CN110938234B - 阻燃性化合物、其制造方法、树脂组合物及其制品 - Google Patents
阻燃性化合物、其制造方法、树脂组合物及其制品 Download PDFInfo
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- CN110938234B CN110938234B CN201811115021.2A CN201811115021A CN110938234B CN 110938234 B CN110938234 B CN 110938234B CN 201811115021 A CN201811115021 A CN 201811115021A CN 110938234 B CN110938234 B CN 110938234B
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- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- -1 Flame-retardant compound Chemical class 0.000 title claims description 48
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- 239000011347 resin Substances 0.000 claims abstract description 146
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- 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 group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 32
- 229910052698 phosphorus Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 20
- 239000004643 cyanate ester Substances 0.000 claims description 18
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
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- DBWGAXVWWNKFNI-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical group [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 DBWGAXVWWNKFNI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
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- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical group C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- XSHWKULGRFTYIT-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C XSHWKULGRFTYIT-UHFFFAOYSA-N 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
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- 230000009477 glass transition Effects 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000004744 fabric Substances 0.000 description 22
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
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- 229910000077 silane Inorganic materials 0.000 description 7
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- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000007928 solubilization Effects 0.000 description 5
- 238000005063 solubilization Methods 0.000 description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- VBQRUYIOTHNGOP-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical group C1=CC=C2P(=O)OC3=CC=CC=C3C2=C1 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
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- 125000005843 halogen group Chemical group 0.000 description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
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- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
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- XDOBJOBITOLMFI-UHFFFAOYSA-N pyrrole-2,5-dione;toluene Chemical compound CC1=CC=CC=C1.O=C1NC(=O)C=C1 XDOBJOBITOLMFI-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000003381 solubilizing effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
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- 239000012745 toughening agent Substances 0.000 description 3
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 2
- IUZZYSCYZLNGRG-UHFFFAOYSA-N [O]P(=O)=O Chemical group [O]P(=O)=O IUZZYSCYZLNGRG-UHFFFAOYSA-N 0.000 description 2
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- AFTLIIOXEHXDOZ-UHFFFAOYSA-N buta-1,3-diene;furan-2,5-dione;styrene Chemical compound C=CC=C.O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 AFTLIIOXEHXDOZ-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- 239000003086 colorant Substances 0.000 description 2
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- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
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- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
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- 150000007527 lewis bases Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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Abstract
本发明公开一种化合物,其可用于树脂组合物中以制作成半固化片、树脂膜、积层板及印刷电路板等物品,使制品在玻璃转化温度、热膨胀率、铜箔拉力、耐热性、介电常数、介电损耗、阻燃性等一个或多个方面得到改善。
Description
技术领域
