JP2008179739A - Epoxy resin, epoxy resin composition and its cured article - Google Patents
Epoxy resin, epoxy resin composition and its cured article Download PDFInfo
- Publication number
- JP2008179739A JP2008179739A JP2007015883A JP2007015883A JP2008179739A JP 2008179739 A JP2008179739 A JP 2008179739A JP 2007015883 A JP2007015883 A JP 2007015883A JP 2007015883 A JP2007015883 A JP 2007015883A JP 2008179739 A JP2008179739 A JP 2008179739A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- group
- resin composition
- epoxy
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 110
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000003566 sealing material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N Phenolphthalein Natural products C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 abstract description 45
- -1 phenolphthalein compound Chemical class 0.000 abstract description 35
- 239000000853 adhesive Substances 0.000 abstract description 12
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000004918 carbon fiber reinforced polymer Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000009970 fire resistant effect Effects 0.000 abstract 1
- 239000012774 insulation material Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000001723 curing Methods 0.000 description 20
- 150000002989 phenols Chemical class 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 9
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 9
- 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 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 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 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000003973 paint Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000011810 insulating material Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000002596 lactones Chemical group 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 2
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical class OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Chemical group 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-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
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical class O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004002 naphthaldehydes Chemical class 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical class O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- VDRZXZXMHDKJLN-UHFFFAOYSA-M (2-methylphenyl)-triphenylphosphanium;bromide Chemical compound [Br-].CC1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 VDRZXZXMHDKJLN-UHFFFAOYSA-M 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- XOJWBPXKYGHCLN-UHFFFAOYSA-N 1,1'-biphenyl;methanol Chemical compound OC.OC.C1=CC=CC=C1C1=CC=CC=C1 XOJWBPXKYGHCLN-UHFFFAOYSA-N 0.000 description 1
- FMGGHNGKHRCJLL-UHFFFAOYSA-N 1,2-bis(chloromethyl)benzene Chemical group ClCC1=CC=CC=C1CCl FMGGHNGKHRCJLL-UHFFFAOYSA-N 0.000 description 1
- UZPZYFDULMKDMB-UHFFFAOYSA-N 1,2-dichloro-3,4-dimethylbenzene Chemical group CC1=CC=C(Cl)C(Cl)=C1C UZPZYFDULMKDMB-UHFFFAOYSA-N 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-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
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 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
Abstract
Description
本発明は電気電子部品用絶縁材料（高信頼性半導体封止材料など）、積層板（プリント配線板、ビルドアップ基板など）やＣＦＲＰを始めとする各種複合材料、接着剤及び塗料等に有用なものであり、これらの中でも特に金属箔張り積層板、ビルドアップ基板及びフレキシブル基板等の電子回路基板を製造する際に有用なエポキシ樹脂と、同エポキシ樹脂を用いた組成物及びその硬化物に関する。 The present invention is useful for insulating materials (such as highly reliable semiconductor encapsulating materials) for electrical and electronic parts, laminated boards (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, and paints. In particular, the present invention relates to an epoxy resin useful in manufacturing an electronic circuit substrate such as a metal foil-clad laminate, a build-up substrate, and a flexible substrate, a composition using the epoxy resin, and a cured product thereof.
エポキシ樹脂組成物は作業性並びにその硬化物の優れた電気特性、耐熱性、接着性及び耐湿性（耐水性）等により電気・電子部品、構造用材料、接着剤及び塗料等の分野で幅広く用いられている。 Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives and paints due to their workability and the excellent electrical properties, heat resistance, adhesion and moisture resistance (water resistance) of their cured products. It has been.
しかしながら、電気・電子分野においては、近年その発展に伴い樹脂組成物の高純度化をはじめ耐湿性、密着性、誘電特性、フィラーの高充填を目的とした低粘度化、成型サイクルの短縮を目的とした反応性アップ等の諸特性の一層の向上が求められている。又、構造材としては、航空宇宙材料、レジャー・スポーツ器具用途などにおいて、軽量で機械物性の優れた材料が求められている。特に半導体封止分野や基板関連分野（基板自体、もしくはその周辺材料）で薄型化の要望が強まるのに伴って、材料には耐熱性はもちろんのこと、柔軟性が求められるようになってきている。更に環境問題としては、近年、難燃剤としてハロゲン系エポキシ樹脂と三酸化アンチモンが特に電気電子部品の難燃剤として多用されているが、これらを使用した製品の廃棄後の不適切な処理がダイオキシン等有毒物質の発生に寄与することが指摘されている。上記の問題を解決する方法の一つとしてリン原子を骨格に有するエポキシ樹脂が提案されており、特に通常のリン酸エステル化合物と比べて安定性の良い環状リン酸エステル化合物が使用されている。またリン酸エステル化合物を使用しなくても、樹脂骨格を選択することで従来品よりも難燃性に優れたエポキシ樹脂が開発されてきている。このようなエポキシ樹脂としてはフェノール−ビフェニルアラルキル型エポキシ樹脂（具体的には日本化薬株式会社製ＮＣ−３０００シリーズ）等が挙げられるが、耐熱性が低い等の問題が残されており、一般に「ハロゲンフリー、リンフリー」と呼ばれる難燃性の要求を満たすためには、より耐熱性が高い難燃性エポキシ樹脂の開発が望まれている。 However, in the electric and electronic fields, with the development in recent years, the purpose is to reduce the viscosity and shorten the molding cycle for the purpose of increasing the purity of the resin composition, moisture resistance, adhesion, dielectric properties, and high filler filling. Further improvement of various properties such as increased reactivity is required. In addition, as a structural material, a lightweight material having excellent mechanical properties is required for use in aerospace materials, leisure / sports equipment, and the like. In particular, as the demand for thinning in the semiconductor encapsulation field and the substrate-related field (the substrate itself or its peripheral materials) has increased, the material is required to have flexibility as well as heat resistance. Yes. In addition, as an environmental problem, in recent years, halogen-based epoxy resins and antimony trioxide are frequently used as flame retardants, especially as flame retardants for electrical and electronic parts, but improper treatment after disposal of products using these is dioxin, etc. It has been pointed out that it contributes to the generation of toxic substances. As one of the methods for solving the above problems, an epoxy resin having a phosphorus atom in the skeleton has been proposed, and in particular, a cyclic phosphate ester compound having better stability than a normal phosphate ester compound is used. Even without using a phosphoric acid ester compound, an epoxy resin superior in flame retardancy than conventional products has been developed by selecting a resin skeleton. Examples of such epoxy resins include phenol-biphenyl aralkyl type epoxy resins (specifically, NC-3000 series manufactured by Nippon Kayaku Co., Ltd.), but problems such as low heat resistance remain. In order to satisfy the requirement of flame retardancy called “halogen-free and phosphorus-free”, development of a flame-retardant epoxy resin having higher heat resistance is desired.
