共縮合物の製造
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、1・6ジヒドロキシナフタレン107g、
3・4キシレノール41g、パラホルムアルデヒド23
g、シュウ酸0.2gを仕込み、110℃に加熱して窒
素気流下で8時間撹拌して反応した。この後、200℃
に加熱し5mmHgで未反応物と水を除去した。得られ
た共縮合物の平均分子量は630であった。Epoxy Resin Production Example 1 Production of Cocondensate 107 g of 1.6 dihydroxynaphthalene was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet.
41 g of 3.4 xylenol, paraformaldehyde 23
g and 0.2 g of oxalic acid were charged, and the mixture was heated to 110 ° C. and stirred under a nitrogen stream for 8 hours to react. After this, 200 ℃
The mixture was heated to 5 mmHg to remove unreacted materials and water. The average molecular weight of the obtained cocondensate was 630.
【0035】エポキシの製造
前記共縮合物の全量とエピクロルヒドリン2000g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6
7gを加え、生成する水を減圧度100〜150mmH
g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。Production of Epoxy The total amount of the above cocondensate, 2000 g of epichlorohydrin and 3 g of tetrabutylammonium bromide were charged and reacted under heating and reflux for 3 hours, and excess epichlorohydrin was removed under reduced pressure. Add the same amount of toluene as the contents, 60
Cool to ℃, attach a water removal device, and add sodium hydroxide 6
7g is added and the generated water is decompressed at 100 to 150mmH.
The ring-closing reaction was carried out while continuously removing with g. After washing with water to remove salts and unreacted alkali, toluene and water were removed under reduced pressure.
【0036】エポキシ樹脂製造例2
共縮合物の製造において、1・6ジヒドロキシナフタレ
ンの替わりに1・4ジヒドロキシナフタレンを80g用
い、3・5キシレノールを61g、パラホルムアルデヒ
ドを21g、カセイソーダを60gとした以外は製造例
1と同様にエポキシ樹脂を製造した。得られた共縮合物
の平均分子量は510であった。Production Example 2 of Epoxy Resin In the production of a cocondensation product, 80 g of 1.4 dihydroxynaphthalene was used instead of 1.6 dihydroxynaphthalene, except that 61 g of 3.5 xylenol, 21 g of paraformaldehyde and 60 g of caustic soda were used. Produced an epoxy resin in the same manner as in Production Example 1. The average molecular weight of the obtained cocondensate was 510.
【0037】エポキシ樹脂製造例3
共縮合物の製造において、1・6ジヒドロキシナフタレ
ンの替わりに2・7ジヒドロキシナフタレンを54g用
い、3・5キシレノールを82g、パラホルムアルデヒ
ドを27g、カセイソーダを53gとした以外は製造例
1と同様にエポキシ樹脂を製造した。得られた共縮合物
の平均分子量は880であった。Epoxy resin production example 3 In the production of a cocondensation product, 54 g of 2.7 dihydroxynaphthalene was used instead of 1.6 dihydroxynaphthalene, 82 g of 3.5 xylenol, 27 g of paraformaldehyde and 53 g of caustic soda were used. Produced an epoxy resin in the same manner as in Production Example 1. The average molecular weight of the obtained cocondensate was 880.
【0038】エポキシ樹脂製造例4
共縮合物の製造において、パラホルムアルデヒドの替わ
りにベンズアルデヒド90g、シュウ酸の替わりにp−
トルエンスルホン酸を用い、その他は製造例2と同様に
エポキシ樹脂を製造した。得られた共縮合物の平均分子
量は1030であった。Production Example 4 of Epoxy Resin In the production of a cocondensation product, 90 g of benzaldehyde was used instead of paraformaldehyde, and p- was used instead of oxalic acid.
An epoxy resin was produced in the same manner as in Production Example 2 except that toluenesulfonic acid was used. The average molecular weight of the obtained cocondensate was 1030.
【0039】エポキシ樹脂製造例5
共縮合物の製造において、ベンズアルデヒドの替わりに
p−ヒドロキシベンズアルデヒド98gを用い、反応温
度を180℃にした以外は製造例4と同様にエポキシ樹
脂を製造した。得られた共縮合物の平均分子量は112
0であった。Epoxy Resin Production Example 5 An epoxy resin was produced in the same manner as in Production Example 4 except that 98 g of p-hydroxybenzaldehyde was used instead of benzaldehyde in the production of the co-condensate, and the reaction temperature was 180 ° C. The average molecular weight of the obtained cocondensate was 112.