本发明主要涉及一种阻燃性化合物、其制造方法、树脂组合物及由其制成的物品,特别是关于一种可应用于半固化片、树脂膜、积层板(例如铜箔基板)及印刷电路板的化合物、其制备方法和树脂组合物。
背景技术
印刷电路板的应用范围广泛,例如工业用大型计算机、通讯仪表、电气测量装置、国防及航空产品和民用电器产品等,大多需要通过印刷电路板作为承载各种电子元件的基础。随着科技进步,各种电子产品皆往小型化、多功能化、高性能化及高可靠性等方面迅速发展。因此,印刷电路板也逐渐趋向高精度、高密度、高性能、微孔化、薄型化和多层化等方面发展。
在印刷电路板的制造与后续其他组件的安装过程中,需要经过回焊工艺,使焊料熔融后将表面组件与印刷电路板上的金属线路相连接。一般制作印刷电路板绝缘层的树脂材料经过回焊工艺的高热冲击后,因热膨胀率的不同,容易产生形变,进而造成基板翘曲变形而平整度降低,并引发后续焊接不良(如虚焊或假焊等)的问题。印刷电路板的高密度化引起发热量增大,如何设法降低绝缘层的热膨胀率并且兼顾其他特性,尤其是介电特性、耐热性、阻燃性等等,已成为此领域中亟待解决的问题。
发明内容
有鉴于现有技术的缺陷,特别是现有阻燃性材料使用于绝缘材料提供阻燃性的同时,可能影响或恶化绝缘材料的其他特性,例如热膨胀率或介电特性,本发明提供一种化合物,其可用于树脂组合物中以制作成半固化片、树脂膜、积层板及印刷电路板等物品,使制品在阻燃性、玻璃转化温度、热膨胀率、铜箔拉力、耐热性、介电常数、介电损耗等一个或多个方面得到改善。
本发明提供一种具有以下式(I)所示结构的化合物:
其中,X代表共价键、-C(CH3)2-、-CH(CH3)-、-CH2-、-SO2-、-S-、或-O-;
Q1及Q2各自独立代表含有C=C不饱和键的官能基团;以及
J1及J2各自独立代表含有磷原子的阻燃性官能基团。
举例而言,Q1及Q2可以各自独立代表C2至C6的含有C=C不饱和键的脂烃基。
举例而言,J1及J2可以各自独立含有P=O双键或P-O单键。
例如,J1及J2可以各自独立具有以下结构:
其中,A为氧原子或硫原子;n1为0或1;虚线表示有键合或无键合;以及R1和R2各自独立为含卤素基团、含或不含双键的烷基、含或不含双键的芳基、烷氧基、芳氧基、含硫烷基、含硫芳基、硅烷基或硅氧烷基,且R1和R2可各自独立经取代或未经取代。
在一个实施例中,J1及J2可以各自独立为磷酸二苯酯官能基团(diphenylphosphate,DPP,其不含羟基的部分)、二苯基磷氧官能基团(diphenylphosphine oxide,DPPO,其不含磷氢键的部分)或9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物官能基团(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO,其不含磷氢键的部分),且前述磷酸二苯酯官能基团、二苯基磷氧官能基团或9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物官能基团都可以视需要经取代或未经取代。
举例而言,式(I)所示结构的化合物可以具有以下结构的任一种:
在一个实施例中,式(I)所示结构的化合物的磷含量介于6.0%及9.0%之间。
在一个实施例中,本发明提供一种式(I)所示结构的化合物的制造方法,包括:将含有磷原子的阻燃性官能基团的化合物与含有C=C不饱和键的双酚类化合物进行反应。
在一个实施例中,式(I)所示结构的化合物可以同时用作树脂组合物的交联剂与阻燃剂。
在一个实施例中,本发明还提供一种树脂组合物,包括式(I)所示结构的化合物及树脂。
举例而言,所述树脂可以是含不饱和键树脂,例如包含一个或多个碳-碳双键、碳-氮双键或碳-氮三键的树脂。具体实例包括但不限于聚烯烃、氰酸酯树脂、马来酰亚胺树脂、乙烯基聚苯醚树脂、苯乙烯、二乙烯基苯、三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯及其预聚物或其组合。
在一个实施例中,所述树脂包含极性树脂及非极性树脂,且所述式(I)所示结构的化合物可提高极性树脂及非极性树脂的相容性(即增溶作用)。优选的,极性树脂及非极性树脂之间不发生分层。
若无特别指明,式(I)所示结构的化合物及树脂两者间的用量比例并不特别限制,例如相较于100重量份的树脂,式(I)所示结构的化合物的含量介于1及100重量份之间。
在一个实施例中,本发明还提供一种由前述树脂组合物制成的物品,其包括半固化片、树脂膜、积层板或印刷电路板。优选的,所述物品在玻璃转化温度、热膨胀率、铜箔拉力、耐热性、介电常数、介电损耗、阻燃性等一个或多个方面得到改善。
附图说明
图1为产物式(II)化合物和原料DABPA的FTIR谱图。
图2为原料DABPA的1H NMR谱图。
图3产物式(II)化合物的1H NMR谱图。