非特許文献１、２には、フェノールフタレイン型のエポキシ樹脂に関する報告がなされているが、その内容は構造に関するものであり、ビスフェノールフルオレン型エポキシ樹脂との比較において、耐熱性やチャー形成能（酸素指数で議論）に劣るとの結論である。またこの報告は硬化剤にトリメトキシボロキシンを使用したものであり、フェノール系硬化剤との組み合わせについては検討されていないのと同時に、硬化物の難燃性についても議論されていない。同文献には、フェノールフタレイン型エポキシ樹脂の合成法、および樹脂物性が記載されており、カラムにてフェノールフタレイン型エポキシ樹脂から高分子量体を除去し、単離したフェノールフタレインのジグリシジルエーテルの評価結果が報告されている。しかしながら、同文献では、カラムクロマトグラフィーで単離された最も分子量の小さいｎ＝０体エポキシ樹脂のエポキシ当量は２３３ｇ／ｅｑ．であり、ｎ＝０体の理論エポキシ当量である２１６よりもかなり大きな値となっている。この原因としては、カラム精製後のエポキシ樹脂中に、クロルヒドリン体やラクトン骨格が開環した構造等、目的物質と分子量の近い副生成物が相当量残存しているためと推定される。特に２官能エポキシ樹脂においては、クロルヒドリン体が残存するとエポキシ当量が大きくなり、架橋密度が上がらないため耐熱性が低下してしまう。実際にこの文献の追試を行ったところ、得られたエポキシ樹脂の精製前のエポキシ当量は２４５ｇ／ｅｑ．であり、この品質のまま最先端の電子・電気用途に使用した場合には、耐熱性不足によって問題の生じることが懸念される。逆にエポキシ当量が本発明請求項１の範囲（２２０〜２３０）よりも低い場合には、開環したラクトン骨格部分がグリシジルエステル化した構造の副生成物が含まれる可能性が高く、この影響で本発明の効果が充分得られない恐れがある。
尚、追試で得られたエポキシ樹脂も精製によって品質が改善される可能性はあるが、カラムクロマトグラフィーによる精製は工業化には現実的でないため、合成段階から効率的に高純度のフェノールフタレイン型エポキシ樹脂を製造する方法が必要である。
Non-Patent Documents 1 and 2 report on phenolphthalein-type epoxy resins, but the contents relate to the structure. Compared with bisphenolfluorene-type epoxy resins, heat resistance and char-forming ability ( It is a conclusion that it is inferior to the oxygen index. In addition, this report uses trimethoxyboroxine as a curing agent, and a combination with a phenolic curing agent has not been studied, and at the same time, the flame retardancy of the cured product has not been discussed. This document describes a synthesis method of phenolphthalein type epoxy resin and resin physical properties. Diglycidyl of phenolphthalein isolated by removing high molecular weight substance from phenolphthalein type epoxy resin in a column. Ether evaluation results have been reported. However, in this document, the epoxy equivalent of the n = 0 epoxy resin having the lowest molecular weight isolated by column chromatography is 233 g / eq. It is considerably larger than 216, which is the theoretical epoxy equivalent of n = 0 isomer. This is presumably because a considerable amount of by-products having a molecular weight close to that of the target substance, such as a structure in which a chlorohydrin body or a lactone skeleton is opened, remain in the epoxy resin after column purification. In particular, in a bifunctional epoxy resin, if the chlorohydrin body remains, the epoxy equivalent increases, and the crosslink density does not increase, resulting in a decrease in heat resistance. When this document was actually reexamined, the epoxy equivalent of the obtained epoxy resin before purification was 245 g / eq. However, there is a concern that problems may arise due to insufficient heat resistance when used in the most advanced electronic and electrical applications with this quality. Conversely, when the epoxy equivalent is lower than the range (220 to 230) of claim 1 of the present invention, there is a high possibility that a by-product having a structure in which the ring-opened lactone skeleton is glycidyl esterified is included. Therefore, the effects of the present invention may not be sufficiently obtained.
Although the quality of the epoxy resin obtained in the follow-up test may be improved by purification, purification by column chromatography is not practical for industrialization, so the high-purity phenolphthalein type can be efficiently used from the synthesis stage. There is a need for a method of producing an epoxy resin.
本発明の目的は、電気電子部品用絶縁材料（高信頼性半導体封止材料など）、積層板（プリント配線板、ビルドアップ基板など）やＣＦＲＰを始めとする各種複合材料、接着剤及び塗料等に有用な難燃性に優れた硬化物を与えうる、特定の分子量分布とエポキシ当量を持つエポキシ樹脂と、同エポキシ樹脂を用いた組成物及びその硬化物を提供することにある。 The object of the present invention is to provide insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulating materials, etc.), laminated plates (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, etc. It is an object to provide an epoxy resin having a specific molecular weight distribution and an epoxy equivalent, a composition using the epoxy resin, and a cured product thereof.
本発明者らは前記課題を解決するため鋭意研究の結果、本発明を完成した。即ち、本発明は、
（１）式（１）
（２）反応の際に酸性触媒を用いることを特徴とする請求項１記載のエポキシ樹脂、
（３）Q及びＲの全てが水素原子である請求項１、２のいずれか一項に記載のエポキシ樹脂、
（４）（１）（２）（３）のいずれか一項に記載のエポキシ樹脂、及び硬化剤を含有してなるエポキシ樹脂組成物、
（５）無機充填剤を含有する（４）記載のエポキシ樹脂組成物、
（６）硬化剤がフェノール系硬化剤である（４）（５）のいずれか一項に記載のエポキシ樹脂組成物、
（７）（４）（５）（６）のいずれか一項に記載のエポキシ樹脂組成物の硬化物、
（８）（４）（５）（６）のいずれか一項に記載のエポキシ樹脂組成物を用いて成型した半導体封止材料、
に関する。
The present inventors have completed the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention
(1) Formula (1)
(2) The epoxy resin according to claim 1, wherein an acidic catalyst is used in the reaction.
(3) All of Q and R are hydrogen atoms, The epoxy resin as described in any one of Claims 1 and 2,
(4) An epoxy resin composition comprising the epoxy resin according to any one of (1), (2) and (3), and a curing agent,
(5) The epoxy resin composition according to (4), which contains an inorganic filler,
(6) The epoxy resin composition according to any one of (4) and (5), wherein the curing agent is a phenol-based curing agent,
(7) A cured product of the epoxy resin composition according to any one of (4), (5), and (6),
(8) A semiconductor sealing material molded using the epoxy resin composition according to any one of (4), (5) and (6),
About.
本発明のエポキシ樹脂を使用したエポキシ樹脂組成物の硬化物は、難燃剤やリン系化合物を使用しなくても難燃性を発現することで組成物中の難燃剤やリン系化合物の低減に寄与するものであり、電気電子部品用絶縁材料（高信頼性半導体封止材料など）、積層板（プリント配線板、ビルドアップ基板など）やＣＦＲＰを始めとする各種複合材料、接着剤及び塗料等に有用である。 The cured product of the epoxy resin composition using the epoxy resin of the present invention exhibits flame retardancy without using a flame retardant or a phosphorus compound, thereby reducing the flame retardant or phosphorus compound in the composition. Contributing materials such as insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulating materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, etc. Useful for.
本発明のエポキシ樹脂は、前記式（１）に記載のフェノールフタレイン類をエピハロヒドリンと反応させることで得られる。 The epoxy resin of the present invention can be obtained by reacting the phenolphthalein described in the formula (1) with epihalohydrin.
