JP2013249280A - Phenolic oligomer, method for producing the same and use thereof - Google Patents
Phenolic oligomer, method for producing the same and use thereof Download PDFInfo
- Publication number
- JP2013249280A JP2013249280A JP2012125256A JP2012125256A JP2013249280A JP 2013249280 A JP2013249280 A JP 2013249280A JP 2012125256 A JP2012125256 A JP 2012125256A JP 2012125256 A JP2012125256 A JP 2012125256A JP 2013249280 A JP2013249280 A JP 2013249280A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- phenolic
- epoxy resin
- group
- oligomer
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 60
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 150000002989 phenols Chemical class 0.000 claims abstract description 26
- 238000000434 field desorption mass spectrometry Methods 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 20
- -1 benzoquinone compound Chemical class 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 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 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 229920000642 polymer Polymers 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 11
- 150000004054 benzoquinones Chemical class 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000005259 measurement Methods 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229940005561 1,4-benzoquinone Drugs 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 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 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000021736 acetylation Effects 0.000 description 5
- 238000006640 acetylation reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 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 4
- 229930003836 cresol Natural products 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- 125000006839 xylylene group Chemical group 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- QTERLAXNZRFFMZ-UHFFFAOYSA-N 1,1-dimethyl-3-(4-methylphenyl)urea Chemical compound CN(C)C(=O)NC1=CC=C(C)C=C1 QTERLAXNZRFFMZ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-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
- PESXPUCWMKUMSI-UHFFFAOYSA-N 3-[2-(dimethylcarbamoylamino)phenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=CC=C1NC(=O)N(C)C PESXPUCWMKUMSI-UHFFFAOYSA-N 0.000 description 1
- KDQTUCKOAOGTLT-UHFFFAOYSA-N 3-[3-(dimethylcarbamoylamino)-4-methylphenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=C(C)C(NC(=O)N(C)C)=C1 KDQTUCKOAOGTLT-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- GCSYGOYJCLNLJT-UHFFFAOYSA-N CC1=C(C=CC=C1)NC(N(C)C)=O.C1(=CC=CC=C1)NC(N(C)C)=O Chemical compound CC1=C(C=CC=C1)NC(N(C)C)=O.C1(=CC=CC=C1)NC(N(C)C)=O GCSYGOYJCLNLJT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PLQFLSNFGHYRJO-UHFFFAOYSA-J [O-]B([O-])[O-].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound [O-]B([O-])[O-].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1.c1ccc(cc1)[P+](c1ccccc1)(c1ccccc1)c1ccccc1 PLQFLSNFGHYRJO-UHFFFAOYSA-J 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 150000001412 amines Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium 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
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明はフェノール系オリゴマー、その製法及び用途に関する。さらに詳しくは、従来公知のフェノール系硬化剤以上の耐熱性と合わせて難燃性にも優れたフェノール系硬化剤として有用なフェノール系オリゴマーに関する。 The present invention relates to a phenolic oligomer, a method for producing the same, and an application thereof. More specifically, the present invention relates to a phenolic oligomer useful as a phenolic curing agent having excellent heat resistance as well as heat resistance higher than that of conventionally known phenolic curing agents.
フェノール系オリゴマーはエポキシ樹脂の硬化剤として大きな一群を占めるなど有用な化合物であり、構造の多様性や低コストの観点から各種産業に用いられている。これらは産業の技術革新にともない様々な要求性能に応えるべく多種多様なものがこれまでに作り出されてきた。 Phenol-based oligomers are useful compounds that occupy a large group as curing agents for epoxy resins, and are used in various industries from the viewpoint of structural diversity and low cost. A wide variety of these products have been created so far to meet various performance requirements accompanying industrial technological innovation.
とりわけ近年では地球環境への配慮により、これまで利用されてきたハロゲン含有系化合物や、アンチモン化合物などの難燃剤に代わる、新規な難燃性エポキシ樹脂組成物の要求が高まっており、汎用パッケージから先端パッケージ用に至る用途で使用されていたフェノールアラルキル樹脂にもハロゲン系難燃剤及びアンチモン化合物を用いなくても優れた難燃性を有することが求められている(例えば特許文献1など)。なかでもビフェニル骨格を導入したフェノールアラルキル樹脂は、高難燃性の硬化剤であることが知られており、先端パッケージ用途で使用されているが、ガラス転移温度(Tg)が低くなるという欠点がある(例えば特許文献2など)。Tgの低下は一般に高温信頼性と耐熱性の低下を引き起こすため、これを改善できるエポキシ樹脂硬化剤の提供が望まれていた。 Particularly in recent years, due to consideration for the global environment, there is an increasing demand for new flame retardant epoxy resin compositions to replace flame retardants such as halogen-containing compounds and antimony compounds that have been used so far. The phenol aralkyl resin that has been used for leading-edge packages is also required to have excellent flame retardancy without using a halogen-based flame retardant and an antimony compound (for example, Patent Document 1). Among them, a phenol aralkyl resin having a biphenyl skeleton introduced therein is known to be a highly flame retardant curing agent and is used in advanced package applications, but has a drawback of low glass transition temperature (Tg). Yes (for example, Patent Document 2). Since a decrease in Tg generally causes a decrease in high temperature reliability and heat resistance, it has been desired to provide an epoxy resin curing agent that can improve this.
一方、耐熱性を有する硬化剤としては、水酸基当量が小さくトリフェノールメタン構造を持つ多官能型フェノール系オリゴマーが代表的である(例えば特許文献3〜4など)。しかしこのようなトリフェノールメタン構造を持つ樹脂は耐燃性に乏しいことが難点であった(例えば特許文献5など)。 On the other hand, as the curing agent having heat resistance, a polyfunctional phenol-based oligomer having a small hydroxyl equivalent and a triphenolmethane structure is representative (for example, Patent Documents 3 to 4). However, it has been difficult for such a resin having a triphenolmethane structure to have poor flame resistance (for example, Patent Document 5).
