JP5214658B2 - Epoxy resin, epoxy resin composition and cured product - Google Patents
Epoxy resin, epoxy resin composition and cured product Download PDFInfo
- Publication number
- JP5214658B2 JP5214658B2 JP2010083524A JP2010083524A JP5214658B2 JP 5214658 B2 JP5214658 B2 JP 5214658B2 JP 2010083524 A JP2010083524 A JP 2010083524A JP 2010083524 A JP2010083524 A JP 2010083524A JP 5214658 B2 JP5214658 B2 JP 5214658B2
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- JP
- Japan
- Prior art keywords
- epoxy resin
- phosphorus
- compound
- containing epoxy
- general formula
- 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.)
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- 229920000647 polyepoxide Polymers 0.000 title claims description 120
- 239000003822 epoxy resin Substances 0.000 title claims description 119
- 239000000203 mixture Substances 0.000 title claims description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims description 80
- 239000011574 phosphorus Substances 0.000 claims description 79
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 78
- -1 heteroaromatic cyclic compound Chemical class 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000000466 oxiranyl group Chemical group 0.000 claims description 9
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000001723 curing Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000004593 Epoxy Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 150000002903 organophosphorus compounds Chemical class 0.000 description 14
- 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 12
- 239000011521 glass Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 8
- 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 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000126 substance 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
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical group C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 3
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical group C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VOORKBJLBDXKGM-UHFFFAOYSA-N (2,3-diethylphenyl)-phenylmethanediamine Chemical compound CCC1=CC=CC(C(N)(N)C=2C=CC=CC=2)=C1CC VOORKBJLBDXKGM-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-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
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 description 1
- SKXCTCCZTWNYMD-UHFFFAOYSA-N 1,2-bis(ethenyl)anthracene Chemical compound C1=CC=CC2=CC3=C(C=C)C(C=C)=CC=C3C=C21 SKXCTCCZTWNYMD-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- QTPLEVOKSWEYAC-UHFFFAOYSA-N 1,2-diphenyl-9h-fluorene Chemical compound C=1C=CC=CC=1C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 QTPLEVOKSWEYAC-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- DAGJULOUFIPTPP-UHFFFAOYSA-N 1-phenylpropane-1,1-diamine Chemical compound CCC(N)(N)C1=CC=CC=C1 DAGJULOUFIPTPP-UHFFFAOYSA-N 0.000 description 1
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LYXAQAXLWMRPOZ-UHFFFAOYSA-N 2-[1-(2-aminophenyl)-9h-fluoren-2-yl]aniline Chemical compound NC1=CC=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=CC=C1N LYXAQAXLWMRPOZ-UHFFFAOYSA-N 0.000 description 1
- QXSVPTMYGFFGQV-UHFFFAOYSA-N 2-dimethylphosphorylbenzene-1,4-diol Chemical compound CP(C)(=O)C1=CC(O)=CC=C1O QXSVPTMYGFFGQV-UHFFFAOYSA-N 0.000 description 1
- LLOXZCFOAUCDAE-UHFFFAOYSA-N 2-diphenylphosphorylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(P(=O)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 LLOXZCFOAUCDAE-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
- OHPBKUJGDFXDRM-UHFFFAOYSA-N 3,4-diethyl-5-(2-phenylpropan-2-yl)benzene-1,2-diamine Chemical compound CCC1=C(N)C(N)=CC(C(C)(C)C=2C=CC=CC=2)=C1CC OHPBKUJGDFXDRM-UHFFFAOYSA-N 0.000 description 1
- BDBMKUGEVIQCGQ-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-dimethylaniline Chemical group C1=C(N)C(C)=C(C)C(C=2C=CC(N)=CC=2)=C1 BDBMKUGEVIQCGQ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- DWGLLTZGGCSKDQ-UHFFFAOYSA-N 5-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)naphthalene-1,6-diol Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=C2C=CC=C(O)C2=CC=C1O DWGLLTZGGCSKDQ-UHFFFAOYSA-N 0.000 description 1
- KSFAWAYSJUPRED-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetramine Chemical compound NC1=C(N)C(N)=CC(C=2C=CC=CC=2)=C1N KSFAWAYSJUPRED-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- ZDGWGNDTQZGISB-UHFFFAOYSA-N acetic acid;perchloric acid Chemical compound CC(O)=O.OCl(=O)(=O)=O ZDGWGNDTQZGISB-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UKNKFVBQMUMOLP-UHFFFAOYSA-N bis(2,3-diaminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C(=C(N)C=CC=2)N)=C1N UKNKFVBQMUMOLP-UHFFFAOYSA-N 0.000 description 1
- AMGAACTXBLZKQR-UHFFFAOYSA-N bis(ethenyl)-methyl-phenylsilane Chemical compound C=C[Si](C)(C=C)C1=CC=CC=C1 AMGAACTXBLZKQR-UHFFFAOYSA-N 0.000 description 1
- GEKAWPIATFUQJW-UHFFFAOYSA-N bis(ethenyl)-phenylphosphane Chemical compound C=CP(C=C)C1=CC=CC=C1 GEKAWPIATFUQJW-UHFFFAOYSA-N 0.000 description 1
- QJPDCMIFPPRCFH-UHFFFAOYSA-N bis(ethenyl)phosphorylbenzene Chemical compound C=CP(=O)(C=C)C1=CC=CC=C1 QJPDCMIFPPRCFH-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- JMCNGFNJWDJIIV-UHFFFAOYSA-N dibutyl(oxo)phosphanium Chemical compound CCCC[P+](=O)CCCC JMCNGFNJWDJIIV-UHFFFAOYSA-N 0.000 description 1
- YVXVNGVYXSQARS-UHFFFAOYSA-N diethyl(oxo)phosphanium Chemical compound CC[P+](=O)CC YVXVNGVYXSQARS-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WQAWEUZTDVWTDB-UHFFFAOYSA-N dimethyl(oxo)phosphanium Chemical compound C[P+](C)=O WQAWEUZTDVWTDB-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
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GELSOTNVVKOYAW-UHFFFAOYSA-N ethyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 GELSOTNVVKOYAW-UHFFFAOYSA-N 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002648 laminated material 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
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- UEJWQQOFBFKFTB-UHFFFAOYSA-M potassium;propane-1,2-diol;hydroxide Chemical compound [OH-].[K+].CC(O)CO UEJWQQOFBFKFTB-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- CMLWFCUAXGSMBB-UHFFFAOYSA-N tris(2,6-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(OC)=C1P(C=1C(=CC=CC=1OC)OC)C1=C(OC)C=CC=C1OC CMLWFCUAXGSMBB-UHFFFAOYSA-N 0.000 description 1
- FUJPAQRDHMJPBB-UHFFFAOYSA-N tris(ethenyl)-phenylsilane Chemical compound C=C[Si](C=C)(C=C)C1=CC=CC=C1 FUJPAQRDHMJPBB-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Epoxy Resins (AREA)
Description
本発明は、電子回路基板に用いられる銅張積層板、フィルム材、樹脂付き銅箔などを製造する樹脂組成物や電子部品に用いられる封止材・成形材・注型材・接着剤・電気絶縁塗料用材料などとして有用な新規な難燃性エポキシ樹脂、エポキシ樹脂組成物及びその硬化物に関する。 The present invention relates to a resin composition for producing a copper clad laminate, a film material, a resin-coated copper foil, etc. used for an electronic circuit board, and a sealing material, a molding material, a casting material, an adhesive, and an electrical insulation used for an electronic component. The present invention relates to a novel flame-retardant epoxy resin useful as a coating material, an epoxy resin composition and a cured product thereof.
