JP5783413B2 - Epoxy resin having new phosphorus atom, epoxy resin composition and cured product thereof - Google Patents
Epoxy resin having new phosphorus atom, epoxy resin composition and cured product thereof Download PDFInfo
- Publication number
- JP5783413B2 JP5783413B2 JP2011205958A JP2011205958A JP5783413B2 JP 5783413 B2 JP5783413 B2 JP 5783413B2 JP 2011205958 A JP2011205958 A JP 2011205958A JP 2011205958 A JP2011205958 A JP 2011205958A JP 5783413 B2 JP5783413 B2 JP 5783413B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- alkylene
- glycol
- group
- diglycidyl ether
- 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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- 239000003822 epoxy resin Substances 0.000 title claims description 113
- 229920000647 polyepoxide Polymers 0.000 title claims description 113
- 239000000203 mixture Substances 0.000 title claims description 60
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 53
- 125000004437 phosphorous atom Chemical group 0.000 title claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 73
- -1 alkylene diglycidyl ether Chemical compound 0.000 claims description 65
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 62
- 239000003063 flame retardant Substances 0.000 claims description 36
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 34
- 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 claims description 28
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 25
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 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 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 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 14
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 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
- 239000011889 copper foil Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- WMPGCOIUVFJFMG-UHFFFAOYSA-N 1-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)naphthalene-2,7-diol Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=C(O)C=CC2=CC=C(O)C=C21 WMPGCOIUVFJFMG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- BRBMYNGGGPTKKL-UHFFFAOYSA-N 1,9-decanediol Chemical compound CC(O)CCCCCCCCO BRBMYNGGGPTKKL-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- WAPRZVXVTPSWEB-UHFFFAOYSA-N 2-[(2-butan-2-ylphenoxy)methyl]oxirane Chemical compound CCC(C)C1=CC=CC=C1OCC1OC1 WAPRZVXVTPSWEB-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- XOSCKTQMAZSFBZ-UHFFFAOYSA-N 2-[[1-[[2,7-bis(oxiran-2-ylmethoxy)naphthalen-1-yl]methyl]-7-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=2CC=3C4=CC(OCC5OC5)=CC=C4C=CC=3OCC3OC3)=CC=C1C=CC=2OCC1CO1 XOSCKTQMAZSFBZ-UHFFFAOYSA-N 0.000 description 1
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- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 150000002013 dioxins Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
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- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- WBSRHBNFOLDTGU-UHFFFAOYSA-N nonane-1,8-diol Chemical compound CC(O)CCCCCCCO WBSRHBNFOLDTGU-UHFFFAOYSA-N 0.000 description 1
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Images
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- Epoxy Resins (AREA)
Description
本発明は、ハロゲンフリーの難燃性組成物として有用な難燃性エポキシ樹脂組成物に関し、具体的には、ハロゲンフリーの難燃組成物として、塗料、半導体封止用組成物又は積層板用ワニスとして有用であり、特に積層板(プリント配線板)用ワニスとして難燃効果のみならず、密着性、耐熱性および耐湿性に優れた積層板を提供し得る難燃性エポキシ樹脂組成物に関する。 The present invention relates to a flame retardant epoxy resin composition useful as a halogen-free flame retardant composition, and specifically, as a halogen-free flame retardant composition, for paints, semiconductor sealing compositions or laminates. The present invention relates to a flame retardant epoxy resin composition that is useful as a varnish and can provide a laminate having excellent adhesion, heat resistance, and moisture resistance as well as a flame retardant effect, particularly as a varnish for a laminate (printed wiring board).
エポキシ樹脂は、高耐熱性、耐湿性等の諸物性に優れる点から半導体封止材やプリント回路基板等の電子部品、電子部品分野、導電ペースト等の導電性接着剤、その他接着剤、複合材料用マトリックス、塗料、フォトレジスト材料、顕色材料等で広く用いられている。 Epoxy resin is excellent in various physical properties such as high heat resistance and moisture resistance. From the point of view of electronic parts such as semiconductor sealing materials and printed circuit boards, electronic parts, conductive adhesives such as conductive paste, other adhesives, composite materials Widely used in matrix, paint, photoresist material, developer material, etc.
半導体封止用材料としては、従来から、プラスチックパッケージ用としてモールディングコンパウンドが多く使用されている。しかし、近年は半導体パッケージの小型・軽量化が進む中、さまざまなパッケージ形態が提案されている。例えば、従来のQFP(クアッドフラットパッケ−ジ)やTSOP(チンスモ−ルアウトラインパッケ−ジ)といったパッケージから、TCP(テープキャリアパッケージ)、BGA(ボールグリッドアレイ)、CSP(チップスケールパッケージ)、MCM(マルチチップモジュール)などへと変化してきている。これらのパッケージに使用される材料として、液状エポキシ樹脂を使用する液状封止材料があげられる。 Conventionally, many molding compounds have been used as a semiconductor sealing material for plastic packages. However, in recent years, various package forms have been proposed as semiconductor packages are becoming smaller and lighter. For example, conventional packages such as QFP (quad flat package) and TSOP (chinsmol outline package), TCP (tape carrier package), BGA (ball grid array), CSP (chip scale package), MCM ( Multi-chip module). Examples of the material used for these packages include a liquid sealing material using a liquid epoxy resin.
一方、電子機器及び通信機器では、絶縁層を有するプリント配線板が用いられている。該絶縁層は、ペースト状又はシート状の絶縁材料を用いて形成されているが、昨今のVOC低減の観点から有機溶剤に希釈した固形エポキシ樹脂から液状エポキシ樹脂への切り替えが進んでいる。 On the other hand, printed wiring boards having an insulating layer are used in electronic devices and communication devices. The insulating layer is formed by using a paste-like or sheet-like insulating material, and switching from a solid epoxy resin diluted in an organic solvent to a liquid epoxy resin is proceeding from the viewpoint of reducing VOCs in recent years.
これらの液状エポキシ樹脂に対する要求性能として、柔軟性や密着性、難燃性の付与がなされていることが挙げられる。エポキシ樹脂の難燃化に対しては、これら電気電子材料部品には、ガラスエポキシ積層板やIC封止材に代表される様に高い難燃性(UL:V−0)が求められる為、通常ハロゲン化されたエポキシ樹脂が用いられていた。例えば、ガラスエポキシ積層板では、難燃化されたFR−4グレードとして、一般に臭素で置換されたエポキシ樹脂を主原料成分とし、これに種々のエポキシ樹脂を混合したエポキシ樹脂と、エポキシ樹脂用硬化剤とを配合して用いられていた。 Examples of the required performance for these liquid epoxy resins include imparting flexibility, adhesion, and flame retardancy. For flame retardancy of epoxy resin, these electrical and electronic material parts are required to have high flame retardancy (UL: V-0) as represented by glass epoxy laminates and IC encapsulants, Usually halogenated epoxy resins have been used. For example, in glass epoxy laminates, as flame retardant FR-4 grade, epoxy resin generally substituted with bromine as the main raw material component, mixed with various epoxy resins, and curing for epoxy resin It was used in combination with an agent.
しかし、このようなハロゲン化されたエポキシ樹脂の使用は、近年のダイオキシンに代表される環境問題の一要因となっている他、高温環境下でのハロゲン解離による電気的な長期信頼性への悪影響などから、ハロゲンの使用量を低減するか、ハロゲンに代替できる他の非ハロゲン系化合物を使用した難燃剤、あるいは他の難燃処方が強く求められている。 However, the use of such halogenated epoxy resins is one of the causes of environmental problems represented by dioxins in recent years, and the adverse effect on electrical long-term reliability due to halogen dissociation in high temperature environments. For these reasons, there is a strong demand for flame retardants using other non-halogen compounds that can reduce the amount of halogen used or replace halogen, or other flame retardant formulations.
そこで、従来より、ハロゲンに代替できる他の非ハロゲン系化合物として、例えば、リン酸エステル系化合物などを添加系難燃剤として使用する技術が種々検討されているが、このような技術は何れも成形品の耐熱性や耐水性等の低下、更にとりわけ電気積層板用途における密着性の低下を来すものであった。
ハロゲンフリーの難燃組成物として、塗料、半導体封止用組成物又は積層板用ワニスとして有用であり、特に積層板(プリント配線板)用ワニスとして難燃効果のみならず、密着性、耐熱性および耐湿性に優れた積層板を提供し得る難燃性エポキシ樹脂組成物として、ビスフェノール型エポキシ樹脂に、ホスファフェナントレン骨格と、フェノール性水酸基を2個有する芳香族基がリン原子に結合した構造とを有するリン化合物を反応させたエポキシ樹脂及び硬化剤を含有するエポキシ樹脂組成物が提案されている。(特許文献1、2及び3参照)
In view of this, various other technologies that use, for example, phosphate ester compounds as additive flame retardants as other non-halogen compounds that can be substituted for halogen have been studied. This resulted in a decrease in the heat resistance and water resistance of the product, and in particular, a decrease in adhesion in electrical laminate applications.