上記課題を改善するため、鋭意検討を行った結果、従来公知のフェノール樹脂をベンゾキノン類で変性処理することにより、所望のフェノール系硬化剤を得ることが可能であることを見出した。
すなわち本発明は、高耐熱性および高難燃性の特性両立を実現する新規なフェノール系硬化剤として有用なフェノール系オリゴマー、その製法及び用途を提供することにある。
As a result of intensive studies to improve the above problems, it has been found that a desired phenolic curing agent can be obtained by modifying a conventionally known phenol resin with benzoquinones.
That is, this invention is providing the phenolic oligomer useful as a novel phenolic hardening | curing agent which implement | achieves the characteristics of high heat resistance and high flame retardance, its manufacturing method, and an application.
本発明は、下記一般式(1)で示されるフェノール性化合物に下記一般式(4)または(5)で示されるベンゾキノン類を、該一般式(1)の架橋基Xのモル数に対して0.2〜5.0モル倍のベンゾキノン類を反応させて得られる反応生成物であって、反応生成物の質量分析(FD−MS)において該フェノール性化合物の分子量と該ベンゾキノン類の分子量を和する分子量を有する成分が観測されることを特徴とするフェノール系オリゴマーを提供する。 In the present invention, the benzoquinone represented by the following general formula (4) or (5) is added to the phenolic compound represented by the following general formula (1) with respect to the number of moles of the crosslinking group X of the general formula (1). A reaction product obtained by reacting 0.2 to 5.0 moles of a benzoquinone compound, wherein the molecular weight of the phenolic compound and the molecular weight of the benzoquinone compound are determined in mass spectrometry (FD-MS) of the reaction product. Provided is a phenolic oligomer characterized in that a component having a molecular weight to be summed is observed.
前記一般式(1)で示されるフェノール性化合物の水酸基当量が60〜250g/eqであり、得られたフェノール系オリゴマーの水酸基当量がフェノール性化合物よりも低い前記したフェノール系オリゴマーは、本発明の好ましい態様である。 The phenolic oligomer represented by the general formula (1) has a hydroxyl group equivalent of 60 to 250 g / eq, and the phenolic oligomer obtained has a hydroxyl group equivalent lower than that of the phenolic compound. This is a preferred embodiment.
本発明はまた、一般式(1)で示されるフェノール性化合物に、一般式(4)または(5)で示されるベンゾキノン類を、一般式(1)の架橋基Xのモル数に対して0.2〜5.0モル倍の割合で反応させる前記したフェノール系オリゴマーの製造方法を提供する。 In the present invention, the benzoquinone represented by the general formula (4) or (5) is added to the phenolic compound represented by the general formula (1) with respect to the number of moles of the crosslinking group X of the general formula (1). Provided is a method for producing the above-described phenolic oligomer that is reacted at a ratio of 2 to 5.0 mole times.
本発明はさらに、前記したフェノール系オリゴマーからなるエポキシ樹脂用硬化剤、該エポキシ樹脂用硬化剤と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。エポキシ樹脂組成物がさらに無機充填剤、硬化促進剤を含有する態様は本発明の好ましい態様である。 The present invention further provides an epoxy resin curing agent comprising the above-described phenolic oligomer, and an epoxy resin composition containing the epoxy resin curing agent and an epoxy resin. An embodiment in which the epoxy resin composition further contains an inorganic filler and a curing accelerator is a preferred embodiment of the present invention.
本発明はさらにまた前記エポキシ樹脂組成物で封止された半導体装置、エポキシ樹脂組成物で作成された基板材料及びエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物を提供する。 The present invention further provides a semiconductor device sealed with the epoxy resin composition, a substrate material made of the epoxy resin composition, and a cured epoxy resin obtained by curing the epoxy resin composition.
本発明により、従来公知のフェノール系硬化剤以上の耐熱性と合わせて難燃性にも優れる新規なフェノール系硬化剤として有用なフェノール系オリゴマーが提供される。 According to the present invention, there is provided a phenolic oligomer useful as a novel phenolic curing agent having excellent heat resistance as well as heat resistance higher than that of conventionally known phenolic curing agents.
本発明は、下記一般式(1)で示されるフェノール性化合物に下記一般式(4)または(5)で示されるベンゾキノン類を、該一般式(1)の架橋基Xのモル数に対して0.2〜5.0モル倍のベンゾキノン類を反応させて得られる反応生成物であって、反応生成物の質量分析(FD−MS)において該フェノール性化合物の分子量と該ベンゾキノン類の分子量を和する分子量を有する成分が観測されることを特徴とするフェノール系オリゴマーを提供する。 In the present invention, the benzoquinone represented by the following general formula (4) or (5) is added to the phenolic compound represented by the following general formula (1) with respect to the number of moles of the crosslinking group X of the general formula (1). A reaction product obtained by reacting 0.2 to 5.0 moles of a benzoquinone compound, wherein the molecular weight of the phenolic compound and the molecular weight of the benzoquinone compound are determined in mass spectrometry (FD-MS) of the reaction product. Provided is a phenolic oligomer characterized in that a component having a molecular weight to be summed is observed.
前記一般式(1)における架橋基Xが、下記一般式(6)または下記一般式(7)で示される2価の炭化水素基を含む基であるフェノール性化合物は、本発明の好ましい態様である。 The phenolic compound in which the bridging group X in the general formula (1) is a group containing a divalent hydrocarbon group represented by the following general formula (6) or the following general formula (7) is a preferred embodiment of the present invention. is there.
また、前記一般式(1)におけるAr1及びAr2が、無置換のフェニル基であるフェノール性化合物は、本発明の好ましい態様である。 Moreover, the phenolic compound whose Ar < 1 > and Ar < 2 > in the said General formula (1) are unsubstituted phenyl groups is a preferable aspect of this invention.