フェノールフタレイン類は、一般にフェノール類とフタル酸類の酸無水物を酸性条件下で反応させることによって合成可能であり、例えばRevistade Chimie(1958),9,151-152「The Synthesis of phenolphtaleine with chlorosulfonic acid as the condensation agent.」にはクロロスルホン酸を使用したフェノールフタレイン類の合成法が記載されている。
具体的なＲ、Ｑに適応可能な置換基としては水素原子、炭素数１〜１０の炭化水素基（メチル基、エチル基、ｎ−プロピル基、イソプロピル基、シクロプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、イソブチル基、シクロブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、イソヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、シクロヘプチル基、ｎ−オクチル基、シクロオクチル基等の鎖状アルキル基または環状アルキル基、アリル基等）、アリール基（環が縮環したものも含む、例えばナフトール）、（フェニル基、ナフチル基、トルイル基等）、炭素数１〜１０のアルコキシ基（メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、シクロプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、イソブトキシ基、シクロブトキシ基、シクロヘキシルオキシ基等の鎖状アルキル基または環状アルキル基、アリルオキシ基等）、又はハロゲン原子（塩素、臭素、ヨウ素、フッ素）のいずれかを表す。具体的な製品としてはフェノールフタレイン、クレゾールフタレイン、ジメトキシフェノールフタレイン、ジクロロフェノールフタレイン等が挙げられるが、本発明においては工業的に入手しやすいことから、特にフェノールフタレインの使用が好ましい。これらフェノールフタレイン類は単独でまたは２種以上を混合して使用することができる。
Phenolphthaleins can generally be synthesized by reacting phenols and phthalic acid anhydrides under acidic conditions.For example, Revistade Chimie (1958), 9, 151-152, “The Synthesis of phenolphtaleine with chlorosulfonic acid as the "condensation agent." describes a method for synthesizing phenolphthaleins using chlorosulfonic acid.
Specific examples of the substituent applicable to R and Q include a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group , Cycloheptyl group, n-octyl group, chain alkyl group such as cyclooctyl group, cyclic alkyl group, allyl group, etc.), aryl group (including those in which the ring is condensed, such as naphthol), (phenyl group, naphthyl) Group, toluyl group, etc.), C1-C10 alkoxy group (methoxy group, ethoxy group, n-propoxy group, isoprop A chain alkyl group such as a xy group, a cyclopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an isobutoxy group, a cyclobutoxy group, a cyclohexyloxy group, a cyclic alkyl group, an allyloxy group), or a halogen One of atoms (chlorine, bromine, iodine, fluorine) is represented. Specific products include phenolphthalein, cresolphthalein, dimethoxyphenolphthalein, dichlorophenolphthalein and the like, but in the present invention, use of phenolphthalein is particularly preferable because it is easily available industrially. . These phenolphthaleins can be used alone or in admixture of two or more.
以下に、本発明のエポキシ樹脂の製造法について記載する。
従来報告されているフェノールフタレインのグリシジル化の手法としては、エピハロヒドリンの存在下、フェノールフタレイン１モルに対し２モルの水酸化ナトリウムを使用して９０℃で３〜４時間反応させるというものであるが、この手法はアルカリ中で一気に反応させることの弊害として、ラクトン環の開環を伴う。本発明においては４級アンモニウム塩、４級ホスホニウム塩、トリフルオロボラン等の酸性触媒存在下で反応を行うことを特徴とする。この方法の場合、フェノールフタレインとエピハロヒドリンとの付加反応が優先的に進行するため、ラクトン環の開環を防ぎながらエーテル化を行うことが可能であり、最後にアルカリ金属水酸化物を使用してエポキシ化を完成させることにより、高純度なエポキシ樹脂を工業的に合成できる。
Below, it describes about the manufacturing method of the epoxy resin of this invention.
A conventionally reported method for glycidylation of phenolphthalein is to react at 90 ° C. for 3 to 4 hours using 2 moles of sodium hydroxide per mole of phenolphthalein in the presence of epihalohydrin. However, this method involves the opening of a lactone ring as an adverse effect of reacting at once in an alkali. In the present invention, the reaction is carried out in the presence of an acidic catalyst such as a quaternary ammonium salt, a quaternary phosphonium salt, or trifluoroborane. In this method, since the addition reaction of phenolphthalein and epihalohydrin proceeds preferentially, it is possible to perform etherification while preventing the lactone ring from opening, and finally, an alkali metal hydroxide is used. By completing the epoxidation, a high-purity epoxy resin can be industrially synthesized.
本発明のエポキシ樹脂を得る反応においては、エピハロヒドリンとしてエピクロルヒドリン、エピブロモヒドリン等が使用できるが、工業的に入手が容易なエピクロルヒドリンが好ましい。エピハロヒドリンの使用量はフェノールフタレイン類の水酸基１モルに対し３．０〜１０．０モル、より好ましくは４．０〜６．０モルである。エピハロヒドリンの使用量が３．０モル未満の場合は反応が不完全となり、溶剤に不溶の物質が多くなることで収率が低下するのに加えて、純度パラメータの１つである塩素量が多くなる傾向がある。１０．０モルを超える量のエピハロヒドリンを使用することは、生産効率やコストを考えると現実的方法ではない。 In the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, but epichlorohydrin which is easily available industrially is preferable. The usage-amount of epihalohydrin is 3.0-10.0 mol with respect to 1 mol of hydroxyl groups of phenolphthalein, More preferably, it is 4.0-6.0 mol. When the amount of epihalohydrin used is less than 3.0 mol, the reaction becomes incomplete, and the yield decreases due to an increase in the amount of insoluble substances in the solvent. In addition, the amount of chlorine, which is one of the purity parameters, is large. Tend to be. Using an epihalohydrin in an amount exceeding 10.0 mol is not a practical method in view of production efficiency and cost.
酸性触媒としては、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド等の４級アンモニウム塩、テトラブチルホスホニウムブロマイド、テトラフェニルホスホニウムブロマイド、メチルテトラフェニルホスホニウムブロマイド、メトキシメチルテトラフェニルホスホニウムクロライド、ベンジルテトラフェニルホスホニウムクロライド、テトラフェニルホスホニウムテトラフルオロボレート等の４級ホスホニウム塩、トリフェニルホスフィン、ジフェニルホスフィン、トリブチルホスフィン等の有機ホスフィン類、オクチル酸スズなどの金属化合物、２−エチル−４−メチルイミダゾール・テトラフェニルボレート、Ｎ−メチルモルホリン・テトラフェニルボレート、トリフルオロボラン等のホウ素化合物などが挙げられる。これらの使用量としては、その触媒能にも依るがフェノールフタレイン類の水酸基１モルに対し通常０．１〜１５ｇであり、好ましくは０．２〜１０ｇである。 As the acidic catalyst, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, methyltetraphenylphosphonium bromide, methoxymethyltetraphenylphosphonium chloride, benzyl Quaternary phosphonium salts such as tetraphenylphosphonium chloride and tetraphenylphosphonium tetrafluoroborate, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, 2-ethyl-4-methylimidazole, Tetraphenylborate, N-methylmorpholine tetraphenylborate And boron compounds such as trifluoroborane the like. The amount of these used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on 1 mol of the hydroxyl group of phenolphthalein, although it depends on its catalytic ability.
本反応においてはアルカリ金属水酸化物を使用する。使用しうるアルカリ金属水酸化物としては水酸化ナトリウム、水酸化カリウム等が挙げられ、固形物をそのまま使用しても、水溶液化したものを使用してもよい。水溶液を使用する場合は、該アルカリ金属水酸化物の水溶液を連続的に反応系内に添加すると共に、減圧下又は常圧下で連続的に留出させた水及びエピハロヒドリンから水のみを分液除去し、得られたエピハロヒドリンを反応系内に連続的に戻す方法でもよい。アルカリ金属水酸化物の使用量はフェノールフタレイン類の水酸基１モルに対して通常１．０〜１．５モルであり、好ましくは１．０〜１．３モルである。 In this reaction, an alkali metal hydroxide is used. Examples of the alkali metal hydroxide that can be used include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used as it is, or an aqueous solution may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and only water is removed from water and epihalohydrin distilled continuously under reduced pressure or normal pressure. Alternatively, the obtained epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 1.0-1.5 mol normally with respect to 1 mol of hydroxyl groups of phenolphthalein, Preferably it is 1.0-1.3 mol.