It is useful as a halogen-free flame retardant composition as a paint, a semiconductor sealing composition, or a varnish for laminates, and particularly as a varnish for laminates (printed wiring boards) as well as flame retardant effects, adhesion and heat resistance As a flame retardant epoxy resin composition capable of providing a laminate having excellent moisture resistance, a structure in which a phosphaphenanthrene skeleton and an aromatic group having two phenolic hydroxyl groups are bonded to a phosphorus atom in a bisphenol type epoxy resin There has been proposed an epoxy resin composition containing an epoxy resin obtained by reacting a phosphorus compound having a hydrogen atom and a curing agent. (See Patent Documents 1, 2, and 3)
一方、難燃性及び靱性に優れたエポキシ樹脂組成物として、分子構造内にリン原子とウレタン結合とを有する2官能型エポキシ樹脂と硬化剤を含有するエポキシ樹脂組成物が提案されている。(特許文献4参照) On the other hand, as an epoxy resin composition excellent in flame retardancy and toughness, an epoxy resin composition containing a bifunctional epoxy resin having a phosphorus atom and a urethane bond in a molecular structure and a curing agent has been proposed. (See Patent Document 4)
しかしながら、上記特許文献1、2及び3に記載のエポキシ樹脂組成物は、得られたリン原子含有エポキシ樹脂が、常温で固形であり、液状或いはペースト状のエポキシ樹脂組成物に用いた場合に、しなやかさに欠けるために、ロール・ツー・ロール工法が困難であるという問題点があり、また、上記特許文献3に成形品の耐熱性、耐水性及び難燃性の改善は図れるものの、硬化物の柔軟性に乏しく、その結果、成形品の密着性、接着性及び強靱性に劣るという問題点もあった。また、上記特許文献4に記載のエポキシ樹脂組成物は、ウレタン結合由来の耐加水分解性に課題があり、長期信頼性の観点から半導体封止用材料やプリント配線板用材料には使用できなかった。 However, the epoxy resin compositions described in the above Patent Documents 1, 2, and 3 are obtained when the obtained phosphorus atom-containing epoxy resin is solid at room temperature and used in a liquid or paste-like epoxy resin composition. Due to lack of flexibility, there is a problem that the roll-to-roll method is difficult, and in Patent Document 3 mentioned above, although the heat resistance, water resistance and flame resistance of the molded product can be improved, the cured product As a result, there was also a problem that the adhesiveness, adhesiveness and toughness of the molded product were inferior. Moreover, the epoxy resin composition described in Patent Document 4 has a problem in hydrolysis resistance derived from a urethane bond, and cannot be used as a semiconductor sealing material or a printed wiring board material from the viewpoint of long-term reliability. It was.
本発明が解決しようとする課題は、ハロゲンによる難燃処方に代わるハロゲンフリーの難燃処方として優れた難燃効果を発現させると共に、成形品の耐熱性、耐水性の物性に優れ、また、硬化物の柔軟性に優れ、電気積層板用途における密着性、接着性及び強靱性に優れる難燃性エポキシ樹脂組成物を提供することにある。 The problem to be solved by the present invention is to develop an excellent flame retardant effect as a halogen-free flame retardant formulation instead of a halogen flame retardant formulation, as well as excellent heat resistance and water resistance of molded products, and curing. An object of the present invention is to provide a flame retardant epoxy resin composition which is excellent in flexibility of an object and excellent in adhesion, adhesiveness and toughness in electrical laminate application.
本発明者等は、上記課題を解決すべく鋭意検討した結果、特定のエポキシ樹脂に特定構造のリン化合物を反応させて変性させて得られるエポキシ樹脂が、密着性、耐熱性、耐水性を改善すると共に、ハロゲンフリーによる難燃化を図ることができ、しかも硬化物の柔軟性に優れ、電気積層板用途における密着性、接着性及び強靱性に優れることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have improved adhesion, heat resistance, and water resistance of an epoxy resin obtained by modifying a specific epoxy resin to react with a phosphorus compound having a specific structure. In addition, it has been found that it can be made flame-retardant by halogen-free, has excellent flexibility of cured products, and has excellent adhesion, adhesion and toughness in electrical laminate application, and has completed the present invention. It was.
即ち、本発明は上記課題を解決するために、(I)ホスファフェナントレン骨格(a−1)と、ホスファフェナントレン骨格(a−1)のリン原子に一分子中にフェノール性水酸基を2個有する芳香族基(a−2)が結合した構造とを有する有機リン化合物(a)と、アルキレンジオールのジグリシジルエーテル(b−1)及び/又はポリアルキレングリコールのジグリシジルエーテル(b−2)とを反応させた構造を有することを特徴とするリン原子を有するエポキシ樹脂(A)を提供する。 That is, in order to solve the above-mentioned problems, the present invention provides (I) a phosphaphenanthrene skeleton (a-1) and two phenolic hydroxyl groups in one molecule on the phosphorus atom of the phosphaphenanthrene skeleton (a-1). An organophosphorus compound (a) having a structure in which an aromatic group (a-2) is bonded, and a diglycidyl ether (b-1) of an alkylene diol and / or a diglycidyl ether (b-2) of a polyalkylene glycol An epoxy resin (A) having a phosphorus atom, characterized by having a structure obtained by reacting with.
また、本発明は上記課題を解決するために、(II)上記(I)に記載のエポキシ樹脂(A)及び硬化剤(B)を含有する難燃性エポキシ樹脂組成物を提供する。 Moreover, in order to solve the said subject, this invention provides the flame retardant epoxy resin composition containing the epoxy resin (A) and hardening | curing agent (B) as described in (II) said (I).
さらに、本発明は上記課題を解決するために、(III)上記(II)に記載の難燃性エポキシ樹脂組成物からなる硬化物を提供する。 Furthermore, in order to solve the said subject, this invention provides the hardened | cured material which consists of a flame-retardant epoxy resin composition as described in (III) said (II).
本発明によれば、ハロゲンによる難燃処方に代わるハロゲンフリーの難燃処方として、優れた難燃効果を発現させると共に、成形品の耐熱性、耐水性に優れ、また、硬化物の柔軟性に優れ、さらに電気積層板用途における密着性、接着性及び強靱性に優れる難燃性エポキシ樹脂組成物を提供することができる。従って、本発明の組成物は、電気電子、接着剤、注型、塗料等種々の分野に使用でき、とりわけ電気積層用途において有用である。 According to the present invention, as a halogen-free flame retardant formulation that replaces the flame retardant formulation with halogen, it exhibits an excellent flame retardant effect, is excellent in heat resistance and water resistance of a molded product, and is flexible in a cured product. It is possible to provide a flame retardant epoxy resin composition which is excellent and has excellent adhesion, adhesiveness and toughness in electrical laminate application. Therefore, the composition of the present invention can be used in various fields such as electrical electronics, adhesives, casting, paints, etc., and is particularly useful in electrical lamination applications.
即ち、本発明のエポキシ樹脂(A)は、ホスファフェナントレン骨格(a−1)と、ホスファフェナントレン骨格(a−1)のリン原子に一分子中にフェノール性水酸基を2個有する芳香族基(a−2)が結合した構造とを有する有機リン化合物(a)と、アルキレンジオールのジグリシジルエーテル(b−1)及び/又はポリアルキレングリコールのジグリシジルエーテル(b−2)とを反応させることによって製造することができる。 That is, the epoxy resin (A) of the present invention includes an phosphaphenanthrene skeleton (a-1) and an aromatic group having two phenolic hydroxyl groups in one molecule on the phosphorus atom of the phosphaphenanthrene skeleton (a-1). An organophosphorus compound (a) having a structure in which (a-2) is bonded to a diglycidyl ether (b-1) of an alkylene diol and / or a diglycidyl ether (b-2) of a polyalkylene glycol. Can be manufactured.
次に、有機リン化合物(a)は、一分子中にフェノール性水酸基を2個有する芳香族基(a−2)をリン原子上に有するものであり、この様な有機リン化合物(a)と上記アルキレンジオールのジグリシジルエーテル(b−1)及び/又はポリアルキレングリコールのジグリシジルエーテル(b−2)とを反応させてエポキシ樹脂(A)とすることにより、最終的な硬化物において、難燃性を向上させるのみならず、耐水性にも優れたものとなり、さらに、当該反応によって生じる水酸基に起因して密着性に優れたものとなる。 Next, the organic phosphorus compound (a) has an aromatic group (a-2) having two phenolic hydroxyl groups in one molecule on the phosphorus atom. Such an organic phosphorus compound (a) and In the final cured product, the epoxy resin (A) is reacted with the diglycidyl ether (b-1) of alkylene diol and / or the diglycidyl ether (b-2) of polyalkylene glycol. In addition to improving the flammability, the water resistance is also excellent, and furthermore, the adhesion is excellent due to the hydroxyl group produced by the reaction.
即ち、有機リン化合物(a)と上記アルキレンジオールのジグリシジルエーテル(b−1)及び/又はポリアルキレングリコールのジグリシジルエーテル(b−2)とを反応させて得られるエポキシ樹脂(A)は、従来の、エポキシ樹脂とリン酸エステルとの反応物において指摘されていた2級水酸基とリン原子の相互作用に起因する密着性の低下を改善することができるとともに、該エポキシ樹脂(A)は、容易に加水分解することがないので、耐水性も向上し、結果的に、耐ハンダ性も飛躍的に向上することとなる。 That is, the epoxy resin (A) obtained by reacting the organophosphorus compound (a) with the diglycidyl ether (b-1) of the alkylene diol and / or the diglycidyl ether (b-2) of the polyalkylene glycol, In addition to being able to improve the decrease in adhesion due to the interaction between secondary hydroxyl groups and phosphorus atoms, which has been pointed out in the conventional reaction product of epoxy resin and phosphate ester, the epoxy resin (A) Since it is not easily hydrolyzed, the water resistance is improved, and as a result, the solder resistance is also greatly improved.