前記式(1)で示されるフェノール性化合物としては、ビスフェノールF、ビスフェノールA、ビスフェノールS、ビス(ヒドロキシフェニル)エーテル、ビス(ヒドロキシフェニル)スルフィド、フェノールノボラック樹脂、クレゾールノボラック樹脂、フェノールアラルキル樹脂、クレゾールアラルキル樹脂、フェノールビフェニルアラルキル樹脂、フェノールナフチルアラルキル樹脂、ナフトールアラルキル樹脂、トリフェノールメタン型ノボラック樹脂、ジシクロペンタジエン変性フェノール樹脂、ジヒドロキシベンゼンまたはジヒドロキシナフタレンのメチレン架橋物、ジヒドロキシベンゼンまたはジヒドロキシナフタレンのキシリレン架橋物などを挙げることができる。とりわけこれらのフェノール性化合物中、耐燃性および高耐熱性の観点から好ましいフェノール性化合物としては、フェノールアラルキル樹脂、クレゾールアラルキル樹脂、フェノールビフェニルアラルキル樹脂、フェノールナフチルアラルキル樹脂、ナフトールアラルキル樹脂、ジヒドロキシベンゼンまたはジヒドロキシナフタレンのキシリレン架橋物を挙げることができる。これらフェノール性化合物の水酸基当量は、60〜250g/eqの範囲内であることが好ましい。 Examples of the phenolic compound represented by the formula (1) include bisphenol F, bisphenol A, bisphenol S, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) sulfide, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol. Aralkyl resin, phenol biphenyl aralkyl resin, phenol naphthyl aralkyl resin, naphthol aralkyl resin, triphenolmethane type novolak resin, dicyclopentadiene modified phenol resin, methylene crosslinked product of dihydroxybenzene or dihydroxynaphthalene, xylylene crosslinked product of dihydroxybenzene or dihydroxynaphthalene And so on. Among these phenolic compounds, preferred phenolic compounds from the viewpoint of flame resistance and high heat resistance include phenol aralkyl resins, cresol aralkyl resins, phenol biphenyl aralkyl resins, phenol naphthyl aralkyl resins, naphthol aralkyl resins, dihydroxybenzene or dihydroxy. A xylylene cross-linked product of naphthalene can be mentioned. The hydroxyl equivalent of these phenolic compounds is preferably in the range of 60 to 250 g / eq.
本発明のフェノール系オリゴマーとしては、原料のフェノール性化合物の水酸基当量と比べると、水酸基当量が低くなっているものが好ましい。水酸基当量が低くなるということは、水酸基が増えていることを意味する。後記実施例1において、得られたフェノール系オリゴマーのFD−MS分析において、フェノール性化合物の分子量とベンゾキノン類の分子量を和する分子量を有する成分が観測されていることから、ベンゾキノン類はフェノール類とマイケル付加してヒドロキノン型に変化し水酸基リッチになっているためと推定される。 As the phenolic oligomer of the present invention, those having a lower hydroxyl equivalent than the hydroxyl equivalent of the starting phenolic compound are preferred. A low hydroxyl equivalent means an increase in hydroxyl groups. In Example 1 described later, in the FD-MS analysis of the obtained phenol-based oligomer, a component having a molecular weight that combines the molecular weight of the phenolic compound and the molecular weight of the benzoquinones is observed. It is presumed that Michael was added to the hydroquinone type and became rich in hydroxyl groups.
本発明のフェノール系オリゴマーの水酸基当量としては、50〜220g/eq、好ましくは80〜180g/eqであることが望ましく、溶融粘度としてはICI溶融粘度計により測定した150℃の溶融粘度として50〜1000mPa・s、好ましくは70〜500mPa・sであることが望ましい。また、本発明のフェノール系オリゴマーの軟化点は、50〜120℃、好ましくは70〜100℃であることが望ましい。 The hydroxyl group equivalent of the phenolic oligomer of the present invention is 50 to 220 g / eq, preferably 80 to 180 g / eq, and the melt viscosity is 50 to 150 ° C. as measured by an ICI melt viscometer. It is 1000 mPa · s, preferably 70 to 500 mPa · s. The softening point of the phenolic oligomer of the present invention is 50 to 120 ° C, preferably 70 to 100 ° C.
本発明のフェノール系オリゴマーは、前記一般式(1)で示されるフェノール性化合物に、前記一般式(4)または(5)で示されるベンゾキノン類を、一般式(1)の架橋基Xのモル数に対して0.2〜5.0モル倍の割合で反応させることによって製造することができる。 In the phenolic oligomer of the present invention, the phenolic compound represented by the general formula (1) is mixed with the benzoquinone represented by the general formula (4) or (5) by the mole of the crosslinking group X of the general formula (1). It can manufacture by making it react in the ratio of 0.2-5.0 mol times with respect to a number.
フェノール性化合物とベンゾキノン類の反応条件には特に制限はないが、反応温度としては80〜200℃程度が好ましい。このとき触媒は必要に応じて添加することができ、原料のフェノール性化合物および反応生成物のフェノール系オリゴマーに対し酸化作用を示さないものが選ばれる。具体的には、塩酸、蟻酸、蓚酸、p−トルエンスルホン酸、トリフルオロメタンスルホン酸などのプロトン酸類、弗化ホウ素、塩化アルミニウム、塩化亜鉛、塩化鉄、塩化錫、塩化チタン、テトラアルコキシチタンなどのルイス酸類、トリエチルアミン、ジメチルアミノピリジン、1,8−ジアザビシクロ(5,4,0)ウンデセン−7などのアミン類が使用される。 Although there is no restriction | limiting in particular in the reaction conditions of a phenolic compound and benzoquinones, About 80-200 degreeC is preferable as reaction temperature. At this time, the catalyst can be added as required, and a catalyst that does not oxidize the phenolic compound as a raw material and the phenolic oligomer as a reaction product is selected. Specifically, proton acids such as hydrochloric acid, formic acid, oxalic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, boron fluoride, aluminum chloride, zinc chloride, iron chloride, tin chloride, titanium chloride, tetraalkoxytitanium, etc. Amines such as Lewis acids, triethylamine, dimethylaminopyridine, 1,8-diazabicyclo (5,4,0) undecene-7 are used.