エポキシ樹脂は接着性、耐熱性、成形性に優れていることから電子部品、電気機器、自動車部品、ＦＲＰ、スポーツ用品などに広範囲に使用されている。なかでも電子部品、電気機器に使用される銅張積層板や封止材には火災の防止・遅延といった安全性が強く要求されていることから、これまでこれらの特性を有する臭素化エポキシ樹脂などが使用されている。比重が大きいという問題を有しているものの、エポキシ樹脂にハロゲン、特に臭素を導入することにより難燃性が付与されることと、エポキシ基は高反応性を有し優れた硬化物が得られることから、臭素化エポキシ樹脂類は有用な電子、電気材料として位置づけられている。しかし、最近の電気機器を見るといわゆる軽薄短小を最重要視する傾向が次第に強くなってきている。このような社会的要求下において比重の大きいハロゲン化物は最近の軽量化傾向の観点からは好ましくない材料であり、また、高温で長期にわたって使用した場合、ハロゲン化物の解離が起こり、これによって配線腐食の発生の恐れがある。
更に使用済みの電子部品、電気機器の燃焼の際にハロゲン化物などの有害物質を発生し、環境安全性の視点からハロゲンの利用が問題視されるようになり、これに代わる材料が研究されるようになった。本発明者はこの課題に鋭意取り組み、電子機器の軽薄短小化や配線腐食の問題、有害なハロゲン化物の発生の無いリン含有エポキシ樹脂を発明した。（特許文献１〜２）しかし、硬化物の耐熱性向上や難燃性の向上などが更に求められている。
Epoxy resins are widely used in electronic parts, electrical equipment, automobile parts, FRP, sports equipment and the like because of their excellent adhesiveness, heat resistance and moldability. In particular, copper-clad laminates and encapsulants used in electronic parts and electrical equipment are strongly required to have safety such as fire prevention and delay. Brominated epoxy resins having these characteristics have been used so far. Is used. Although it has the problem of high specific gravity, flame resistance is imparted by introducing halogen, especially bromine, into the epoxy resin, and the epoxy group has high reactivity and an excellent cured product can be obtained. Thus, brominated epoxy resins are positioned as useful electronic and electrical materials. However, when looking at recent electrical equipment, the tendency to place the highest importance on so-called lightness and thinness is becoming increasingly strong. Under such social demands, halides with a large specific gravity are undesirable materials from the viewpoint of recent light weight trends, and when used at high temperatures for a long period of time, halides dissociate, which causes corrosion of wiring. There is a risk of occurrence.
Furthermore, when used electronic parts and electrical equipment are burned, harmful substances such as halides are generated, and the use of halogens has become a problem from the viewpoint of environmental safety, and alternative materials are studied. It became so. The present inventor has eagerly addressed this problem and invented a phosphorus-containing epoxy resin free from light and thin electronic devices, wiring corrosion problems, and generation of harmful halides. (Patent Documents 1 and 2) However, there is a further demand for improvement in heat resistance and flame retardancy of cured products.
しかしながら、リン含有エポキシ樹脂において難燃性を向上するため、リン含有率を高めようとした場合、リン化合物の変性率を高くする必要があり、エポキシ樹脂の粘度が高くなり取り扱いが難しくなる。そればかりか、ガラス転移温度、接着力等の硬化物物性も極端に低下してしまう。このように、高い難燃性と優れた硬化物物性を与えるエポキシ樹脂を得ることは難しかった。従って、本発明の目的は高い難燃性と優れた硬化物物性を与えるリン含有エポキシ樹脂、リン含有エポキシ樹脂組成物、ならびにその硬化物を提供することにある。 However, in order to improve the flame retardancy in the phosphorus-containing epoxy resin, when the phosphorus content is to be increased, it is necessary to increase the modification rate of the phosphorus compound, and the viscosity of the epoxy resin becomes high and handling becomes difficult. In addition, the physical properties of the cured product such as the glass transition temperature and the adhesive strength are extremely lowered. Thus, it has been difficult to obtain an epoxy resin that provides high flame retardancy and excellent cured product properties. Accordingly, an object of the present invention is to provide a phosphorus-containing epoxy resin, a phosphorus-containing epoxy resin composition, and a cured product thereof that give high flame retardancy and excellent cured product properties.
本発明者は前記の課題を解決するため鋭意研究を重ねた結果、リン含有率を低くしても硬化物の難燃性を著しく損なうことなく、優れた硬化物物性を与えるリン含有エポキシ樹脂に必須な骨格を見出し本願発明のリン含有エポキシ樹脂として完成したものである。前記の課題を解決するための手段は以下のようなものである。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have developed a phosphorus-containing epoxy resin that gives excellent cured material properties without significantly impairing the flame retardancy of the cured product even when the phosphorus content is lowered. The essential skeleton was found and the phosphorus-containing epoxy resin of the present invention was completed. Means for solving the above-mentioned problems are as follows.
すなわち、本発明は
（１）一般式１および／または一般式２で示されるオキシラン環以外の−Ｃ−Ｏ−Ｃ−骨格を含まないエポキシ樹脂と一般式３で示されるリン含有化合物を反応して得られるリン含有率０．２重量％〜６重量％のリン含有エポキシ樹脂。
That is, the present invention reacts (1) an epoxy resin containing no —C—O—C— skeleton other than the oxirane ring represented by the general formula 1 and / or the
（２）（１）のリン含有エポキシ樹脂と硬化剤を必須として含有することを特徴としたリン含有エポキシ樹脂組成物
（３）（２）のリン含有エポキシ樹脂組成物を硬化して得られる硬化物。
に関する。
(2) A phosphorus-containing epoxy resin composition characterized by containing the phosphorus-containing epoxy resin of (1) and a curing agent as essential components (3) Curing obtained by curing the phosphorus-containing epoxy resin composition of (2) object.
About.
本発明のリン含有エポキシ樹脂はリン含有率を下げても十分な難燃性と優れた硬化物物性を有するエポキシ樹脂を提供することができ、該エポキシ樹脂を含有した本発明のエポキシ樹脂を使用して得られた成形物の評価を行った結果、従来のリン含有エポキシ樹脂よりも優れた難燃性と優れた硬化物物性を持つ硬化物を得ることが可能である。該エポキシ樹脂組成物及びその硬化物は電子部品に用いられる、封止材、成形材、注型材、接着剤、フィルム材、電気絶縁塗料用材料などとして有用であることがわかった。 The phosphorus-containing epoxy resin of the present invention can provide an epoxy resin having sufficient flame retardancy and excellent cured product properties even when the phosphorus content is lowered, and the epoxy resin of the present invention containing the epoxy resin is used. As a result of evaluating the molded product thus obtained, it is possible to obtain a cured product having flame retardancy superior to conventional phosphorus-containing epoxy resins and excellent cured product properties. It was found that the epoxy resin composition and its cured product are useful as a sealing material, a molding material, a casting material, an adhesive, a film material, a material for an electrical insulating paint, etc. used for electronic parts.
従来のリン含有エポキシ樹脂は有機リン化合物を反応するエポキシ樹脂として、フェノール化合物またはアルコール化合物とエピクロルヒドリンを反応した様々なグリシジルエーテル型エポキシ樹脂が用いられてきた。グリシジルエーテル型リン含有エポキシ樹脂にはオキシラン環以外に−Ｃ−Ｏ−Ｃ−骨格いわゆるエーテル構造を持つ。そのため硬化物の難燃性を発現するには、エポキシ樹脂のリン含有率を２重量％以上にする必要があった。
本発明のリン含有エポキシ樹脂においてリン含有率を従来のリン含有エポキシ樹脂と同じにした場合、難燃性試験の残炎時間が大幅に短縮でき、硬化物に特徴を与えるために難燃性は持たない他の特徴を持つ樹脂を配合することができ、配合の自由度が向上することができる。例えば耐熱性を有するエポキシ樹脂として、ESF-300（新日鐵化学株式会社製、ジフェニルフルオレン型エポキシ樹脂）、可とう性を有するエポキシ樹脂としてYD-172（東都化成株式会社製、ダイマー酸変性エポキシ樹脂）などが配合できるが特にこれらに限定されるものではない。
In the conventional phosphorus-containing epoxy resins, various glycidyl ether type epoxy resins obtained by reacting a phenol compound or an alcohol compound with epichlorohydrin have been used as an epoxy resin for reacting an organic phosphorus compound. In addition to the oxirane ring, the glycidyl ether type phosphorus-containing epoxy resin has a —C—O—C— skeleton so-called ether structure. Therefore, in order to express the flame retardancy of the cured product, the phosphorus content of the epoxy resin has to be 2% by weight or more.
When the phosphorus content in the phosphorus-containing epoxy resin of the present invention is the same as that of the conventional phosphorus-containing epoxy resin, the after-flame time of the flame retardancy test can be greatly shortened, and the flame retardancy is to give characteristics to the cured product. Resins having other characteristics not possessed can be blended, and the degree of freedom of blending can be improved. For example, ESF-300 (diphenylfluorene type epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd.) is used as a heat-resistant epoxy resin, and YD-172 (manufactured by Tohto Kasei Co., Ltd., dimer acid-modified epoxy is used as a flexible epoxy resin. Resin) and the like can be blended, but is not particularly limited thereto.
