TWI684624B - Phosphorus-containing epoxy resin composition and hardened product - Google Patents
Phosphorus-containing epoxy resin composition and hardened product Download PDFInfo
- Publication number
- TWI684624B TWI684624B TW108128757A TW108128757A TWI684624B TW I684624 B TWI684624 B TW I684624B TW 108128757 A TW108128757 A TW 108128757A TW 108128757 A TW108128757 A TW 108128757A TW I684624 B TWI684624 B TW I684624B
- Authority
- TW
- Taiwan
- Prior art keywords
- phosphorus
- epoxy resin
- containing epoxy
- resin composition
- parts
- Prior art date
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 307
- 239000011574 phosphorus Substances 0.000 title claims abstract description 297
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 272
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 247
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 247
- 239000000203 mixture Substances 0.000 title claims abstract description 110
- -1 phenol compound Chemical class 0.000 claims abstract description 84
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 239000004848 polyfunctional curative Substances 0.000 claims description 17
- 239000004593 Epoxy Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 description 33
- 239000011347 resin Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 229910000831 Steel Inorganic materials 0.000 description 19
- 239000010959 steel Substances 0.000 description 19
- 239000003063 flame retardant Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 239000002966 varnish Substances 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000005011 phenolic resin Substances 0.000 description 12
- 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 11
- 239000002904 solvent Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000007865 diluting Methods 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 9
- 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 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 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 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 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 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229960004337 hydroquinone Drugs 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 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 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000000654 additive Substances 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 150000003017 phosphorus Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 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 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- UJVZTVDVOXMSRT-UHFFFAOYSA-N 3,5-diphenyl-2-phenylphosphanylnaphthalene-1,4-diol Chemical compound C1(=CC=CC=C1)C1=C2C(=C(C(=C(C2=CC=C1)O)PC1=CC=CC=C1)C1=CC=CC=C1)O UJVZTVDVOXMSRT-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 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
- 238000009835 boiling Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-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
- UXMYUFHUUYBDLL-UHFFFAOYSA-N 2,2-dimethyl-3-(oxiran-2-ylmethoxy)propan-1-ol Chemical compound OCC(C)(C)COCC1CO1 UXMYUFHUUYBDLL-UHFFFAOYSA-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
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-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
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical group O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
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- VPSQKMGMWFLAOE-UHFFFAOYSA-N 2-diphenylphosphanylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 VPSQKMGMWFLAOE-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- UYWWLYCGNNCLKE-UHFFFAOYSA-N 2-pyridin-4-yl-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1C1=CC=NC=C1 UYWWLYCGNNCLKE-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- ZXRJUBLHFHDUJH-UHFFFAOYSA-N 3-ethylbenzene-1,2-diamine Chemical compound CCC1=CC=CC(N)=C1N ZXRJUBLHFHDUJH-UHFFFAOYSA-N 0.000 description 1
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- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 239000006087 Silane Coupling Agent Substances 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- HLPKYOCVWVMBMR-UHFFFAOYSA-N azane benzylbenzene Chemical compound N.N.C=1C=CC=CC=1CC1=CC=CC=C1 HLPKYOCVWVMBMR-UHFFFAOYSA-N 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
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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
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 1
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- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
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- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 150000004820 halides Chemical class 0.000 description 1
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- OGEROIBRQCWGOI-UHFFFAOYSA-N hexanedioic acid;hydrazine Chemical compound NN.NN.OC(=O)CCCCC(O)=O OGEROIBRQCWGOI-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) 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
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
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- 239000010445 mica Substances 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 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
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical compound [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3272—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
- C08G59/1422—Polycondensates modified by chemical after-treatment with inorganic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/30—Environmental or health characteristics, e.g. energy consumption, recycling or safety issues
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本發明之課題在於提供一種提高含磷率，具有充分之難燃性，並且為低黏度，對有機溶劑之溶解性良好之含磷環氧樹脂組成物。 The object of the present invention is to provide a phosphorus-containing epoxy resin composition that improves the phosphorus content, has sufficient flame retardancy, and has low viscosity and good solubility in organic solvents.
本發明之含磷環氧樹脂組成物相對於具有下述通式(1)之結構之含磷率為2~7質量%之範圍內之含磷環氧樹脂100質量份，溶解5~45質量份之下述通式(2)所表示之含磷之酚化合物，且於室溫下無析出。 The phosphorus-containing epoxy resin composition of the present invention contains 100 parts by mass of phosphorus-containing epoxy resin in the range of 2 to 7% by mass with respect to the phosphorus content of the structure having the following general formula (1), and dissolves 5 to 45 parts by mass A portion of the phosphorus-containing phenol compound represented by the following general formula (2), and no precipitation at room temperature.
(式中，R1及R2表示碳數1~6之烴基，可相同，亦可不同，亦可與磷原子一同成為環狀；i表示0或1) (In the formula, R 1 and R 2 represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a ring together with a phosphorus atom; i represents 0 or 1)
(式中，R3及R4表示碳數1~6之烴基，可相同，亦可不同，亦可與磷原子一同成為環狀；n表示0或1；A表示碳數6~20之芳烴三基) (In the formula, R 3 and R 4 represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and may also form a ring together with a phosphorus atom; n represents 0 or 1; A represents an aromatic hydrocarbon having 6 to 20 carbon atoms. Three bases)
Description
本發明係關於一種由含磷環氧樹脂及含磷之酚化合物所構成之具有難燃性之含磷環氧樹脂組成物及其硬化物。 The present invention relates to a flame retardant phosphorus-containing epoxy resin composition composed of a phosphorus-containing epoxy resin and a phosphorus-containing phenol compound and its hardened product.
環氧樹脂由於接著性、耐熱性、成形性優異，故廣泛用於以電氣-電子領域為首之產業用途中。尤其是於電氣-電子領域所使用之積層板之情形時，就防止機器使用時發生火災之目的等安全性之方面而言，強烈要求難燃性。先前，作為對積層板賦予難燃性之方法，較多地將溴系難燃劑、氮系難燃劑、以及磷系難燃劑單獨或組合應用，進而較多地應用上述難燃劑中使用無機系難燃助劑之系統。然而，關於近年之環境問題，使用鹵素化合物時，疑於該積層板經燃燒處理之過程中生成有害之鹵化物，對不使用溴系難燃劑之所謂無鹵素難燃系統之要求變得強烈。因此，習知技術中，為了不使用溴系難燃劑而對積層板賦予難燃性，不得不使用氮系難燃劑、磷系難燃劑，但氮系難燃劑對於賦予難燃性並不足，磷系難燃劑之中，紅磷之安全性不足，磷酸系化合物為液狀，故容易產生滲出之問題，於使用磷酸酯類之情形時，焊料耐熱性或接著性降低，難以作為積層板使用。 Epoxy resins are widely used in industrial applications including electrical and electronic fields due to their excellent adhesion, heat resistance, and moldability. Especially in the case of laminates used in the electrical and electronic fields, in terms of safety, such as the purpose of preventing fires when the equipment is used, flame retardancy is strongly required. Previously, as a method of imparting flame retardancy to laminates, bromine-based flame retardants, nitrogen-based flame retardants, and phosphorus-based flame retardants were mostly used alone or in combination, and the above-mentioned flame retardants were frequently used. A system using inorganic flame retardant additives. However, regarding environmental issues in recent years, when using halogen compounds, it is suspected that harmful halides are generated during the combustion process of the laminate, and the requirement for a so-called halogen-free flame-retardant system that does not use bromine-based flame retardants becomes strong . Therefore, in the conventional technology, in order to impart flame retardancy to the laminate without using bromine-based flame retardants, it is necessary to use nitrogen-based flame retardants and phosphorus-based flame retardants, but nitrogen-based flame retardants are not Not enough, among phosphorus-based flame retardants, the safety of red phosphorus is insufficient, and the phosphoric acid-based compound is liquid, so it is prone to bleed out problems. In the case of using phosphate esters, the solder heat resistance or adhesion is reduced, which is difficult Used as a laminate.
對於上述問題，於專利文獻1、2中揭示使10-(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製造之商品名HCA-HQ)與環氧樹脂類以特定之莫耳比反應而獲得之熱硬化性樹脂及組成物。又，於專利文獻3中揭示使具有二官能以上之環氧基之樹脂與二苯基氧膦基對苯二酚(diphenylphosphinyl hydroquinone)反應而成之含磷環氧樹脂。然而，藉由此種磷化合物與環氧樹脂之反應而獲得之含磷環氧樹脂隨著含磷率變高，分子量變大，故有獲得充分之難燃性之樹脂清漆之黏度較高，操作時之作業性或對玻璃布等基材之含浸性變差之問題。進而，由於因含磷環氧樹脂之分子量變高而使硬化物之交聯密度降低，故難以獲得較高玻璃轉移溫度。 For the above problems, it is disclosed in Patent Documents 1 and 2 that 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd.) Trade name HCA-HQ) Thermosetting resins and compositions obtained by reacting epoxy resins with a specific molar ratio. In addition, Patent Document 3 discloses a phosphorus-containing epoxy resin obtained by reacting a resin having an epoxy group having more than two functions with diphenylphosphinyl hydroquinone. However, the phosphorus-containing epoxy resin obtained by the reaction of this phosphorus compound with an epoxy resin becomes higher as the phosphorus content becomes higher and the molecular weight becomes larger, so the resin varnish with sufficient flame retardancy has a higher viscosity, The problem is that the workability during operation or the impregnability to the glass cloth and other substrates become poor. Furthermore, since the molecular weight of the phosphorus-containing epoxy resin becomes higher, the cross-linking density of the cured product is lowered, so it is difficult to obtain a higher glass transition temperature.
對此，專利文獻4中揭示藉由製成殘留有源自含磷之酚化合物之羥基的含磷環氧樹脂而減小分子量，降低黏度之方法。然而，於該方法中，必須使含磷之酚化合物與環氧樹脂進行一定程度之反應，故就黏度之降低之觀點而言不足。 In this regard, Patent Document 4 discloses a method of reducing the molecular weight and reducing the viscosity by preparing a phosphorus-containing epoxy resin in which hydroxyl groups derived from a phosphorus-containing phenol compound are left. However, in this method, the phosphorus-containing phenol compound must be reacted with the epoxy resin to a certain extent, so it is insufficient from the viewpoint of viscosity reduction.