前記一般式(1)で示されるフェノール性化合物が反応系中に生成する条件下でベンゾキノン類と反応させることもできる。このようなフェノール性化合物が反応系中で生成する条件下として、例えば下記一般式(8)又は(9)で示される化合物1モルに対しフェノールを1.5〜25モル倍量で反応させる条件などを挙げることができる。 It can also be reacted with benzoquinones under conditions where the phenolic compound represented by the general formula (1) is generated in the reaction system. As conditions under which such a phenolic compound is produced in the reaction system, for example, conditions in which phenol is reacted in an amount of 1.5 to 25 moles per mole of the compound represented by the following general formula (8) or (9) And so on.
本発明のフェノール系オリゴマーは、エポキシ樹脂の硬化剤のほか、エピクロロヒドリンとの反応により合成することができるエポキシ樹脂の原料等の使用が可能である。以下に、エポキシ樹脂の硬化剤への使用について説明する。 In addition to the epoxy resin curing agent, the phenolic oligomer of the present invention can be used as an epoxy resin raw material that can be synthesized by reaction with epichlorohydrin. Below, use to the hardening | curing agent of an epoxy resin is demonstrated.
本発明のエポキシ樹脂組成物は、前記したエポキシ樹脂硬化剤とエポキシ樹脂とを含むエポキシ樹脂組成物である。エポキシ樹脂組成物において、上記エポキシ樹脂硬化剤とともに使用することができるエポキシ樹脂としては、例えばビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノールビフェニルアラルキル型エポキシ樹脂、フェノール、ナフトールなどのキシリレン結合によるアラルキル樹脂のエポキシ化物、ジシクロペンタジエン型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂などのグリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂などの一分子中にエポキシ基を2個以上有するエポキシ化合物が挙げられる。これらエポキシ樹脂は単独使用でも2種類以上併用してもよい。耐湿性、熱時低弾性率、難燃性を考慮すると、ビスフェノールF型エポキシ樹脂、ビフェニル型エポキシ樹脂などの2官能型エポキシ樹脂や、フェノ−ルビフェニルアラルキル型エポキシ樹脂、フェノール、ナフトールなどのキシリレン結合によるアラルキル樹脂のエポキシ化物などから選ばれる芳香環の多い多官能型エポキシ樹脂を使用するのが好ましい。 The epoxy resin composition of the present invention is an epoxy resin composition containing the above-described epoxy resin curing agent and an epoxy resin. Examples of the epoxy resin that can be used with the epoxy resin curing agent in the epoxy resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolak type epoxy resin, and biphenyl type epoxy. Resin, phenol biphenyl aralkyl type epoxy resin, epoxidized aralkyl resin by xylylene bond such as phenol, naphthol, glycidyl ether type epoxy resin such as dicyclopentadiene type epoxy resin, dihydroxynaphthalene type epoxy resin, triphenolmethane type epoxy resin, Examples include epoxy compounds having two or more epoxy groups in one molecule such as glycidyl ester type epoxy resin and glycidyl amine type epoxy resin. It is. These epoxy resins may be used alone or in combination of two or more. In consideration of moisture resistance, low elastic modulus during heat and flame retardancy, bifunctional epoxy resins such as bisphenol F type epoxy resin and biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, xylylene such as phenol and naphthol It is preferable to use a polyfunctional epoxy resin having many aromatic rings selected from epoxidized aralkyl resins by bonding.
エポキシ樹脂の硬化に際しては、硬化促進剤として、エポキシ樹脂をフェノール系硬化剤で硬化させるための公知の硬化促進剤を用いることができ、例えば、3級アミン化合物、4級アンモニウム塩、イミダゾール類、尿素化合物、ホスフィン化合物、ホスホニウム塩などを挙げることができる。より具体的には、トリエチルアミン、トリエチレンジアミン、ベンジルジメチルアミン、2,4,6−トリス(ジメチルアミノメチル)フェノール、1,8−ジアザビシクロ(5,4,0)ウンデセン−7などの3級アミン化合物、2−メチルイミダゾール、2,4−ジメチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾールなどのイミダゾール類、3−フェニル−1,1−ジメチルウレア、3−(o−メチルフェニル)−1,1−ジメチルウレア、3−(p−メチルフェニル)−1,1−ジメチルウレア、1,1’−フェニレンビス(3,3−ジメチルウレア)、1,1’−(4−メチル−m−フェニレン)−ビス(3,3−ジメチルウレア)などの尿素化合物、トリフェニルホスフィン、トリブチルホスフィン、トリ(p−メチルフェニル)ホスフィン、トリ(ノニルフェニル)ホスフィンなどのホスフィン化合物、トリフェニルホスホニオフェノラート、テトラフェニルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムテトラナフトエ酸ボレートなどのホスホニウム塩を挙げることができる。これら硬化促進剤は、単独で使用することができるし、2種類以上を併用してもよい。 In curing the epoxy resin, a known curing accelerator for curing the epoxy resin with a phenolic curing agent can be used as a curing accelerator, such as a tertiary amine compound, a quaternary ammonium salt, an imidazole, Examples include urea compounds, phosphine compounds, and phosphonium salts. More specifically, tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 Imidazoles such as 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 3-phenyl-1,1-dimethylurea 3- (o-methylphenyl) -1,1-dimethylurea, 3- (p-methylphenyl) -1,1-dimethylurea, 1,1′-phenylenebis (3,3-dimethylurea), 1 , 1 ′-(4-methyl-m-phenylene) -bis (3,3-dimethylurea) and other urea compounds, Phosphine compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphoniphenolate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetranaphthoate borate, etc. Mention may be made of phosphonium salts. These curing accelerators can be used alone or in combination of two or more.
本発明のエポキシ樹脂組成物には、必要に応じて無機充填剤、カップリング剤、離型剤、着色剤、難燃剤、低応力剤などを添加または予め反応して用いることができる。また他の硬化剤を併用することもできる。このような他の硬化剤の例として、フェノールノボラック樹脂、フェノールアラルキル樹脂、フェノールビフェニルアラルキル樹脂、フェノールナフチルアラルキル樹脂、ナフトールアラルキル樹脂、トリフェノールメタン型ノボラック樹脂などを挙げることができる。 In the epoxy resin composition of the present invention, an inorganic filler, a coupling agent, a release agent, a colorant, a flame retardant, a low stress agent, or the like can be added or reacted in advance if necessary. Other curing agents can be used in combination. Examples of such other curing agents include phenol novolak resins, phenol aralkyl resins, phenol biphenyl aralkyl resins, phenol naphthyl aralkyl resins, naphthol aralkyl resins, and triphenolmethane type novolak resins.