本発明におけるリン含有エポキシ樹脂は一般式１および／または一般式２で示されるオキシラン環以外の−Ｃ−Ｏ−Ｃ−骨格を含まないエポキシ樹脂と一般式３、一般式４で示される有機リン化合物類を反応して得られる、リン含有率０．２重量％〜６重量％のリン含有エポキシ樹脂。
The phosphorus-containing epoxy resin in the present invention is an epoxy resin containing no —C—O—C— skeleton other than the oxirane ring represented by the general formula 1 and / or the
一般式1中のＡｒは芳香族炭化水素基、環式不飽和置換基、複素環式置換基または複素芳香環式置換基を示す。具体的に芳香族炭化水素基は、ベンゼン、ナフタレン、アントラセン、フェナントラセン、アズレン、ビフェニル等であり、環式不飽和置換基は、シクロヘキセン、インデン等であり、複素環式置換基はピロール、イミダゾール、ピラゾール、ピリジン、ピリダジン、ピリミジン、ピラジン、チアゾール、イソチアゾール等1つ以上のヘテロ原子を含むものであり、複素芳香環式置換基はベンゾイミダゾール、イミダゾピリジン等が含まれるがこれらに限定されるものではない。式中のｎは１〜３の整数を示し、ｍは０または１を示し、ｌは１〜１２を示し、より好ましくはｌ＝２〜１０。 Ar in the general formula 1 represents an aromatic hydrocarbon group, a cyclic unsaturated substituent, a heterocyclic substituent or a heteroaromatic substituent. Specifically, the aromatic hydrocarbon group is benzene, naphthalene, anthracene, phenanthracene, azulene, biphenyl, etc., the cyclic unsaturated substituent is cyclohexene, indene, etc., and the heterocyclic substituent is pyrrole, It contains one or more heteroatoms such as imidazole, pyrazole, pyridine, pyridazine, pyrimidine, pyrazine, thiazole, isothiazole, and heteroaromatic substituents include but are not limited to benzimidazole, imidazopyridine, etc. It is not something. In the formula, n represents an integer of 1 to 3, m represents 0 or 1, l represents 1 to 12, and more preferably l = 2 to 10.
一般式１で示されるエポキシ樹脂は、例えば、多価ビニル化合物を直接酸化して得られる樹脂分子中にオキシラン環以外の−Ｃ−Ｏ−Ｃ−骨格を含まないエポキシ樹脂であり、このエポキシ樹脂は特許文献３の製法を参考にして多価ビニル化合物を直接酸化反応することで製造することができる。
The epoxy resin represented by the general formula 1 is, for example, an epoxy resin that does not contain a —C—O—C— skeleton other than an oxirane ring in a resin molecule obtained by directly oxidizing a polyvalent vinyl compound. Can be produced by directly oxidizing a polyvalent vinyl compound with reference to the production method of
一般式１におけるこれらエポキシの原料の多価ビニル化合物としては、例えば構造異性体を含むジビニルベンゼンが汎用的な代表例として挙げられるが、その他にもジビニルジメチルベンゼン、オクタヒドロジビニルペンタレン、ジビニルナフタレン、ジビニルビフェニル、ジビニルアントラセン、トリビニルベンゼン、テトラビニルシクロブタジエン、テトラビニルベンゼン、ジエテニルフェニルホスフィン、メチルフェニルジビニルシラン、フェニルトリビニルシラン、フェニルジビニルホスフィンオキシド等も用いても良い。何れも化合物の構造内にエーテル骨格を有さないこととし、芳香環を有する構造がより好ましい。 Examples of the polyvalent vinyl compound as a raw material for these epoxies in the general formula 1 include divinylbenzene containing a structural isomer as a typical representative example, but other examples include divinyldimethylbenzene, octahydrodivinylpentalene, divinylnaphthalene. Divinylbiphenyl, divinylanthracene, trivinylbenzene, tetravinylcyclobutadiene, tetravinylbenzene, diethenylphenylphosphine, methylphenyldivinylsilane, phenyltrivinylsilane, phenyldivinylphosphine oxide, and the like may also be used. In any case, the structure of the compound has no ether skeleton, and a structure having an aromatic ring is more preferable.
一般式２中のＡｒは芳香族炭化水素基、環式不飽和置換基、複素環式置換基または複素芳香環式置換基を示す。具体的に芳香族炭化水素基は、ベンゼン、ナフタレン、アントラセン、フェナントラセン、アズレン、ビフェニル等であり、環式不飽和置換基はシクロヘキセン、インデン等であり、複素環式置換基はピロール、イミダゾール、ピラゾール、ピリジン、ピリダジン、ピリミジン、ピラジン、チアゾール、イソチアゾール等1つ以上のヘテロ原子を含むものであり、複素芳香環式置換基はベンゾイミダゾール、イミダゾピリジン等が含まれるがこれらに限定されるものではない。式中のｎは１〜３の整数を示し、ｍは０または１を示し、ｌは１〜１２を示し、より好ましくは２〜１０。
Ar in the
一般式２で示されるエポキシ樹脂は、例えば、活性水素を持つアミン化合物とエピクロルヒドリンとの反応から得られる樹脂分子中にオキシラン環以外の−Ｃ−Ｏ−Ｃ−骨格を含まないグリシジルアミン型のエポキシ樹脂であり、その製法は既に公知である。具体的にはエポトートＹＨ−４３４Ｌ（テトラグリシジルジアミノジフェニルメタン、東都化成株式会社製）が挙げられるが、これに限定されるものではない。
The epoxy resin represented by the
一般式２のエポキシ樹脂は原料としてアミン化合物が挙げられる。例えばアニリン、フェニレンジアミン、トルイジン、キシリジン、ジエチルトルエンジアミン、フェニルメタン、ジアミノフェニルタン、ジアミノフェニルプロパン、ジアミノフェニルケトン、ジアミノジフェニルスルフィド、ジアミノジフェニルスルホン、ビス（アミノフェニル）フルオレン、ジアミノジエチルジメチルジフェニルメタン、ジアミノジフェニルエーテル、ジアミノベンズアニリド、ジアミノビフェニル、ジメチルジアミノビフェニル、ビフェニルテトラアミン、ビスアミノフェニルアントラセン、ビスアミノフェノキシベンゼン、ビスアミノフェノキシフェニルエーテル、ビスフェノキシビフェニル、ビスアミノフェノキシフェニルスルホン、ビスアミノフェノキシフェニルプロパン、ジアミノナフタレン、アセトグアナミン等のメラミン誘導体類が挙げられるが、これら何れも化合物の構造内にエーテル骨格を有さないこととし、芳香環を有する構造がより好ましい。
The epoxy resin of the
一般式３中のＲ２、Ｒ３は水素または、炭化水素基を示す。それぞれ異なっていても同一でも良く、Ｒ２とＲ３が結合し、環を形成してもよい。ｊは０または１の整数を示す、Yは水素または一般式４を示す。一般式４のＡｒは芳香族炭化水素化合物、環式不飽和化合物、複素環式化合物または複素芳香環式化合物を示す。具体的に芳香族炭化水素基は、ベンゼン、ナフタレン、アントラセン、フェナントラセン、アズレン、ビフェニル等であり、環式不飽和置換基はシクロヘキセン、インデン等であり、複素環式置換基はピロール、イミダゾール、ピラゾール、ピリジン、ピリダジン、ピリミジン、ピラジン、チアゾール、イソチアゾール等1つ以上のヘテロ原子を含むものであり、複素芳香環式置換基はベンゾイミダゾール、イミダゾピリジン等が含まれるがこれらに限定されるものではない。式中のｉは１〜１１の整数を示す。好ましくは２〜４。
R2 and R3 in the
本発明において有機リン化合物は一般式３で示される化合物であれば特に限定されないが、一般式３中のＹが水素の具体例としてはジメチルホスフィン、ジエチルホスフィン、ジフェニルホスフィン、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド（ＨＣＡ三光株式会社製、以下ＨＣＡと記す）、ジメチルホスフィンオキサイド、ジエチルホスフィンオキサイド、ジブチルホスフィンオキサイド、ジフェニルホスフィンオキサイド、１，４−シクロオクチレンホスフィンオキサイド、１，５−シクロオクチレンホスフィンオキサイド（ＣＰＨＯ日本化学工業株式会社製）、一般式３中のＹが一般式４のＡｒ基を持つ場合の具体例としては、ジメチルホスフィニルハイドロキノン、ジエチルホスフィニルハイドロキノン、ジフェニルホスフィニルハイドロキノン、１０−（２，５−ジヒドロキシフェニル）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド（ＨＣＡ−ＨＱ三光株式会社製、以下ＨＣＡ−ＨＱと記す）、１０−（２，５−ジヒドロキシナフチル）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１，４−シクロオクチレンホスホニルハイドロキノン、１，５−シクロオクチレンホスホニルハイドロキノン（ＣＰＨＯ−ＨＱ 日本化学工業株式会社製）等が挙げられる。これらのリン化合物は単独でも２種類以上混合して使用しても良く、これらに限定されるものではない。
In the present invention, the organic phosphorus compound is not particularly limited as long as it is a compound represented by the
本発明に用いる有機リン化合物類とエポキシ樹脂との反応は公知の方法で行うことが可能である。反応温度として１００℃〜２００℃、より好ましくは１００℃〜１８０℃で攪拌下行うことができる。反応時間はエポキシ当量の測定を行って決定することができる。測定にはＪＩＳ Ｋ−７２３６の方法により測定可能である。２官能エポキシ樹脂類（Ａ）と有機リン化合物類との反応によりエポキシ当量は大きくなっていき、理論エポキシ当量との比較により反応終点を決定できる。 The reaction between the organophosphorus compounds and the epoxy resin used in the present invention can be carried out by a known method. The reaction temperature can be 100 to 200 ° C., more preferably 100 to 180 ° C. with stirring. The reaction time can be determined by measuring the epoxy equivalent. Measurement can be performed by the method of JIS K-7236. The epoxy equivalent is increased by the reaction between the bifunctional epoxy resins (A) and the organophosphorus compound, and the end point of the reaction can be determined by comparison with the theoretical epoxy equivalent.