又，專利文獻5中揭示由於若僅利用含磷環氧樹脂則無法獲得充分之難燃性，故將磷化合物溶解於含磷環氧樹脂清漆而提高含磷率之方法，但溶劑必須使用N,N-二甲基甲醯胺等高沸點溶劑，亦有磷化合物容易析出之問題。專利文獻6中揭示將HCA-HQ藉由微粉碎為平均粒徑10μm、最大粒徑40μm之大小而分散於樹脂清漆之方法，但有相較於使用高沸點溶劑使磷化合物溶解之情形黏度更容易變高，為了充分進行硬化反應，必須充分檢討硬化條件之問題。 In addition, Patent Document 5 discloses that a method of dissolving a phosphorus compound in a phosphorus-containing epoxy resin varnish to increase the phosphorus content rate is not sufficient if only phosphorus-containing epoxy resins are used, but the solvent must use N , N-dimethylformamide and other high-boiling solvents also have the problem that phosphorus compounds are easily precipitated. Patent Document 6 discloses a method of dispersing HCA-HQ into a resin varnish by finely pulverizing it to an average particle size of 10 μm and a maximum particle size of 40 μm, but it has a higher viscosity than the case where a high boiling point solvent is used to dissolve the phosphorus compound It is easy to become high, in order to fully carry out the hardening reaction, it is necessary to fully review the problem of hardening conditions.
[專利文獻1]日本專利-3092009 [Patent Literature 1] Japanese Patent-3092009
[專利文獻2]日本特開平11-279258 [Patent Literature 2] Japanese Patent Laid-Open No. 11-279258
[專利文獻3]日本特開平5-214070 [Patent Document 3] Japanese Patent Laid-Open No. 5-214070
[專利文獻4]日本特開2012-172079 [Patent Document 4] Japanese Laid-Open Patent 2012-172079
[專利文獻5]日本特開2002-249540 [Patent Document 5] Japanese Laid-Open Patent 2002-249540
[專利文獻6]日本特開2003-011269 [Patent Literature 6] Japanese Patent Application Publication 2003-011269
[專利文獻7]日本特開昭60-126293 [Patent Document 7] Japanese Patent Laid-Open No. 60-126293
[專利文獻8]日本特開昭61-236787 [Patent Document 8] Japanese Patent Laid-Open No. 61-236787
[非專利文獻1]zh. Obshch. Khim，42(11)，第2415-2418頁(1972年) [Non-Patent Document 1] zh. Obshch. Khim, 42(11), pages 2415-2418 (1972)
關於至今所使用之含磷環氧樹脂或含磷環氧樹脂組成物，若欲為了提高難燃性而提高含磷率，則對溶劑之溶解性變差，進而，由於黏度變高，故難以應用於積層板。進而，含磷之酚化合物缺乏對有機溶劑之溶解性，用作基板用途之摻合物時，難以作為均勻之樹脂清漆而應用。本發明為鑒於上述習知技術所具有之課題而成者，提供一種藉由提高含磷率而具有充分之難燃性，並且黏度較低，對有機溶劑之溶解性良好，對纖維狀基材之含浸性等作業性非常優異之環氧樹脂組成物。 Regarding the phosphorus-containing epoxy resin or phosphorus-containing epoxy resin composition used hitherto, if the phosphorus content is to be increased in order to improve the flame retardancy, the solubility to the solvent becomes poor, and further, the viscosity becomes high, making it difficult Used in laminates. Furthermore, the phosphorus-containing phenol compound lacks solubility in organic solvents and is difficult to apply as a uniform resin varnish when used as a blend for substrate applications. The present invention has been made in view of the problems of the above-mentioned conventional technology, and provides a flame retardant which has sufficient flame retardancy by increasing the phosphorus content, and has a low viscosity, good solubility in organic solvents, and a fibrous base material An epoxy resin composition with excellent workability such as impregnation.
即，本發明係：(1).一種含磷環氧樹脂組成物，其相對於具有下述通式(1)之結構之含磷率為2~7質量%之範圍內之含磷環氧樹脂100質量份，溶解5~45質量份之下述通式(2)所表示之含磷之酚化合物，且於室溫下無析出，
(式中，R1及R2表示碳數1~6之烴基，可相同，亦可不同，亦可與磷原子一同成為環狀；i表示0或1) (In the formula, R 1 and R 2 represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a ring together with a phosphorus atom; i represents 0 or 1)
(式中，R3及R4表示碳數1~6之烴基，可相同，亦可不同，亦可與磷原子一同成為環狀；n表示0或1；A表示碳數6~20之芳烴三基(arenetriyl))；(2).如(1)項記載之含磷環氧樹脂組成物，其係摻合環氧樹脂(B)而成；(3).如(2)項記載之含磷環氧樹脂組成物，其特徵在於含磷率為2質量%以上；(4).如(1)至(3)項中任一項記載之含磷環氧樹脂組成物，其係摻合硬化劑(C)而成；(5).一種預浸體，其係將(1)至(4)項中任一項記載之含磷環氧樹脂組成物含浸於纖維狀基材而成；(6).一種硬化物，其係使(1)至(4)項中任一項記載之含磷環氧樹脂組成物硬化而成；(7).一種硬化物，其係使(5)項記載之預浸體硬化而成。 (In the formula, R 3 and R 4 represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and may also form a ring together with a phosphorus atom; n represents 0 or 1; A represents an aromatic hydrocarbon having 6 to 20 carbon atoms. (Arenetriyl)); (2). The phosphorus-containing epoxy resin composition described in (1), which is blended with epoxy resin (B); (3). As described in (2) Phosphorus-containing epoxy resin composition, characterized in that the phosphorus-containing rate is 2% by mass or more; (4). The phosphorus-containing epoxy resin composition described in any one of items (1) to (3), which is doped It is formed by mixing hardener (C); (5). A prepreg, which is made by impregnating the fibrous base material with the phosphorus-containing epoxy resin composition described in any one of (1) to (4) ; (6) A hardened product made by hardening the phosphorus-containing epoxy resin composition described in any one of (1) to (4); (7). A hardened product made of (5 ) The prepreg described in the item is hardened.
關於本發明之含磷環氧樹脂組成物，發現先前難以溶解之含磷之酚化合物可溶解於特定之含磷環氧樹脂中，從而完成本發明，兼具由高含磷率所得之難燃性及由低樹脂黏度所得之作業性之提高。關於本發明之含磷環氧樹脂組成物，於積層板製作中對玻璃布等纖維狀基材之含浸變得容易，並且難燃性提高，故可用於電子、電氣領域中之印刷配線基板材料、密封材料、澆鑄成型材料、接著材料、以及航空宇宙領域或車輛、橋樑、風車等所使用之複合材料等需要難燃性之領域。 Regarding the phosphorus-containing epoxy resin composition of the present invention, it has been found that a phosphorus-containing phenol compound that was previously difficult to dissolve can be dissolved in a specific phosphorus-containing epoxy resin, thereby completing the present invention, and possessing a flame retardant obtained from a high phosphorus content rate Performance and workability improvement due to low resin viscosity. Regarding the phosphorus-containing epoxy resin composition of the present invention, it is easy to impregnate the fibrous base material such as glass cloth in the manufacture of laminates, and the flame retardancy is improved, so it can be used as a printed wiring board material in the electronic and electrical fields , Sealing materials, casting molding materials, adhesive materials, and aerospace fields or composite materials used in vehicles, bridges, windmills and other fields that require flame retardancy.
以下，對本發明之實施形態詳細地進行說明。 Hereinafter, the embodiments of the present invention will be described in detail.
本發明中所使用之含磷環氧樹脂為於其分子內具有下述通式(1)所表示之化學結構者，例如，可使下述通式(2)及/或下述通式(3)所表示之磷化合物與環氧樹脂反應而合成。 The phosphorus-containing epoxy resin used in the present invention has a chemical structure represented by the following general formula (1) in its molecule. For example, the following general formula (2) and/or the following general formula ( 3) The phosphorus compound represented is synthesized by reacting with epoxy resin.
(式中，R1及R2表示碳數1~6之烴基，可相同，亦可不同，亦可與磷原子一同成為環狀；i表示0或1) (In the formula, R 1 and R 2 represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a ring together with a phosphorus atom; i represents 0 or 1)
(式中，R3及R4表示碳數1~6之烴基，可相同，亦可不同，亦可與磷原子一同成為環狀；n表示0或1；A表示碳數6~20之芳烴三基) (In the formula, R 3 and R 4 represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and may also form a ring together with a phosphorus atom; n represents 0 or 1; A represents an aromatic hydrocarbon having 6 to 20 carbon atoms. Three bases)
(式中，R5及R6表示碳數1~6之烴基，可相同，亦可不同，亦可與磷原子一同成為環狀；j表示0或1) (In the formula, R 5 and R 6 represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and may form a ring together with a phosphorus atom; j represents 0 or 1)
作為上述通式(2)或上述通式(3)所表示之磷化合物，例如可列舉：10-(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製造，商品名HCA-HQ)、10-(1,4-二羥基萘)-10H-9-氧雜-10-磷雜菲-10-氧化物(以下記為HCA-NQ)、二苯基氧膦基對苯二酚(北興化學工業股份有限公司製造，商品名PPQ)、二苯基苯膦基-1,4-二羥基萘、1,4-伸環辛基氧膦基-1,4-苯二酚(日本化學工業股份有限公司製造，商品名CPHO-HQ)、1,5-伸環辛基氧膦基-1,4-苯二酚(日本化學工業股份有限公司製造，商品名CPHO-HQ)等含磷之酚類，9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製造，商品名HCA)、1,4-伸環辛基氧化膦與1,5-伸環辛基氧化膦之混合物(日本化學工業股份有限公司製造，商品名CPHO)、二苯基氧化膦等，但不限定於該等。 Examples of the phosphorus compound represented by the general formula (2) or the general formula (3) include: 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene- 10-oxide (manufactured by Sanko Co., Ltd., trade name HCA-HQ), 10-(1,4-dihydroxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter described It is HCA-NQ), diphenylphosphinohydroquinone (manufactured by Beixing Chemical Industry Co., Ltd., trade name PPQ), diphenylphenylphosphino-1,4-dihydroxynaphthalene, 1,4-extension Cycloctylphosphinyloxy-1,4-benzenediol (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO-HQ), 1,5-cyclooctylphosphinyloxy-1,4-benzenediol ( Manufactured by Nippon Chemical Industry Co., Ltd. under the trade name CPHO-HQ) and other phosphorus-containing phenols, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanguang Co., Ltd., Trade name HCA), a mixture of 1,4-cyclooctylphosphine oxide and 1,5-cyclooctylphosphine oxide (manufactured by Nippon Chemical Industry Co., Ltd., trade name CPHO), diphenylphosphine oxide, etc., but Not limited to these.