图4为产物式(II)化合物和原料DABPA的GPC曲线图。
具体实施方式
为使本领域技术人员可了解本发明的特点及功效,以下谨就说明书及权利要求书中提及的术语及用语进行一般性的说明及定义。除非另有指明,否则文中使用的所有技术及科学上的字词,皆具有本领域技术人员对于本发明所了解的通常意义,当有冲突情形时,应以本说明书的定义为准。
首先,本文某些部分是利用“一”、“一种”、“一个”或类似用语来描述本发明所述的成分和技术特征,此种描述只是为了方便表达,并对本发明的技术特征提供一般性的意义。因此,除非另有指明,否则此种描述应理解为包括一个或至少一个,且单数也同时包括复数。
在本文中,用语“包含”、“包括”、“具有”、“含有”或其他任何类似用语均属于开放性连接词(open-ended transitional phrase),其意图涵盖非排他性的包括物。举例而言,含有多个要素的组合物或制品并不仅限于本文所列出的该要素而已,而是还可包括未明确列出但却是该组合物或制品通常固有的其他要素。除此之外,除非有相反的明确说明,否则用语“或”是指包括性的“或”,而不是指排他性的“或”。例如,以下任何一种情况均满足条件“A或B”:A为真(或存在)且B为伪(或不存在)、A为伪(或不存在)且B为真(或存在)、A和B均为真(或存在)。此外,在本文中,用语“包含”、“包括”、“具有”、“含有”的解读应视为已具体公开并同时涵盖“由…所组成”及“实质上由…所组成”等封闭式或半封闭式连接词。
在本文中,所有以数值范围或百分比范围形式界定的特征或条件仅是为了简洁及方便。据此,数值范围或百分比范围的描述应视为已涵盖且具体公开所有可能的次范围及范围内的个别数值,特别是整数数值。举例而言,“1至8”的范围描述应视为已经具体公开如1至7、2至8、2至6、3至6、4至8、3至8等等所有次范围,特别是由所有整数数值所界定的次范围,且应视为已经具体公开范围内如1、2、3、4、5、6、7、8等个别数值。除非另有指明,否则前述解释方法适用于本发明全文的所有内容,不论范围广泛与否。
如果数量或其他数值或参数是以范围、优选范围或一系列上限与下限表示,则其应理解成是本文已特定公开了由任一对该范围的上限或优选值与该范围的下限或优选值构成的所有范围,不论该等范围是否有分别公开。此外,本文中若提到数值的范围时,除非另有说明,否则该范围应包括其端点以及范围内的所有整数与分数。
在本文中,在可达成发明目的的前提下,数值应理解成具有该数值有效位数的精确度。举例来说,数字40.0则应理解成涵盖从39.50至40.49的范围。
在本文中,对于使用马库什组(Markush group)或选项式用语以描述本发明特征或实例的情形,本领域技术人员应了解马库什组或选项列表内所有成员的次群组或任何个别成员也可用于描述本发明。举例而言,如果X描述成“选自由X1、X2及X3所组成的群组”,也表示已经完全描述出X为X1的主张与X为X1和/或X2的主张。再者,对于使用马库什组或选项式用语以描述本发明的特征或实例,本领域技术人员应了解马库什组或选项列表内所有成员的次群组或个别成员的任何组合也可用于描述本发明。据此,举例而言,若X描述成“选自由X1、X2及X3所组成的群组”,且Y描述成“选自由Y1、Y2及Y3所组成的群组”,则表示已经完全描述出X为X1或X2或X3而Y为Y1或Y2或Y3的主张。
以下具体实施方式本质上仅是示例性的,并不意图限制本发明及其用途。此外,本文并不受前述现有技术或发明内容或以下具体实施方式或实施例中所描述的任何理论的限制。
化合物
在一个实施例中,本发明提供的化合物可具有以下式(I)所示结构:
其中,X代表共价键、-C(CH3)2-、-CH(CH3)-、-CH2-、-SO2-、-S-、或-O-;
Q1及Q2各自独立代表含有C=C不饱和键的官能基团;以及
J1及J2各自独立代表含有磷原子的阻燃性官能基团。
在一个实施例中,Q1及Q2相对于X的位置可以分别是邻位或间位,也可以同时是邻位,或者同时是间位。
在一个实施例中,Q1及Q2各自独立代表C2至C6的含有C=C不饱和键的脂烃基。举例而言,Q1及Q2各自独立可以是C2、C3、C4、C5或C6烯基,例如但不限于乙烯基、丙烯基或烯丙基。
在一个实施例中,J1及J2各自独立含有P=O双键或P-O单键。举例而言,J1及J2可以各自独立具有以下结构:
其中,A为氧原子或硫原子;n1为0或1;虚线表示有键合或无键合;以及R1和R2各自独立为含卤素基团、含或不含双键的烷基、含或不含双键的芳基、烷氧基、芳氧基、含硫烷基、含硫芳基、硅烷基或硅氧烷基。若无特别指明,R1和R2可各自独立经取代或未经取代。举例而言,R1和R2可各自独立经C1至C6的烷基所取代。
若无特别指明,本发明公开的各种化合物的官能基团具有以下定义。