また、反応の速度が遅い場合、必要に応じて触媒を使用して生産性の改善を計ることができる。具体的にはベンジルジメチルアミン等の第３級アミン類、テトラメチルアンモニウムクロライド等の第４級アンモニウム塩類、トリフェニルホスフィン、トリス（２，６−ジメトキシフェニル）ホスフィン等のホスフィン類、エチルトリフェニルホスホニウムブロマイド等のホスホニウム塩類、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類等各種触媒が使用可能である。 Further, when the reaction rate is slow, productivity can be improved by using a catalyst as necessary. Specifically, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium Various catalysts such as phosphonium salts such as bromide and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used.
本発明組成物には特性を損ねない範囲で本発明のリン含有エポキシ樹脂以外のエポキシ樹脂類を配合してもよい。 You may mix | blend epoxy resins other than the phosphorus containing epoxy resin of this invention with the range which does not impair a characteristic to this invention composition.
本発明のエポキシ樹脂組成物中の全エポキシ樹脂成分に対するリン含有率を特に規定する必要はないが、難燃性の観点からはリン含有率が高い方が好ましく、硬化物物性の向上の観点からリン含有率が低い方が好ましい。従って両方を満足させるには、好ましくは０．２重量％から６重量％であり、より好ましくは１重量％から４重量％であり、さらに好ましくは１．５重量％から３重量％である。 Although it is not necessary to prescribe | regulate especially the phosphorus content rate with respect to all the epoxy resin components in the epoxy resin composition of this invention, from the viewpoint of a flame retardance, the one where a phosphorus content rate is higher is preferable, and a viewpoint of the improvement of hardened | cured material physical property. A lower phosphorus content is preferred. Therefore, in order to satisfy both, it is preferably 0.2% by weight to 6% by weight, more preferably 1% by weight to 4% by weight, and further preferably 1.5% by weight to 3% by weight.
本発明の硬化剤としては、フェノールノボラック樹脂を代表とする各種多価フェノール樹脂類や酸無水物類、ジシアンジアミンやジエチルジアミノジフェニルメタンを代表とするアミン類、ヒドラジッド類、酸性ポリエステル類等の通常使用されるエポキシ樹脂用硬化剤を使用することができ、これらの硬化剤は１種類だけ使用しても２種類以上使用しても良い。 As the curing agent of the present invention, various polyhydric phenol resins and acid anhydrides typified by phenol novolac resins, amines typified by dicyandiamine and diethyldiaminodiphenylmethane, hydrazides, acidic polyesters, etc. The epoxy resin curing agent used can be used, and these curing agents may be used alone or in combination of two or more.
また、本発明エポキシ樹脂組成物は必要に応じて硬化促進剤を使用することができる。硬化促進剤としては、ホスフィン類、四級ホスホニウム塩類、三級アミン類、四級アンモニウム塩類、イミダゾール化合物類、三フッ化ホウ素錯体類、３−（３，４−ジクロロジフェニル）−１，１−ジメチルウレア、３−（４−クロロフェニル）−１，１−ジメチルウレア、３−フェニル−１，１−ジメチルウレア等が挙げられるがこれらに限定されるものではない。 Moreover, a hardening accelerator can be used for this invention epoxy resin composition as needed. Examples of the curing accelerator include phosphines, quaternary phosphonium salts, tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3- (3,4-dichlorodiphenyl) -1,1- Examples include, but are not limited to, dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, and 3-phenyl-1,1-dimethylurea.
これら硬化促進剤は併用するエポキシ樹脂、使用するエポキシ樹脂硬化剤の種類、成型方法、硬化温度、要求特性によるが、エポキシ樹脂１００部に対して０．０１〜２０重量部の範囲が好ましく、さらには０．１〜１０重量部が好ましい。 These curing accelerators depend on the epoxy resin used together, the type of epoxy resin curing agent used, the molding method, the curing temperature, and the required characteristics, but are preferably in the range of 0.01 to 20 parts by weight with respect to 100 parts of the epoxy resin. Is preferably 0.1 to 10 parts by weight.
本発明のエポキシ樹脂組成物は、必要に応じて無機充填剤、有機充填剤を配合することができる。充填剤の例としては、溶融シリカ、結晶シリカ、アルミナ、窒化ケイ素、水酸化アルミニウム、タルク、マイカ、炭酸カルシウム、ケイ酸カルシウム、水酸化カルシウム、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、窒化ホウ素、炭素、炭素繊維、ガラス繊維、アルミナ繊維、シリカアルミナ繊維、炭化ケイ素繊維、ポリエステル繊維、セルロース繊維、アラミド繊維等が挙げられる。これら充填剤はエポキシ樹脂組成物中の１〜９５重量％が好ましい。 The epoxy resin composition of this invention can mix | blend an inorganic filler and an organic filler as needed. Examples of fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon , Carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber and the like. These fillers are preferably 1 to 95% by weight in the epoxy resin composition.
本発明のエポキシ樹脂組成物は、さらに必要に応じてシランカップリング剤、酸化防止剤、離型剤、消泡剤、乳化剤、揺変性付与剤、平滑剤、難燃剤、顔料等の各種添加剤を配合することができる。これら添加剤はエポキシ樹脂組成物全量中の０．０１〜２０重量％の範囲が好ましい。 The epoxy resin composition of the present invention further includes various additives such as a silane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, a flame retardant, and a pigment as necessary. Can be blended. These additives are preferably in the range of 0.01 to 20% by weight based on the total amount of the epoxy resin composition.
本発明のエポキシ樹脂組成物は、公知のエポキシ樹脂組成物と同様な方法により成型、硬化して硬化物とすることができる。成型方法、硬化方法は公知のエポキシ樹脂組成物と同様の方法をとることができ、本発明エポキシ樹脂組成物固有の方法は不要である。 The epoxy resin composition of the present invention can be molded and cured by the same method as known epoxy resin compositions to obtain a cured product. The molding method and the curing method can be the same methods as known epoxy resin compositions, and the method unique to the epoxy resin composition of the present invention is unnecessary.
本発明のエポキシ樹脂硬化物は塗膜、接着層、成型物、積層物、フィルム等の形態をとることができる。 The cured epoxy resin of the present invention can take the form of a coating film, an adhesive layer, a molded product, a laminate, a film and the like.