よって、特に電気積層板用途において、難燃性と共に、耐水性が飛躍的に向上するほか、ガラスクロスや銅箔との密着性にも特に優れたものとなるため、高温高湿処理、煮沸処理、PCT(プレッシャークッカーテスト)処理に対して優れた耐性を発現する。 Therefore, especially in the electrical laminate application, water resistance is dramatically improved along with flame retardancy, and particularly excellent adhesion to glass cloth and copper foil. Excellent resistance to PCT (pressure cooker test) treatment.
一分子中にフェノール性水酸基を2個有する芳香族基(a−2)としては、ジヒドロキシフェニル基(a−2−1)、ジヒドロキシナフチル基(a−2−2)、ジヒドロキシアントラニル基などが挙げられる。これらの芳香族基は、その芳香環にアルキル基が置換した構造を有するものであっても良い。これらの芳香族基の中でも、ジヒドロキシフェニル基(a−2−1)、ジヒドロキシナフチル基(a−2−2)が特に好ましい。 Examples of the aromatic group (a-2) having two phenolic hydroxyl groups in one molecule include a dihydroxyphenyl group (a-2-1), a dihydroxynaphthyl group (a-2-2), and a dihydroxyanthranyl group. It is done. These aromatic groups may have a structure in which an alkyl group is substituted on the aromatic ring. Among these aromatic groups, dihydroxyphenyl group (a-2-1) and dihydroxynaphthyl group (a-2-2) are particularly preferable.
前記有機リン化合物(a)としては、一般式(1) The organophosphorus compound (a) has the general formula (1)
(式中、R1、R2及びR3は、各々独立的に、水素原子又はアルキル基を表わすが、R1、R2及びR3は、水素原子であることが好ましい。)
で表わされる化合物
及び一般式(2)
(In the formula, R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group, but R 1 , R 2 and R 3 are preferably hydrogen atoms.)
And a compound represented by the general formula (2)
で表わされる化合物が好ましい。これらの化合物を用いることにより、難燃効果及び耐水性が顕著なものとなり好ましい。これらの化合物は単独で用いても、2種以上併用してもよい。
The compound represented by these is preferable. Use of these compounds is preferable because the flame retardancy and water resistance become remarkable. These compounds may be used alone or in combination of two or more.
このような一般式(1)及び一般式(2)で表わされる有機リン化合物(a)としては、例えば、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、10−(3−メチル−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、10−(4−メチル−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、5,8−ジメチル−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、5,8−ジメチル−10−(3−メチル−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、5,8−ジメチル−10−(4−メチル−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、10−(2,7−ジヒドロキシナフチル)−9,10−ジヒドロ−9−オキサ−10−ホスファフェナンスレン−10−オキサイド、5,8−ジメチル−10−(2,7−ジヒドロキシナフチル)−9,10−ジヒドロ−9−オキサ−10−ホスファフェナンスレン−10−オキサイド、8−メトキシ−10−(2,7−ジヒドロキシナフチル)−9,10−ジヒドロ−9−オキサ−10−ホスファフェナンスレン−10−オキサイドなどが挙げられるが、これらの中でも、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−オキサイド及び10−(2,7−ジヒドロキシナフチル)−9,10−ジヒドロ−9−オキサ−10−ホスファフェナンスレン−10−オキサイド及び10−(2,7−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−オキサイドが特に好ましい。 Examples of the organic phosphorus compound (a) represented by the general formula (1) and the general formula (2) include 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene. -10-oxide, 10- (3-methyl-2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (4-methyl-2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 5,8-dimethyl-10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 5,8-Dimethyl-10- (3-methyl-2,5-dihydroxyphenyl) -10H-9-oxa-10-phospha Enanthrene-10-oxide, 5,8-dimethyl-10- (4-methyl-2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7- Dihydroxynaphthyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5,8-dimethyl-10- (2,7-dihydroxynaphthyl) -9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 8-methoxy-10- (2,7-dihydroxynaphthyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Among these, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phos Faphenanthrene-10-oxide and 10- (2,7-dihydroxynaphthyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10- (2,7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide is particularly preferred.
アルキレンジオールのジグリシジルエーテル(b−1)は、アルキレンジオールとエピクロルヒドリン、エピブロムヒドリンの如きエピハロヒドリンとを定法に従ってグリシジル化反応させることによって、容易に製造することができる。 The diglycidyl ether (b-1) of an alkylene diol can be easily produced by subjecting an alkylene diol and an epihalohydrin such as epichlorohydrin or epibromohydrin to a glycidylation reaction according to a standard method.
アルキレンジオールとしては、エチレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,5−ヘプタンジオール、1,6−ヘキサンジオール、1,7−ヘプタンジオール、1,8−オクタンジオール、1,9−ノナンジオール、1,10−デカンジオールの如き炭素原子数3〜10の直鎖状アルキレンジオール、1,2−プロパンジオール、1,3−ブタンジオール、1,4−ヘプタンジオール、1,5−ヘキサンジオール、1,6−ヘプタンジオール、1,7−オクタンジオール、1,8−ノナンジオール、1,9−デカンジオールの如き炭素原子数3〜10の分岐状アルキレンジオールが挙げられる。これらの中でも、直鎖状アルキレンジオールが好ましく、炭素原子数2〜6の直鎖状アルキレンジオールが特に好ましく、エチレングリコール及び1,6−ヘキサンジオールが更に好ましい。 Examples of the alkylene diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, C3-C10 linear alkylene diol such as 1,9-nonanediol, 1,10-decanediol, 1,2-propanediol, 1,3-butanediol, 1,4-heptanediol, 1 Branched alkylene diols having 3 to 10 carbon atoms such as 1,5-hexanediol, 1,6-heptanediol, 1,7-octanediol, 1,8-nonanediol, and 1,9-decanediol. Among these, a linear alkylene diol is preferable, a linear alkylene diol having 2 to 6 carbon atoms is particularly preferable, and ethylene glycol and 1,6-hexanediol are more preferable.
また同様に、ポリアルキレングリコールのジグリシジルエーテル(b−2)も、ポリアルキレングリコールとエピクロルヒドリン、エピブロムヒドリンの如きエピハロヒドリンとを定法に従ってグリシジル化反応させることによって、容易に製造することができる。 Similarly, diglycidyl ether (b-2) of polyalkylene glycol can be easily produced by subjecting polyalkylene glycol and epihalohydrin such as epichlorohydrin and epibromohydrin to glycidylation reaction according to a standard method.
ポリアルキレングリコールとしては、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコールの如きポリエチレングリコールおよび分子量分布を有し、その繰り返し数の平均が4〜22のポリエチレングリコール混合物、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコールの如きポリプロピレングリコールおよび分子量分布を有し、その繰り返し数の平均が4〜22のポリプロピレングリコール混合物、ジブチレングリコール、トリブチレングリコール、テトラブチレングリコールの如きポリブチレングリコール、ジペンテニレングリコール、トリペンテニレングリコール、テトラペンテニレングリコールの如きポリペンテニレングリコールおよび分子量分布を有し、その繰り返し数の平均が4〜22のポリペンテニレングリコール混合物、ジヘキセニレングリコール、トリヘキセニレングリコール、テトラヘキセニレングリコールの如きポリヘキセニレングリコールおよび分子量分布を有し、その繰り返し数の平均が4〜22のポリヘキセニレングリコール混合物、ジヘプテニレングリコール、トリヘプテニレングリコール、テトラヘプテニレングリコールの如きポリヘプテニレングリコールおよび分子量分布を有し、その繰り返し数の平均が4〜22のポリヘプテニレングリコール混合物、ジオクテニレングリコール、トリオクテニレングリコール、テトラオクテニレングリコールの如きポリオクテニレングリコールおよび分子量分布を有し、その繰り返し数の平均が4〜22のポリオクテニレングリコール混合物、ジノナニレングリコール、トリノナニレングリコール、テトラノナニレングリコールの如きポリノナニレングリコールおよび分子量分布を有し、その繰り返し数の平均が4〜22のポリノナニレングリコール混合物、ジデカニレングリコール、トリデカニレングリコール、テトラデカニレングリコールの如きポリデカニレングリコールなどのアルキレン部分が炭素原子数2〜10のポリアルキレングリコールおよびこれら混合物が挙げられる。これらの中でも、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコールの如きアルキレン部分が炭素原子数2〜4のポリアルキレングリコールが特に好ましく、ジエチレングリコールや分子量分布を有し、その繰り返し数の平均が4〜22のポリエチレングリコール混合物が更に好ましい。 Polyalkylene glycols include polyethylene glycols such as diethylene glycol, triethylene glycol and tetraethylene glycol, and polyethylene glycol mixtures having a molecular weight distribution and an average repeating number of 4 to 22, dipropylene glycol, tripropylene glycol and tetrapropylene. Polypropylene glycol such as glycol and a polypropylene glycol mixture having a molecular weight distribution and an average number of repetitions of 4 to 22, polybutylene glycol such as dibutylene glycol, tributylene glycol and tetrabutylene glycol, dipentenylene glycol, Polypentenylene glycol, such as pentenylene glycol, tetrapentenylene glycol, and molecular weight distribution, A polypentenylene glycol mixture having an average of 4 to 22, polyhexenylene glycol such as dihexenylene glycol, trihexenylene glycol and tetrahexenylene glycol, and a molecular weight distribution, the average number of repetitions of which is 4 to A polyheptenylene glycol mixture such as 22 polyhexenylene glycol mixtures, diheptenylene glycol, triheptenylene glycol, tetraheptenylene glycol and a molecular weight distribution, the average of which is 4 to 22 A polyoctenylene glycol mixture such as a tenylene glycol mixture, dioctenylene glycol, trioctenylene glycol, tetraoctenylene glycol and a molecular weight distribution, and an average number of repetitions of 4 to 22 polyoctenylene glycol mixture, dino Polynonanylene glycols such as nylene glycol, trinonanylene glycol, tetranonanylene glycol, and polynonanylene glycol mixtures having a molecular weight distribution and an average number of repetitions of 4 to 22, didecanylene glycol, tridecanylene glycol And polyalkylene glycols such as polydecanylene glycol such as tetradecanylene glycol and the like, and polyalkylene glycols having 2 to 10 carbon atoms and mixtures thereof. Among these, an alkylene moiety such as polyethylene glycol, polypropylene glycol, and polybutylene glycol is particularly preferably a polyalkylene glycol having 2 to 4 carbon atoms, which has diethylene glycol or a molecular weight distribution, and the average number of repetitions thereof is 4 to 22. More preferred are polyethylene glycol mixtures.