又，於合成含磷環氧樹脂時與上述磷化合物反應之環氧樹脂於分子內具有至少1.5個環氧基，更佳為具有2個以上。尤其於併用通式(3)之磷化合物之情形時，較佳為使用具有3個以上之環氧基者。作為環氧樹脂之例，可列舉：Epotohto YD-128、Epotohto YD-8125(新日鐵住金化學股份有限公司製造，雙酚A型環氧樹脂)、Epotohto YDF-170、Epotohto YDF-8170(新日鐵住金化學股份有限公司製造，雙酚F型環氧樹脂)、YSLV-80XY(新日鐵住金化學股份有限公司製造，四甲基雙酚F型環氧樹脂)、Epotohto YDC-1312(新日鐵住金化學股份有限公司製造，對苯二酚型環氧樹脂)、jER YX-4000H(三菱化學股份有限公司製造，聯苯型環氧樹脂)、Epotohto YDPN-638、Epotohto YDPN-63X(新日鐵住金化學股份有限公司製造，苯酚酚醛清漆型環氧樹脂)、Epotohto YDCN-701(新日鐵住金化學股份有限公司製造，甲酚酚醛清漆型環氧樹脂)、Epotohto ZX-1201(新日鐵住金化學股份有限公司製造，雙酚茀型環氧樹脂)、TX-0710(新日鐵住金化學股份有限公司製造，雙酚S型環氧樹脂)、Epiclon EXA-1515(大日本化學工業股份有限公司製造，雙酚S型環氧樹脂)、NC-3000(日本化藥股份有限公司製造，聯苯芳烷基苯酚型環氧樹脂)、Epotohto ZX-1355、Epotohto ZX-1711(新日鐵住金化學股份有限公司製造，萘二酚型環氧樹脂)、Epotohto ESN-155(新日鐵住金化學股份有限公司製造，β-萘酚芳烷基型環氧樹脂)、Epotohto ESN-355、Epotohto ESN-375(新日鐵住金化學股份有限公司製造，二萘酚芳烷基型環氧樹脂)、Epotohto ESN475V，Epotohto ESN-485(新日鐵住金化學股份有限公司製造，α-萘酚芳烷基型環氧樹脂)、EPPN-501H(日本化藥股份有限公司製造，三苯基甲烷型環氧樹脂)、Sumiepoxy TMH-574(住友化學
股份有限公司製造，三苯基甲烷型環氧樹脂)、YSLV-120TE(新日鐵住金化學股份有限公司製造，雙硫醚型環氧樹脂)、Epotohto ZX-1684(新日鐵住金化學股份有限公司製造，間苯二酚型環氧樹脂)、Denacol EX-201(Nagase ChemteX股份有限公司製造，間苯二酚型環氧樹脂)、Epiclon HP-7200H(DIC股份有限公司製造，二環戊二烯型環氧樹脂)等由多酚樹脂之酚化合物與表鹵醇所製造之環氧樹脂、TX-0929、TX-0934、TX-1032(新日鐵住金化學股份有限公司製造，伸烷基二醇型環氧樹脂)等由醇化合物與表鹵醇所製造之環氧樹脂、Celloxide 2021(大賽璐化學工業股份有限公司製造，脂肪族環狀環氧樹脂)、Epotohto YH-434(新日鐵住金化學股份有限公司製造，二胺基二苯基甲烷四環氧丙胺)等由胺化合物與表鹵醇所製造之環氧樹脂、jER 630(三菱化學股份有限公司製造，胺基苯酚型環氧樹脂)、Epotohto FX-289B、Epotohto FX-305、TX-0932A(新日鐵住金化學股份有限公司製造，含磷環氧樹脂)等使環氧樹脂與磷化合物等改質劑反應而獲得之含磷環氧樹脂、胺酯(urethane)改質環氧樹脂、含
上述通式(2)及/或上述通式(3)之磷化合物與環氧樹脂之反應可使用包括專利文獻1、2、3所記載之方法在內之作為酚化合物與環氧樹脂之反應方法之Advance法等公知公用之方法。此時，關於磷化合物與環氧樹脂之比率，反應後所獲得之含磷環氧樹脂之含磷率必須設為2~7質量%之範圍，更佳為2.5~5質量%之範圍。若含磷率較少，則有本發明所使用之含磷之酚化合物與含磷環氧樹脂之溶解性變差之虞，若含磷率較多，則有含磷環氧樹脂之黏度變高，溶解含磷之酚化合物亦變得困難之虞。 The reaction of the phosphorus compound of the general formula (2) and/or the general formula (3) with the epoxy resin can be used as the reaction of the phenol compound and the epoxy resin including the methods described in Patent Documents 1, 2, and 3. The advancement method and other publicly known methods. At this time, regarding the ratio of the phosphorus compound to the epoxy resin, the phosphorus content of the phosphorus-containing epoxy resin obtained after the reaction must be set in the range of 2 to 7 mass%, more preferably in the range of 2.5 to 5 mass%. If the phosphorus content is low, the solubility of the phosphorus-containing phenol compound used in the present invention and the phosphorus-containing epoxy resin may be deteriorated. If the phosphorus content is high, the viscosity of the phosphorus-containing epoxy resin may change High, dissolving phosphorus-containing phenol compounds also becomes difficult.
又，於磷化合物與環氧樹脂之反應中，可視需要為了促進反應而使用反應觸媒。作為可使用之觸媒，例如，可列舉：三苯基膦、三(2,6-二甲氧基苯基)膦等膦類，正丁基三苯基溴化鏻、乙基三苯基碘化鏻等四級鏻鹽類，2-乙基-4-甲咪唑、2-苯咪唑等咪唑類，四甲基氯化銨、四乙基溴化銨等四級銨鹽類，三乙胺、二甲苄胺等三級胺類等公知慣用之觸媒，但並不限定於該等。關於使用該等觸媒之情形之使用量，相對於環氧樹脂與磷化合物之合計質量100份，較佳為0.002~2質量份之範圍。若量變多，則有對本發明之含磷環氧樹脂組成物之穩定性造成不良影響之虞。 In addition, in the reaction between the phosphorus compound and the epoxy resin, a reaction catalyst may be used as necessary to promote the reaction. Examples of usable catalysts include phosphines such as triphenylphosphine and tri(2,6-dimethoxyphenyl)phosphine, n-butyltriphenylphosphonium bromide, and ethyltriphenylphosphonium. Quaternary phosphonium salts such as phosphonium iodide, imidazoles such as 2-ethyl-4-methylimidazole and 2-benzimidazole, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide, triethyl Well-known and commonly used catalysts such as amines and tertiary amines such as tertiary amines are not limited to these. The amount of use in the case of using these catalysts is preferably in the range of 0.002 to 2 parts by mass relative to 100 parts by mass of the total mass of epoxy resin and phosphorus compound. If the amount is increased, there is a possibility of adversely affecting the stability of the phosphorus-containing epoxy resin composition of the present invention.
作為溶解於含磷環氧樹脂之含磷之酚化合物，為具有上述通式(2)所示之結構者。具體而言，例如可列舉：HCA-HQ、HCA-NQ、PPQ、二苯基苯膦基-1,4-二羥基萘、CPHO-HQ、CPHO-HQ等含磷之酚類，但並不限定於該等。又，該等含磷之酚化合物亦可併用2種以上。 The phosphorus-containing phenol compound dissolved in the phosphorus-containing epoxy resin has a structure represented by the general formula (2). Specifically, for example, phosphorus-containing phenols such as HCA-HQ, HCA-NQ, PPQ, diphenylphenylphosphino-1,4-dihydroxynaphthalene, CPHO-HQ, CPHO-HQ, etc., but not Limited to such. In addition, these phosphorus-containing phenol compounds may be used in combination of two or more.
又，該等含磷之酚化合物可藉由上述通式(3)之化合物、具體而言例如HCA或二苯基膦等具有直接鍵結於磷原子之活性氫基之磷化合物與1,4-苯醌或1,4-萘醌等醌類之反應而獲得。關於該等合成法，於專利文獻7、專利文獻8、非專利文獻1中示有合成方法，但並不限定於此。又，亦可於含磷環氧樹脂中合成含磷之酚化合物。 In addition, these phosphorus-containing phenol compounds can be selected from the compounds of the above general formula (3), specifically, such as HCA or diphenylphosphine, which have an active hydrogen group directly bonded to a phosphorus atom and 1,4 -Obtained by the reaction of quinones such as benzoquinone or 1,4-naphthoquinone. Regarding these synthesis methods, Patent Document 7, Patent Document 8, and Non-Patent Document 1 show synthesis methods, but it is not limited thereto. In addition, phosphorus-containing phenol compounds can also be synthesized in phosphorus-containing epoxy resins.
本發明之特徵在於：於特定之含磷環氧樹脂中溶解特定之含磷之酚化合物，所謂於含磷環氧樹脂中溶解有含磷之酚化合物之狀態，意指於室溫下於含磷環氧樹脂中未觀察到含磷之酚樹脂之固體。具體而言，意指如下狀態：於含磷環氧樹脂組成物為固體之情形時，藉由加熱熔融等而消泡，於液體之情形時直接消泡，於23℃之環境下，使用20倍之顯微鏡 確認到源自含磷之酚化合物之固體未析出。又，意指如下狀態：於含磷環氧樹脂組成物溶解於溶劑之情形時，藉由直接於室溫下利用20倍之顯微鏡觀察，確認源自含磷之酚化合物之固體未析出。 The present invention is characterized in that a specific phosphorus-containing phenol compound is dissolved in a specific phosphorus-containing epoxy resin. The state in which the phosphorus-containing phenol compound is dissolved in the phosphorus-containing epoxy resin means that it contains No phosphorus-containing phenol resin solids were observed in the phosphorus epoxy resin. Specifically, it means a state where the phosphorus-containing epoxy resin composition is solid, defoamed by heating and melting, etc., and defoamed directly in the case of liquid, and used in an environment of 23° C. for 20 Microscope It was confirmed that the solid derived from the phosphorus-containing phenol compound did not precipitate. In addition, it means a state where, when the phosphorus-containing epoxy resin composition is dissolved in a solvent, by directly observing with a microscope at 20 times at room temperature, it is confirmed that the solid derived from the phosphorus-containing phenol compound is not precipitated.