本発明のリン含有エポキシ樹脂の全塩素量は得られる硬化物の電気的信頼性の低下と相関があり、増加すれば硬化物の電気的信頼性は低下し、少なければ電気的信頼性は向上する。許容できる硬化物の電気的信頼性から考えて、本発明のリン含有エポキシ樹脂の全塩素量は０．２重量％以下が好ましく、より好ましくは一般的な封止材用エポキシ樹脂と等しく０．０９重量％以下であり、さらに好ましくは０．０５重量％以下である。 The total chlorine content of the phosphorus-containing epoxy resin of the present invention correlates with a decrease in the electrical reliability of the obtained cured product. If it is increased, the electrical reliability of the cured product is lowered, and if it is less, the electrical reliability is improved. To do. In view of the electrical reliability of the cured product that can be tolerated, the total chlorine content of the phosphorus-containing epoxy resin of the present invention is preferably 0.2% by weight or less, and more preferably 0. It is 09 weight% or less, More preferably, it is 0.05 weight% or less.
以下、合成例、実施例及び比較例に基づき、本発明を具体的に説明するが、本発明の技術的範囲は実施例のみに制限されるものではない。なお、実施例と比較例における各成分の配合部数は、特に断らない限り重量部を示すものである。 Hereinafter, the present invention will be specifically described based on synthesis examples, examples, and comparative examples, but the technical scope of the present invention is not limited only to the examples. In addition, unless otherwise indicated, the compounding part number of each component in an Example and a comparative example shows a weight part.
また、本発明では以下の分析方法を使用した。
エポキシ当量：ＪＩＳ Ｋ−７２３６に記載の方法。即ち、試料をクロロホルム１０ｍＬに溶解し、無水酢酸２０ｍＬ、２０％の臭化テトラエチルアンモニウム酢酸溶液１０ｍＬをそれぞれ加えて、電位差滴定装置を用いて０．１ｍｏｌ／Ｌ過塩素酸酢酸標準液で滴定を行い、各試薬の濃度と添加量ならびに滴定量から、エポキシ樹脂に含まれるエポキシ当量を測定した。
In the present invention, the following analysis method was used.
Epoxy equivalent: The method described in JIS K-7236. That is, dissolve a sample in 10 mL of chloroform, add 20 mL of acetic anhydride and 10 mL of 20% tetraethylammonium bromide solution, and perform titration with a 0.1 mol / L perchloric acid acetic acid standard solution using a potentiometric titrator. The epoxy equivalent contained in the epoxy resin was measured from the concentration and addition amount of each reagent and the titration amount.
全塩素量：ＪＩＳ Ｋ−７２４３−３に記載の方法。即ち、試料をジエチレングリコールモノブチルエーテル２５ｍＬに溶解し、１ｍｏｌ／Ｌ水酸化カリウムの１，２−プロパンジオール溶液２５ｍＬを加えて、ホットプレート上にて１０分間加熱還流下で反応させる。室温まで冷却後、５０ｍＬの無水酢酸を加えて、電位差滴定装置を用いて０．０１ｍｏｌ／Ｌ硝酸銀溶液で滴定を行い、各試薬の濃度と添加量ならびに滴定量から、エポキシ樹脂に含まれる全塩素量を測定した。 Total chlorine content: The method described in JIS K-7243-3. That is, a sample is dissolved in 25 mL of diethylene glycol monobutyl ether, 25 mL of a 1-mol / L potassium hydroxide 1,2-propanediol solution is added, and the mixture is reacted on a hot plate for 10 minutes under heating and reflux. After cooling to room temperature, 50 mL of acetic anhydride is added, and titration is performed with a 0.01 mol / L silver nitrate solution using a potentiometric titrator. From the concentration, addition amount, and titration of each reagent, total chlorine contained in the epoxy resin The amount was measured.
粘度：ＪＩＳ Ｋ−７２３３に記載の方法。即ち、５００ｍＬの円筒缶に樹脂４００ｇをはかりとって、２５±０．２℃の恒温水槽で５時間放置して恒温にし、回転粘度計のローターを樹脂に浸漬して測定した。 Viscosity: The method described in JIS K-7233. That is, 400 g of resin was weighed in a 500 mL cylindrical can, left in a constant temperature water bath at 25 ± 0.2 ° C. for 5 hours, and the temperature was measured by immersing the rotor of a rotational viscometer in the resin.
軟化点：ＪＩＳ Ｋ−７２３４に記載の方法。即ち、環球法で、規定の環に試料を充填し、グリセリン浴中に水平に支え、試料中央に規定の球を置き、５℃／ｍｉｎで昇温して測定した。 Softening point: The method described in JIS K-7234. That is, by a ring and ball method, a sample was filled in a specified ring, supported horizontally in a glycerin bath, a specified ball was placed at the center of the sample, and the temperature was increased at 5 ° C./min.
リン含有率：試料に硫酸、塩酸、過塩素酸を加え、加熱して湿式灰化し、全てのリン原子を正リン酸とした。硫酸酸性溶液中でメタバナジン酸塩およびモリブデン酸塩を反応させ、生じたリンバナードモリブデン酸錯体の４２０ｎｍにおける吸光度を測定し、予め作成した検量線により求めたリン原子含有量を重量％で表し、エポキシ樹脂に含まれるリン含有率を測定した。 Phosphorus content: Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ash to convert all phosphorus atoms into normal phosphoric acid. Reaction of metavanadate and molybdate in a sulfuric acid acidic solution, the absorbance at 420 nm of the resulting limpavandemolybdate complex was measured, and the phosphorus atom content determined by a pre-prepared calibration curve was expressed in weight%. The phosphorus content contained in the resin was measured.
溶融粘度：コーンプレート型粘度計（東亜工業株式会社製、ＭＯＥＤＬ ＣＶ−１Ｓ）を用い、ローターは１０ポアズコーン（Φ：１９．５ｍｍ、θ：０．５°）を使用して、１００℃の測定温度で測定した。 Melt viscosity: Measurement at 100 ° C. using a cone-plate viscometer (manufactured by Toa Kogyo Co., Ltd., MOEDL CV-1S) and a rotor using 10 poise cone (Φ: 19.5 mm, θ: 0.5 °) Measured at temperature.
難燃性：ＵＬ（Ｕｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ．）規格、ＵＬ９４垂直試験法に準じて測定を行い、同規格の判定基準である、Ｖ−０、Ｖ−１、Ｖ−２、ＮＧ（難燃性なし）の４水準で判定した（後になるほど難燃性が悪い）。 Flame retardancy: Measured according to UL (Underwriters Laboratories Inc.) standard, UL94 vertical test method, V-0, V-1, V-2, NG (no flame retardancy) as the criteria of the standard )) (Flame retardance is worse as later).
残炎時間：ＵＬ（Ｕｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ．）規格、ＵＬ９４垂直試験法に準じて測定を行い、同規格の試験片５本の合計有炎燃焼時間を計測した。 Afterflame time: Measurement was performed in accordance with UL (Underwriters Laboratories Inc.) standard, UL94 vertical test method, and the total flame burning time of five test pieces of the same standard was measured.
接着性：ＪＩＳ Ｃ−６４８１ ５．７に準じた方法。即ち、プリプレグ１枚と残りの３枚の間で直角方向に５０ｍｍ／ｍｉｎの速度で剥離を行い測定した。 Adhesiveness: A method according to JIS C-6481 5.7. That is, the measurement was performed by peeling between one prepreg and the remaining three sheets at a speed of 50 mm / min in the perpendicular direction.
吸湿率：ＪＩＳ Ｃ−６４８１ ５．１３に準じた方法。即ち、５０ｍｍ×５０ｍｍにカットした試験片を用いて、５０℃のオーブン中で２４時間乾燥した後の乾燥重量を測定し、引き続き８５℃／８５％ＲＨに調整した処理槽内に７２時間保管した後の重量を測定し、乾燥重量からの増加分に基づいて吸湿率を測定した。 Moisture absorption: A method according to JIS C-6481 5.13. That is, using a test piece cut to 50 mm × 50 mm, the dry weight after drying in an oven at 50 ° C. for 24 hours was measured, and subsequently stored in a treatment tank adjusted to 85 ° C./85% RH for 72 hours. The subsequent weight was measured, and the moisture absorption rate was measured based on the increase from the dry weight.
ガラス転移温度：ＪＩＳ Ｃ−６４８１ ５．１７のＴＭＡ法に準じた方法。なお、ＴＭＡ装置はエスアイアイ・ナノテクノロジー株式会社製ＴＭＡ／ＳＳ１２０Ｕを使用した。 Glass transition temperature: A method according to the TMA method of JIS C-6481 5.17. The TMA apparatus used was TMA / SS120U manufactured by SII Nano Technology.