無機充填剤の例として、非晶性シリカ、結晶性シリカ、アルミナ、ガラス、珪酸カルシウム、マグネサイト、クレー、タルク、マイカ、マグネシア、硫酸バリウムなどを挙げることができるが、とくに非晶性シリカ、結晶性シリカ、硫酸バリウムが好ましい。また優れた成形性を維持しつつ充填剤の配合量を高めたい場合は、細密充填を可能とするような粒度分布の広い球形の充填剤を使用することが好ましい。 Examples of inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesite, clay, talc, mica, magnesia, barium sulfate, etc., especially amorphous silica, Crystalline silica and barium sulfate are preferred. When it is desired to increase the blending amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine packing.
カップリング剤の例としては、メルカプトシラン系、ビニルシラン系、アミノシラン系、エポキシシラン系などのシランカップリング剤やチタンカップリング剤を、離型剤の例としてはカルナバワックス、パラフィンワックスなど、また着色剤としてはカーボンブラックなどをそれぞれ例示することができる。難燃剤の例としては、リン化合物、金属水酸化物など、低応力剤の例としては、シリコンゴム、変性ニトリルゴム、変性ブタジエンゴム、変性シリコンオイルなどを挙げることができる。 Examples of coupling agents include mercaptosilane-based, vinylsilane-based, aminosilane-based, and epoxysilane-based silane coupling agents and titanium coupling agents. Examples of mold release agents include carnauba wax, paraffin wax, and coloring. Examples of the agent include carbon black. Examples of the flame retardant include phosphorus compounds and metal hydroxides, and examples of the low stress agent include silicon rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.
本発明のエポキシ樹脂硬化剤とエポキシ樹脂との配合比は、耐熱性、機械的特性などを考慮すると、水酸基/エポキシ基の当量比が0.5〜1.5、特に0.8〜1.2の範囲にあることが好ましい。また他の硬化剤と併用する場合においても水酸基/エポキシ基の当量比が上記割合となるようにするのが好ましい。硬化促進剤は、硬化特性や諸物性を考慮すると、エポキシ樹脂100重量部に対して0.1〜5重量部の範囲で使用するのが好ましい。無機充填剤の配合率については、その種類によっても異なるが、半田耐熱性、成形性(溶融粘度、流動性)、低応力性、低吸水性などを考慮すると、無機充填剤を組成物全体の60〜93重量%を占めるような割合で配合することが好ましい。 The mixing ratio of the epoxy resin curing agent and the epoxy resin of the present invention is such that the equivalent ratio of hydroxyl group / epoxy group is 0.5 to 1.5, particularly 0.8 to 1. A range of 2 is preferable. Further, even when used in combination with another curing agent, it is preferable that the equivalent ratio of hydroxyl group / epoxy group is the above-mentioned ratio. The curing accelerator is preferably used in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin in consideration of curing characteristics and various physical properties. The blending ratio of the inorganic filler varies depending on the type, but considering the solder heat resistance, moldability (melt viscosity, fluidity), low stress, low water absorption, etc., the inorganic filler is added to the entire composition. It is preferable to mix | blend in the ratio which occupies 60 to 93 weight%.
エポキシ樹脂組成物を成形材料として調製する場合の一般的な方法としては、所定の割合の各原料を、例えばミキサーによって充分混合後、熱ロールやニーダーなどによって混練処理を加え、さらに冷却固化後適当な大きさ粉砕し、必要に応じタブレット化するなどの方法を挙げることができる。このようにして得た成形材料は、例えば低圧トランスファー成形などにより半導体を封止し、半導体装置を製造することができる。 As a general method for preparing an epoxy resin composition as a molding material, a predetermined proportion of each raw material is sufficiently mixed by, for example, a mixer, then kneaded by a hot roll or a kneader, and further cooled and solidified. Examples of the method include pulverization of a large size and tableting as necessary. The molding material thus obtained can be used for sealing a semiconductor by, for example, low-pressure transfer molding to manufacture a semiconductor device.
エポキシ樹脂組成物を絶縁層材料として調製する場合の一般的な方法としては、所定の割合の各原料を溶剤に溶解させ、これを回路基板に塗布するための層間絶縁用ワニスとすることができ、これをガラス繊維に含浸させて加熱処理を行うことにより該用途のプリプレグとすることができ、またはこれを支持フィルム上で加熱処理してフィルム状とした該用途の接着シートとすることができる。これらはいずれの形態で使用しても層間絶縁層とすることができる。 As a general method for preparing an epoxy resin composition as an insulating layer material, a predetermined proportion of each raw material can be dissolved in a solvent, and this can be used as an interlayer insulating varnish for application to a circuit board. The glass sheet can be impregnated with a glass fiber and subjected to a heat treatment to obtain a prepreg for the application, or it can be a heat treatment on a support film to form a film-like adhesive sheet. . Any of these forms can be used as an interlayer insulating layer.
エポキシ樹脂組成物の硬化は、上記いずれの製品形態であっても例えば100〜250℃の温度範囲で行うことができる。 Curing of the epoxy resin composition can be performed in a temperature range of 100 to 250 ° C., for example, in any product form.
以下に実施例、比較例によって本発明をより具体的に説明するが、本発明はこれらの例によって何ら制限されるものではない。 The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples.