針對使含磷之酚化合物溶解於含磷環氧樹脂之方法，並無特別規定，可將事先合成或市售之含磷之酚化合物混合於含磷環氧樹脂內，又亦可藉由於含磷環氧樹脂內合成含磷之酚化合物而獲得目標之含磷環氧樹脂組成物。進而，亦可藉由使含磷之酚化合物與表鹵醇反應而一面合成含磷環氧樹脂一面溶解殘存之磷化合物。 There is no specific requirement for the method of dissolving the phosphorus-containing phenol compound in the phosphorus-containing epoxy resin. The phosphorus-containing phenol compound synthesized in advance or commercially available can be mixed in the phosphorus-containing epoxy resin. A phosphorus-containing phenol compound is synthesized in the phosphorus epoxy resin to obtain the target phosphorus-containing epoxy resin composition. Furthermore, it is also possible to dissolve the remaining phosphorus compound while synthesizing the phosphorus-containing epoxy resin by reacting the phosphorus-containing phenol compound with epihalohydrin.
含磷之酚化合物對含磷環氧樹脂之溶解可無溶劑、或者併用溶劑進行，可藉由進行不會產生含磷環氧樹脂與含磷之酚化合物之反應之程度的加熱攪拌而溶解。 The dissolution of the phosphorus-containing phenol compound to the phosphorus-containing epoxy resin can be performed without a solvent or a combination of solvents, and can be dissolved by heating and stirring to the extent that no reaction between the phosphorus-containing epoxy resin and the phosphorus-containing phenol compound occurs.
於在含磷環氧樹脂中合成含磷之酚化合物之情形時，可於含磷環氧樹脂中添加上述通式(3)之磷化合物及醌化合物進行反應。該反應中，較佳為併用溶劑。作為可使用之溶劑，較佳為非質子性溶劑，例如，可列舉甲苯、二甲苯、甲醇、乙醇、2-丁氧基乙醇、二烷基醚、二醇醚、丙二醇單甲醚、二
關於調整使含磷之酚化合物與表鹵醇反應時之反應比率、反應條件，亦可調整含磷環氧樹脂中溶解有含磷之酚化合物的環氧樹脂組成物。 Regarding the adjustment of the reaction ratio and reaction conditions when the phosphorus-containing phenol compound and epihalohydrin are reacted, the epoxy resin composition in which the phosphorus-containing phenol compound is dissolved in the phosphorus-containing epoxy resin can also be adjusted.
含磷之酚化合物缺乏對有機溶劑之溶解性，故無論藉由任一方法，若溶劑之使用量過多，則均有含磷之酚化合物不溶解於含磷環氧樹 脂中而析出之虞，故作為有機溶劑量，較佳為含磷環氧樹脂組成物總質量中之50質量%以下。 Phosphorus-containing phenol compounds lack solubility in organic solvents, so no matter which method is used, if too much solvent is used, the phosphorus-containing phenol compounds will not dissolve in the phosphorus-containing epoxy tree There is a possibility of precipitation in the fat, so the amount of the organic solvent is preferably 50% by mass or less of the total mass of the phosphorus-containing epoxy resin composition.
又，任一方法中進行溶解時之溫度均較佳為100~200℃，更佳為120~160℃。若溶解溫度較低，則有溶解速度變慢之虞，若溶解溫度較高，則有酚基與環氧基之反應與溶解一併進行，黏度變高，故變得難以操作之虞。 In addition, the temperature during the dissolution in any method is preferably 100 to 200°C, more preferably 120 to 160°C. If the dissolution temperature is low, the dissolution rate may become slow. If the dissolution temperature is high, the reaction of the phenol group and the epoxy group may proceed together with the dissolution, and the viscosity may become high, making it difficult to handle.
又，關於此處所使用之含磷之酚化合物，相對於含磷環氧樹脂100質量份，必須設為5~45質量份，就難燃性之觀點而言，進而理想為設為10~45質量份。於含磷之酚化合物少於5質量份之情形時，為了獲得難燃性，必須提高含磷環氧樹脂之含磷率，樹脂黏度變高，故含磷之酚樹脂之溶解變難，於含磷環氧樹脂之含磷率較低之情形時，雖容易溶解，但無法獲得難燃性。於含磷之酚化合物較多之情形時，有未完全溶解之虞。 In addition, the phosphorus-containing phenol compound used here must be 5 to 45 parts by mass relative to 100 parts by mass of the phosphorus-containing epoxy resin, and from the viewpoint of flame retardancy, it is more preferably 10 to 45 Quality parts. In the case where the phosphorus-containing phenol compound is less than 5 parts by mass, in order to obtain flame retardancy, it is necessary to increase the phosphorus content of the phosphorus-containing epoxy resin, and the resin viscosity becomes high, so the dissolution of the phosphorus-containing phenol resin becomes difficult. When the phosphorus content of the phosphorus-containing epoxy resin is low, although it is easy to dissolve, flame retardancy cannot be obtained. When there are many phosphorus-containing phenol compounds, it may not be completely dissolved.
再者，於稱為本發明之含磷環氧樹脂組成物時，只要無特別說明，則以包含以下全部之含義而使用：由具有通式(1)之結構之含磷環氧樹脂及通式(2)所表示之含磷之酚化合物所構成之含磷環氧樹脂組成物(a)、由具有通式(1)之結構之含磷環氧樹脂、通式(2)所表示之含磷之酚化合物及環氧樹脂(B)所構成之含磷環氧樹脂組成物(b)、由具有通式(1)之結構之含磷環氧樹脂、通式(2)所表示之含磷之酚化合物及硬化劑(C)所構成之含磷環氧樹脂組成物(c1)、及由具有通式(1)之結構之含磷環氧樹脂、通式(2)所表示之含磷之酚化合物、環氧樹脂(B)及硬化劑(C)所構成之含磷環氧樹脂組成物(c2)，文理上明確之情形時，表示各任意之含磷環氧樹脂組成物。又，於對各含磷環氧樹脂組成物進而摻合 某物之情形時，將構成各含磷環氧樹脂組成物之各成分之總合計作為基準。即，於對含磷環氧樹脂組成物(a)進而摻合某物之情形時，具有通式(1)之結構之含磷環氧樹脂及通式(2)所表示之含磷之酚化合物2成分之合計量成為基準，於對含磷環氧樹脂組成物(c2)進而摻合某物之情形時，具有通式(1)之結構之含磷環氧樹脂、通式(2)所表示之含磷之酚化合物、環氧樹脂(B)及硬化劑(C)4成分之合計量成為基準。 In addition, when referred to as the phosphorus-containing epoxy resin composition of the present invention, unless otherwise specified, it is used to include the following meanings: the phosphorus-containing epoxy resin having the structure of the general formula (1) and The phosphorus-containing epoxy resin composition (a) composed of the phosphorus-containing phenol compound represented by the formula (2), represented by the phosphorus-containing epoxy resin having the structure of the general formula (1), and represented by the general formula (2) The phosphorus-containing epoxy resin composition (b) composed of a phosphorus-containing phenol compound and an epoxy resin (B), represented by a phosphorus-containing epoxy resin having the structure of general formula (1), and general formula (2) The phosphorus-containing epoxy resin composition (c1) composed of a phosphorus-containing phenol compound and a hardener (C), and represented by the phosphorus-containing epoxy resin having the structure of the general formula (1), the general formula (2) Phosphorus-containing epoxy resin composition (c2) composed of a phosphorus-containing phenol compound, an epoxy resin (B) and a hardener (C), when the situation is clear in the art, it means each of the phosphorus-containing epoxy resin compositions . In addition, it is further blended with each phosphorus-containing epoxy resin composition In the case of something, the total sum of the components that make up each phosphorus-containing epoxy resin composition is used as a reference. That is, in the case where the phosphorus-containing epoxy resin composition (a) is further blended, the phosphorus-containing epoxy resin having the structure of the general formula (1) and the phosphorus-containing phenol represented by the general formula (2) The total amount of the compound 2 component becomes the standard. In the case where the phosphorus-containing epoxy resin composition (c2) is further blended, the phosphorus-containing epoxy resin having the structure of the general formula (1), the general formula (2) The total amount of the four components of the phosphorus-containing phenol compound, epoxy resin (B), and hardener (C) shown becomes the standard.
可對本發明之含磷環氧樹脂組成物(a)進而添加環氧樹脂(B)。於該情形時，混合環氧樹脂(B)之方法並無特別規定，可使用通常使用之方法進行。又，加熱混合之情形時，較理想為於200℃以下進行，進而理想為於160℃以下進行。混合溫度為200℃以上時，有產生含磷環氧樹脂組成物(b)中之環氧基之反應，黏度變高，操作變得困難之可能性。 An epoxy resin (B) may be further added to the phosphorus-containing epoxy resin composition (a) of the present invention. In this case, the method of mixing the epoxy resin (B) is not particularly limited, and it can be carried out by a commonly used method. In the case of heating and mixing, it is more preferably performed at 200°C or lower, and further preferably 160°C or lower. When the mixing temperature is 200° C. or higher, the reaction of the epoxy group in the phosphorus-containing epoxy resin composition (b) may occur, the viscosity may increase, and the operation may become difficult.
作為此處所使用之環氧樹脂(B)，與合成含磷環氧樹脂時所使用之環氧樹脂同樣地於分子內具有至少1.5個環氧基，更佳為具有2個以上者。該等環氧樹脂可單獨使用，或組合2種以上使用。 The epoxy resin (B) used here has at least 1.5 epoxy groups in the molecule, more preferably two or more, as in the epoxy resin used in the synthesis of the phosphorus-containing epoxy resin. These epoxy resins can be used alone or in combination of two or more.
此時，關於環氧樹脂(B)之量，就難燃性之觀點而言，較佳為將添加環氧樹脂(B)之含磷環氧樹脂組成物(b)整體之含磷率設為2質量%以上。若含磷環氧樹脂組成物(b)中之含磷率較少，則有不表現難燃性之虞。 At this time, regarding the amount of the epoxy resin (B), from the viewpoint of flame retardancy, it is preferable to set the phosphorus content rate of the entire phosphorus-containing epoxy resin composition (b) to which the epoxy resin (B) is added. More than 2% by mass. If the phosphorus-containing rate in the phosphorus-containing epoxy resin composition (b) is small, there is a possibility that flame retardancy will not be exhibited.