It was 0.
【0040】エポキシ樹脂製造例6
共縮合物の製造において、ベンズアルデヒドの替わりに
グリオキザール25gを用い、その他は製造例4と同様
にエポキシ樹脂を製造した。得られた共縮合物の平均分
子量は750であった。Epoxy Resin Production Example 6 An epoxy resin was produced in the same manner as in Production Example 4 except that 25 g of glyoxal was used instead of benzaldehyde in the production of the cocondensate. The average molecular weight of the obtained cocondensate was 750.
【0041】エポキシ樹脂製造例7
共縮合物の製造において、ベンズアルデヒドの替わりに
テレフタルアルデヒド57gを用い、その他は製造例4
と同様にエポキシ樹脂を製造した。得られた共縮合物の
平均分子量は760であった。Production Example 7 of Epoxy Resin In the production of the co-condensate, 57 g of terephthalaldehyde was used in place of benzaldehyde, and other production example 4 was used.
An epoxy resin was produced in the same manner as in. The average molecular weight of the obtained cocondensate was 760.
【0042】実施例1〜7及び比較例1
エポキシ樹脂として、エポキシ樹脂製造例1〜7で得ら
れた各エポキシ樹脂、市販のo−クレゾールノボラック
エポキシ樹脂(日本化薬(株)のEOCN1020)及
び市販の臭素化フェノールノボラックエポキシ樹脂(日
本化薬(株)のBREN−S)を用い、硬化剤としては
フェノールノボラック樹脂(荒川化学(株)のタマノー
ル752)を、硬化促進剤としてはトリフェニルフォス
フィン、充填剤としては球状シリカ(三菱金属(株)の
BF100)、及びその他の材料として三酸化アンチモ
ン、シランカップリング剤、ワックス、カーボンブラッ
クを用い、表1に示す割合で配合して、二本ロールで7
0〜110℃の温度にて混練したのち冷却し、紛砕して
半導体封止用エポキシ樹脂組成物を調製した。Examples 1 to 7 and Comparative Example 1 As the epoxy resin, each epoxy resin obtained in Production Examples 1 to 7 of epoxy resin, commercially available o-cresol novolac epoxy resin (EOCN1020 manufactured by Nippon Kayaku Co., Ltd.), and A commercially available brominated phenol novolac epoxy resin (BREN-S manufactured by Nippon Kayaku Co., Ltd.) was used, a phenol novolac resin (Tamanol 752 manufactured by Arakawa Chemical Co., Ltd.) was used as a curing agent, and triphenylphosphine was used as a curing accelerator. Fins, spherical silica (BF100 manufactured by Mitsubishi Metals Co., Ltd.) as a filler, and antimony trioxide, a silane coupling agent, a wax, and a carbon black as other materials are blended in the proportions shown in Table 1, and 7 with this roll
After kneading at a temperature of 0 to 110 ° C., the mixture was cooled and pulverized to prepare an epoxy resin composition for semiconductor encapsulation.
【0043】得られた組成物を、175℃、100kg
/cm2、3分間の硬化条件で成形し、ついで180
℃、6時間の条件でポストキュアーさせ成形試験片を作
成した。The composition obtained was treated at 175 ° C. and 100 kg.
/ Cm 2 , molded under curing conditions of 3 minutes, then 180
Post-curing was performed under the conditions of ° C and 6 hours to prepare a molded test piece.
【0044】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
べるとともに、耐ヒートショック性を次のように試験し
た。The bending strength (high temperature strength) of the obtained test piece at 200 ° C., the glass transition temperature, the coefficient of thermal expansion, 85
The water absorption after a humidity test at 500 ° C. and 85% RH for 500 hours was examined, and the heat shock resistance was tested as follows.