ＩＲスペクトル：フーリエ変換赤外分光光度計（パーキンエルマー社製 Ｓｐｅｃｔｕｍ Ｏｎｅ）を用い、液膜法（ＫＢｒ）により測定した。 IR spectrum: Measured by a liquid film method (KBr) using a Fourier transform infrared spectrophotometer (Spectum One manufactured by Perkin Elmer).
ゲルパーミエーションクロマトグラフィー測定：ゲルパーミエーションクロマトグラフィー装置（東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ、溶出溶剤：テトラヒドロフラン）で測定した。横軸は溶離時間（分）を、左軸はｍＶを、右軸は標準ポリスチレン検量線の分子量（Ｍ）の対数をそれぞれ表している。 Gel permeation chromatography measurement: Measured with a gel permeation chromatography apparatus (HLC-8220GPC, manufactured by Tosoh Corporation, elution solvent: tetrahydrofuran). The horizontal axis represents the elution time (minutes), the left axis represents mV, and the right axis represents the logarithm of the molecular weight (M) of the standard polystyrene calibration curve.
実施例１．
攪拌装置、温度計、窒素ガス導入装置、及び冷却管を備えた４つ口のガラス製セパラブルフラスコに、一般式１のエポキシ樹脂として、ＴＸ−１０１１（東都化成株式会社製、ジビニルビフェニル型エポキシ樹脂、エポキシ当量：１１９ｇ／ｅｑ）６００．０ｇ、有機リン化合物としてＤＯＰＯ−ＨＱ（三光株式会社製、商品名：ＨＣＡ−ＨＱ、水酸基当量：１６２ｇ／ｅｑ、リン含有率：９．５重量％）１１２．５ｇを仕込み、マントルヒーターで１３０℃まで撹拌しながら加熱して、１３０℃に達したところで１時間温度を保った後、触媒としてトリフェニルホスフィン（北興化学株式会社製、製品名：ＴＰＰ）０．１１ｇを加え、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−１）７１３ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−１）の性状を表１に示す。
Example 1.
To a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, TX-1011 (manufactured by Tohto Kasei Co., Ltd., divinylbiphenyl type epoxy) as an epoxy resin of general formula 1 Resin, epoxy equivalent: 119 g / eq) 600.0 g, DOPO-HQ (trade name: HCA-HQ, hydroxyl equivalent: 162 g / eq, phosphorus content: 9.5% by weight) as an organic phosphorus compound 112.5 g was charged and heated with stirring to 130 ° C. with a mantle heater. After reaching 130 ° C., the temperature was maintained for 1 hour, and then triphenylphosphine as a catalyst (product name: TPP) 0.11 g was added and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain 713 g of a phosphorus-containing epoxy resin (E-1). Obtained. Table 1 shows the properties of the obtained phosphorus-containing epoxy resin (E-1).
実施例２．
攪拌装置、温度計、窒素ガス導入装置、及び冷却管を備えた４つ口のガラス製セパラブルフラスコに、一般式２のエポキシ樹脂として、エポトートＹＨ−４３４Ｌ（東都化成株式会社製、テトラグリシジルアミン樹脂、エポキシ当量：１１８ｇ／ｅｑ）３５０．０ｇ、有機リン化合物としてＤＯＰＯ（三光株式会社製、商品名：ＨＣＡ、リン含有率：１４．２重量％）５７．４ｇを仕込み、マントルヒーターで１３０℃まで撹拌しながら加熱して、１３０℃に達したところで触媒としてトリフェニルホスフィン（前述）０．０６ｇを加え、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−２）４０７ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−２）の性状を表１に示す。
Example 2
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introduction device, and a cooling tube, Epototo YH-434L (manufactured by Tohto Kasei Co., Ltd., tetraglycidylamine) as an epoxy resin of the
実施例３．
攪拌装置、温度計、窒素ガス導入装置、及び冷却管を備えた４つ口のガラス製セパラブルフラスコに、一般式１のエポキシ樹脂として、エポトートＴＸ−１０１０（ジビニルベンゼン型エポキシ樹脂）２００．０ｇ、有機リン化合物としてＤＯＰＯ−ＨＱ（三光株式会社製、商品名：ＨＣＡ−ＨＱ、水酸基当量：１６２ｇ／ｅｑ、リン含有率：９．５重量％）５３．３ｇを仕込み、マントルヒーターで１３０℃まで撹拌しながら加熱して、１３０℃に達したところで触媒としてトリフェニルホスフィン（前述）０．０５ｇを加え、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−３）２５３ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−３）の性状を表１に示す。
Example 3
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling pipe, Epototo TX-1010 (divinylbenzene type epoxy resin) 200.0 g as an epoxy resin of the general formula 1 In addition, 53.3 g of DOPO-HQ (trade name: HCA-HQ, hydroxyl group equivalent: 162 g / eq, phosphorus content: 9.5 wt%) manufactured by Sanko Co., Ltd. as an organic phosphorus compound was charged to 130 ° C. with a mantle heater. When the temperature reached 130 ° C. while stirring, 0.05 g of triphenylphosphine (described above) was added as a catalyst, and the reaction was continued for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. -3) 253 g was obtained. Table 1 shows the properties of the obtained phosphorus-containing epoxy resin (E-3).
実施例４．
攪拌装置、温度計、窒素ガス導入装置、及び冷却管を備えた４つ口のガラス製セパラブルフラスコに、一般式１のエポキシ樹脂として、エポトートＴＸ−１０１１（前述）２５０．０ｇ、有機リン化合物として有機リン化合物としてＤＯＰＯ−ＮＱ（９，１０−ジハイドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドの１，４−ナフトキノン付加物、水酸基当量：１８７ｇ／ｅｑ、リン含有量：８．１重量％）８２．０ｇを仕込み、マントルヒーターで１３０℃まで撹拌しながら加熱して、１３０℃に達したところで触媒として触媒として２エチル４メチルイミダゾール（四国化成株式会社製、製品名：２Ｅ４ＭＺ）０．０８ｇを加え、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−４）３３２ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−４）の性状を表１に示す。
Example 4
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, 250.0 g of Epototo TX-1011 (described above) as an epoxy resin of the general formula 1, organophosphorus compound As an organic phosphorus compound, DOPO-NQ (1,4-naphthoquinone adduct of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hydroxyl equivalent: 187 g / eq, phosphorus content: 8. 1 wt%) 82.0 g was charged and heated to 130 ° C. with stirring with a mantle heater. When the temperature reached 130 ° C., 2-ethyl 4-methylimidazole as a catalyst (manufactured by Shikoku Kasei Co., Ltd., product name: 2E4MZ) Add 0.08 g and react for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. To give the E-4) 332g. Properties of the obtained phosphorus-containing epoxy resin (E-4) are shown in Table 1.
実施例５．
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた４つ口のガラス製セパラブルフラスコに、有機リン化合物としてＤＯＰＯ（前述）２５．４ｇとトルエン２００ｇを仕込み、窒素雰囲気下で攪拌しながら加熱して完全に溶解した。その後、キノン類として１，４−ナフトキノン（川崎化成株式会社製、３％含水品）１４．９ｇを反応熱による昇温に注意しながら分割投入した。この時の１，４−ナフトキノンとＤＯＰＯのモル比は１，４−ナフトキノン／ＤＯＰＯ＝０．８０であった。加熱反応後、一般式１エポキシ樹脂として、ＴＸ−１０１１（前述）１５０．０ｇを仕込み、窒素ガスを導入しながら攪拌を行い、１３０℃まで加熱を行ってトルエンを系外に除去した。その後触媒としてトリフェニルホスフィン（前述）を０．０４ｇ添加して、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−５）１９０ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−５）の性状を表１に示す。
Example 5 FIG.
Into a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device, 25.4 g of DOPO (described above) and 200 g of toluene as an organophosphorus compound were charged and stirred in a nitrogen atmosphere. The solution was completely dissolved by heating. Thereafter, 14.9 g of 1,4-naphthoquinone (manufactured by Kawasaki Kasei Co., Ltd., 3% water-containing product) as quinones was added in portions while paying attention to temperature rise by reaction heat. The molar ratio of 1,4-naphthoquinone to DOPO at this time was 1,4-naphthoquinone / DOPO = 0.80. After the heating reaction, 150.0 g of TX-1011 (described above) was charged as an epoxy resin of general formula 1, stirred while introducing nitrogen gas, and heated to 130 ° C. to remove toluene out of the system. Thereafter, 0.04 g of triphenylphosphine (described above) was added as a catalyst and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain 190 g of phosphorus-containing epoxy resin (E-5). Properties of the obtained phosphorus-containing epoxy resin (E-5) are shown in Table 1.