アルキレンジオールのジグリシジルエーテル(b−1)及びポリアルキレングリコールのジグリシジルエーテル(b−2)は、ハロゲンフリーで優れた難然効果を発現することからハロゲン原子非含有のアルキレンジオールのジグリシジルエーテル及びポリアルキレングリコールのジグリシジルエーテルが好ましい。ここで、ハロゲン原子非含有のアルキレンジオールのジグリシジルエーテル及びポリアルキレングリコールのジグリシジルエーテルとは、アルキレンジオールのジグリシジルエーテル又はポリアルキレングリコールのジグリシジルエーテルを製造する際、エピハロヒドリンと反応させるアルキレンジオール又はポリアルキレングリコール中にハロゲン原子が含まれていないか或いはハロゲン原子で実質的に変性されていないアルキレンジオールのジグリシジルエーテル又はポリアルキレングリコールのジグリシジルエーテルである。即ち、アルキレンジオールのジグリシジルエーテル及びポリアルキレングリコールのジグリシジルエーテルには、通常のエピハロヒドリンの使用により混入されるハロゲン分は含んでいてもよく、その割合は、具体的には5000ppm以下であることが好ましい。 Diglycidyl ether (b-1) of alkylene diol and diglycidyl ether (b-2) of polyalkylene glycol are halogen-free and exhibit an excellent difficult effect. Therefore, diglycidyl ether of alkylene diol containing no halogen atom And diglycidyl ethers of polyalkylene glycols are preferred. Here, the diglycidyl ether of alkylene diol containing no halogen atom and the diglycidyl ether of polyalkylene glycol are alkylene diols to be reacted with epihalohydrin when producing diglycidyl ether of alkylene diol or diglycidyl ether of polyalkylene glycol. Or, it is a diglycidyl ether of an alkylene diol or a diglycidyl ether of a polyalkylene glycol which does not contain a halogen atom in the polyalkylene glycol or is not substantially modified with a halogen atom. That is, the diglycidyl ether of alkylene diol and the diglycidyl ether of polyalkylene glycol may contain a halogen content mixed by the use of normal epihalohydrin, and the ratio is specifically 5000 ppm or less. Is preferred.
アルキレンジオールのジグリシジルエーテル(b−1)及びポリアルキレングリコールのジグリシジルエーテル(b−2)は、その使用にあたって1種類のみに限定されるものではなく、2種類以上の併用も可能である。また、上記のアルキレンジオールのジグリシジルエーテル(b−1)及びポリアルキレングリコールのジグリシジルエーテル(b−2)と共に、以下の化合物、即ち、n−ブチルグリシジルエーテル、アリルグリシジルエーテル、2−エチルヘキシルグリシジルエーテル、スチレンオキサイド、フェニルグリシジルエーテル、クレジルグリシジルエーテル、P.Sec−ブチルフェニルグリシジルエーテル、グリシジルメタクリレート、ビニルシクロヘキセンモノエポキサイド等の1官能性エポキシ化合物を一部用いることもできる。 The diglycidyl ether (b-1) of the alkylene diol and the diglycidyl ether (b-2) of the polyalkylene glycol are not limited to only one type, and two or more types can be used in combination. Further, together with the above-mentioned diglycidyl ether (b-1) of alkylene diol and diglycidyl ether (b-2) of polyalkylene glycol, the following compounds: n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl Ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, P.I. A part of monofunctional epoxy compounds such as Sec-butylphenyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene monoepoxide can also be used.
以上の有機リン化合物(a)と、アルキレンジオールのジグリシジルエーテル(b−1)又はポリアルキレングリコールのジグリシジルエーテル(b−2)とを反応させてエポキシ樹脂(A)とする方法は、特に制限されるものではなく、適度なグラフト化率が得られ、かつゲル化が起こらない反応条件を適宜選択すればよい。具体的な反応条件としては、例えば、必要に応じて触媒の存在下、上記各原料を20〜200℃で反応させる方法が挙げられる。 The method of reacting the above organophosphorus compound (a) with diglycidyl ether (b-1) of alkylene diol or diglycidyl ether (b-2) of polyalkylene glycol to obtain an epoxy resin (A) is particularly The reaction conditions are not limited, and an appropriate grafting rate may be obtained and reaction conditions that do not cause gelation may be appropriately selected. Specific reaction conditions include, for example, a method of reacting the above raw materials at 20 to 200 ° C. in the presence of a catalyst as necessary.
ここで、使用し得る触媒は、特に制限されるものではないが、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、トリエチルアミン、ベンジルジメチルアミン等の第三級アミン、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、イミダゾール化合物、トリフェニルホスフィン等が挙げられる。 Here, the catalyst that can be used is not particularly limited, but examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, tertiary amines such as triethylamine and benzyldimethylamine, and tetramethylammonium. Examples include quaternary ammonium salts such as chloride, imidazole compounds, and triphenylphosphine.
また、当該反応は、必要に応じて有機溶剤存在下で行うことが、反応を制御しやすくなる点から好ましい。使用し得る有機溶剤として、エポキシ樹脂に対して不活性な点から、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、メタノール、エタノール、イソプロピルアルコール、n−ブタノール、メトキシプロパノール、メチルセロソルブ、エチルカルビトール、酢酸エチル、キシレン、トルエン、シクロヘキサノール、N,N−ジメチルホルムアミド等が好ましい。 In addition, the reaction is preferably performed in the presence of an organic solvent as necessary from the viewpoint of easy control of the reaction. As an organic solvent that can be used, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, n-butanol, methoxypropanol, methyl cellosolve, ethyl carbitol, acetic acid from the point of inertness to the epoxy resin. Ethyl, xylene, toluene, cyclohexanol, N, N-dimethylformamide and the like are preferable.
以上のようにして得られるエポキシ樹脂(A)の中でも、一般式(3) Among the epoxy resins (A) obtained as described above, the general formula (3)
で表わされるエポキシ樹脂及び一般式(4)
Epoxy resin represented by the general formula (4)
(式中、R1、R2及びR3は、各々独立的に、水素原子又はアルキル基を表わし、R4は、アルキレン鎖又はポリエーテル鎖を表わし、nは0〜10の整数を表わす。)
で表わされるエポキシ樹脂が好ましく、上記一般式(3)及び一般式(4)において、R1、R2及びR3が水素原子であり、かつ、R4が−CH2CH2CH2CH2CH2CH2−、−CH2CH2OCH2CH2−又は−(CH2CH2O)n−CH2CH2−(分子量分布を有し、nの平均が4〜22のポリエチレングリコール)であるエポキシ樹脂が特に好ましい。また、上記一般式(3)及び一般式(4)において、nが0〜5の整数であるエポキシ樹脂が好ましく、nが0〜3の整数であるエポキシ樹脂が特に好ましい。
(Wherein R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group, R 4 represents an alkylene chain or a polyether chain, and n represents an integer of 0 to 10). )
In general formula (3) and general formula (4), R 1 , R 2 and R 3 are hydrogen atoms, and R 4 is —CH 2 CH 2 CH 2 CH 2. CH 2 CH 2 —, —CH 2 CH 2 OCH 2 CH 2 — or — (CH 2 CH 2 O) n—CH 2 CH 2 — (polyethylene glycol having a molecular weight distribution and an average n of 4 to 22) An epoxy resin is particularly preferred. Moreover, in the said General formula (3) and General formula (4), the epoxy resin whose n is an integer of 0-5 is preferable, and the epoxy resin whose n is an integer of 0-3 is especially preferable.