作為可用於本發明之含磷環氧樹脂組成物[(a)或(b)]之硬化劑(C)，可使用用於環氧樹脂之公知公用者，具體而言，例如可列舉：鄰苯二酚、間苯二酚、對苯二酚等羥基苯類，聯萘酚類、聯苯酚類、三苯酚類、雙酚A、雙酚F、雙酚S、三羥基苯基甲烷、三羥基苯基乙烷、Shonol
BRG-555(昭和電工股份有限公司製造之苯酚酚醛清漆樹脂)、甲酚酚醛清漆樹脂、烷基苯酚酚醛清漆樹脂、芳烷基苯酚酚醛清漆樹脂、含三
對於本發明之含磷環氧樹脂組成物，於調整流動性或黏度等之情形時，可於不損害物性之範圍使用稀釋劑。稀釋劑較佳為反應性稀釋 劑，亦可為非反應性稀釋劑。作為反應性稀釋劑，可列舉：烯丙基環氧丙醚、2-乙基己基環氧丙醚、苯基環氧丙醚等單官能環氧丙醚類，間苯二酚環氧丙醚、新戊二醇環氧丙醚、1,6-己二醇二環氧丙醚等二官能環氧丙醚類，甘油聚環氧丙醚、三羥甲基丙烷聚環氧丙醚、新戊四醇聚環氧丙醚等多官能環氧丙醚類。作為非反應性稀釋劑，可列舉：苄醇、二乙二醇丁醚、松油等。關於該等稀釋劑，相對於含磷環氧樹脂組成物100質量份，較佳為設為30質量份以下。若稀釋劑之添加量較多，則於非反應性稀釋劑之情形時有產生自硬化物之滲出之虞，於反應性稀釋劑之情形時亦有硬化反應未充分進行而滲出之虞。 For the phosphorus-containing epoxy resin composition of the present invention, when adjusting fluidity, viscosity, etc., a diluent can be used in a range that does not impair physical properties. The diluent is preferably reactive dilution The agent can also be a non-reactive diluent. Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether, and resorcinol glycidyl ether. , Neopentyl glycol glycidyl ether, 1,6-hexanediol diglycidyl ether and other bifunctional glycidyl ethers, glycerin polypropylene oxide, trimethylol propane polypropylene oxide, new Multifunctional glycidyl ethers such as pentaerythritol polyglycidyl ether. Examples of non-reactive diluents include benzyl alcohol, diethylene glycol butyl ether, and pine oil. The diluent is preferably 30 parts by mass or less with respect to 100 parts by mass of the phosphorus-containing epoxy resin composition. If the amount of the diluent added is large, there may be bleed out from the hardened material in the case of non-reactive diluent, and there may be bleed out in the case of the reactive diluent that the hardening reaction does not proceed sufficiently.
又，可於本發明之含磷環氧樹脂組成物中視需要使用硬化促進劑。例如，可列舉：膦類、四級鏻鹽類、三級胺類、四級銨鹽類、咪唑化合物類、三氟化硼錯合物類、3-(3,4-二氯二苯基)-1,1-二甲基脲、3-(4-氯苯基)-1,1-二甲基脲、3-苯基-1,1-二甲基脲等。該等硬化促進劑根據所使用之環氧樹脂、併用之環氧樹脂硬化劑之種類、成形方法、硬化溫度、其他要求特性而異，相對於含磷環氧樹脂組成物100質量份，較佳為0.01~10質量份之範圍。 In addition, a hardening accelerator may be used in the phosphorus-containing epoxy resin composition of the present invention as needed. For example, phosphines, quaternary phosphonium salts, tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3-(3,4-dichlorodiphenyl) )-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, etc. These hardening accelerators vary according to the type of epoxy resin used, the epoxy resin hardener used together, the molding method, the curing temperature, and other required characteristics, and are preferably 100 parts by mass of the phosphorus-containing epoxy resin composition. 0.01 to 10 parts by mass.
關於本發明之含磷環氧樹脂組成物，亦可於不損害特性之範圍摻合其他熱硬化性樹脂、熱塑性樹脂。例如可列舉：酚樹脂、丙烯酸樹脂、石油樹脂、茚樹脂、薰草哢-茚樹脂、苯氧基樹脂、聚胺酯、聚酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、聚醚碸、聚碸、聚醚醚酮、聚苯硫醚、聚乙烯醇縮甲醛、苯乙烯順丁烯二酸樹脂等，但並不限定於該等。關於該等熱硬化性樹脂、熱塑性樹脂，較理想為以相對於含磷環氧樹 脂組成物100質量份不超過50質量份之方式摻合。於摻合量超過50質量份之情形時，有硬化物中之含磷率降低，無法獲得充分之難燃性之虞。 With regard to the phosphorus-containing epoxy resin composition of the present invention, other thermosetting resins and thermoplastic resins may be blended as long as the properties are not impaired. Examples include: phenol resin, acrylic resin, petroleum resin, indene resin, lavender-indene resin, phenoxy resin, polyurethane, polyester, polyamide, polyimide, polyimide, imide, poly Etherimine, polyether sulfone, poly sulfone, polyether ether ketone, polyphenylene sulfide, polyvinyl formal, styrene maleic acid resin, etc., but not limited to these. Regarding these thermosetting resins and thermoplastic resins, it is preferable The fat composition is blended in such a way that 100 parts by mass does not exceed 50 parts by mass. When the blending amount exceeds 50 parts by mass, the phosphorus content in the hardened product may decrease, and sufficient flame retardancy may not be obtained.
關於本發明之含磷環氧樹脂組成物，可視需要摻合無機填充劑、有機填充劑。作為填充劑之例，可列舉：熔融二氧化矽、結晶二氧化矽、氧化鋁、氮化矽、氫氧化鋁、軟水鋁石、滑石、焙燒滑石、黏土、高嶺土、雲母、碳酸鈣、矽酸鈣、氫氧化鈣、氫氧化鎂、碳酸鎂、碳酸鋇、硫酸鋇、氮化硼、氧化鈦、玻璃粉末、二氧化矽(silica)中空球、碳、碳纖維、玻璃纖維、氧化鋁纖維、二氧化矽-氧化鋁纖維、碳化矽纖維、聚酯纖維、纖維素纖維、芳族聚醯胺纖維、合成纖維、陶瓷纖維等。關於該等填充劑，相對於含磷環氧樹脂組成物100質量份，較佳為1~80質量份。若較少，則不表現無機填充劑、有機填充劑之特性，若較多，則有硬化後亦變脆，硬化物無法獲得充分之機械物性之虞。 With regard to the phosphorus-containing epoxy resin composition of the present invention, an inorganic filler and an organic filler may be blended as necessary. Examples of fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, talc, roasted talc, clay, kaolin, mica, calcium carbonate, and silicic acid. Calcium, calcium hydroxide, magnesium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, titanium oxide, glass powder, silica hollow ball, carbon, carbon fiber, glass fiber, alumina fiber, Silicon oxide-alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aromatic polyamide fiber, synthetic fiber, ceramic fiber, etc. The filler is preferably 1 to 80 parts by mass relative to 100 parts by mass of the phosphorus-containing epoxy resin composition. If it is less, the characteristics of the inorganic filler and the organic filler are not expressed, and if it is more, it may become brittle after curing, and the cured product may not obtain sufficient mechanical properties.
關於本發明之含磷環氧樹脂組成物，亦可進而視需要摻合矽烷偶合劑、抗氧化劑、脫模劑、消泡劑、乳化劑、觸變性賦予劑、平滑劑、難燃劑、顏料等各種添加劑。該等添加劑較佳為樹脂組成物總質量中之0.01~20質量%之範圍。 The phosphorus-containing epoxy resin composition of the present invention may further be blended with silane coupling agent, antioxidant, mold release agent, defoamer, emulsifier, thixotropy-imparting agent, smoothing agent, flame retardant, pigment And other additives. These additives are preferably in the range of 0.01 to 20% by mass in the total mass of the resin composition.
本發明之含磷環氧樹脂組成物可藉由與公知之環氧樹脂組成物相同之方法進行硬化而製成硬化物。溶解於含磷環氧樹脂之酚化合物與含磷環氧樹脂或環氧樹脂(B)之環氧基產生硬化反應，有助於硬化。然而，硬化方法可採用與公知之環氧樹脂組成物相同之方法，不需要本發明之樹脂組成物固有之方法。 The phosphorus-containing epoxy resin composition of the present invention can be cured by the same method as a known epoxy resin composition to produce a cured product. The phenol compound dissolved in the phosphorus-containing epoxy resin has a hardening reaction with the epoxy group of the phosphorus-containing epoxy resin or epoxy resin (B), which helps hardening. However, the hardening method may use the same method as the known epoxy resin composition, and does not require the method inherent to the resin composition of the present invention.
本發明之含磷環氧樹脂組成物可藉由含浸於纖維狀基材而 製成印刷配線板等中所使用之預浸體。作為纖維狀基材，可使用玻璃等之無機纖維、或聚酯等、聚胺、聚丙烯酸、聚醯亞胺、克維拉等之有機質纖維之織布或不織布，但並不限定於此。作為由本發明之含磷環氧樹脂組成物製造預浸體之方法，並無特別限定，例如係浸漬於將上述含磷環氧樹脂組成物利用溶劑進行黏度調整而製成之樹脂清漆加以含浸後，加熱乾燥，將樹脂成分半硬化(B階段化)而獲得者，例如可以100~200℃加熱乾燥1~40分鐘。此處，關於預浸體中之樹脂量，較佳為將樹脂成分設為30~80質量%。 The phosphorus-containing epoxy resin composition of the present invention can be impregnated with a fibrous substrate A prepreg used in printed wiring boards, etc. As the fibrous base material, woven fabrics or non-woven fabrics of inorganic fibers such as glass, organic fibers such as polyester, polyamine, polyacrylic acid, polyimide, and kevira can be used, but it is not limited thereto. The method for producing a prepreg from the phosphorus-containing epoxy resin composition of the present invention is not particularly limited. For example, it is impregnated with a resin varnish made by adjusting the viscosity of the phosphorus-containing epoxy resin composition with a solvent and then impregnating , Heat-dried, and obtained by semi-hardening the resin component (stage B), for example, it can be heated and dried at 100 to 200°C for 1 to 40 minutes. Here, regarding the amount of resin in the prepreg, it is preferable to set the resin component to 30 to 80% by mass.