反応の際に、必要に応じてメタノール、エタノール、イソプロピルアルコールなどのアルコール類、ジメチルスルホン、ジメチルスルホキシド、テトラヒドロフラン、ジオキサン等の非プロトン性極性溶媒などを添加してもよい。しかしながら、アルコール類を添加すると副生成物（アルコール類のエポキシ化物等）が多く出来る傾向にあることから、その使用には十分注意する必要がある。 In the reaction, alcohols such as methanol, ethanol and isopropyl alcohol, aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran and dioxane may be added as necessary. However, when alcohols are added, there is a tendency to increase by-products (such as epoxidized products of alcohols).
アルコール類を使用する場合、その使用量はエピハロヒドリンの使用量に対し通常２〜５０重量％、好ましくは４〜２０重量％である。また非プロトン性極性溶媒を用いる場合、その使用量はエピハロヒドリンの使用量に対し通常５〜２００重量％、好ましくは１０〜１５０重量％である。 When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic polar solvent, the usage-amount is 5-200 weight% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 10-150 weight%.
以下に好ましい反応条件の一例を記載する。
本発明のエポキシ樹脂の合成手法としては、（ａ）フェノールフタレイン類とエピハロヒドリン、酸性触媒、必要に応じて有機溶剤および添加剤の混合物を、６０〜１００℃で加熱撹拌してフェノールフタレイン類とエピハロヒドリンとのエーテル化反応を進行させた後、（ｂ）アルカリ金属水酸化物を４５〜８０℃の温度条件下で逐次的あるいは連続的に添加することでエポキシ化を行い、（ｃ）反応を十分に進行させるために４５〜８０℃で後反応を行う、という（ａ）−（ｃ）の３工程を有することが好ましい。工程（ｃ）は省くことも出来るが、この場合はエポキシ化反応が充分行われない可能性がある。反応時間は、反応温度にも依るが（ａ）は１〜４時間、（ｂ）は１〜３時間、（ｃ）は０．５〜３時間程度が好ましい。
An example of preferable reaction conditions is described below.
As a method for synthesizing the epoxy resin of the present invention, (a) phenolphthaleins are prepared by heating and stirring a mixture of phenolphthaleins and epihalohydrin, an acidic catalyst, and if necessary, an organic solvent and additives at 60 to 100 ° C. And (b) an epoxidation by sequentially or continuously adding an alkali metal hydroxide under a temperature condition of 45 to 80 ° C. It is preferable to have three steps (a) to (c) in which a post-reaction is performed at 45 to 80 ° C. in order to sufficiently progress the process. Although the step (c) can be omitted, in this case, the epoxidation reaction may not be sufficiently performed. Although the reaction time depends on the reaction temperature, (a) is preferably 1 to 4 hours, (b) is preferably 1 to 3 hours, and (c) is preferably about 0.5 to 3 hours.
これらのエポキシ化反応の反応物から、水洗後あるいは水洗無しに加熱減圧下でエピハロヒドリンや溶媒等を除去することで本発明のエポキシ樹脂を得られるが、より加水分解性ハロゲンの少ないエポキシ樹脂を得るために、エピハロヒドリンや溶剤等を除去したエポキシ樹脂をトルエンやメチルイソブチルケトンなどの溶剤に再溶解した後に、水酸化ナトリウムや水酸化カリウムなどのアルカリ金属水酸化物（固形あるいは、水もしくはアルコールの溶液）、を加えて更に反応を行い、閉環を確実なものにすることが好ましい。この場合アルカリ金属水酸化物の使用量は、フェノールフタレイン類の水酸基１モルに対して通常０．０１〜０．３モル、好ましくは０．０５〜０．２モルである。反応温度は通常５０〜１２０℃、反応時間は通常０．５〜２時間である。 From these reaction products of the epoxidation reaction, the epoxy resin of the present invention can be obtained by removing the epihalohydrin, the solvent, or the like under heating and reduced pressure after washing with or without washing with water. However, an epoxy resin with less hydrolyzable halogen is obtained. Therefore, after re-dissolving the epoxy resin from which epihalohydrin or solvent has been removed in a solvent such as toluene or methyl isobutyl ketone, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide (solid or a solution of water or alcohol) It is preferable to carry out the reaction further by adding) to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per mol of the hydroxyl group of the phenolphthalein. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
反応終了後、生成した塩を濾過、水洗などにより除去し、更に加熱減圧下溶剤を留去することにより本発明のエポキシ樹脂が得られる。 After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.
このようにして得られる本発明のエポキシ樹脂は、エポキシ当量２２０〜２３０ｇ／ｅｑ．軟化点５５〜６０℃、全塩素量５００〜１５００ｐｐｍの特性を持つ。 The epoxy resin of the present invention thus obtained has an epoxy equivalent of 220 to 230 g / eq. It has a softening point of 55 to 60 ° C. and a total chlorine content of 500 to 1500 ppm.
本発明のエポキシ樹脂はエポキシアクリレート及びその誘導体、カーボネート樹脂、オキサゾリドン樹脂等へ誘導することができる。 The epoxy resin of the present invention can be derived into epoxy acrylate and derivatives thereof, carbonate resin, oxazolidone resin and the like.
以下、本発明のエポキシ樹脂組成物について説明する。
本発明のエポキシ樹脂組成物は本発明のエポキシ樹脂と硬化剤を含有することを特徴とする。この組成物中には本発明のエポキシ樹脂は単独で使用しても良いし、本発明のエポキシ樹脂と他のエポキシ樹脂とを併用で使用しても良い。併用する場合、本発明のエポキシ樹脂が、樹脂中のエポキシ樹脂の総量に対して占める割合は５重量％以上が好ましく、特に１０重量％以上が好ましい。
Hereinafter, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing agent. In this composition, the epoxy resin of the present invention may be used alone, or the epoxy resin of the present invention and another epoxy resin may be used in combination. When used together, the proportion of the epoxy resin of the present invention to the total amount of the epoxy resin in the resin is preferably 5% by weight or more, particularly preferably 10% by weight or more.
本発明のエポキシ樹脂と併用されうる他のエポキシ樹脂の具体例としては、ビスフェノール類（ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビフェノール、ビスフェノールＡＤ等）、フェノール類（フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等）と各種アルデヒド（ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等）との重縮合物、フェノール類と各種ジエン化合物（ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等）との重合物、フェノール類とケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等）との重縮合物、フェノール類と芳香族ジメタノール類（ベンゼンジメタノール、ビフェニルジメタノール等）との重縮合物、フェノール類と芳香族ジクロロメチル類（α，α’−ジクロロキシレン、ビスクロロメチルビフェニル等）との重縮合物、フェノール類と芳香族ビスアルコキシメチル類（ビスメトキシメチルベンゼン、ビスメトキシメチルビフェニル、ビスフェノキシメチルビフェニル等）との重縮合物、ビスフェノール類と各種アルデヒドの重縮合物、アルコール類等をグリシジル化したグリシジルエーテル系エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂等が挙げられるが、通常用いられるエポキシ樹脂であればこれらに限定されるものではない。これらは単独で用いてもよく、２種以上を用いてもよい。 Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic substitution). Phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, croton Polycondensates with aldehydes, cinnamaldehyde, etc., phenols and various diene compounds (disi Polymers with lopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl) Ketones, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.), phenols and aromatic dichloromethyls (α, α ' -Polycondensates with dichloroxylene, bischloromethylbiphenyl, etc.), phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxyme) Glycidyl ether epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin obtained by glycidylation of alcohols, etc. However, the epoxy resin is not limited thereto as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more.