在本文中,术语“卤素”表示氯、溴或碘;术语“烷基”表示直链或支链的饱和烃基,例如C1至C6的饱和烃基,如甲基、乙基、丙基、异丙基、丁基、戊基、己基等,且不以此为限;术语“芳基”表示芳香族环系统,例如C6至C18的芳香族取代基,例如苯基、萘基、联苯基、蔥基等,且不以此为限;术语“烷氧基”表示含有氧原子的烷基,如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、戊氧基、己氧基等,且不以此为限;术语“芳氧基”表示含有氧原子的芳基;术语“含硫烷基”表示含有硫原子的烷基;术语“含硫芳基”表示含有硫原子的芳基;术语“硅烷基”表示含有Si–H或Si–Si键合的取代基;术语“硅氧烷基”表示含有Si–O键合的取代基。其中,若“烷基”、“烷氧基”或“含硫烷基”含有支链,则最长碳链的碳数可以是例如C6。
在一个实施例中,J1及J2各自独立具有以下结构:
其中,A、Y和T各自独立为氧原子或硫原子;n1、m1和c1各自独立为0或1,且当m1或c1为0时,表示P直接与苯环键合;虚线表示有键合或无键合;R3和R4各自独立为氢、烷基、烯基、含或不含双键的芳基、烷氧基、芳氧基、含硫烷基、含硫芳基、硅烷基或硅氧烷基,且R3和R4可各自独立经取代或未经取代;以及a和b各自独立为1至3的整数,且若虚线表示有键合,则a+b≦4,若虚线表示无键合,则a+b≦5。
在一个实施例中,J1及J2各自独立具有以下结构:
其中,A、Y和T各自独立为氧原子或硫原子;n1为0或1;m1和c1同时为0或1,且当m1或c1为0时,表示P直接与R6或R5键合;以及R5和R6各自独立为含卤素基团、烷基、烯基、含或不含双键取代基的芳基、烷氧基、芳氧基、含硫烷基、含硫芳基、硅烷基或硅氧烷基,且R5和R6可各自独立经取代或未经取代。
在一个实施例中,J1及J2各自独立为磷酸二苯酯官能基团(diphenyl phosphate,DPP)、二苯基磷氧官能基团(diphenylphosphine oxide,DPPO)或9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物官能基团(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)。若无特别指明,前述磷酸二苯酯官能基团、二苯基磷氧官能基团或9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物官能基团都可以视需要经取代或未经取代,例如,在苯环位置经C1至C6的烷基所取代。
举例而言,式(I)所示结构的化合物可具有任一种以下结构:
在一个实施例中,式(I)所示结构的化合物具有较高的磷含量,例如磷含量大于或等于6.0%,或大于或等于7.0%。例如,式(I)所示结构的化合物的磷含量介于6.0%及9.0%之间。
本发明提供的式(I)化合物磷含量高且含有两单位反应官能团,因此在含双键树脂的体系(如文后所述)中,不仅能提高体系交联密度,也能赋予材料优良的阻燃性。
举例而言,式(I)化合物相较于DABPA、二乙烯基苯(DVB)、TAIC或者其他传统交联剂,能够在BMI、聚苯醚(PPO)等含双键树脂体系中提供优异的阻燃性。
举例而言,式(I)化合物相较于间苯二酚双(磷酸二苯酯)(RDP)、双酚A双(磷酸二苯酯)(BDP)、间苯二酚双[二(2,6-二甲基苯基)磷酸酯](RDX,市售品名PX-200)等传统磷酸酯阻燃剂相比,具有与其相当的阻燃效果的同时,还具有可参与反应的C=C不饱和键官能基团(即Q1及Q2官能基团),能够交联至树脂体系中,不仅能提升材料玻璃转化温度,而且解决了传统磷酸酯阻燃剂在材料高温处理时,容易分解游离至树脂组合物固化层表面,所造成稳定性、耐热性或抗离子迁移性等问题。
举例而言,式(I)化合物的空间结构具有很高的对称性、极性较低,且可不含羟基等高极性、强吸水性基团,其介电特性优异。应用在高速高频信号传输中,在提供阻燃、提高交联密度的同时,并不影响(劣化)材料的Dk/Df。
举例而言,式(I)化合物还具备增加物料互溶的增溶作用。例如,式(I)化合物能增加极性树脂(例如BMI树脂)及非极性树脂(例如聚烯烃树脂)的相溶性,以防止树脂析出而导致上胶操作困难、半固化片表面成膜、外观不良且易粘手的问题出现。
化合物的制造方法
在一个实施例中,本发明提供上述式(I)化合物的制造方法,主要步骤包括将含有磷原子的阻燃性官能基团的化合物与含有C=C不饱和键的双酚类化合物进行反应。
举例而言,可将含有磷原子的阻燃性官能基团的化合物与含有C=C不饱和键的双酚类化合物在溶剂中加热回流反应,而获得式(I)化合物。
在一个实施例中,回流时间可介于1小时及10小时之间,例如介于2小时及10小时之间或介于4小时及8小时之间。加热回流的反应温度可介于50℃及200℃之间,例如介于50℃及180℃之间或例如70℃及150℃之间。