又，為了將利用上述方式製成之預浸體硬化，可使用通常製造印刷配線板時所使用之積層板之硬化方法，但並不限定於此。例如，於使用預浸體形成積層板之情形時，將預浸體積層一片或複數片，於單側或兩側配置金屬箔而構成積層物，對該積層物加熱、加壓，進行積層一體化。此處，作為金屬箔，可使用銅、鋁、黃銅、鎳等之單獨、合金、複合之金屬箔。可藉由將此處製成之積層物加壓加熱，使預浸體硬化而獲得積層板，藉由將溫度設為160~220℃、壓力設為50~500N/cm2、加熱加壓時間設為40~240分鐘，可獲得目標之硬化物。若加熱溫度較低，則硬化反應未充分地進行，若較高，則有含磷環氧樹脂組成物開始分解之虞。又，若加壓壓力較低，則有樹脂流動，無法獲得希望厚度之硬化物的可能性。進而，若加熱加壓時間較短，則有硬化反應未充分地進行之可能性，若較長，則有產生預浸體中之含磷環氧樹脂組成物之熱分解之可能性。因此，較佳為以上述條件進行管理。 In addition, in order to harden the prepreg produced by the above-mentioned method, a method of hardening a laminate used in the manufacture of a printed wiring board may be used, but it is not limited thereto. For example, in the case of using a prepreg to form a laminate, one or more prepreg volume layers are arranged on one or both sides to form a laminate, and the laminate is heated and pressurized to integrate the laminate Change. Here, as the metal foil, individual, alloy, or composite metal foils of copper, aluminum, brass, nickel, and the like can be used. A laminate can be obtained by pressing and heating the laminate made here to harden the prepreg, by setting the temperature to 160 to 220°C, the pressure to 50 to 500 N/cm 2 , and the heating and pressing time Set to 40~240 minutes to obtain the target hardened product. If the heating temperature is low, the curing reaction does not proceed sufficiently, and if it is high, the phosphorus-containing epoxy resin composition may start to decompose. In addition, if the pressurization pressure is low, the resin may flow, and a cured product of a desired thickness may not be obtained. Furthermore, if the heating and pressurizing time is short, the curing reaction may not proceed sufficiently, and if it is long, the phosphorus-containing epoxy resin composition in the prepreg may thermally decompose. Therefore, it is preferable to manage under the above conditions.
由於本發明之含磷環氧樹脂組成物有較高含磷率，故具有優 異之難燃性，並由於為低黏度，故對玻璃布等纖維狀基材之含浸性良好，作業性優異。可知含磷環氧樹脂硬化物之難燃性或耐熱性、接著性良好，作為電氣-電子零件所使用之密封材料、覆銅積層板、絕緣塗料、難燃塗料、複合材料、絕緣難燃接著劑等之材料有用。 Since the phosphorus-containing epoxy resin composition of the present invention has a high phosphorus content, it has excellent Due to its low flame retardancy and low viscosity, it has good impregnability with fiber base materials such as glass cloth and excellent workability. It is known that the phosphorus-containing epoxy resin hardened material has good flame retardancy, heat resistance, and adhesion, and is used as a sealing material for electrical and electronic parts, a copper-clad laminate, an insulating coating, a flame retardant coating, a composite material, and an insulating flame retardant adhesive Materials such as agents are useful.
以下，基於實施例及比較例具體地說明本發明，但本發明並不限定於以下實施例。又，只要無特別說明，則份表示「質量份」，%表示「質量%」。再者，實施例及比較例之分析方法、測定方法係利用以下方法實施。 Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, unless otherwise specified, the part means "mass part" and% means "mass %". In addition, the analysis method and measurement method of an Example and a comparative example were implemented by the following method.
環氧當量：依據JIS K7236。 Epoxy equivalent: according to JIS K7236.
酚性羥基當量：對試樣添加含有4%之甲醇之THF，並添加10%四丁基氫氧化銨，使用紫外可見分光光度計測定波長400nm至250nm間之吸光度。根據藉由同樣之測定方法求出之校正曲線，以羥基每1當量之試樣之重量的形式求出酚性羥基。 Phenolic hydroxyl equivalent: Add THF containing 4% methanol to the sample, and add 10% tetrabutylammonium hydroxide. Use an ultraviolet-visible spectrophotometer to measure the absorbance between 400nm and 250nm. Based on the calibration curve obtained by the same measurement method, the phenolic hydroxyl group was calculated as the weight of the hydroxyl group per equivalent of the sample.
黏度：使用東機產業股份有限公司製造之B型黏度計TVB-10H，於25℃進行測定。 Viscosity: Use B-type viscometer TVB-10H manufactured by Toki Industry Co., Ltd. to measure at 25℃.
含磷率：對試樣添加硫酸、鹽酸、過氯酸，進行加熱而進行濕式灰化，將全部磷原子製成正磷酸。於硫酸酸性溶液中使偏釩酸鹽及鉬酸鹽反應，測定生成之磷釩鉬酸錯合物於420nm之吸光度，以%表示藉由事先製成之校正曲線求出之磷原子含量。積層板之含磷率係以相對於積層板之樹脂成分之含有率之形式表示。 Phosphorus content: add sulfuric acid, hydrochloric acid, perchloric acid to the sample, heat it to perform wet ashing, and make all phosphor atoms into orthophosphoric acid. The metavanadate and molybdate were reacted in an acidic sulfuric acid solution to determine the absorbance of the generated phosphovanadate-molybdic acid complex at 420 nm, and the percentage of phosphorus atoms determined by a calibration curve prepared in advance was expressed in %. The phosphorus content of the laminate is expressed in terms of the content of the resin component of the laminate.
玻璃轉移溫度：依據IPC-TM650 2.4.25c進行測定。 Glass transition temperature: measured according to IPC-TM650 2.4.25c.
難燃性：依據UL(Underwriter Laboratorics)標準實施測定。評價係以 V-0、V-1、V-2記錄。又，將5根之殘焰時間之合計記錄為殘焰時間合計。 Flame retardancy: Measured according to UL (Underwriter Laboratorics) standards. Evaluation is based on V-0, V-1, V-2 records. In addition, the total residual flame time of 5 roots is recorded as the total residual flame time.
溶解性：於固體之情形時，藉由加熱熔融等進行消泡，於液體之情形時直接消泡，於23℃之環境下使用20倍之顯微鏡，確認源自含磷之酚化合物之固體未析出。以○表示未析出者，以×表示析出者。 Solubility: in the case of solids, defoaming by heating and melting, etc., and in the case of liquids, defoaming directly, using a 20x microscope in an environment of 23°C, confirm that the solids derived from the phosphorus-containing phenol compound are not Precipitate. ○ indicates the unprecipitated person, and × indicates the precipitator.
實施例1 Example 1
對具備攪拌裝置、溫度計、冷凝管、及氮氣導入管之四口可分離式燒瓶中，添加57.7份作為環氧樹脂之苯酚酚醛清漆型環氧樹脂(新日鐵住金化學股份有限公司製造，商品名Epotohto YDPN-638)及42.3份作為磷化合物之9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製造，商品名HCA)，於160℃反應5小時，藉此獲得環氧當量766g/eq、含磷率6.0%之含磷環氧樹脂。對其中添加10份作為含磷之酚化合物之10-(1,4-二羥基萘)-10H-9-氧雜-10-磷雜菲(三光股份有限公司製造，商品名HCA-NQ)，於120℃攪拌2小時，藉此，獲得目標之含磷環氧樹脂組成物。所獲得之含磷環氧樹脂組成物均勻地溶解，含磷率為6.2%。將該含磷環氧樹脂組成物利用甲基乙基酮(以下稱為MEK)稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為9800mPa‧s。 To a four-neck separable flask equipped with a stirring device, a thermometer, a condenser tube, and a nitrogen gas introduction tube, add 57.7 parts of a phenol novolac-type epoxy resin as an epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., commodity Name Epotohto YDPN-638) and 42.3 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanguang Co., Ltd., trade name HCA) as a phosphorus compound at 160°C After 5 hours of reaction, a phosphorus-containing epoxy resin having an epoxy equivalent of 766 g/eq and a phosphorus content of 6.0% was obtained. Add 10 parts of 10-(1,4-dihydroxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene (manufactured by Sanko Co., Ltd., trade name HCA-NQ) as a phosphorus-containing phenol compound, The mixture was stirred at 120°C for 2 hours to obtain the target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 6.2%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting the phosphorus-containing epoxy resin composition with methyl ethyl ketone (hereinafter referred to as MEK) to 70% of the solid content is 9800 mPa‧s.
實施例2 Example 2
作為環氧樹脂，變更為66.2份YDPN-638，作為磷化合物，變更為33.8份HCA，作為含磷之酚化合物，變更為20份10-(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物(三光股份有限公司製造，商品名HCA-HQ)，除此以外，進行與實施例1相同之操作，獲得環氧當量460g/eq、含磷率4.2%之含磷環氧樹脂後，將HCA-HQ溶解，獲得目標之含磷環氧樹脂組成物。所 獲得之含磷環氧樹脂組成物均勻地溶解，含磷率為5.6%。將該含磷環氧樹脂組成物利用MEK稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為1040mPa‧s。 As an epoxy resin, it was changed to 66.2 parts of YDPN-638, as a phosphorus compound, to 33.8 parts of HCA, and as a phosphorus-containing phenol compound, to 20 parts of 10-(2,5-dihydroxyphenyl)-10H-9 -Oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA-HQ), except that the same operation as in Example 1 was carried out to obtain an epoxy equivalent of 460 g/eq, containing After phosphorus-containing epoxy resin with a phosphorus rate of 4.2%, HCA-HQ is dissolved to obtain the target phosphorus-containing epoxy resin composition. Place The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 5.6%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting the phosphorus-containing epoxy resin composition with MEK to 70% of the solid content is 1040 mPa‧s.
實施例3 Example 3
作為環氧樹脂，變更為71.8份YDPN-638，作為磷化合物，變更為28.2份HCA，作為含磷之酚化合物，變更為45份HCA-NQ，除此以外，進行與實施例1相同之操作，獲得環氧當量363g/eq、含磷率4.0%之含磷環氧樹脂後，將HCA-NQ溶解，獲得目標之含磷環氧樹脂組成物。所獲得之含磷環氧樹脂組成物均勻地溶解，含磷率為5.3%。將該含磷環氧樹脂組成物利用MEK稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為1010mPa‧s。 The epoxy resin was changed to 71.8 parts of YDPN-638, the phosphorus compound was changed to 28.2 parts HCA, and the phosphorus-containing phenol compound was changed to 45 parts HCA-NQ, except that the same operation as in Example 1 was carried out. After obtaining a phosphorus-containing epoxy resin with an epoxy equivalent of 363g/eq and a phosphorus content of 4.0%, dissolve HCA-NQ to obtain the target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 5.3%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting the phosphorus-containing epoxy resin composition with MEK to 70% of the solid content is 1010 mPa‧s.