本発明のエポキシ樹脂組成物における硬化剤としては、例えばアミン系化合物、酸無水物系化合物、アミド系化合物、フェノ−ル系化合物などが挙げられるが、本発明の効果である難燃性という意味ではフェノール系化合物が特に好ましい。用いうる硬化剤の具体例としては、ビスフェノール類（ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビフェノール、ビスフェノールＡＤ等）、フェノール類（フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等）と各種アルデヒド（ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等）との重縮合物、フェノール類と各種ジエン化合物（ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等）との重合物、フェノール類とケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等）との重縮合物、フェノール類と芳香族ジメタノール類（ベンゼンジメタノール、ビフェニルジメタノール等）との重縮合物、フェノール類と芳香族ジクロロメチル類（α，α’−ジクロロキシレン、ビスクロロメチルビフェニル等）との重縮合物、フェノール類と芳香族ビスアルコキシメチル類（ビスメトキシメチルベンゼン、ビスメトキシメチルビフェニル、ビスフェノキシメチルビフェニル等）との重縮合物、ビスフェノール類と各種アルデヒドの重縮合物、及びこれらの変性物等が挙げられるが、これらに限定されるものではない。フェノール系以外の硬化剤の具体例としては、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂、などのアミン系、アミド系化合物、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、などの酸無水物系化合物、イミダゾ−ル、トリフルオロボラン−アミン錯体、グアニジン誘導体などが挙げられるがこれらに限定されるものではない。これらは単独で用いてもよく、２種以上を併用してもよい。フェノール系硬化剤と他の硬化剤を併用する場合、本発明のエポキシ樹脂が、組成物中のエポキシ樹脂中の総量に対して占める割合は１０重量％以上が好ましく、特に３０重量％以上が好ましい。 Examples of the curing agent in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like. Then, a phenol type compound is particularly preferable. Specific examples of usable curing agents include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, vinyl Polymers of chlorhexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) Polycondensates, phenols and aromatic dimethanols (benzenedimethanol, biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethyl) Polycondensates with biphenyl, etc., polycondensates with phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), bis Polycondensates of phenol compounds and various aldehydes, and and modified products thereof, but is not limited thereto. Specific examples of curing agents other than phenolic amines include amines such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and polyamide resins synthesized from linolenic acid dimer and ethylenediamine. Amide compounds, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride , And the like, imidazole, trifluoroborane-amine complexes, guanidine derivatives, and the like, but are not limited thereto. These may be used alone or in combination of two or more. When the phenolic curing agent is used in combination with another curing agent, the proportion of the epoxy resin of the present invention relative to the total amount in the epoxy resin in the composition is preferably 10% by weight or more, particularly preferably 30% by weight or more. .
本発明のエポキシ樹脂組成物において硬化剤の使用量は、エポキシ樹脂のエポキシ基１当量に対して０．５〜１．５当量が好ましく、０．６〜１．２当量が特に好ましい。エポキシ基１当量に対して、０．５当量に満たない場合、あるいは１．５当量を超える場合には、硬化が不完全になり良好な硬化物性が得られない恐れがある。 In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
また上記硬化剤を用いる際に硬化促進剤を併用しても差し支えない。用いうる硬化促進剤としては、例えば、２−メチルイミダゾール、２−エチルイミダゾール、２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、２−（ジメチルアミノメチル）フェノール、トリエチレンジアミン、トリエタノールアミン、１，８−ジアザビシクロ（５，４，０）ウンデセン−７等の第３級アミン類、トリフェニルホスフィン、ジフェニルホスフィン、トリブチルホスフィン等の有機ホスフィン類、オクチル酸スズなどの金属化合物、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・エチルトリフェニルボレート等のテトラ置換ホスホニウム・テトラ置換ボレート、２−エチル−４−メチルイミダゾール・テトラフェニルボレート、Ｎ−メチルモルホリン・テトラフェニルボレート等のテトラフェニルボロン塩などが挙げられるが、これらに限定されるものではない。硬化促進剤を使用する場合の使用量は、エポキシ樹脂１００重量部に対して０．０１〜１５重量部を必要に応じて用いる。 Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, Triethanolamine, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, Tetra-substituted phosphonium tetra-borate such as tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl triphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, N-methylmol Such as tetraphenyl boron salts such as phosphorus-tetraphenylborate and the like, but not limited thereto. When using a hardening accelerator, the usage-amount is 0.01-15 weight part with respect to 100 weight part of epoxy resins as needed.
更に、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やシランカップリング材、離型剤、着色剤等の種々の配合剤、各種熱硬化性樹脂、各種添加剤を添加することができる。 Furthermore, various compounding agents such as inorganic fillers, silane coupling materials, mold release agents, colorants, various thermosetting resins, and various additives are added to the epoxy resin composition of the present invention as necessary. be able to.
無機充填剤としては、結晶シリカ、溶融シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、窒化アルミニウム、ジルコニア、フォステライト、ステアタイト、スピネル、チタニア、タルク、石英粉、アルミニウム粉末、グラファイト、クレー、酸化鉄、酸化チタン、アスベスト、マイカ、ガラス粉末、ガラス繊維、ガラス不織布または、カーボン繊維等の粉体、繊維又はこれらを球形化したビーズ等が挙げられるが、これらに限定されるものではない。これらは単独で用いても２種以上を併用してもよく、また、シランカップリング剤のような表面処理剤を無機充填剤と併用することも好ましい。これら無機充填剤は、用途によりその使用量は異なるが、例えば半導体の封止剤用途に使用する場合はエポキシ樹脂組成物の硬化物の耐熱性、耐湿性、力学的性質、難燃性などの面からエポキシ樹脂組成物中に好ましくは２０重量％以上、より好ましくは３０重量％以上、更に好ましくは４０〜９５重量％の割合で添加するのがよい。 Inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, aluminum nitride, zirconia, fosterite, steatite, spinel, titania, talc, quartz powder , Aluminum powder, graphite, clay, iron oxide, titanium oxide, asbestos, mica, glass powder, glass fiber, glass nonwoven fabric, or carbon fiber powder, fiber or beads made from these, and the like. It is not limited to. These may be used alone or in combination of two or more, and it is also preferable to use a surface treatment agent such as a silane coupling agent in combination with an inorganic filler. These inorganic fillers may be used in different amounts depending on the application. For example, when used for semiconductor encapsulants, the heat resistance, moisture resistance, mechanical properties, flame retardancy, etc. of the cured epoxy resin composition From the surface, it is preferably added to the epoxy resin composition in an amount of preferably 20% by weight or more, more preferably 30% by weight or more, and still more preferably 40 to 95% by weight.
着色剤としては、例えばカーボンブラック、フタロシアニンブルー、フタロシアニングリーン等が挙げられるが、これらに限定されるものではない。 Examples of the colorant include, but are not limited to, carbon black, phthalocyanine blue, and phthalocyanine green.