[実施例1]
フェノール47.6g(0.507モル)、4,4’−ビスメトキシメチルビフェニル20.0g(0.083モル)、1,4−ベンゾキノン4.7g(0.044モル)を、下部に抜出口のある4つ口フラスコに仕込み、撹拌させながら内温を90℃まで上げて10%トリフルオロメタンスルホン酸水溶液0.36gを滴下した。その後、130℃に昇温し3時間保持しながら水と反応で生じるメタノールはそのまま系外へ揮散させた。この段階で未反応の4,4’−ビスメトキシメチルビフェニル及び1,4−ベンゾキノンは残存しておらず、全て反応したことをガスクロマトグラフィで確認後、未反応フェノールがガスクロマトグラフィで未検出になるまで30torr、150℃の減圧下でフェノールを除去した。この反応生成物を150℃で抜き出し、黒褐色のフェノール系オリゴマー(1)33.8gを得た。JIS K 2207に基づき、このフェノール系オリゴマー(1)の軟化点を測定したところ82℃であった。またICI溶融粘度計により測定した150℃における溶融粘度は170mPa・sであった。さらにアセチル化逆滴定法により測定した水酸基当量は174g/eqであった。
続いて、上記フェノール系オリゴマー(1)の質量分析を行った。
FD−MS測定条件
(1)測定機:日本電子製 JMS−700高分解能質量検出器
(2)測定条件:カソード電圧 −10kV
(3)測定方法:試料の2%DMSO溶液をFDエミッタに塗布し測定
FD−MS分析を行った結果、フェノール2分子と4,4’−ビスメトキシメチルビフェニル1分子の縮合物に相当するM+=366とその1,4−ベンゾキノンの付加物に相当するM+=474、フェノール3分子と4,4’−ビスメトキシメチルビフェニル2分子の縮合物に相当するM+=638とその1,4−ベンゾキノンの付加物に相当するM+=746が確認された。FD−MS法分子量測定のチャートを図1に示した。
[Example 1]
47.6 g (0.507 mol) of phenol, 20.0 g (0.083 mol) of 4,4′-bismethoxymethylbiphenyl, and 4.7 g (0.044 mol) of 1,4-benzoquinone are extracted at the bottom. Into a four-necked flask, the internal temperature was raised to 90 ° C. while stirring, and 0.36 g of a 10% aqueous trifluoromethanesulfonic acid solution was added dropwise. Then, while raising the temperature to 130 ° C. and maintaining for 3 hours, methanol produced by the reaction with water was volatilized out of the system as it was. At this stage, unreacted 4,4′-bismethoxymethylbiphenyl and 1,4-benzoquinone do not remain, and after confirming that all have reacted by gas chromatography, unreacted phenol becomes undetected by gas chromatography. The phenol was removed under reduced pressure at 30 torr and 150 ° C. This reaction product was extracted at 150 ° C. to obtain 33.8 g of a blackish brown phenol oligomer (1). Based on JIS K2207, when the softening point of this phenolic oligomer (1) was measured, it was 82 degreeC. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 170 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 174 g / eq.
Subsequently, mass analysis of the phenolic oligomer (1) was performed.
FD-MS measurement conditions (1) Measuring machine: JEOL JMS-700 high-resolution mass detector (2) Measurement conditions: Cathode voltage -10kV
(3) Measurement method: 2% DMSO solution of sample was applied to FD emitter and measured. As a result of FD-MS analysis, M corresponding to a condensate of two molecules of phenol and one molecule of 4,4′-bismethoxymethylbiphenyl. + = 366 and M + = 474 corresponding to an adduct of 1,4-benzoquinone and M + = 638 corresponding to a condensate of 3 molecules of phenol and 2 molecules of 4,4′-bismethoxymethylbiphenyl and 1, M + = 746 corresponding to an adduct of 4-benzoquinone was confirmed. A chart of molecular weight measurement by FD-MS method is shown in FIG.
[実施例2]
フェノール51.3g(0.545モル)、4,4’−ビスメトキシメチルビフェニル18.0g(0.074モル)、1,4−ベンゾキノン7.9g(0.074モル)以外は、実施例1と同様にして行い、黒褐色のフェノール系オリゴマー(2)37.8gを得た。JIS K 2207に基づき、このフェノール系オリゴマー(2)の軟化点を測定したところ73℃であった。またICI溶融粘度計により測定した150℃における溶融粘度は80mPa・sであった。さらにアセチル化逆滴定法により測定した水酸基当量は153g/eqであった。
得られたフェノール系オリゴマー(2)のFD−MS分析を行い、実施例1と同様のスペクトルを得た。
[Example 2]
Example 1 except 51.3 g (0.545 mol) of phenol, 18.0 g (0.074 mol) of 4,4′-bismethoxymethylbiphenyl, and 7.9 g (0.074 mol) of 1,4-benzoquinone In the same manner as above, 37.8 g of a blackish brown phenol oligomer (2) was obtained. Based on JIS K2207, when the softening point of this phenolic oligomer (2) was measured, it was 73 degreeC. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 80 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 153 g / eq.
The obtained phenol-based oligomer (2) was subjected to FD-MS analysis, and the same spectrum as in Example 1 was obtained.
[実施例3]
フェノール37.3g(0.397モル)、4,4’−ビスメトキシメチルビフェニル13.2g(0.055モル)、1,4−ベンゾキノン10.5g(0.099モル)以外は、実施例1と同様にして行い、黒褐色のフェノール系オリゴマー(3)33.5gを得た。JIS K 2207に基づき、このフェノール系オリゴマー(3)の軟化点を測定したところ83℃であった。またICI溶融粘度計により測定した150℃における溶融粘度は160mPa・sであった。さらにアセチル化逆滴定法により測定した水酸基当量は135g/eqであった。
得られたフェノール系オリゴマー(3)のFD−MS分析を行い、実施例1と同様のスペクトルを得た。
[Example 3]
Example 1 except 37.3 g (0.397 mol) of phenol, 13.2 g (0.055 mol) of 4,4′-bismethoxymethylbiphenyl and 10.5 g (0.099 mol) of 1,4-benzoquinone In the same manner as above, 33.5 g of a black-brown phenol oligomer (3) was obtained. Based on JIS K 2207, the softening point of the phenolic oligomer (3) was measured and found to be 83 ° C. The melt viscosity at 150 ° C. measured by an ICI melt viscometer was 160 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 135 g / eq.