在一个实施例中,适合的溶剂包括但不限于甲苯(TL)、二甲基乙酰胺(DMAC)、二甲基甲酰胺(DMF)、2-丙醇甲基醚(PM)、丙二醇甲醚醋酸酯(PMA)、环己酮(CYC)、丙酮、丁酮(MEK)或其组合。
含有磷原子的阻燃性官能基团的化合物与含有C=C不饱和键的双酚类化合物两者的用量并不特别限制。
在一个实施例中,含有磷原子的阻燃性官能基团的化合物与含有C=C不饱和键的双酚类化合物的摩尔比为0.1:1至过量。过量是指含有磷原子的阻燃性官能基团与含有C=C不饱和键的双酚类化合物中酚羟基的摩尔比大于1:1(官能基团的摩尔数=化合物质量/化合物分子量*化合物结构中官能基团的个数),例如但不限于2:1、3:1、4:1或5:1等等。优选含有磷原子的阻燃性官能基团与含有C=C不饱和键的双酚类化合物中酚羟基的摩尔比介于0.5:1及4:1之间,更优选介于1:1及3:1之间。
在一个实施例中,在反应步骤后,可进一步视需要使用例如但不限于甲苯清洗初产物,以除去反应中的副产物及不纯物,进而提高所制得的化合物的纯度。
作为反应物之一,所述含有C=C不饱和键的双酚类化合物可具有以下式(V)结构,其中X、Q1及Q2的定义如前文所述。举例而言,含有C=C不饱和键的双酚类化合物可以是含C=C不饱和键的联苯二酚,例如5,5’-二烯丙基-2,2’-联苯二酚。
作为反应物之一,所述含有磷原子的阻燃性官能基团的化合物可以是J1-(R7)n或J2-(R7)n,其中,n为1至3的整数,J1及J2的各种结构式与定义如前文所述,而R7代表卤素,例如氯。举例而言,含有磷原子的阻燃性官能基团的化合物可以是磷酸酯(例如磷酸二苯酯)的卤化物、磷氧化合物(例如二苯基磷氧或三氯氧磷)的卤化物或9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的卤化物。若无特别指明,前述卤化物可以视需要经取代或未经取代,例如经C1至C6的烷基所取代。
举例而言,含有磷原子的阻燃性官能基团的化合物可以是但不限于任一种具有以下式(VI)至式(IX)结构的化合物:
在一个实施例中,前述式(I)化合物的制造方法包括:将含有磷原子的阻燃性官能基团的化合物与含有C=C不饱和键的双酚类化合物进行反应,生成式(I)中J1及/或J2中至少一者包含有至少一个卤素原子的化合物,其可进一步作为反应物,再与含有单官能活性氢的化合物进行反应,如制备例3的实施例。
在一个实施例中,所述含有单官能活性氢的化合物可以是但不限于烷基醇、芳基酚、含双键的烷基醇、含双鍵的芳基酚、烷氧基醇、芳氧基醇、烷基硫醇或芳基硫醇,优选为芳基酚,例如苯酚或2,6-二甲基苯酚。此外,所述活性氢与可以和活性氢反应的基团(例如含有磷原子的阻燃性官能基团的化合物上的卤素原子)两者的摩尔比可以是0.1:1至过量,例如但不限于1:1至4:1之间。单官能活性氢的反应可以在含有磷原子的阻燃性官能基团的化合物与含有C=C不饱和键的双酚类化合物反应的相同条件下进行,也可在降低温度及/或缩短反应时间的条件下进行。
具体而言,在一个实施例中,本发明所提供的上述式(I)化合物的制造方法可以采用以下任一种合成路线,但不以此为限:
(1)将含有C=C不饱和键的双酚类化合物在催化剂(例如路易斯酸催化剂,如AlCl3)存在下与含有磷原子的阻燃性官能基团的化合物(例如磷酸二苯酯的卤化物、二苯基磷氧的卤化物、DOPO的卤化物)进行反应,一步得到式(I)化合物。
(2)将含有C=C不饱和键的双酚类化合物在催化剂(例如路易斯酸催化剂,如AlCl3)存在下与含有磷原子的阻燃性官能基团的化合物(例如三氯氧磷,POCl3)进行反应,生成式(I)中J1及/或J2中至少一者包含有至少一个卤素原子的化合物,其可进一步作为反应物,再与含有单官能活性氢的化合物(例如2,6-二甲基苯酚的羟基中的活性氢)进行反应,两步得到式(I)化合物。
化合物的合成与定性
制备例1
在1升的三颈瓶中,插入温度计和冷凝管,加入100毫升甲苯、0.6摩尔(约185克)的二烯丙基双酚A(DABPA)、1.3摩尔(约308克)的二苯基次膦酰氯(chlorodiphenylphosphineoxide,DPP-Cl)以及3.0克的无水三氯化铝。搅拌使之充分溶解,升温至140℃反应6至8小时。反应完成后冷却至室温,过滤并用碱液萃取,最后减压除去溶剂得到产物即式(II)化合物(即DABPA-bisDPP),产率为95.5%。
图1为产物式(II)化合物和原料DABPA的FTIR谱图。上方的曲线为原料DABPA的曲线,下方的曲线为产物式(II)化合物。通过对比发现,产物的FTIR曲线中,3435cm-1处的羟基吸收峰消失,说明羟基基本反应完全。特征峰出现在1592cm-1(P=O)、692~727cm-1(P-Ph)、1109cm-1(P-O)、1637cm-1(C=C)。727cm-1和692cm-1处出现的吸收峰,对应的是二苯基磷氧官能基团上的弯曲振动吸收峰,可证明DABPA上的羟基经反应后,已经成功接上了二苯基磷氧官能基团。