比較例１．
攪拌装置、温度計、窒素ガス導入装置、及び冷却管を備えた４つ口のガラス製セパラブルフラスコに、エポキシ樹脂としてエポトートＴＸ−０９１７（東都化成株式会社製、エチレンオキサイドハドロキノンジグリシジルエーテル樹脂、エポキシ当量：１７３ｇ／ｅｑ）６３２．０ｇ、有機リン化合物としてＤＯＰＯ−ＨＱ（前述）１６８．０ｇを仕込み、マントルヒーターで１３０℃まで撹拌しながら加熱して、１３０℃に達したところで触媒としてトリフェニルホスフィン（前述）０．１７ｇを加え、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−６）７９５ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−６）の性状を表２に示す。
Comparative Example 1
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, Epototo TX-0917 (manufactured by Toto Kasei Co., Ltd., ethylene oxide hadoquinone diglycidyl ether resin) , Epoxy equivalent: 173 g / eq) 632.0 g, DOPO-HQ (previously described) 168.0 g as an organophosphorus compound was charged with stirring to 130 ° C. with a mantle heater, and when 130 ° C. was reached, 0.17 g of phenylphosphine (described above) was added and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain 795 g of a phosphorus-containing epoxy resin (E-6). Table 2 shows the properties of the obtained phosphorus-containing epoxy resin (E-6).
比較例２．
攪拌装置、温度計、窒素ガス導入装置、及び冷却管を備えた４つ口のガラス製セパラブルフラスコに、エポキシ樹脂としてエポトートＴＸ−０９２９（東都化成株式会社製、パラキシレンジメタノールグリシジルエーテル樹脂、エポキシ当量：１４４ｇ／ｅｑ）３５０．０ｇ、有機リン化合物としてＤＯＰＯ−ＨＱ（前述）６５．６ｇを仕込み、マントルヒーターで１３０℃まで撹拌しながら加熱して、１３０℃に達したところで触媒としてトリフェニルホスフィン（前述）０．０７ｇを加え、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−７）４１５ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−７）の性状を表２に示す。
Comparative Example 2
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, Epototo TX-0929 (manufactured by Toto Kasei Co., Ltd., paraxylene dimethanol glycidyl ether resin, Epoxy equivalent: 144 g / eq) 350.0 g, DOPO-HQ (previously described) 65.6 g as an organophosphorus compound was charged with heating to 130 ° C. with a mantle heater, and when it reached 130 ° C., triphenyl was used as a catalyst. 0.07 g of phosphine (described above) was added and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain 415 g of phosphorus-containing epoxy resin (E-7). Table 2 shows the properties of the obtained phosphorus-containing epoxy resin (E-7).
比較例３．
攪拌装置、温度計、窒素ガス導入装置、及び冷却管を備えた４つ口のガラス製セパラブルフラスコに、エポキシ樹脂としてエポトートＴＸ−０９３４（東都化成株式会社製、オキシメチレンビフェニルジグリシジルエーテル樹脂、エポキシ当量：１８４ｇ／ｅｑ）３５０．０ｇ、有機リン化合物としてＤＯＰＯ−ＨＱ（前述）９３．３ｇを仕込み、マントルヒーターで１３０℃まで撹拌しながら加熱して、１３０℃に達したところで触媒としてトリフェニルホスフィン（前述）０．０９ｇを加え、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−８）４４４．３ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−８）の性状を表２に示す。
Comparative Example 3
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling tube, Epototo TX-0934 (manufactured by Tohto Kasei Co., Ltd., oxymethylene biphenyl diglycidyl ether resin, Epoxy equivalent: 184 g / eq) 350.0 g, DOPO-HQ (previously described) 93.3 g as an organic phosphorus compound, heated to 130 ° C. with stirring with a mantle heater, and when it reached 130 ° C., triphenyl as a catalyst Phosphine (described above) 0.09 g was added and reacted for 4 hours while maintaining the reaction temperature at 160 ° C. to 165 ° C. to obtain 444.3 g of phosphorus-containing epoxy resin (E-8). Table 2 shows the properties of the obtained phosphorus-containing epoxy resin (E-8).
比較例４．
攪拌装置、温度計、窒素ガス導入装置、及び冷却管を備えた４つ口のガラス製セパラブルフラスコに、エポキシ樹脂としてエポトートＴＸ−０９３４（前述）２００．０ｇ、有機リン化合物としてＤＯＰＯ−ＮＱ（前述）６５．５ｇを仕込み、マントルヒーターで１３０℃まで撹拌しながら加熱して、１３０℃に達したところで触媒としてトリフェニルホスフィン（前述）０．０７ｇを加え、反応温度を１６０℃〜１６５℃に保ちながら４時間反応して、リン含有エポキシ樹脂（Ｅ−９）２６６ｇを得た。得られたリン含有エポキシ樹脂（Ｅ−９）の性状を表２に示す。
Comparative Example 4
In a four-necked glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, and a cooling pipe, 200.0 g of Epototo TX-0934 (described above) as an epoxy resin and DOPO-NQ (as an organic phosphorus compound) 65.5 g of the above) was added and heated with stirring to 130 ° C. with a mantle heater. When the temperature reached 130 ° C., 0.07 g of triphenylphosphine (described above) was added as a catalyst, and the reaction temperature was raised to 160 ° C. to 165 ° C. The reaction was carried out for 4 hours while maintaining, to obtain 266 g of a phosphorus-containing epoxy resin (E-9). Table 2 shows the properties of the obtained phosphorus-containing epoxy resin (E-9).
実施例６、７、比較例５，６
表３に示す配合処方によりリン含有エポキシ樹脂、硬化剤、硬化促進剤等を配合した。リン含有エポキシ樹脂をメチルエチルケトンで溶解させ、あらかじめメチルセロソルブ、ジメチルホルムアミドに溶解させておいた硬化剤としてジシアンジアミド（ＤＩＣＹ、活性水素当量：２１．０ｇ／ｅｑ）と硬化促進剤として２エチル４メチルイミダゾール（前述）を加えて、不揮発分が５０重量％になるように樹脂組成物ワニスを調製した。その後、得られた樹脂ワニスを用い、基材であるガラスクロス（日東紡績株式会社製、ＷＥＡ １１６Ｅ １０６Ｓ １３６、厚み１００μｍ）に含浸させ、含浸させたガラスクロスを１５０℃の熱風循環式オーブンで８分間乾燥を行い、プリプレグを得た。次いで、得られたプリプレグ４枚を重ね、１３０℃×１５分及び１７０℃×２．０ＭＰａ×７０分間の条件で加熱と加圧を行い０．５ｍｍ厚の積層板を得た。得られた各々の積層板について、難燃性、接着性、ガラス転移温度の各物性を試験した。その結果を表４に示す。
Examples 6 and 7, Comparative Examples 5 and 6
A phosphorus-containing epoxy resin, a curing agent, a curing accelerator and the like were blended according to the blending formulation shown in Table 3. A phosphorus-containing epoxy resin is dissolved with methyl ethyl ketone, and dicyandiamide (DICY, active hydrogen equivalent: 21.0 g / eq) as a curing agent previously dissolved in methyl cellosolve and dimethylformamide, and 2-ethyl 4-methylimidazole (as a curing accelerator) The resin composition varnish was prepared so that the nonvolatile content was 50% by weight. Thereafter, the obtained resin varnish was used to impregnate a glass cloth as a base material (WEA 116E 106S 136,
比較例５，６はぐオキシラン環以外に−Ｃ−Ｏ−Ｃ−骨格を有するリン含有エポキシ樹脂を使用しているため、難燃性（ＵＬ−９４）としては満たしているが残炎時間が長く、ガラス転移温度も低い。それに対し実施例は全て、難燃性を確保しながら、接着性は良く、ガラス転移温度も高い。 Comparative Examples 5 and 6 Since a phosphorus-containing epoxy resin having a —C—O—C— skeleton other than the oxirane ring is used, the flame retardancy (UL-94) is satisfied, but the afterflame time is long. Also, the glass transition temperature is low. In contrast, all the examples have good adhesion and high glass transition temperature while ensuring flame retardancy.