The obtained phenol-based oligomer (3) was subjected to FD-MS analysis, and the same spectrum as in Example 1 was obtained.
[実施例4]
フェノール38.5g(0.409モル)、4,4’−ビスメトキシメチルビフェニル13.2g(0.055モル)、1,4−ベンゾキノン14.5g(0.136モル)以外は、実施例1と同様にして行い、黒褐色のフェノール系オリゴマー(4)39.0gを得た。JIS K 2207に基づき、このフェノール系オリゴマー(4)の軟化点を測定したところ91℃であった。またICI溶融粘度計により測定した150℃における溶融粘度は320mPa・sであった。さらにアセチル化逆滴定法により測定した水酸基当量は124g/eqであった。
得られたフェノール系オリゴマー(4)のFD−MS分析を行い、実施例1と同様のスペクトルを得た。
[Example 4]
Example 1 except 38.5 g (0.409 mol) of phenol, 13.2 g (0.055 mol) of 4,4′-bismethoxymethylbiphenyl, and 14.5 g (0.136 mol) of 1,4-benzoquinone In the same manner as above, 39.0 g of a black-brown phenol oligomer (4) was obtained. Based on JIS K 2207, the softening point of this phenol oligomer (4) was measured and found to be 91 ° C. The melt viscosity at 150 ° C. measured by an ICI melt viscometer was 320 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 124 g / eq.
The obtained phenol-based oligomer (4) was subjected to FD-MS analysis, and the same spectrum as in Example 1 was obtained.
[実施例5]
フェノール47.3g(0.504モル)、4,4’−ビスメトキシメチルビフェニ13.0g(0.054モル)、1,4−ベンゾキノン17.8g(0.168モル)以外は、実施例1と同様にして行い、黒褐色のフェノール系オリゴマー(5)42.3gを得た。JIS K 2207に基づき、このフェノール系オリゴマー(5)の軟化点を測定したところ93℃であった。またICI溶融粘度計により測定した150℃における溶融粘度は250mPa・sであった。さらにアセチル化逆滴定法により測定した水酸基当量は120g/eqであった。
得られたフェノール系オリゴマー(5)のFD−MS分析を行い、実施例1と同様のスペクトルを得た。
実施例1〜5で得られたフェノール系オリゴマー(1)〜(5)の物性を、後記比較例1で使用したトリフェノールメタン構造型樹脂(JIS K 2207に基づき測定した軟化点は82℃、ICI溶融粘度計により測定した150℃における溶融粘度は110mPa・s、水酸基当量100g/eq、エア・ウォーター(株)製HE910−10)と対比して表1及び表2に示した。
[Example 5]
Example 1 except for 47.3 g (0.504 mol) of phenol, 13.0 g (0.054 mol) of 4,4′-bismethoxymethylbiphenyl, and 17.8 g (0.168 mol) of 1,4-benzoquinone In the same manner as above, 42.3 g of a black-brown phenol oligomer (5) was obtained. Based on JIS K2207, when the softening point of this phenolic oligomer (5) was measured, it was 93 degreeC. The melt viscosity at 150 ° C. measured with an ICI melt viscometer was 250 mPa · s. Furthermore, the hydroxyl group equivalent measured by the acetylation back titration method was 120 g / eq.
The obtained phenol-based oligomer (5) was subjected to FD-MS analysis, and the same spectrum as in Example 1 was obtained.
For the physical properties of the phenolic oligomers (1) to (5) obtained in Examples 1 to 5, the triphenolmethane structure type resin used in Comparative Example 1 described later (softening point measured based on JIS K 2207 is 82 ° C., The melt viscosity at 150 ° C. measured with an ICI melt viscometer is shown in Tables 1 and 2 in comparison with 110 mPa · s, hydroxyl equivalent 100 g / eq, HE910-10 manufactured by Air Water Co., Ltd.).
[実施例6]
下記一般式(10)で示されるエポキシ樹脂A(ビフェニルアラルキル型、エポキシ当量272g/eq、日本化薬(株)製NC−3000)、実施例1で得たフェノール系オリゴマー(1)、溶融シリカ及びウレア系硬化促進剤(サンアプロ(株)社製U−CAT 3513N 脂肪族ジメチルウレア)を表2に示す割合で配合し、充分に混合した後、85℃±3℃の2本ロールで3分混練し、冷却、粉砕することにより、成形用組成物を得た。トランスファー成形機でこの成形用組成物を、圧力100kgf/cm2で175℃、5分間成形した後、180℃、8時間のポストキュアを行い、ガラス転移温度(Tg)用及び難燃性試験用のテストピースを得た。
[Example 6]
Epoxy resin A represented by the following general formula (10) (biphenyl aralkyl type, epoxy equivalent 272 g / eq, NC-3000 manufactured by Nippon Kayaku Co., Ltd.), phenolic oligomer (1) obtained in Example 1, fused silica And a urea-based curing accelerator (U-CAT 3513N aliphatic dimethylurea manufactured by San Apro Co., Ltd.) at a ratio shown in Table 2 and mixed well, and then 3 minutes with two rolls at 85 ° C. ± 3 ° C. The molding composition was obtained by kneading, cooling, and pulverizing. This molding composition was molded at 175 ° C. for 5 minutes at a pressure of 100 kgf / cm 2 using a transfer molding machine, followed by post-cure at 180 ° C. for 8 hours, for glass transition temperature (Tg) and for flame retardancy test I got a test piece.
[物性測定方法]
これら成形材料の物性を、次の方法により測定した。
(1)ガラス転移温度(Tg)
TMAにより、昇温速度10℃/分の条件で線膨張係数を測定し、線膨張係数の変曲点をTgとした。
[Physical property measurement method]
The physical properties of these molding materials were measured by the following method.
(1) Glass transition temperature (Tg)
The linear expansion coefficient was measured by TMA at a temperature increase rate of 10 ° C./min, and the inflection point of the linear expansion coefficient was defined as Tg.