【0045】耐ヒートショック性
ダイボンディングプレート上に半導体素子を置き、小型
IC成形品を10個作成する。85℃、85%RH、7
2時間後、液体窒素と260℃の半田浴にそれぞれ10
秒間浸せきし、クラックの発生が生じた個数を調べた。A semiconductor element is placed on a heat shock resistant die bonding plate, and ten small IC molded products are prepared. 85 ° C, 85% RH, 7
After 2 hours, 10 times each in liquid nitrogen and a solder bath at 260 ° C.
It was soaked for a second, and the number of occurrence of cracks was examined.
【0046】これらの結果を表2に示す。The results are shown in Table 2.
【0047】[0047]
【表1】 [Table 1]
【0048】[0048]
【表2】 [Table 2]
【0049】[0049]
【発明の効果】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、しかもキシレノールを分子中に骨格として
含むため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きわめて少ないためICの封止
に適する。EFFECT OF THE INVENTION The epoxy resin composition of the present invention has a high glass transition temperature of a cured resin, excellent heat resistance, high mechanical strength, and low moisture absorption rate since it contains xylenol in the molecule as a skeleton. It is suitable for IC encapsulation because it has excellent crack resistance and extremely few cracks even during soldering.
フロントページの続き (72)発明者 秋月 伸也 大阪府茨木市下穂積1丁目1番2号 日東 電工株式会社内Continued front page (72) Inventor Shinya Akizuki 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Electric Works Co., Ltd.
Claims (2)
をアルデヒドで共縮合した平均分子量300〜2000
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
ンとから製造された多官能性エポキシ樹脂を含有するエ
ポキシ樹脂、硬化剤、硬化促進剤を必須成分とするエポ
キシ樹脂組成物。1. An average molecular weight of 300 to 2000 obtained by co-condensing dihydroxynaphthalene and xylenol with an aldehyde.
An epoxy resin composition containing, as essential components, an epoxy resin containing a polyfunctional epoxy resin produced from the polyhydroxynaphthalene-based compound and epihalohydrin, a curing agent, and a curing accelerator.
とアルデヒドの共縮合物において、1分子中にジヒドロ
キシナフタレン分子単位70〜30モル%とキシレノー
ル分子単位を30〜70モル%(アルデヒド分子単位除
外換算)含み、平均分子量が400〜1500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とから
製造された多官能性エポキシ樹脂を含有するエポキシ樹
脂、硬化剤、硬化促進剤を必須成分とするエポキシ樹脂
組成物。2. A cocondensation product of dihydroxynaphthalene, xylenol, and aldehyde, containing 70 to 30 mol% of dihydroxynaphthalene molecular units and 30 to 70 mol% of xylenol molecular units (converted to exclude aldehyde molecular units) in one molecule, and averaging An epoxy resin composition containing, as essential components, an epoxy resin containing a polyfunctional epoxy resin produced from a polyhydroxynaphthalene compound having a molecular weight of 400 to 1500 and epihalohydrin, a curing agent, and a curing accelerator.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18635691A JPH0525248A (en) | 1991-07-25 | 1991-07-25 | Epoxy resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18635691A JPH0525248A (en) | 1991-07-25 | 1991-07-25 | Epoxy resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0525248A true JPH0525248A (en) | 1993-02-02 |
Family
ID=16186935
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18635691A Pending JPH0525248A (en) | 1991-07-25 | 1991-07-25 | Epoxy resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0525248A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010047169A1 (en) * | 2008-10-22 | 2010-04-29 | Dic株式会社 | Curable resin composition and cured product thereof, printed circuit board, and epoxy resin and method for producing same |
-
1991
- 1991-07-25 JP JP18635691A patent/JPH0525248A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010047169A1 (en) * | 2008-10-22 | 2010-04-29 | Dic株式会社 | Curable resin composition and cured product thereof, printed circuit board, and epoxy resin and method for producing same |
JP4591801B2 (en) * | 2008-10-22 | 2010-12-01 | Dic株式会社 | Curable resin composition, cured product thereof, printed wiring board, epoxy resin, and production method thereof |
JPWO2010047169A1 (en) * | 2008-10-22 | 2012-03-22 | Dic株式会社 | Curable resin composition, cured product thereof, printed wiring board, epoxy resin, and production method thereof |
US8168731B2 (en) | 2008-10-22 | 2012-05-01 | Dic Corporation | Curable resin composition, cured product thereof, printed wiring board, epoxy resin, and process for producing the same |
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