アルキレンジオールのジグリシジルエーテル(b−1)及びポリアルキレングリコールのジグリシジルエーテル(b−2)に対する有機リン化合物(a)の変性割合は、最終的な組成物における全エポキシ樹脂成分を基準に定められる。 The modification ratio of the organophosphorus compound (a) to the diglycidyl ether (b-1) of the alkylene diol and the diglycidyl ether (b-2) of the polyalkylene glycol is determined based on the total epoxy resin components in the final composition. It is done.
即ち、本発明の難燃性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量は、2〜8重量%の範囲にあることが望ましいが、エポキシ樹脂(A)に加え、更にその他のエポキシ樹脂を併用する場合には、これも加えた全エポキシ樹脂重量を基準にリン含有量が2〜8重量%の範囲となるように選択される。 That is, the phosphorus content with respect to all the epoxy resin components in the flame retardant epoxy resin composition of the present invention is preferably in the range of 2 to 8% by weight, but in addition to the epoxy resin (A), other epoxy When the resin is used in combination, the phosphorus content is selected in the range of 2 to 8% by weight based on the total weight of the epoxy resin added.
ここで、リン含有量が2重量%より少ないと密着性、耐水性、難燃性の改善効果が得られず、逆にリン含有量が8重量%より多いと機械的物性の低下が認められる。特に、リン原子含有量が当該範囲にある場合、ビスフェノールA型エポキシ樹脂よりも良好な密着性の硬化物を得ることができる。また、組成物中のエポキシ樹脂成分としてエポキシ樹脂(A)のみを使用するのであれば、エポキシ樹脂(A)中のリン原子含有量が2〜8重量%の範囲となることは勿論のことである。 Here, if the phosphorus content is less than 2% by weight, the effect of improving the adhesion, water resistance and flame retardancy cannot be obtained. Conversely, if the phosphorus content is more than 8% by weight, a decrease in mechanical properties is observed. . In particular, when the phosphorus atom content is in this range, a cured product having better adhesion than the bisphenol A type epoxy resin can be obtained. In addition, if only the epoxy resin (A) is used as the epoxy resin component in the composition, it goes without saying that the phosphorus atom content in the epoxy resin (A) is in the range of 2 to 8% by weight. is there.
ここで、本発明においてリン含有量とは、具体的には、次の方法にて測定される値である。即ち、 Here, in the present invention, the phosphorus content is specifically a value measured by the following method. That is,
(i)試料(全エポキシ樹脂成分)1gに硝酸25ml及び過塩素酸10mlを加えて内容物を5〜10mlになるまで加熱分解しこの液を1000mlメスフラスコに蒸留水で希釈する。 (I) 25 ml of nitric acid and 10 ml of perchloric acid are added to 1 g of a sample (all epoxy resin components), and the contents are thermally decomposed to 5 to 10 ml, and this solution is diluted with distilled water in a 1000 ml volumetric flask.
(ii)次いで、この試料液10mlを100mlメスフラスコに入れ、硝酸10ml、0.25%バナジン酸アンモニウム溶液を10ml及び5%モリブデン酸アンモニウム溶液10mlを加えた後、蒸留水で標線まで希釈しよく振り混ぜ、放置するこの発色液を石英セルに入れ、分光光度計を用いて波長440nmの条件でブランク液を対照にして試料およびリン標準液の吸光度を測定する。ここで、リン標準液はリン酸カリウムを蒸留水でP=0.1mg/mlとして調整した液を100mlメスフラスコに10ml入れて蒸留水で希釈したものである。 (Ii) Next, 10 ml of this sample solution was put into a 100 ml volumetric flask, 10 ml of nitric acid, 10 ml of 0.25% ammonium vanadate solution and 10 ml of 5% ammonium molybdate solution were added, and then diluted to the mark with distilled water. Shake well and leave this coloring solution in a quartz cell, and measure the absorbance of the sample and phosphorous standard solution using a spectrophotometer at a wavelength of 440 nm with the blank solution as a control. Here, the phosphorus standard solution is prepared by adding 10 ml of a solution prepared by adjusting potassium phosphate to P = 0.1 mg / ml with distilled water and diluting with distilled water.
(iii)吸光度の測定結果を基に以下の式よりリン含有量(重量%)求める。 (Iii) The phosphorus content (% by weight) is obtained from the following formula based on the measurement result of absorbance.
リン含有量(%)=試料の吸光度/リン標準液の吸光度/試料(g) Phosphorus content (%) = absorbance of sample / absorbance of phosphorus standard solution / sample (g)
この様に最終的に得られるエポキシ樹脂(A)は、エポキシ当量が100〜1500g/eqの範囲が好ましいが、なかでも、硬化物の機械的性能、耐熱性などの点から200〜700g/eqの範囲がより好ましい。 The epoxy resin (A) finally obtained in this way preferably has an epoxy equivalent of 100 to 1500 g / eq, but in particular, 200 to 700 g / eq from the viewpoint of the mechanical performance and heat resistance of the cured product. The range of is more preferable.
また、前記その他のエポキシ樹脂としては、例えば、具体的には、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールAD型エポキシ樹脂、テトラメチルビスフェノールA型エポキシ樹脂、ビスフェノールS型エポキシ樹脂等のビスフェノール型エポキシ樹脂、レゾルシノールジグリシジルエーテル、1−6ジヒドロキシナフタレンのジグリシジルエーテル、ジメチルビスフェノールCジグリシジルエーテル等の2官能型エポキシ樹脂、1,6−ジグリシジルオキシナフタレン型エポキシ樹脂、1−(2,7−ジグリシジルオキシナフチル)−1−(2−グリシジルオキシナフチル)メタン、1,1−ビス(2,7−ジグリシジルオキシナフチル)メタン、1,1−ビス(2,7−ジグリシジルオキシナフチル)−1−フェニル−メタン等のナフタレン系エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビスフェノールADノボラック樹脂等のノボラック型エポキシ樹脂、シクロヘキセンオキサイド基を有するエポキシ樹脂、トリシクロデセンオキサイド基を有するエポキシ樹脂、シクロペンテンオキサイド基を有するエポキシ樹脂、ジシクロペンタジエン型フェノール樹脂のエポキシ化物等の環式脂肪族エポキシ樹脂、フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、ジグリシジルp−オキシ安息香酸、ダイマー酸グリシジルエステル、トリグリシジルエステル等のグリシジルエステル型エポキシ樹脂、ジグリシジルアニリン、テトラグリシジルアミノジフェニルメタン、トリグリシジルp−アミノフェノール、トリグリシジル−p−アミノフェノール、テトラグリシジルメタキシリレンジアミン、ジグリシジルトルイジン、テトラグリシジルビスアミノメチルシクロヘキサン等のグリシジルアミン型エポキシ樹脂、ジグリシジルヒダントイン、グリシジルグリシドオキシアルキルヒダントイン等のヒダントイン型エポキシ樹脂、トリアリルイソシアヌレート、トリグリシジルイソシアヌレート等の複素環式エポキシ樹脂、フロログリシノールトリグリシジルエーテル、トリヒドロキシビフェニルトリグリシジルエーテル、トリヒドロキシフェニルメタントリグリシジルエーテル、グリセリントリグリシジルエーテル、2−[4−(2,3−エポキシプロポキシ)フェニル]−2−[4−[1,1−ビス[4−(2,3−エポキシプロポキシ)フェニル]エチル]フェニル]プロパン、1,3−ビス[4−[1−[4−(2,3−エポキシプロポキシ)フェニル]−1−[4−[1−[4−(2,3−エポキシプロポキシ)フェニル]−1−メチルエチル]フェニル]エチル]フェノキシ]−2−プロパノール等の3官能型エポキシ樹脂、テトラヒドロキシフェニルエタンテトラグリシジルエーテル、テトラグリシジルベンゾフェノン、ビスレゾルシノールテトラグリシジルエーテル、テトラグリシドキシビフェニル等の4官能型エポキシ樹脂などが挙げられる。なお、本発明でいう「全エポキシ樹脂成分」とは、エポキシ樹脂(A)と他のエポキシ樹脂との全量を意味する。 Examples of the other epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, tetramethylbisphenol A type epoxy resins, and bisphenol S type epoxy resins. Bifunctional phenolic resin such as bisphenol type epoxy resin, resorcinol diglycidyl ether, diglycidyl ether of 1-6 dihydroxynaphthalene, dimethylbisphenol C diglycidyl ether, 1,6-diglycidyloxynaphthalene type epoxy resin, 1- (2 , 7-diglycidyloxynaphthyl) -1- (2-glycidyloxynaphthyl) methane, 1,1-bis (2,7-diglycidyloxynaphthyl) methane, 1,1-bis (2,7-diglycidyloxy) Naf 1) Naphthalene type epoxy resin such as 1-phenyl-methane, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, novolak type epoxy resin such as bisphenol AD novolak resin, and cyclohexene oxide group Epoxy resin having tricyclodecene oxide group, epoxy resin having cyclopentene oxide group, cycloaliphatic epoxy resin such as epoxidized product of dicyclopentadiene type phenol resin, diglycidyl phthalate, dihydrotetrahydrophthalate Such as glycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid, dimer acid glycidyl ester, triglycidyl ester, etc. Ricidyl ester type epoxy resin, diglycidylaniline, tetraglycidylaminodiphenylmethane, triglycidyl p-aminophenol, triglycidyl-p-aminophenol, tetraglycidylmetaxylylenediamine, diglycidyltoluidine, tetraglycidylbisaminomethylcyclohexane, etc. Glycidylamine type epoxy resin, diglycidylhydantoin, hydantoin type epoxy resin such as glycidylglycidoxyalkylhydantoin, heterocyclic epoxy resin such as triallyl isocyanurate, triglycidyl isocyanurate, phloroglicinol triglycidyl ether, trihydroxybiphenyl Triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl Ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, 1, 3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] Trifunctional epoxy resins such as phenyl] ethyl] phenoxy] -2-propanol, tetrafunctional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidylbenzophenone, bisresorcinol tetraglycidyl ether, tetraglycidoxybiphenyl, etc. Can be mentioned. The “total epoxy resin component” in the present invention means the total amount of the epoxy resin (A) and other epoxy resins.