實施例4 Example 4
作為環氧樹脂，變更為84.5份YDPN-638，作為磷化合物，變更為15.5份HCA，作為含磷之酚化合物，變更為40份HCA-NQ，除此以外，進行與實施例1相同之操作，獲得環氧當量247g/eq、含磷率2.2%之含磷環氧樹脂後，將HCA-NQ溶解，獲得目標之含磷環氧樹脂組成物。所獲得之含磷環氧樹脂組成物均勻地溶解，含磷率為3.9%。將該含磷環氧樹脂組成物利用MEK稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為530mPa‧s。 The epoxy resin was changed to 84.5 parts of YDPN-638, the phosphorus compound was changed to 15.5 parts of HCA, and the phosphorus-containing phenol compound was changed to 40 parts of HCA-NQ, except that the same operation as in Example 1 was carried out. After obtaining a phosphorus-containing epoxy resin with an epoxy equivalent of 247g/eq and a phosphorus content of 2.2%, dissolve HCA-NQ to obtain the target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 3.9%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting this phosphorus-containing epoxy resin composition with MEK to 70% of the solid content is 530 mPa‧s.
實施例5 Example 5
作為環氧樹脂，變更為63.8份YDPN-638及10份雙酚F型液狀環氧樹脂(新日鐵住金化學股份有限公司製造，商品名Epotohto YDF-170)，作為 磷化合物，變更為15.6份HCA及10.6份HCA-HQ，作為含磷之酚化合物，變更為5份HCA-NQ，除此以外，進行與實施例1相同之操作，獲得環氧當量355g/eq、含磷率3.2%之含磷環氧樹脂後，將HCA-NQ溶解，獲得目標之含磷環氧樹脂組成物。所獲得之含磷環氧樹脂組成物均勻地溶解，含磷率為3.5%。將該含磷環氧樹脂組成物利用MEK稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為650mPa‧s。 As epoxy resin, it was changed to 63.8 parts of YDPN-638 and 10 parts of bisphenol F liquid epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name Epotohto YDF-170) as The phosphorus compound was changed to 15.6 parts HCA and 10.6 parts HCA-HQ, and the phosphorus-containing phenol compound was changed to 5 parts HCA-NQ, except that the same operation as in Example 1 was performed to obtain an epoxy equivalent of 355 g/eq 3. After phosphorus-containing epoxy resin with phosphorus content of 3.2%, dissolve HCA-NQ to obtain the target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 3.5%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting the phosphorus-containing epoxy resin composition with MEK to 70% of the solid content is 650 mPa‧s.
實施例6 Example 6
作為環氧樹脂，變更為55.6份鄰甲酚酚醛清漆型環氧樹脂(新日鐵住金化學股份有限公司製造，商品名Epotohto YDCN-700-7)及20份YDF-170，作為磷化合物，變更為16.4份HCA及8.0份HCA-NQ，作為含磷之酚化合物，變更為8份HCA-HQ，除此以外，進行與實施例1相同之操作，獲得環氧當量365g/eq、含磷率3.0%之含磷環氧樹脂後，將HCA-HQ溶解，獲得目標之含磷環氧樹脂組成物。所獲得之含磷環氧樹脂組成物均勻地溶解，含磷率為3.5%。將該含磷環氧樹脂組成物利用MEK稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為600mPa‧s。 As epoxy resin, changed to 55.6 parts o-cresol novolac epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name Epotohto YDCN-700-7) and 20 parts YDF-170, as phosphorus compound, changed It was 16.4 parts HCA and 8.0 parts HCA-NQ. As the phosphorus-containing phenol compound, it was changed to 8 parts HCA-HQ. Except that, the same operation as in Example 1 was carried out to obtain an epoxy equivalent of 365 g/eq and a phosphorus content rate After 3.0% phosphorus-containing epoxy resin, HCA-HQ is dissolved to obtain the target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 3.5%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting the phosphorus-containing epoxy resin composition with MEK to 70% of the solid content is 600 mPa‧s.
比較例1 Comparative example 1
對具備攪拌裝置、溫度計、冷凝管、及氮氣導入管之四口可分離式燒瓶中添加100份YDPN-638及28份HCA-NQ，於120℃實施攪拌，但即便進行6小時之攪拌，亦無法完全溶解。 Add 100 parts of YDPN-638 and 28 parts of HCA-NQ to a four-port separable flask equipped with a stirring device, thermometer, condenser, and nitrogen introduction tube, and stir at 120°C, but even after 6 hours of stirring, Not completely dissolved.
比較例2 Comparative example 2
作為環氧樹脂，變更為88份YDPN-638，作為磷化合物，變更為12份HCA，作為含磷之酚化合物，變更為4份HCA-HQ，除此以外，進行與實施 例1相同之操作，獲得環氧當量226g/eq、含磷率1.7%之含磷環氧樹脂後，將HCA-NQ溶解，獲得目標之含磷環氧樹脂組成物。所獲得之含磷環氧樹脂組成物均勻地溶解，含磷率為2.0%。將該含磷環氧樹脂組成物利用MEK稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為500mPa‧s。 Changed to 88 parts of YDPN-638 as epoxy resin, 12 parts of HCA as phosphorus compound, and 4 parts of HCA-HQ as phosphorus-containing phenol compound. In the same operation as in Example 1, after obtaining a phosphorus-containing epoxy resin having an epoxy equivalent of 226 g/eq and a phosphorus content of 1.7%, HCA-NQ was dissolved to obtain the target phosphorus-containing epoxy resin composition. The obtained phosphorus-containing epoxy resin composition was uniformly dissolved, and the phosphorus content was 2.0%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting this phosphorus-containing epoxy resin composition with MEK to 70% of the solid content is 500 mPa‧s.
比較例3 Comparative Example 3
作為環氧樹脂，變更為88份YDPN-638，作為磷化合物，變更為12份HCA，作為含磷之酚化合物，變更為13份HCA-HQ，除此以外，進行與實施例1相同之操作，獲得環氧當量226g/eq、含磷率1.7%之含磷環氧樹脂後，HCA-NQ之結晶不溶解，無法獲得目標之含磷環氧樹脂組成物。 The epoxy resin was changed to 88 parts of YDPN-638, the phosphorus compound was changed to 12 parts of HCA, and the phosphorus-containing phenol compound was changed to 13 parts of HCA-HQ, except that the same operation as Example 1 was carried out. After obtaining a phosphorus-containing epoxy resin with an epoxy equivalent of 226g/eq and a phosphorus content of 1.7%, the crystals of HCA-NQ are not dissolved, and the target phosphorus-containing epoxy resin composition cannot be obtained.
比較例4 Comparative Example 4
作為環氧樹脂，變更為49.3份YDPN-638，作為磷化合物，變更為50.7份HCA，作為含磷之酚化合物，變更為8份HCA-HQ，除此以外，進行與實施例1相同之操作，獲得環氧當量2285g/eq、含磷率7.2%之含磷環氧樹脂後，HCA-NQ之結晶不溶解，無法獲得目標之含磷環氧樹脂組成物。 The epoxy resin was changed to 49.3 parts of YDPN-638, the phosphorus compound was changed to 50.7 parts of HCA, and the phosphorus-containing phenol compound was changed to 8 parts of HCA-HQ, except that the same operation as Example 1 was carried out. After obtaining a phosphorus-containing epoxy resin with an epoxy equivalent of 2285g/eq and a phosphorus content of 7.2%, the crystals of HCA-NQ are not dissolved, and the target phosphorus-containing epoxy resin composition cannot be obtained.
將實施例1~6、及比較例1~4之含磷環氧樹脂組成物之溶解性示於表1。 Table 1 shows the solubility of the phosphorus-containing epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4.
實施例7 Example 7
對實施例3所獲得之含磷環氧樹脂組成物75份添加作為環氧樹脂(B) 之三苯基甲烷型環氧樹脂(日本化藥股份有限公司製造，商品名EPPN-501H)25份、作為硬化劑(C)之苯酚酚醛清漆樹脂(昭和電工股份有限公司製造，商品名Shonol BRG-557)25.6份，作為硬化觸媒之2-乙基-4-甲咪唑(四國化成股份有限公司製造，商品名Curezol 2E4MZ)0.1份，使用MEK使不揮發成分成為50%，獲得樹脂清漆。將所獲得之樹脂清漆含浸於玻璃布(型號調查)後，以150℃進行10分鐘之乾燥，藉此獲得預浸體。將所獲得之預浸體4片及銅箔(三井金屬礦業股份有限公司製造，商品名3EC-III，厚度35μm)重疊，以130℃×15分鐘+190℃×80分鐘之溫度條件以2MPa之壓力進行真空壓製，獲得0.5mm厚之積層板之硬化物。 Add 75 parts of the phosphorus-containing epoxy resin composition obtained in Example 3 as an epoxy resin (B) Triphenylmethane epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name EPPN-501H) 25 parts, phenol novolak resin (manufactured by Showa Denko Co., Ltd., trade name Shonol BRG) as a hardener (C) -557) 25.6 parts, 0.1 parts of 2-ethyl-4-methimidazole (made by Shikoku Chemicals Co., Ltd., trade name Curezol 2E4MZ) as a hardening catalyst, using MEK to make the non-volatile component 50%, and obtain a resin varnish . After impregnating the obtained resin varnish with a glass cloth (model survey), it was dried at 150°C for 10 minutes to obtain a prepreg. 4 pieces of the obtained prepreg and copper foil (Mitsui Metal Mining Co., Ltd., trade name 3EC-III, thickness 35 μm) are overlapped, and the temperature conditions of 130 ℃ × 15 minutes + 190 ℃ × 80 minutes to 2 MPa Vacuum pressing was used to obtain the hardened product of the 0.5 mm thick laminate.
實施例8 Example 8
對於實施例3所獲得之含磷環氧樹脂組成物70份，將作為環氧樹脂(B)之苯乙烯改質苯酚酚醛清漆型環氧樹脂(新日鐵住金化學股份有限公司製造，商品名TX-1210-90)設為30份，將作為硬化劑(C)之雙氰胺(DICY)設為2.0份，將作為硬化觸媒之2E4MZ設為0.9份，除此以外，利用與實施例7相同之方法獲得預浸體及積層板之硬化物。 For 70 parts of the phosphorus-containing epoxy resin composition obtained in Example 3, styrene modified phenol novolak type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name) as epoxy resin (B) TX-1210-90) is set to 30 parts, dicyandiamide (DICY) as hardener (C) is set to 2.0 parts, and 2E4MZ as hardening catalyst is set to 0.9 parts. 7 Obtain the hardened product of prepreg and laminate by the same method.