添加剤としては、例えばポリブタジエン及びこの変性物、アクリロニトリル共重合体の変性物、ポリフェニレンエーテル、ポリスチレン、ポリエチレン、ポリイミド、フッ素樹脂、マレイミド系化合物、シアネート樹脂（もしくはそのプレポリマー）、シリコーンゲル、シリコーンオイル等が挙げられるが、これらに限定されるものではない。 Examples of additives include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluorine resin, maleimide compound, cyanate resin (or prepolymer thereof), silicone gel, and silicone oil. However, it is not limited to these.
上記各成分を均一に混合することにより得られる本発明のエポキシ樹脂組成物は、従来知られている方法と同様の方法で容易に硬化することができる。例えば、エポキシ樹脂と硬化剤、並びに必要により硬化促進剤や無機充填剤等の各種添加剤を、必要に応じて押出機、ニーダ、ロール等を用いて均一に混合することで得られた本発明の硬化性樹脂組成物を、溶融注型法あるいはトランスファー成型法やインジェクション成型法、圧縮成型法などによって成型後、８０〜２００℃で２〜１０時間加熱することで硬化物を得ることができる。 The epoxy resin composition of the present invention obtained by uniformly mixing the above components can be easily cured by a method similar to a conventionally known method. For example, the present invention obtained by uniformly mixing an epoxy resin and a curing agent, and if necessary, various additives such as a curing accelerator and an inorganic filler, if necessary, using an extruder, a kneader, a roll, etc. The cured product can be obtained by molding the curable resin composition by melt casting, transfer molding, injection molding, compression molding, or the like, followed by heating at 80 to 200 ° C. for 2 to 10 hours.
また本発明のエポキシ樹脂組成物は、必要により溶剤を含有していてもよい。溶剤を含有するエポキシ樹脂組成物（以下ワニスと表記）をガラス繊維、カ−ボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの基材に含浸させた後に加熱乾燥して得られたプリプレグを熱プレス成形することにより、本発明のエポキシ樹脂組成物の硬化物とすることができる。ワニス中の溶剤含有量は、ワニスの総重量に対して通常１０〜７０重量％、好ましくは１５〜７０重量％程度である。該溶剤としては、例えばγ−ブチロラクトン類、Ｎ−メチルピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルイミダゾリジノン等のアミド系溶剤、テトラメチレンスルフォン等のスルフォン類、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルモノアセテート、プロピレングリコールモノブチルエーテル等のエーテル系溶剤、好ましくは低級アルキレングリコールモノ又はジ低級アルキルエーテル、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、好ましくは２つのアルキル基が同一でも異なってもよいジ低級アルキルケトン、トルエン、キシレンなどの芳香族系溶剤が挙げられる。これらは単独で使用しても、また２種類以上を混合で使用してもよい。 Moreover, the epoxy resin composition of this invention may contain the solvent if needed. A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper with an epoxy resin composition containing a solvent (hereinafter referred to as varnish) and then drying by heating. Can be made into a cured product of the epoxy resin composition of the present invention by hot press molding. The solvent content in the varnish is usually about 10 to 70% by weight, preferably about 15 to 70% by weight, based on the total weight of the varnish. Examples of the solvent include amide solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone, Sulfones such as tetramethylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, preferably lower alkylene glycol mono or di-lower alkyl ether, methyl ethyl ketone Ketone solvents such as methyl isobutyl ketone, preferably di-lower alkyl ketones in which two alkyl groups may be the same or different, and Ene, and an aromatic solvent such as xylene. These may be used alone or in combination of two or more.
また、剥離フィルム上に前記ワニスを塗布後、加熱下で溶剤を除去してＢステージ化を行うことにより、接着剤として有用なシート状の組成物を得ることが出来る。このシート状組成物は多層基板などにおける層間絶縁層として使用することが出来る。 Moreover, after apply | coating the said varnish on a peeling film, a sheet-like composition useful as an adhesive agent can be obtained by removing a solvent under heating and carrying out B-staging. This sheet-like composition can be used as an interlayer insulating layer in a multilayer substrate or the like.
本発明で得られる硬化物は、エポキシ樹脂等の熱硬化性樹脂が使用される各種用途に使用できる。具体的な用途としては、接着剤、塗料、コーティング剤、成形材料（シート、フィルム、ＦＲＰ等を含む）、絶縁材料（プリント基板、電線被覆等を含む）、封止剤の他、他樹脂等への添加剤等が挙げられる。 The cured product obtained in the present invention can be used in various applications in which a thermosetting resin such as an epoxy resin is used. Specific applications include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealants, other resins, etc. And the like.
接着剤の用途としては、土木用、建築用、自動車用、一般事務用、医療用の他、電子材料用等が挙げられる。これらのうち電子材料用としては、ビルドアップ基板等の多層基板の層間接着剤、ダイボンディング剤やアンダーフィル等の半導体用接着剤、ＢＧＡ補強用アンダーフィル、異方性導電性フィルム（ＡＣＦ）及び異方性導電性ペースト（ＡＣＰ）等の実装用接着剤等が挙げられる。 Applications of the adhesive include civil engineering, architectural, automotive, general office, medical, electronic materials, and the like. Among these, for electronic materials, interlayer adhesives for multilayer substrates such as build-up substrates, semiconductor adhesives such as die bonding agents and underfills, BGA reinforcing underfills, anisotropic conductive films (ACF) and Examples thereof include an adhesive for mounting such as anisotropic conductive paste (ACP).
封止剤としては、コンデンサ、トランジスタ、ダイオード、発光ダイオード、ＩＣやＬＳＩ類及びそれらのＣＯＢ、ＣＯＦ、ＴＡＢ等に用いられるポッティング封止剤、ディッピング封止剤及びトランスファーモールド封止剤や、フリップチップなどのアンダーフィル、ＱＦＰ、ＢＧＡ及びＣＳＰなどのＩＣパッケージ類を実装する際の封止剤等が挙げられる。 Sealing agents include capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, and potting sealants, dipping sealants and transfer mold sealants used for COB, COF, TAB, etc., and flip chips. And under seal such as QFP, BGA, and CSP.
次に本発明を実施例により更に具体的に説明するが、以下において部は特に断わりのない限り重量部である。尚、本発明はこれら実施例に限定されるものではない。また実施例において、エポキシ当量はＪＩＳ Ｋ−７２３６、軟化点はＪＩＳ Ｋ−７２３４に準じた方法で測定した。 EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. Moreover, in the Example, the epoxy equivalent was measured by the method according to JIS K-7236, and the softening point according to JIS K-7234.