(2)難燃性
厚み1.6mm×幅10mm×長さ135mmのサンプルを用い、UL−94Vに準拠して残炎時間を測定し、難燃性を評価した。
(2) Flame retardancy Using a sample having a thickness of 1.6 mm × width 10 mm ×
これらの評価結果を表3に示す。 These evaluation results are shown in Table 3.
[実施例7]
実施例1で得たフェノール系オリゴマー(1)の代わりに、実施例2で得たフェノール系オリゴマー(2)を用い、配合割合を表1のようにした以外は、実施例6と同様にして成形用組成物を調製し、その評価を行った。その結果を表3に示す。
[Example 7]
Instead of the phenolic oligomer (1) obtained in Example 1, the phenolic oligomer (2) obtained in Example 2 was used, and the blending ratio was as shown in Table 1, and was the same as in Example 6. A molding composition was prepared and evaluated. The results are shown in Table 3.
[実施例8]
実施例1で得たフェノール系オリゴマー(1)の代わりに、実施例3で得たフェノール系オリゴマー(3)を用い、配合割合を表1のようにした以外は、実施例6と同様にして成形用組成物を調製し、その評価を行った。その結果を表3に示す。
[Example 8]
Instead of the phenolic oligomer (1) obtained in Example 1, the phenolic oligomer (3) obtained in Example 3 was used, and the blending ratio was as shown in Table 1, and was the same as in Example 6. A molding composition was prepared and evaluated. The results are shown in Table 3.
[実施例9]
実施例1で得たフェノール系オリゴマー(1)の代わりに、実施例4で得たフェノール系オリゴマー(4)を用い、配合割合を表1のようにした以外は、実施例6と同様にして成形用組成物を調製し、その評価を行った。その結果を表4に示す。
[Example 9]
Instead of the phenolic oligomer (1) obtained in Example 1, the phenolic oligomer (4) obtained in Example 4 was used, and the blending ratio was changed as shown in Table 1, and the same procedure as in Example 6 was performed. A molding composition was prepared and evaluated. The results are shown in Table 4.
[実施例10]
実施例1で得たフェノール系オリゴマー(1)の代わりに、実施例5で得たフェノール系オリゴマー(5)を用い、配合割合を表1のようにした以外は、実施例6と同様にして成形用組成物を調製し、その評価を行った。その結果を表4に示す。
[Example 10]
Instead of the phenolic oligomer (1) obtained in Example 1, the phenolic oligomer (5) obtained in Example 5 was used, and the blending ratio was as shown in Table 1, and was the same as in Example 6. A molding composition was prepared and evaluated. The results are shown in Table 4.
[比較例1]
実施例1で得たフェノール系オリゴマー(1)の代わりに、下記一般式(11)で示されるトリフェノールメタン構造型樹脂HE910−10を用いると共に、配合割合を表1のようにした以外は、実施例6と同様にして成形用組成物を調製し、その評価を行った。その結果を表4に示す。
[Comparative Example 1]
Instead of using the phenolic oligomer (1) obtained in Example 1 and using the triphenolmethane structural resin HE910-10 represented by the following general formula (11), the blending ratio was as shown in Table 1, A molding composition was prepared and evaluated in the same manner as in Example 6. The results are shown in Table 4.
(式中、m+mは1〜10の数)
(Where m + m is a number from 1 to 10)
表3及び4より、実施例6〜10の硬化物は全て比較例1の硬化物のガラス転移温度以上であり優れた高耐熱性を持つことがわかる。一方、実施例6〜10の硬化物の燃焼時間は、比較例1の硬化物のFmax、Ftotalのいずれも80%以下と短く、本発明が与える硬化剤は優れた自己消火性も併せ持つことがわかる。 From Tables 3 and 4, it can be seen that the cured products of Examples 6 to 10 are all higher than the glass transition temperature of the cured product of Comparative Example 1 and have excellent high heat resistance. On the other hand, the burn times of the cured products of Examples 6 to 10 are both as short as 80% or less of Fmax and Ftotal of the cured product of Comparative Example 1, and the curing agent provided by the present invention may have excellent self-extinguishing properties. Recognize.
本発明により、従来公知のフェノール系硬化剤以上の耐燃性を持ち、かつ高難燃性も兼備する新規なフェノール系オリゴマーが提供される。
本発明により提供されるフェノール系オリゴマーは、高耐熱性と高難燃性がすぐれたフェノール系オリゴマーであり、高耐熱性と高難燃性の両立が求められる用途にも好適に使用される。本発明により提供されるフェノール系オリゴマーは、フェノール系オリゴマーのさらなる多様性を広げるものであり、本材料を使用する産業分野の技術的要請に応えるものであって、車載用電子部品用途などの高耐熱用途での貢献が期待されるものである。
According to the present invention, there is provided a novel phenolic oligomer having a flame resistance higher than that of a conventionally known phenolic curing agent and having high flame retardancy.
The phenol-based oligomer provided by the present invention is a phenol-based oligomer having high heat resistance and high flame retardancy, and is suitably used for applications that require both high heat resistance and high flame retardancy. The phenolic oligomer provided by the present invention expands further diversity of the phenolic oligomer, and meets the technical demands of the industrial field using this material. It is expected to contribute to heat-resistant applications.
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JP2016113549A (en) * | 2014-12-16 | 2016-06-23 | Dic株式会社 | Benzoxazine compound, benzoxazine resin, method of producing benzoxazine resin, curable resin composition, cured article hereof, frp material, semiconductor encapsulation material, varnish, circuit board, prepreg and build-up film |
JP2016113581A (en) * | 2014-12-17 | 2016-06-23 | Dic株式会社 | Benzoxazine compound, benzoxazine resin, method of producing benzoxazine resin, curable resin composition, cured article hereof, frp material, semiconductor encapsulation material, varnish, circuit board, prepreg and build-up film |
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JP2016113581A (en) * | 2014-12-17 | 2016-06-23 | Dic株式会社 | Benzoxazine compound, benzoxazine resin, method of producing benzoxazine resin, curable resin composition, cured article hereof, frp material, semiconductor encapsulation material, varnish, circuit board, prepreg and build-up film |
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