實施例9 Example 9
對於實施例3所獲得之含磷環氧樹脂組成物70份，將作為環氧樹脂(B)之TX-1210-90設為30份，將作為硬化劑(C)之BRG-557設為19.9份，將作為硬化觸媒之2E4MZ設為0.9份，除此以外，利用與實施例7相同之方法獲得預浸體及積層板之硬化物。 For 70 parts of the phosphorus-containing epoxy resin composition obtained in Example 3, TX-1210-90 as the epoxy resin (B) was set to 30 parts, and BRG-557 as the hardener (C) was set to 19.9 The cured parts of the prepreg and the laminate were obtained by the same method as in Example 7 except that the curing catalyst 2E4MZ was set to 0.9 parts.
實施例10 Example 10
對於實施例3所獲得之含磷環氧樹脂組成物85份，將作為環氧樹脂(B) 之雙酚A型固形環氧樹脂(新日鐵住金化學股份有限公司製造，商品名Epotohto YD-903N)設為15份，將作為硬化劑(C)之DICY設為1.3份，將作為硬化觸媒之2E4MZ設為0.9份，除此以外，利用與實施例7相同之方法獲得預浸體及積層板之硬化物。 85 parts of the phosphorus-containing epoxy resin composition obtained in Example 3 will be used as the epoxy resin (B) Bisphenol A-type solid epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name Epotohto YD-903N) is set to 15 parts, and DICY as a hardener (C) is set to 1.3 parts, which will be used as a hardening contact Except that the 2E4MZ of the medium was set to 0.9 parts, the cured product of the prepreg and the laminate was obtained by the same method as in Example 7.
比較例5 Comparative example 5
對於比較例2所獲得之含磷環氧樹脂組成物70份，將作為環氧樹脂(B)之TX-1210-90設為30份，將作為硬化劑(C)之DICY設為4.4份，將作為硬化觸媒之2E4MZ設為0.9份，除此以外，利用與實施例7相同之方法獲得預浸體及積層板之硬化物。 For 70 parts of the phosphorus-containing epoxy resin composition obtained in Comparative Example 2, TX-1210-90 as the epoxy resin (B) was set to 30 parts, and DICY as the hardener (C) was set to 4.4 parts. The cured product of the prepreg and the laminate was obtained in the same manner as in Example 7 except that the curing catalyst 2E4MZ was set to 0.9 parts.
比較例6 Comparative Example 6
對具備攪拌裝置、溫度計、冷凝管、及氮氣導入裝置之四口之玻璃製之可分離式燒瓶添加23.5份HCA、4.3份1,4-萘醌、及100份甲苯，於75℃進行30分鐘攪拌後，於110℃進行90分鐘脫水反應，然後添加72.2份YDPN-638後，升溫而進行甲苯之去除。其後，添加0.01份作為觸媒之三苯基膦(TPP)，於160℃反應4小時，藉此，獲得環氧當量348g/eq、含磷率1.5%之含磷環氧樹脂。將該含磷環氧樹脂組成物利用MEK稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為1730mPa‧s。 Add 23.5 parts of HCA, 4.3 parts of 1,4-naphthoquinone, and 100 parts of toluene to a four-port glass separable flask equipped with a stirring device, thermometer, condenser, and nitrogen introduction device, and perform at 75°C for 30 minutes After stirring, dehydration reaction was carried out at 110° C. for 90 minutes, then 72.2 parts of YDPN-638 was added, and then the temperature was raised to remove toluene. Thereafter, 0.01 parts of triphenylphosphine (TPP) as a catalyst was added and reacted at 160° C. for 4 hours, thereby obtaining a phosphorus-containing epoxy resin having an epoxy equivalent of 348 g/eq and a phosphorus content rate of 1.5%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting this phosphorus-containing epoxy resin composition with MEK to 70% of the solid content is 1730 mPa‧s.
對於所獲得之含磷環氧樹脂設為70份，將作為環氧樹脂(B)之TX-1210-90設為30份，將作為硬化劑(C)之BRG-557設為24.3份，將作為硬化觸媒之2E4MZ設為0.9份，除此以外，利用與實施例7相同之方法獲得預浸體及積層板之硬化物。 The obtained phosphorus-containing epoxy resin was set to 70 parts, TX-1210-90 as the epoxy resin (B) was set to 30 parts, and BRG-557 as the hardener (C) was set to 24.3 parts. The cured product of the prepreg and the laminate was obtained by the same method as in Example 7 except that the curing catalyst 2E4MZ was set to 0.9 parts.
比較例7 Comparative Example 7
對具備攪拌裝置、溫度計、冷凝管、及氮氣導入管之四口可分離式燒瓶中，添加作為環氧樹脂之64.1份YDPN-638及作為磷化合物之20.9份HCA、15份HCA-HQ，於160℃進行5小時反應，藉此，獲得環氧當量444g/eq、酚性羥基當量1750g/eq、含磷率3.0%之含磷環氧樹脂。將該含磷環氧樹脂組成物利用MEK稀釋為固形物成分70%而成之含磷環氧樹脂組成物清漆之黏度為440mPa‧s。 To a four-neck separable flask equipped with a stirring device, a thermometer, a condenser tube, and a nitrogen introduction tube, add 64.1 parts of YDPN-638 as an epoxy resin and 20.9 parts of HCA and 15 parts of HCA-HQ as a phosphorus compound. The reaction was carried out at 160°C for 5 hours, thereby obtaining a phosphorus-containing epoxy resin having an epoxy equivalent of 444 g/eq, a phenolic hydroxyl equivalent of 1750 g/eq, and a phosphorus content rate of 3.0%. The viscosity of the phosphorus-containing epoxy resin composition varnish prepared by diluting the phosphorus-containing epoxy resin composition with MEK to 70% of the solid content is 440 mPa‧s.
對所獲得之含磷環氧樹脂70份，將作為環氧樹脂(B)之TX-1210-90設為30份，將作為硬化劑(C)之BRG-557設為29.4份，將作為硬化觸媒之2E4MZ設為0.9份，除此以外，利用與實施例7相同之方法獲得預浸體及積層板之硬化物。 For 70 parts of the obtained phosphorus-containing epoxy resin, TX-1210-90 as the epoxy resin (B) was set to 30 parts, and BRG-557 as the hardener (C) was set to 29.4 parts, which was used as the hardening The 2E4MZ of the catalyst was set to 0.9 parts, except that the cured product of the prepreg and the laminate was obtained in the same manner as in Example 7.
將實施例7~10、及比較例5~7之積層板之物性結果示於表2。 Table 2 shows the physical property results of the laminates of Examples 7 to 10 and Comparative Examples 5 to 7.
關於如實施例所示般對含磷環氧樹脂中添加含磷之酚樹脂而成者，確認可於特定之條件下溶解於樹脂中，獲得均勻之組成物。可確認該等化合物黏度充分低，操作性亦良好。又，關於所獲得之硬化物，亦確認表現充分之難燃性。 Regarding those obtained by adding phosphorus-containing phenol resin to the phosphorus-containing epoxy resin as shown in the examples, it was confirmed that they can be dissolved in the resin under specific conditions to obtain a uniform composition. It can be confirmed that these compounds have sufficiently low viscosity and good operability. Also, regarding the obtained hardened product, it was confirmed that the flame retardant exhibited sufficient performance.
相對於此，比較例1中，嘗試使含磷之酚樹脂溶解於不含磷 之環氧樹脂中，但確認含磷之酚化合物未完全溶解，為不均勻之狀態。 In contrast, in Comparative Example 1, an attempt was made to dissolve the phosphorus-containing phenol resin in a phosphorus-free In the epoxy resin, it is confirmed that the phosphorus-containing phenol compound is not completely dissolved and is in a non-uniform state.
比較例2中，使用含磷環氧樹脂使含磷之酚樹脂溶解，但含磷環氧樹脂組成物中之含磷率低於2%，故可溶解之含磷之酚樹脂之量較少，使用該含磷環氧樹脂組成物之積層板之難燃性較低(比較例5)。又，嘗試使含磷之酚樹脂進一步溶解，但未完全溶解，若為比較例3之量，則即便目視亦可確認含磷之酚樹脂析出。 In Comparative Example 2, the phosphorus-containing epoxy resin was used to dissolve the phosphorus-containing phenol resin, but the phosphorus content of the phosphorus-containing epoxy resin composition was less than 2%, so the amount of soluble phosphorus-containing phenol resin was small The laminate using the phosphorus-containing epoxy resin composition has low flame retardancy (Comparative Example 5). In addition, an attempt was made to further dissolve the phosphorus-containing phenol resin, but it was not completely dissolved. If it is the amount of Comparative Example 3, precipitation of the phosphorus-containing phenol resin can be confirmed even by visual observation.
比較例4中，使用含磷環氧樹脂使含磷之酚樹脂溶解，但含磷環氧樹脂組成物中之含磷率超過7%，故含磷環氧樹脂之黏度變高，無法使含磷之酚樹脂溶解。 In Comparative Example 4, the phosphorus-containing epoxy resin was used to dissolve the phosphorus-containing phenol resin, but the phosphorus-containing epoxy resin composition contained more than 7% phosphorus, so the viscosity of the phosphorus-containing epoxy resin became higher and the Phosphorus phenol resin dissolves.
比較例6為使用專利文獻2之含磷環氧樹脂之積層板之評價，難燃性略差，耐熱性亦略差。 Comparative Example 6 is an evaluation of a laminate using a phosphorus-containing epoxy resin of Patent Document 2. The flame retardancy is slightly poor, and the heat resistance is also slightly poor.
比較例7為使用專利文獻4之含磷環氧樹脂之積層板之評價，難燃性略差，耐熱性亦略差。 Comparative Example 7 is an evaluation of a laminate using the phosphorus-containing epoxy resin of Patent Document 4, and the flame retardancy is slightly inferior and the heat resistance is also slightly inferior.
由實施例、比較例可知，於特定之含磷環氧樹脂中溶解有特定之含磷之酚化合物，為低黏度，作業性優異，表現較高之難燃性。又，關於本發明之組成物，可知即便摻合提高耐熱性、介電常數、接著力之環氧樹脂(B)，亦可獲得難燃性，尤其是介電特性變低。 It can be seen from the examples and comparative examples that a specific phosphorus-containing phenol compound dissolved in a specific phosphorus-containing epoxy resin has a low viscosity, is excellent in workability, and exhibits high flame retardancy. In addition, it is known that the composition of the present invention can achieve flame retardancy even if an epoxy resin (B) that improves heat resistance, dielectric constant, and adhesive strength is blended, and particularly has low dielectric properties.
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