実施例８〜１０、比較例７、８
表５に示す配合処方によりリン含有エポキシ樹脂、硬化剤、硬化促進剤等を配合した。硬化剤として、ジエチルジアミノジフェニルメタン（日本化薬株式会社製、商品名：カヤハードＡＡ、活性水素当量：６３ｇ／ｅｑ、粘度：２，５００ｍＰａ・ｓ）を、硬化促進剤として２エチル４メチルイミダゾール（前述）を用いて、５０℃に加熱しながら、撹拌し均一化してエポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を脱泡して金型に注型し、１５０℃×１２０分の温度条件で硬化させて２ｍｍ厚の硬化物試験片を得た。得られた硬化物試験片について、難燃性、ガラス転移温度の各物性を試験した。その結果を表６に示す。なお、比較例１４では、エポキシ樹脂として、エポトートＺＸ−１０５９（東都化成株式会社製、ビスフェノールＦジグリシジルエーテル樹脂とビスフェノールＡジグリシジルエーテル樹脂の混合物、エポキシ当量：１６５ｇ／ｅｑ、全塩素：０．０８重量％、粘度：２，３００ｍＰａ・ｓ）を使用し、添加型難燃剤として、１，３−フェニレンビス−ジ−２，６−キシレニルホスフェート（大八化学工業株式会社製、商品名：ＰＸ−２００、リン含有量：９．０重量％）を、エポキシ樹脂組成物中のリン含有率が２．０重量％になるように添加した。
Examples 8 to 10, Comparative Examples 7 and 8
A phosphorus-containing epoxy resin, a curing agent, a curing accelerator, and the like were blended according to the blending formulation shown in Table 5. Diethyldiaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayahard AA, active hydrogen equivalent: 63 g / eq, viscosity: 2,500 mPa · s) as a curing agent, and 2-ethyl 4-methylimidazole (as described above) as a curing accelerator. The mixture was stirred and homogenized while heating to 50 ° C. to obtain an epoxy resin composition. The obtained epoxy resin composition was defoamed and poured into a mold, and cured under a temperature condition of 150 ° C. × 120 minutes to obtain a cured product test piece having a thickness of 2 mm. About the obtained hardened | cured material test piece, each physical property of a flame retardance and a glass transition temperature was tested. The results are shown in Table 6. In Comparative Example 14, as epoxy resin, Epototo ZX-1059 (manufactured by Tohto Kasei Co., Ltd., a mixture of bisphenol F diglycidyl ether resin and bisphenol A diglycidyl ether resin, epoxy equivalent: 165 g / eq, total chlorine: 0. 08 wt%, viscosity: 2,300 mPa · s), and 1,3-phenylenebis-di-2,6-xylenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name) as an additive-type flame retardant : PX-200, phosphorus content: 9.0% by weight) was added so that the phosphorus content in the epoxy resin composition was 2.0% by weight.
比較例５，６はオキシラン環以外にーＣ−Ｏ−Ｃ−骨格を有するリン含有エポキシ樹脂を使用しているため、難燃性（ＵＬ−９４）としては満たしているが残炎時間が長く、ガラス転移温度も低い。比較例１４は一般的に使用されている低塩素液状樹脂に難燃剤を配合したエポキシ樹脂組成物だが、リン含有率を実施例と合わせても難燃性は悪く、ガラス転移温度も低い。それに対し実施例は全て、十分な難燃性を確保しながら、高いガラス転移温度を示している。 Since Comparative Examples 5 and 6 use a phosphorus-containing epoxy resin having a —C—O—C— skeleton in addition to the oxirane ring, the flame retardancy (UL-94) is satisfied, but the afterflame time is long. Also, the glass transition temperature is low. Comparative Example 14 is an epoxy resin composition in which a flame retardant is blended with a low-chlorine liquid resin that is generally used, but the flame retardancy is poor and the glass transition temperature is low even when the phosphorus content is combined with the examples. In contrast, all the examples show high glass transition temperatures while ensuring sufficient flame retardancy.
実施例１３〜１４、比較例１５〜１７
表７に示す配合処方によりリン含有エポキシ樹脂、硬化剤、硬化促進剤等を配合した。硬化剤として、トリフェニルメタン型フェノール樹脂（群栄化学工業株式会社製、商品名：ＴＭＰ−１００、水酸基当量：９７．５ｇ／ｅｑ、軟化点：１０７℃）を用い、１２０℃に加熱しながら、撹拌し、均一化してエポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を脱泡して金型に注型し、１５０℃×１２０分＋１８０℃×６０分の温度条件で硬化させて２ｍｍ厚の硬化物試験片を得た。得られた硬化物試験片について、成形性、難燃性、吸湿率の各物性を試験した。その結果を表８に示す。なお、実施例１３ではリン含有エポキシ樹脂以外のエポキシ樹脂として、エポトートＺＸ−１０５９（前述）を併用し、比較例１７ではリン含有エポキシ樹脂以外のエポキシ樹脂として、エポトートＺＸ−１５４２（東都化成株式会社製、トリメチロールプロパンポリグリシジルエーテル樹脂、エポキシ当量：１２２ｇ／ｅｑ、全塩素：０．０６５重量％、粘度：８０ｍＰａ・ｓ）を併用した。
Examples 13-14, Comparative Examples 15-17
A phosphorus-containing epoxy resin, a curing agent, a curing accelerator, and the like were blended according to the blending formulation shown in Table 7. As a curing agent, triphenylmethane type phenol resin (manufactured by Gunei Chemical Industry Co., Ltd., trade name: TMP-100, hydroxyl group equivalent: 97.5 g / eq, softening point: 107 ° C.) is used while heating to 120 ° C. The mixture was stirred and homogenized to obtain an epoxy resin composition. The obtained epoxy resin composition was defoamed and poured into a mold and cured under a temperature condition of 150 ° C. × 120 minutes + 180 ° C. × 60 minutes to obtain a 2 mm thick cured product test piece. About the obtained hardened | cured material test piece, each physical property of a moldability, a flame retardance, and a moisture absorption rate was tested. The results are shown in Table 8. In Example 13, Epototo ZX-1059 (described above) was used in combination as an epoxy resin other than the phosphorus-containing epoxy resin. In Comparative Example 17, Epototo ZX-1542 (Toto Kasei Co., Ltd.) was used as an epoxy resin other than the phosphorus-containing epoxy resin. And trimethylolpropane polyglycidyl ether resin, epoxy equivalent: 122 g / eq, total chlorine: 0.065 wt%, viscosity: 80 mPa · s).
比較例１０、比較例１１はオキシラン環以外に−Ｃ−Ｏ−Ｃ−骨格を有するリン含有エポキシ樹脂を使用しているため、難燃性（ＵＬ−９４）としては満たしているが残炎時間が長く、ガラス転移温度も低い。実施例１１と比較例１２は難燃性を持たないエポキシ樹脂を１０重量部配合した。比較例１２では難燃性が足りずＶ−２となってしまった。それに対し実施例は全て、難燃性を確保しながら、接着力も良い。このことから、本発明のリン含有エポキシ樹脂は従来のリン含有エポキシ樹脂よりも配合の自由度がある。 Since Comparative Example 10 and Comparative Example 11 use a phosphorus-containing epoxy resin having a —C—O—C— skeleton in addition to the oxirane ring, the flame retardancy (UL-94) is satisfied, but the after flame time Is long and the glass transition temperature is low. In Example 11 and Comparative Example 12, 10 parts by weight of an epoxy resin having no flame retardancy was blended. In Comparative Example 12, the flame retardancy was insufficient and V-2 was obtained. On the other hand, all the examples have good adhesion while ensuring flame retardancy. From this, the phosphorus containing epoxy resin of this invention has the freedom degree of a mixing | blending than the conventional phosphorus containing epoxy resin.
本発明のエポキシ樹脂組成物は低粘度組成物でありながらその硬化物は難燃性、耐湿性に優れるため、注型材、積層材、封止材、複合材などに利用することが出来る。 Although the epoxy resin composition of the present invention is a low-viscosity composition, the cured product is excellent in flame retardancy and moisture resistance, and thus can be used for casting materials, laminated materials, sealing materials, composite materials, and the like.
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