実施例１
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらフェノールフタレイン３２０部、エピクロルヒドリン８３２部、テトラメチルアンモニウムクロライド１０部を加え、９０℃にまで昇温してそのまま２時間攪拌した。次いで温度を６５℃に下げ、フレーク状の水酸化ナトリウム８４部を９０分かけて分割添加した後、更に６５℃で１時間、７０℃で１５分、後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレーターを用いて１４０℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去して残留物を得た。この残留物に、メチルイソブチルケトン７６０部を加え溶解し、７５℃まで昇温した後に撹拌下で３０重量％の水酸化ナトリウム水溶液２４部を加え、更に１時間反応を行った。反応終了後、洗浄水が中性になるまで水洗を行い、得られた溶液からロータリーエバポレーターを用いて１８０℃で減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂（ＥＰＰ１）を４１８部得た。得られたエポキシ樹脂のエポキシ当量は２２３ｇ／ｅｑ．、軟化点は５８℃、１５０℃における溶融粘度は０．０５Ｐａ・ｓ、全塩素は７４０ｐｐｍであった。
Example 1
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 320 parts of phenolphthalein, 832 parts of epichlorohydrin, and 10 parts of tetramethylammonium chloride are added while purging with nitrogen, and the temperature is raised to 90 ° C. for 2 hours. Stir. Next, the temperature was lowered to 65 ° C., and 84 parts of flaky sodium hydroxide were added in portions over 90 minutes, and then a post reaction was performed at 65 ° C. for 1 hour and at 70 ° C. for 15 minutes. After completion of the reaction, washing with water was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator to obtain a residue. To this residue, 760 parts of methyl isobutyl ketone was added and dissolved. After the temperature was raised to 75 ° C., 24 parts of a 30 wt% aqueous sodium hydroxide solution was added with stirring, and the reaction was further continued for 1 hour. After completion of the reaction, washing with water is carried out until the washing water becomes neutral. Methyl isobutyl ketone and the like are distilled off from the obtained solution under reduced pressure at 180 ° C. using a rotary evaporator (EPP1) of the present invention. 418 parts of was obtained. The epoxy equivalent of the obtained epoxy resin is 223 g / eq. The softening point was 58 ° C., the melt viscosity at 150 ° C. was 0.05 Pa · s, and the total chlorine was 740 ppm.
実施例２
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらフェノールフタレイン１６０部、エピクロルヒドリン４５０部、ベンジルトリフェニルホスフィンブロマイド２．５部を加え、８０℃まで昇温してそのまま３時間攪拌した。次いで温度を７０℃に下げ、フレーク状の水酸化ナトリウム５０部を９０分かけて分割添加した後、更に７０℃で１時間、後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレーターを用いて１４０℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去して残留物を得た。この残留物にメチルイソブチルケトン３８０部を加えて溶解し、７０℃にまで昇温した後に撹拌下で１５重量％の水酸化カリウム水溶液１２部を加え、更に１時間反応を行った。反応終了後、洗浄水が中性になるまで水洗を行い、得られた溶液からロータリーエバポレーターを用いて１８０℃で減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂（ＥＰＰ２）を２０１部得た。得られたエポキシ樹脂のエポキシ当量は２２１ｇ／ｅｑ．、軟化点は５７℃、１５０℃における溶融粘度は０．０５Ｐａ・ｓ、全塩素は６９０ｐｐｍであった。
Example 2
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 160 parts of phenolphthalein, 450 parts of epichlorohydrin and 2.5 parts of benzyltriphenylphosphine bromide are added while purging with nitrogen. Stir for 3 hours. Next, the temperature was lowered to 70 ° C., 50 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then a post reaction was performed at 70 ° C. for 1 hour. After completion of the reaction, washing with water was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator to obtain a residue. To this residue, 380 parts of methyl isobutyl ketone was added and dissolved. After the temperature was raised to 70 ° C., 12 parts of a 15 wt% aqueous potassium hydroxide solution was added with stirring, and the reaction was further continued for 1 hour. After completion of the reaction, washing with water is carried out until the washing water becomes neutral, and the epoxy resin of the present invention (EPP2) is obtained by distilling off methyl isobutyl ketone and the like from the resulting solution at 180 ° C. under reduced pressure using a rotary evaporator. 201 parts were obtained. The epoxy equivalent of the obtained epoxy resin is 221 g / eq. The softening point was 57 ° C., the melt viscosity at 150 ° C. was 0.05 Pa · s, and the total chlorine was 690 ppm.
実施例３
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらフェノールフタレイン１６０部、エピクロロヒドリン５００部、エチルトリフェニルホスフィンクロライド１．５部を加え、９０℃まで昇温した。次いでフレーク状の水酸化ナトリウム１００部を添加した後、更に９０℃で４時間、後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレーターを用いて１８０℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去して残留物を得た。この残留物にメチルイソブチルケトン３８０部を加え溶解し、７０℃にまで昇温した後に撹拌下で３０重量％の水酸化ナトリウム水溶液１２部を加え、１時間反応を行った。反応終了後、洗浄水が中性になるまで水洗を行い、得られた溶液からロータリーエバポレーターを用いて１８０℃で減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂（ＥＰＰ３）を２０４部得た。得られたエポキシ樹脂のエポキシ当量は２２６ｇ／ｅｑ．、軟化点は５８℃、１５０℃における溶融粘度は０．０６Ｐａ・ｓ、全塩素は８１０ｐｐｍであった。
Example 3
To a flask equipped with a stirrer, reflux condenser and stirrer, add 160 parts of phenolphthalein, 500 parts of epichlorohydrin and 1.5 parts of ethyltriphenylphosphine chloride while purging with nitrogen, and raise the temperature to 90 ° C. did. Next, after adding 100 parts of flaky sodium hydroxide, a post reaction was further performed at 90 ° C. for 4 hours. After completion of the reaction, washing was carried out with water, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 180 ° C. using a rotary evaporator to obtain a residue. To this residue, 380 parts of methyl isobutyl ketone was added and dissolved. After the temperature was raised to 70 ° C., 12 parts of a 30 wt% aqueous sodium hydroxide solution was added with stirring and reacted for 1 hour. After completion of the reaction, washing with water is carried out until the washing water becomes neutral, and methyl isobutyl ketone and the like are distilled off from the obtained solution under reduced pressure at 180 ° C. using a rotary evaporator (EPP3) of the present invention. 204 parts were obtained. The epoxy equivalent of the obtained epoxy resin is 226 g / eq. The softening point was 58 ° C., the melt viscosity at 150 ° C. was 0.06 Pa · s, and the total chlorine was 810 ppm.
比較例１
非特許文献１に記載の手法を用いてフェノールフタレインのエポキシ樹脂を製造した。
撹拌機、温度計、コンデンサを備えたフラスコに窒素ガスパージしながら、フェノールフタレイン１６１部、エピクロルヒドリン５５５部を加え、撹拌下で９０℃まで昇温した。次いでペレット状の水酸化ナトリウム８０部を２４０分かけて分割添加した後、更に９０℃で反応をつづけ、溶液の色が淡黄色〜黄色になった時点（1時間後）で反応を終了し、副生した塩化ナトリウムをろ過により除去した。さらに塩化ナトリウムのウエットケーキからエピクロルヒドリン１００部で反応性生物を抽出・ろ過した。得られたエピクロルヒドリン溶液から、ロータリーエバポレーターを用いて減圧下、１７０℃でエピクロルヒドリン等を留去することにより比較用のエポキシ樹脂（ＥＰＰ４）２０１部を得た。得られたエポキシ樹脂のエポキシ当量は２４５ｇ／ｅｑ．、軟化点は６８℃、粘度は０．１３Ｐａ・ｓ、全塩素量は２９００ｐｐｍであった。
Comparative Example 1
Using the method described in Non-Patent Document 1, an epoxy resin of phenolphthalein was produced.
While purging nitrogen gas into a flask equipped with a stirrer, thermometer and condenser, 161 parts of phenolphthalein and 555 parts of epichlorohydrin were added, and the temperature was raised to 90 ° C. with stirring. Next, 80 parts of pelleted sodium hydroxide was added in portions over 240 minutes, and then the reaction was continued at 90 ° C., and the reaction was terminated when the color of the solution became pale yellow to yellow (after 1 hour). By-product sodium chloride was removed by filtration. Furthermore, reactive organisms were extracted and filtered from a sodium chloride wet cake with 100 parts of epichlorohydrin. From the resulting epichlorohydrin solution, 201 parts of an epoxy resin (EPP4) for comparison was obtained by distilling off epichlorohydrin and the like at 170 ° C. under reduced pressure using a rotary evaporator. The epoxy equivalent of the obtained epoxy resin is 245 g / eq. The softening point was 68 ° C., the viscosity was 0.13 Pa · s, and the total chlorine content was 2900 ppm.