图2为原料DABPA的1H NMR谱图。化学位移δ=1.54ppm为-CH3质子峰(即图2中的“a”位置);δ=3.30ppm为烯丙基上的-CH2-质子峰(即图2中的“b”位置);δ=4.85ppm为羟基峰(即图2中的“f”位置);δ=5.14ppm为烯丙基双键CH2质子峰(即图2中的“c”位置);δ=6.0ppm为烯丙基-CH=上质子峰(即图2中的“d”位置);δ=6.7~7.2ppm为苯环上质子峰(即图2中的“e”位置)。
图3为产物式(II)化合物的1H NMR谱图。δ=4.85ppm处的羟基峰消失,而在δ=7.4~8.0ppm处出现非常强的二苯基磷氧官能基团上苯环的质子峰(即图3中的“g”位置),其他质子峰化学位移与原料基本一致,说明原料DABPA上的羟基已经被二苯基磷氧官能基团取代。
图4为原料DABPA和产物式(II)化合物的GPC曲线图。右边的曲线为原料DABPA的曲线,左边的曲线为产物式(II)化合物的曲线。相比原料DABPA,产物式(II)化合物的流出时间变小,分子量增大,说明了二苯基磷氧官能基团成功接上了DABPA,使得分子量增大。GPC曲线只有一个单峰,且峰型对称,说明合成的产物纯度较高,且DABPA上两端的羟基基本上已完全接上二苯基磷氧官能基团。
制备例2
在1升的三颈瓶中,插入温度计和冷凝管,加入100毫升甲苯、0.2摩尔(约61.7克)的二烯丙基双酚A(DABPA)、1.0摩尔(约153克)的三氯氧磷(POCl3)及1.0克的无水三氯化铝。搅拌使之充分溶解,升温至120℃反应4小时。减压蒸馏除去过量的三氯氧磷,接着向反应瓶中加入1.5摩尔(约141克)的苯酚和0.5克三氯化铝,升温至150℃反应6小时。反应完成后冷却至室温,过滤并用碱液萃取,最后减压除去溶剂得到产物即式(III)化合物,产率为92.5%。
制备例3
在1升的三颈瓶中,插入温度计和冷凝管,加入100毫升甲苯、0.2摩尔(约61.7克)的二烯丙基双酚A(DABPA)、1.0摩尔(约153克)的三氯氧磷(POCl3)及1.0克的无水三氯化铝。搅拌使之充分溶解,升温至120℃反应4小时。减压蒸馏除去过量的三氯氧磷,接着向反应瓶中加入1.5摩尔(约183克)的2,6-二甲基苯酚和0.5克三氯化铝,升温至150℃反应6小时。反应完成后冷却至室温,过滤并用碱液萃取,最后减压除去溶剂得到产物即式(IV)化合物,产率为90.5%。
树脂组合物
本发明公开的各种式(I)化合物可用于树脂组合物中,作为交联剂及/或阻燃剂。
具体而言,于本发明中,树脂组合物可包括式(I)化合物及树脂。例如,树脂组合物可包括,相较于100重量份的树脂,1至100重量份的式(I)化合物。举例而言,以100重量份的树脂为基础,式(I)化合物的用量可为但不限于1至100重量份,例如5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90或95重量份。
适用于本发明树脂组合物的树脂种类并不特别限制,且可为各种用于半固化片、树脂膜、积层板或印刷电路板制备的树脂。
在一个实施例中,所述树脂包含极性树脂及非极性树脂,且所述式(I)化合物可提高极性树脂及非极性树脂的相容性。上述极性树脂可以是但不限于环氧树脂、聚苯醚树脂、苯并噁嗪树脂、马来酰亚胺树脂、氰酸酯树脂或马来酸酐化苯乙烯-丁二烯共聚物。上述非极性树脂可以是但不限于聚丁二烯均聚物、苯乙烯丁二烯共聚物、氢化苯乙烯丁二烯共聚物、苯乙烯-丁二烯-二乙烯基苯三元聚合物、苯乙烯异戊二烯共聚物或其他碳氢樹脂。一般而言,若将非极性树脂溶液与极性树脂溶液混合,容易因极性差异导致相容性变差,而出现分层问题。当在上述同时含有极性树脂及非极性树脂的混合树脂体系中加入适量本发明的式(I)化合物(例如阻燃性达到V1或V0的使用量),无法预料的提高了混合树脂体系的相容性及稳定性,起到增溶的作用。
另一方面,在一个实施例中,所述树脂为含不饱和键树脂。含不饱和键树脂的实例包括但不限于包含一个或多个碳-碳双键的树脂、包含一个或多个碳-氮双键的树脂或包含一个或多个碳-氮三键的树脂。举例而言,在一个实施例中,含不饱和键树脂为乙烯基树脂。
举例而言,所述含不饱和键树脂包含聚烯烃、氰酸酯树脂、马来酰亚胺树脂、乙烯基聚苯醚树脂、苯乙烯、二乙烯基苯、三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯及其预聚物或其组合。
在一个实施例中,本发明的树脂组合物包括式(I)化合物及聚烯烃,其中聚烯烃包括但不限于苯乙烯-丁二烯-二乙烯基苯三元聚合物(styrene-butadiene-divinylbenzeneterpolymer)、苯乙烯-丁二烯-马来酸酐三元聚合物(styrene-butadiene-maleicanhydride terpolymer)、乙烯基-聚丁二烯-氨基甲酸酯寡聚物(vinyl-polybutadiene-urethane oligomer)、苯乙烯丁二烯共聚物(styrene-butadiene copolymer)、苯乙烯异戊二烯共聚物(styrene-isoprene copolymer)、聚丁二烯均聚物和马来酸酐化苯乙烯-丁二烯共聚物中的至少一种或其组合。