次に、本発明の難燃性エポキシ樹脂組成物に用いられる硬化剤(B)としては、特に限定されるものではないが、例えば、ジシアンジアミド、イミダゾール、BF3−アミン錯体、グアニジン誘導体等の潜在性アミン系硬化剤、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホンなどの芳香族アミン類、シクロホスファゼンオリゴマー、フェノール類とトリアジン環を有する化合物、或いはフェノール類とトリアジン環とアルデヒド類の混合物または縮合物等の窒素原子含有化合物、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールAノボラック樹脂、ポリアミド樹脂、無水マレイン酸、無水フタル酸、無水ヘキサヒドロフタル酸、無水ピロメリット酸などの酸無水物系硬化剤などが挙げられる。これらの硬化剤は、単独で用いることも、2種以上を併用して用いることもできる。 Next, the curing agent (B) used in the flame retardant epoxy resin composition of the present invention is not particularly limited, but for example, dicyandiamide, imidazole, BF 3 -amine complexes, guanidine derivatives and the like Amine-based curing agent, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, cyclophosphazene oligomer, compounds having phenols and triazine rings, or mixtures or condensates of phenols, triazine rings and aldehydes Nitrogen-containing compounds such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, polyamide resin, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, etc. And the like. These curing agents can be used alone or in combination of two or more.
これらのなかでも特に、密着性と難然効果が相乗的に向上する点からジシアンジアミドに代表される窒素原子を含有する硬化剤、フェノール類とトリアジン環とアルデヒド類の混合物または縮合物が好ましい。 Among these, a curing agent containing a nitrogen atom typified by dicyandiamide, a mixture of phenols, triazine rings and aldehydes or a condensate is preferable in terms of synergistically improving adhesion and difficult effects.
本発明の難燃性エポキシ樹脂組成物には、硬化促進剤を併用することもできる。そのような硬化促進剤としては、公知慣用のものがいずれも使用できる。そのような硬化促進剤としては、例えば、ベンジルジメチルアミンの如き第3級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩などが挙げられる。これらの硬化促進剤は、単独で用いることも、2種以上を併用して用いることもできる。 A curing accelerator can also be used in combination with the flame retardant epoxy resin composition of the present invention. As such a curing accelerator, any known one can be used. Examples of such curing accelerators include tertiary amines such as benzyldimethylamine, imidazole, organic acid metal salts, Lewis acids, amine complex salts, and the like. These curing accelerators can be used alone or in combination of two or more.
また、本発明の難燃性エポキシ樹脂組成物には、上記した各成分に加え、更に有機溶剤(C)を使用してもよく、特に電気積層板用組成物としては、この有機溶剤(C)は必須の成分となる。ここで、使用し得る有機溶媒(C)は、特に限定されるものではないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、メタノール、エタノール、イソプロピルアルコール、n−ブタノール、メトキシプロパノール、メチルセロソルブ、エチルカルビトール、酢酸エチル、キシレン、トルエン、シクロヘキサノール、N,N−ジメチルホルムアミドなどが挙げられる。これらの溶剤は、単独で用いることも、適宜、2種または、それ以上の混合溶剤として用いることもできる。 In addition to the above-described components, an organic solvent (C) may be further used for the flame retardant epoxy resin composition of the present invention. In particular, the organic solvent (C ) Is an essential component. Here, the organic solvent (C) that can be used is not particularly limited. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, n-butanol, methoxypropanol, methyl cellosolve, ethyl Examples thereof include carbitol, ethyl acetate, xylene, toluene, cyclohexanol, N, N-dimethylformamide and the like. These solvents can be used singly or as a mixed solvent of two or more as appropriate.
有機溶媒の使用量は特に制限されるものではないが、特に電気積層板用としては、ガラスクロスへの含侵性の点から、固形分換算で20〜80重量%となる範囲であることが好ましい。 The amount of the organic solvent used is not particularly limited, but particularly for electric laminates, from the viewpoint of impregnation into glass cloth, it may be in the range of 20 to 80% by weight in terms of solid content. preferable.
本発明の本発明の難燃性エポキシ樹脂組成物には、さらに必要に応じて種々の添加剤、難燃剤、充填剤等を適宜配合することができる。 In the flame-retardant epoxy resin composition of the present invention, various additives, flame retardants, fillers and the like can be appropriately blended as necessary.
また、本発明の熱硬化性樹脂組成物には、必要に応じて、他の熱硬化性樹脂を適宜併用することもできる。他の熱硬化性樹脂としては、例えば、シアネートエステル化合物、ビニルベンジル化合物、アクリル化合物、マレイミド化合物などが挙げられる。上記した他の熱硬化性樹脂を併用する場合、その使用量は、本発明の効果を阻害しなければ、特に制限を受けないが、本発明の熱硬化性樹脂組成物に対して1〜80重量%の範囲であることが好ましい。 Moreover, the thermosetting resin composition of this invention can also use other thermosetting resin together suitably as needed. Examples of other thermosetting resins include cyanate ester compounds, vinyl benzyl compounds, acrylic compounds, maleimide compounds, and the like. When the other thermosetting resins described above are used in combination, the amount used is not particularly limited as long as the effect of the present invention is not impaired, but is 1 to 80 with respect to the thermosetting resin composition of the present invention. It is preferably in the range of% by weight.
本発明の難燃性エポキシ樹脂組成物は、電気積層板用として極めて有用であるが、硬化剤と組み合わせによって、例えば、接着剤、注型、塗料等の各種用途に使用できる。即ち、本発明のエポキシ樹脂組成物は、耐熱性を低下させることなく、しかも、柔軟性と密着性に優れた非ハロゲン系の難燃性硬化物を得られることから、封止、積層、塗料などの用途特にガラスエポキシ積層板やIC封止材用に適し、さらに金属密着性に優れるのでレジストや塗料用途にも適する被覆用エポキシ樹脂組成物を提供することができる。また、電気積層板用としては、銅箔との密着性に優れる点から樹脂付き銅箔等のいわゆるビルドアップ積層板用組成物として特に有用である。 The flame-retardant epoxy resin composition of the present invention is extremely useful as an electrical laminate, but can be used in various applications such as adhesives, casting, paints, etc., in combination with a curing agent. That is, since the epoxy resin composition of the present invention can obtain a non-halogen flame-retardant cured product excellent in flexibility and adhesion without deteriorating heat resistance, sealing, lamination, coating In particular, it is suitable for glass epoxy laminates and IC encapsulants, and since it has excellent metal adhesion, a coating epoxy resin composition suitable for resist and paint applications can be provided. Moreover, for electrical laminates, it is particularly useful as a composition for so-called build-up laminates such as resin-coated copper foils because of its excellent adhesion to copper foils.
上記した本発明の難燃性エポキシ樹脂組成物から積層板を製造する方法としては、特に制限されなく、公知慣用の方法によって製造することができるが、例えば、ガラスクロス等の基板に本発明のエポキシ樹脂組成物を樹脂量30〜70重量%となる割合で含浸してプリプレグとし、次いでこのプリプレグの1〜10枚を加熱プレスして得る方法が挙げられる。 The method for producing a laminate from the flame retardant epoxy resin composition of the present invention described above is not particularly limited and can be produced by a known and commonly used method. For example, the present invention can be applied to a substrate such as a glass cloth. There is a method in which the epoxy resin composition is impregnated at a ratio of 30 to 70% by weight to obtain a prepreg, and then 1 to 10 sheets of the prepreg are heated and pressed.
次に本発明を参考例、実施例および比較例により具体的に説明する。尚、例中において「部」および「%」は特に断りのない限りすべて重量基準である。尚、GPC測定、NMR、MSスペクトルは以下の条件にて測定した。また、リン含有量は、以下の方法にて測定した。 Next, the present invention will be described specifically with reference examples, examples and comparative examples. In the examples, “parts” and “%” are all based on weight unless otherwise specified. GPC measurement, NMR, and MS spectrum were measured under the following conditions. Moreover, phosphorus content was measured with the following method.