比較例２
非特許文献１に記載の手法を用いてビスフェノールフルオレンのエポキシ樹脂を製造した。
撹拌機、温度計、コンデンサを備えたフラスコに窒素ガスパージしながら、４、４´−ビスフェノール−９、９´−フルオレン１７５部、エピクロルヒドリン５５５部を加え、撹拌下で９０℃まで昇温した。次いでペレット状の水酸化ナトリウム８０部を２４０分かけて分割添加した後、更に９０℃で1時間反応を行い、副生した塩化ナトリウムをろ過により除去した。さらに塩化ナトリウムのウエットケーキからエピクロルヒドリン１００部で反応性生物を抽出・ろ過した。得られたエピクロルヒドリン溶液から、ロータリーエバポレーターを用いて減圧下１２０℃で共沸により水を除去し、水がほとんど出なくなった時点で溶剤留去を停止、そのまま室温に放置することでエポキシ樹脂の結晶体を得た。得られた結晶体をろ過、乾燥することにより比較用のエポキシ樹脂（ＥＢＰＦ１）を無色の結晶粉体として１２９部得た。得られたエポキシ樹脂のエポキシ当量は２５４ｇ／ｅｑ．、融点は１４２℃、全塩素は３４００ｐｐｍであった。
Comparative Example 2
A bisphenolfluorene epoxy resin was produced using the method described in Non-Patent Document 1.
While purging a nitrogen gas purge to a flask equipped with a stirrer, thermometer and condenser, 175 parts of 4,4′-bisphenol-9, 9′-fluorene and 555 parts of epichlorohydrin were added, and the temperature was raised to 90 ° C. with stirring. Next, 80 parts of pelleted sodium hydroxide was added in portions over 240 minutes, and the reaction was further carried out at 90 ° C. for 1 hour, and sodium chloride by-produced was removed by filtration. Furthermore, reactive organisms were extracted and filtered from a sodium chloride wet cake with 100 parts of epichlorohydrin. From the resulting epichlorohydrin solution, water was removed by azeotropic distillation at 120 ° C. under reduced pressure using a rotary evaporator. When water almost disappeared, the solvent distillation was stopped and the solution was allowed to stand at room temperature to leave the epoxy resin crystals. Got the body. The obtained crystal was filtered and dried to obtain 129 parts of a comparative epoxy resin (EBPF1) as a colorless crystal powder. The epoxy equivalent of the obtained epoxy resin is 254 g / eq. The melting point was 142 ° C., and the total chlorine was 3400 ppm.
実施例４，５、比較例３、４
実施例１で得られた本発明のエポキシ樹脂（ＥＰＰ１）と比較例１〜２で得られたエポキシ樹脂（ＥＰＰ４、ＥＢＰＦ１）に、硬化剤としてフェノールノボラック（明和化成工業株式会社製 水酸基当量１９９ｇ／ｅｑ．）、又はＫＡＹＡＨＡＲＤ ＧＰＨ−６５（日本化薬株式会社製 フェノールアラルキル樹脂 水酸基当量１９９ｇ／ｅｑ．）を、硬化促進剤としてトリフェニルホスフィン（ＴＰＰ）を、またそれ以外の成分としては、フィラーとしてＭＳＲ−２２１２（株式会社龍森製）を、ワックスとしてカルナバ１号（株式会社セラリカNODA製）を、カップリング剤としてＫＢＭ−３０３（信越化学工業株式会社）を下記表１に示す配合比（重量部）で配合してエポキシ樹脂組成物を得作成した。
Examples 4 and 5, Comparative Examples 3 and 4
The epoxy resin (EPP1) of the present invention obtained in Example 1 and the epoxy resin (EPP4, EBPF1) obtained in Comparative Examples 1 and 2 were combined with phenol novolac (Maywa Kasei Kogyo Co., Ltd., hydroxyl equivalent 199 g / eq.), or KAYAHARD GPH-65 (manufactured by Nippon Kayaku Co., Ltd., phenol aralkyl resin, hydroxyl group equivalent 199 g / eq.), triphenylphosphine (TPP) as a curing accelerator, and other components as fillers MSR-2212 (manufactured by Tatsumori Co., Ltd.), Carnauba No. 1 (manufactured by Celerica NODA Co., Ltd.) as the wax, and KBM-303 (Shin-Etsu Chemical Co., Ltd.) as the coupling agent are shown in Table 1 below (weight) Part) to obtain an epoxy resin composition.
作成したエポキシ樹脂組成物からトランスファー成型（１７５℃ ６０秒）により樹脂成形体を作成し、これらの成形体に１６０℃で２時間、更に１８０℃で８時間の加熱処理を施して物性評価用の物を得た。 From the prepared epoxy resin composition, resin molded bodies were prepared by transfer molding (175 ° C. 60 seconds), and these molded bodies were subjected to heat treatment at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours for evaluation of physical properties. I got a thing.
得られた硬化物の物性を測定した結果を表２に示す。なお、物性値の測定は以下の方法で行った。
・ガラス転移温度（ＤＭＡ）：ＪＩＳ K−７２４４に準拠。
・ガラス転移温度（ＴＭＡ）：熱機械測定装置真空理工（株）製 ＴＭ−７０００ 昇温速度：２℃／ｍｉｎ．
・難燃性 ： ＵＬ−９４に準拠
The results of measuring the physical properties of the obtained cured product are shown in Table 2. The physical property values were measured by the following methods.
Glass transition temperature (DMA): Conforms to JIS K-7244.
-Glass transition temperature (TMA): TM-7000, manufactured by Vacuum Mechanical Engineering Co., Ltd. Vacuum Riko Co., Ltd. Temperature rising rate: 2 ° C / min.
・ Flame retardance: Conforms to UL-94
本発明のエポキシ樹脂は、フェノールフタレイン骨格を有するエポキシ樹脂の特徴を際立たせたものであり、従来報告されているフェノールフタレイン型エポキシ樹脂との比較において、その硬化物の耐熱性や吸湿性に優れたものである。さらに、本発明のエポキシ樹脂とフェノール系硬化剤及び無機充填材を含有する組成物は、フルオレン骨格を有するエポキシ樹脂組成物との比較において、その硬化物の難燃性に優れたものである。これらのことから、本発明のエポキシ樹脂は電気電子部品用絶縁材料（高信頼性半導体封止材料など）、積層板（プリント配線板、ビルドアップ基板など）やＣＦＲＰを始めとする各種複合材料、接着剤及び塗料等に有用である。 The epoxy resin of the present invention highlights the characteristics of an epoxy resin having a phenolphthalein skeleton, and in comparison with the conventionally reported phenolphthalein type epoxy resin, the heat resistance and hygroscopicity of the cured product. It is an excellent one. Furthermore, the composition containing the epoxy resin of the present invention, a phenolic curing agent and an inorganic filler is excellent in flame retardancy of the cured product in comparison with an epoxy resin composition having a fluorene skeleton. From these facts, the epoxy resin of the present invention is an insulating material for electrical and electronic parts (such as a highly reliable semiconductor encapsulating material), a laminated board (such as a printed wiring board, a build-up board) and various composite materials including CFRP, Useful for adhesives and paints.
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