1)GPC:
・装置:東ソー株式会社製 HLC−8220 GPC、カラム:東ソー株式会社製 TSK−GEL G2000HXL+G2000HXL+G3000HXL+G4000HXL
・溶媒:テトラヒドロフラン
・流速:1ml/min
・検出器:RI
1) GPC:
・ Device: HLC-8220 GPC manufactured by Tosoh Corporation, Column: TSK-GEL G2000HXL + G2000HXL + G3000HXL + G4000HXL manufactured by Tosoh Corporation
・ Solvent: Tetrahydrofuran ・ Flow rate: 1 ml / min
・ Detector: RI
2)NMR:日本電子株式会社製 NMR GSX270 2) NMR: NMR GSX270 manufactured by JEOL Ltd.
3)MS :日本電子株式会社製 二重収束型質量分析装置 AX505H(FD505H) 3) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.
[リン含有量測定法]
試料1gに硝酸25ml及び過塩素酸10mlを加えて内容物を5〜10mlになるまで加熱分解し、この液を1000mlメスフラスコに蒸留水で希釈する。この試料液10mlを100mlメスフラスコに入れ、硝酸10ml、0.25%バナジン酸アンモニウム溶液を10ml及び5%モリブデン酸アンモニウム溶液10mlを加えた後、蒸留水で標線まで希釈しよく振り混ぜ、放置するこの発色液を石英セルに入れ、分光光度計を用いて波長440nmの条件でブランク液を対照にして試料およびリン標準液の吸光度を測定する。リン標準液はリン酸カリウムを蒸留水でP=0.1mg/mlとして調整した液を100mlメスフラスコに10ml入れて蒸留水で希釈する。次いで、リン含有量を次式より求める。
[Phosphorus content measurement method]
Nitric acid (25 ml) and perchloric acid (10 ml) are added to 1 g of the sample to thermally decompose the contents to 5 to 10 ml, and this liquid is diluted with distilled water in a 1000 ml volumetric flask. Add 10 ml of this sample solution to a 100 ml volumetric flask, add 10 ml of nitric acid, 10 ml of 0.25% ammonium vanadate solution and 10 ml of 5% ammonium molybdate solution, dilute to the mark with distilled water, mix well, and leave to stand. This color developing solution is put in a quartz cell, and the absorbance of the sample and phosphorous standard solution is measured using a spectrophotometer under the condition of a wavelength of 440 nm using the blank solution as a control. As a phosphorus standard solution, 10 ml of a solution prepared by adjusting potassium phosphate to P = 0.1 mg / ml with distilled water is added to a 100 ml volumetric flask and diluted with distilled water. Subsequently, phosphorus content is calculated | required from following Formula.
リン含有量(%)=試料の吸光度/リン標準液の吸光度/試料(g) Phosphorus content (%) = absorbance of sample / absorbance of phosphorus standard solution / sample (g)
実施例1
温度計、冷却管、分留管及び撹拌器を取り付けたフラスコに、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(三光化学株式会社製)324部(1モル)及び1,6−ヘキサンジオールジグリシジルエーテル(阪本薬品製の「SR−16HL」、エポキシ当量122g/eq)488部(2モル)を仕込み、150℃下、窒素を吹き込みながら撹拌して溶解した。その後、テトラメチルアンモニウムクロライド1.0gを50%水溶液として添加した後、150℃で4時間攪拌して、リン含有量3.9%、エポキシ当量450g/eq、25℃E型粘度130万mPa・sのリン含有エポキシ樹脂(A−1)787部を得た。得られたリン含有エポキシ樹脂のGPCチャートを図1に、C13NMRチャートを図2に、MSスペクトルを図3にそれぞれ示した。MSスペクトルから下記構造式で表わされる目的のリン化合物のピーク(m/z=785)が検出された。
Example 1
To a flask equipped with a thermometer, a condenser tube, a fractionating tube and a stirrer, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd.) ) 324 parts (1 mol) and 1,6-hexanediol diglycidyl ether (“SR-16HL”, Sakamoto Yakuhin, epoxy equivalent 122 g / eq) 488 parts (2 mol) were charged, and nitrogen was blown at 150 ° C. The solution was dissolved while stirring. Thereafter, 1.0 g of tetramethylammonium chloride was added as a 50% aqueous solution, followed by stirring at 150 ° C. for 4 hours, a phosphorus content of 3.9%, an epoxy equivalent of 450 g / eq, a 25 ° C. E-type viscosity of 1.3 million mPa · 787 parts of phosphorus-containing epoxy resin (A-1) of s was obtained. The GPC chart of the obtained phosphorus-containing epoxy resin is shown in FIG. 1, the C 13 NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. The peak (m / z = 785) of the target phosphorus compound represented by the following structural formula was detected from the MS spectrum.
実施例2
実施例1において、1,6−ヘキサンジオールジグリシジルエーテルに代えて、ジエチレングリコールジグリシジルエーテル(ナガセケムテックス製の「EX−850」、エポキシ当量123g/eq)492部(2モル)を用いた以外は、実施例1と同様にして、リン含有量3.8%、エポキシ当量452g/eq、25℃E型粘度200万mPa・sのリン含有エポキシ樹脂(A−2)790部を得た。
Example 2
In Example 1, instead of 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether (“EX-850” manufactured by Nagase ChemteX, epoxy equivalent 123 g / eq) 492 parts (2 mol) was used. In the same manner as in Example 1, 790 parts of a phosphorus-containing epoxy resin (A-2) having a phosphorus content of 3.8%, an epoxy equivalent of 452 g / eq, and a 25 ° C. E-type viscosity of 2 million mPa · s was obtained.
実施例3
実施例1において、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−オキサイドに代えて、10−(2,7−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374部(1モル)を用いた以外は、実施例1と同様にして、燐含有量3.6%、エポキシ当量460g/eq、25℃E型粘度150万mPa・sの燐含有エポキシ樹脂(A−3)830部を得た。
Example 3
In Example 1, instead of 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydroxynaphthyl) -10H-9- Phosphorus content 3.6%, epoxy equivalent 460 g / eq, 25 °
実施例4
実施例1において、1,6−ヘキサンジオールジグリシジルエーテルに代えて、繰り返し単位が平均9のポリエチレングリコールジグリシジルエーテル(ナガセケムテックス製の「EX−830」、エポキシ当量270g/eq)1080部(2モル)を用いた以外は実施例1、と同様にして、燐含有量2.2%、エポキシ当量841g/eq、25℃E型粘度10万mPa・sの燐含有エポキシ樹脂(A−4)1400部を得た。
Example 4
In Example 1, instead of 1,6-hexanediol diglycidyl ether, 1080 parts of polyethylene glycol diglycidyl ether having an average of 9 repeating units (“EX-830” manufactured by Nagase ChemteX, epoxy equivalent 270 g / eq) ( 2 mol) was used in the same manner as in Example 1 except that a phosphorus-containing epoxy resin (A-4) having a phosphorus content of 2.2%, an epoxy equivalent of 841 g / eq, and a 25 ° C. E-type viscosity of 100,000 mPa · s. ) 1400 parts were obtained.
比較合成例1
実施例1において、1,6−ヘキサンジオールジグリシジルエーテルに代えて、ビスフェノールF型液状エポキシ樹脂(DIC株式会社製の「エピクロン830S」、エポキシ当量170g/eq)680部(2モル)を用いた以外は、実施例1と同様にして、リン含有量3.1%、エポキシ当量475g/eq、軟化点90℃のリン含有エポキシ樹脂(A’−1)997重量を得た。
Comparative Synthesis Example 1
In Example 1, instead of 1,6-hexanediol diglycidyl ether, 680 parts (2 mol) of a bisphenol F type liquid epoxy resin (“Epiclon 830S” manufactured by DIC Corporation, epoxy equivalent 170 g / eq) was used. Otherwise, in the same manner as in Example 1, 997 weight of phosphorus-containing epoxy resin (A′-1) having a phosphorus content of 3.1%, an epoxy equivalent of 475 g / eq, and a softening point of 90 ° C. was obtained.
比較合成例2
実施例1において、1,6−ヘキサンジオールジグリシジルエーテルに代えて、水添ビスフェノールAジグリシジルエーテル(三菱化学社製の「YX−8000」、エポキシ当量205g/eq)820部(2モル)を用いた以外は、実施例1と同様にして、リン含有量2.9%、エポキシ当量686g/eq、25℃E型粘度900万mPa・sのリン含有エポキシ樹脂(A’−2)1087重量を得た。
Comparative Synthesis Example 2
In Example 1, instead of 1,6-hexanediol diglycidyl ether, 820 parts (2 mol) of hydrogenated bisphenol A diglycidyl ether (“YX-8000” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 205 g / eq) was used. Except for use, in the same manner as in Example 1, phosphorus content 2.9%, epoxy equivalent 686 g / eq, 25 ° C. E type viscosity 9 million mPa · s phosphorus-containing epoxy resin (A′-2) 1087 weight Got.
比較合成例3
実施例1において、1,6−ヘキサンジオールジグリシジルエーテルに代えて、トリメチロールプロパンポリグリシジルエーテル樹脂(東都化成株式会社製の「エポトートZX−1542」、エポキシ当量118g/eq)708部(2モル)を用いた以外は、実施例1と同様にして、リン含有量3.0%、エポキシ当量335g/eq、25℃E型粘度600万mPa・sのリン含有エポキシ樹脂(A’−3)1030重量を得た。
Comparative Synthesis Example 3
In Example 1, instead of 1,6-hexanediol diglycidyl ether, 708 parts (2 mol) of trimethylolpropane polyglycidyl ether resin (“Epototo ZX-1542” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 118 g / eq) ) Was used in the same manner as in Example 1 except that a phosphorus-containing epoxy resin (A′-3) having a phosphorus content of 3.0%, an epoxy equivalent of 335 g / eq, and a 25 ° C. E-type viscosity of 6 million mPa · s. 1030 weight was obtained.
比較合成例4(リン含有ウレタン変性エポキシ樹脂(B−4)の合成)
温度計、冷却管、分留管、窒素ガス導入管及び撹拌器を取り付けたフラスコに、ビスフェノールA型液状エポキシ樹脂(エポキシ当量188g/eq、水酸基価19.3KOHmg/g、DIC株式会社製「エピクロン850S」)188g(エポキシ基1.0当量)及び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:三光化学株式会社製)72.1g(P−H基濃度0.3当量)を仕込み、トリフェニルホスフィン0.135gを添加した後、150℃に昇温して、7時間撹拌して、エポキシ当量とGPC測定によってHCAが実質的に消滅したことを確認して中間体を得た。次いで、反応系内にトリレンジイソシアネート(TDI:NCO当量87g/eq.、三井化学ポリウレタン株式会社製:コスモネートT−100)27.5g(イソシアネート基0.3当量)を添加して、130℃で3時間撹拌して、IR測定でイソシアネート基が実質的に消滅したことを確認して、目的のリン原子含有ウレタン変性エポキシ樹脂(A’−4)を得た。得られたエポキシ樹脂(A’−4)のエポキシ当量は440g/eq.、軟化点92℃、リン原子含有量3.5質量%であった。
Comparative Synthesis Example 4 (Synthesis of phosphorus-containing urethane-modified epoxy resin (B-4))
A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube and a stirrer was added to a bisphenol A type liquid epoxy resin (epoxy equivalent 188 g / eq, hydroxyl value 19.3 KOH mg / g, manufactured by DIC Corporation “Epicron” 850S ") 188 g (1.0 equivalent of epoxy group) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA: Sanko Chemical Co., Ltd.) 72.1 g (PH group concentration) 0.3 equivalents), 0.135 g of triphenylphosphine was added, the temperature was raised to 150 ° C., and the mixture was stirred for 7 hours. It was confirmed that the HCA substantially disappeared by epoxy equivalent and GPC measurement. To obtain an intermediate. Next, 27.5 g (isocyanate group 0.3 equivalent) of tolylene diisocyanate (TDI: NCO equivalent 87 g / eq., Manufactured by Mitsui Chemicals Polyurethane Co., Ltd .: Cosmonate T-100) was added to the reaction system at 130 ° C. The mixture was stirred for 3 hours, and it was confirmed by IR measurement that the isocyanate group had substantially disappeared. Thus, the target phosphorus atom-containing urethane-modified epoxy resin (A′-4) was obtained. The epoxy equivalent of the obtained epoxy resin (A′-4) was 440 g / eq., A softening point of 92 ° C., and a phosphorus atom content of 3.5% by mass.
比較合成例5(リン含有液状エポキシ樹脂(B−5)の合成)
温度計、冷却管、分留管、窒素ガス導入管及び撹拌器を取り付けた4つ口セパラブルフラスコに、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(三光化学(株)製商品名:HCA)100部及びキシレン100部を仕込み、窒素ガス雰囲気中、撹拌しながら140℃に昇温した。同温度を保持しながら、これにグリシジルメタクリレート65.7部を1時間かけて滴下した後、さらに140℃にて3時間反応させた。反応終了後、10torr、140℃にてキシレンを留去することにより、目的のリン含有液状エポキシ樹脂(A’−5)165部を得た。得られたエポキシ樹脂(A’−5)のエポキシ当量は375g/eq、50℃における粘度は150mPa・sであった。
Comparative Synthesis Example 5 (Synthesis of phosphorus-containing liquid epoxy resin (B-5))
9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko Chemical Co., Ltd.) was added to a four-necked separable flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube and a stirrer. (Product name: HCA) 100 parts and
実施例5〜8及び比較例1〜5(エポキシ樹脂組成物の調整及び物性評価)
下記表1に記載の配合に従い、硬化剤としてDIC製のフェノールノボラック樹脂「TD−2131」を配合し、更に硬化触媒として2−エチル−4−メチルイミダゾール(2E4MZ)を加え、最終的に各組成物の不揮発分(N.V.)が58質量%となるようにメチルエチルケトンを配合して調整した。
Examples 5 to 8 and Comparative Examples 1 to 5 (Adjustment of epoxy resin composition and evaluation of physical properties)
In accordance with the formulation shown in Table 1 below, a phenol novolak resin “TD-2131” manufactured by DIC is blended as a curing agent, and 2-ethyl-4-methylimidazole (2E4MZ) is further added as a curing catalyst. Methyl ethyl ketone was blended and adjusted so that the nonvolatile content (NV) of the product was 58% by mass.
[ドレープ性試験]
幅25mm、長さ500mm、厚み20μmのPET上にスクリーン印刷で全面塗布し、80℃で20分間、乾燥させたPETを、片端から100mmを架台に固定し、もう一方の片端から400mmを垂下させた。10分後、垂下させた基板の先端までの架台固定部からの垂直距離Aと架台固定部端100mmの位置から基板の先端までの水平距離Bを計測し、次式より垂れ角度θ(゜)を求め、ドレープ性の指標とした。
[Drapability test]
A PET with a width of 25 mm, a length of 500 mm, and a thickness of 20 μm, coated on the whole surface by screen printing and dried at 80 ° C. for 20 minutes, 100 mm from one end is fixed to the frame, and 400 mm is drooped from the other end. It was. After 10 minutes, the vertical distance A from the gantry fixing part to the tip of the suspended board and the horizontal distance B from the position of the gantry fixing
垂れ角度θ(゜)=tan−1(A/B) Hanging angle θ (°) = tan −1 (A / B)
[積層板作成条件]
基材:100μm 日東紡績株式会社製 プリント配線基板用ガラスクロス「2116」
プライ数:6
銅箔:18μm 日鉱金属株式会社製 TCR箔
プリプレグ化条件:160℃/2分
硬化条件:200℃、2.9MPa、2.0時間
成形後板厚:0.8mm、樹脂量40%
上記条件で作成した硬化物を試験片として用い、以下の各種の評価を行った。結果を表1に示す。
[Lamination board creation conditions]
Base material: 100 μm Nitto Boseki Co., Ltd. Printed wiring board glass cloth “2116”
Number of plies: 6
Copper foil: 18 μm Nikko Metal Co., Ltd. TCR foil prepreg condition: 160 ° C./2 minutes Curing condition: 200 ° C., 2.9 MPa, 2.0 hours after forming plate thickness: 0.8 mm,
The following various evaluation was performed using the hardened | cured material created on the said conditions as a test piece. The results are shown in Table 1.
[耐はんだ試験]
各実施例及び各比較例の試験片をそれぞれ3個用意し、121℃プレッシャークッカー試験機に6時間放置後、288℃半田浴に30秒浸漬し膨れの有無を目視にて確認した。膨れの無いものを○、膨れの有るものを×とした。
[Solder resistance test]
Three test pieces of each example and each comparative example were prepared, left in a 121 ° C. pressure cooker tester for 6 hours, immersed in a 288 ° C. solder bath for 30 seconds, and visually checked for swelling. The thing without a swelling was set as (circle) and the thing with a swelling was set as *.
[3点曲げ伸び率]
試験片を25mm×75mmの大きさに切り出し、JIS K 6911に従って、島津製作所株式会社製の「AUTOGRAPH AG−I」を用いて測定し、曲げのび率を求めた。
[3-point bending elongation]
The test piece was cut into a size of 25 mm × 75 mm and measured according to JIS K 6911 using “AUTOGRAPH AG-I” manufactured by Shimadzu Corporation to determine the bending elongation.
[ピール強度]JIS−K6481に準拠した。 [Peel Strength] Conforms to JIS-K6481.
[強度層間剥離強度]JIS−K6481に準拠した。 [Strength delamination strength] Conforms to JIS-K6481.
[燃焼試験]試験方法はUL−94垂直試験に準拠。 [Burn test] The test method conforms to the UL-94 vertical test.
Claims (11)
で表わされる化合物又は一般式(2)
で表わされる化合物である請求項2記載のエポキシ樹脂(A)。 The organophosphorus compound (a) is represented by the general formula (1)
Or a compound represented by the general formula (2)
The epoxy resin (A) according to claim 2, which is a compound represented by the formula:
で表わされるエポキシ樹脂及び/又は一般式(4)
で表わされるエポキシ樹脂である請求項3記載のエポキシ樹脂(A)。 General formula (3)
And / or general formula (4)
Claim 3 wherein the epoxy resin in an epoxy resin represented by (A).
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