在一个实施例中,本发明的树脂组合物包括式(I)化合物及氰酸酯树脂,其中氰酸酯树脂包括但不限于具有Ar-O-C≡N结构的氰酸酯树脂(Ar为芳香基)、酚醛型氰酸酯树脂、双酚A型氰酸酯树脂、双酚A酚醛型氰酸酯树脂、双酚F型氰酸酯树脂、双酚F酚醛型氰酸酯树脂、含双环戊二烯结构的氰酸酯树脂、含萘环结构的氰酸酯树脂或酚酞型氰酸酯树脂。氰酸酯树脂的实例包括但不限于:商品名为Primaset PT-15、PT-30S、PT-60S、CT-90、BADCY、BA-100-10T、BA-200、BA-230S、BA-300S、BTP-2500、BTP-6020S、DT-4000、DT-7000、Methylcy、ME-240S等由Lonza生产的氰酸酯树脂。
在一个实施例中,本发明的树脂组合物包括式(I)化合物及马来酰亚胺树脂,其中马来酰亚胺树脂包括但不限于4,4′-二苯甲烷双马来酰亚胺(4,4′-diphenylmethanebismaleimide)、苯甲烷马来酰亚胺寡聚物(oligomer of phenylmethanemaleimide)、间-伸苯基双马来酰亚胺(m-phenylenebismaleimide)、双酚A二苯基醚双马来酰亚胺(bisphenol A diphenyl ether bismaleimide)、3,3′-二甲基-5,5′-二乙基-4,4′-二苯基甲烷双马来酰亚胺(3,3’-dimethyl-5,5’-diethyl-4,4′-diphenylmethanebismaleimide)、4-甲基-1,3-伸苯基双马来酰亚胺(4-methyl-1,3-phenylenebismaleimide)、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷(1,6-bismaleimide-(2,2,4-trimethyl hexane)、2,3-二甲基苯马来酰亚胺(N-2,3-Xylylmaleimide)、2,6-二甲基苯马来酰亚胺(N-2,6-Xylenemaleimide)、N-苯基马来酰亚胺(N-phenylmaleimide)和上述化合物的预聚体(例如二烯丙基化合物与马来酰亚胺化合物的预聚物)。
在一个实施例中,本发明的树脂组合物包括式(I)化合物及乙烯基聚苯醚树脂,其中乙烯基聚苯醚树脂是指封端基团具有不饱和双键的聚苯醚树脂,包括但不限于末端甲基丙烯酸酯聚苯醚树脂、末端乙烯苄基聚苯醚树脂、乙烯苄基改质双酚A聚苯醚树脂和乙烯基扩链聚苯醚树脂中的至少一种。具体实例包括Sabic公司贩卖的SA-9000或三菱瓦斯化学贩卖的OPE-2st。所述乙烯基扩链聚苯醚树脂可包括公开于美国专利申请案公开第2016/0185904 A1号中的各类聚苯醚树脂,其全部内容以引用的方式纳入本文。
除式(I)化合物及前述树脂外,本发明的树脂组合物还可以视需要包括无机填充物、硬化促进剂、溶剂、硅烷偶合剂、表面活性剂、染色剂、增韧剂或其任一种组合。若无特别指明,前述成分的用量并不特别限制,在可达成本发明技术目的的条件下的各种用量均可。举例而言,相较于1至100重量份的前述树脂(含不饱和键树脂或极性树脂及非极性树脂)而言,前述任一种成分的用量可介于0.01至100重量份之间。举例而言,相较于100重量份的前述树脂,前述任一种成分的用量可以是0.01重量份至100重量份、0.01重量份至200重量份或0.01重量份至300重量份。
在一个实施例中,以100重量份的树脂为基础,本发明的树脂组合物可进一步添加10至200重量份的无机填充物,例如10至100重量份,用以增加树脂组合物的热传导性、改良其热膨胀性及机械强度等特性的至少一种,且所添加的无机填充物可均匀分布于该树脂组合物中。
举例而言,本发明可适用的无机填充物并不特别限定为任何具体类型,可以包括如二氧化硅(熔融态、非熔融态、多孔质或中空型)、氧化铝、氢氧化铝、氧化镁、氢氧化镁、碳酸钙、氮化铝、氮化硼、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、钻石粉、类钻石粉、石墨、碳酸镁、钛酸钾、陶瓷纤维、云母、勃姆石(boehmite,AlOOH)、钼酸锌、钼酸铵、硼酸锌、磷酸钙、煅烧滑石、滑石、氮化硅、莫莱石(mullite)、煅烧高岭土、黏土、玻璃珠、中空玻璃珠、碱式硫酸镁晶须(basic magnesium sulfate whisker)、莫莱石晶须(mullitewhisker)、硫酸钡、氢氧化镁晶须(magnesium hydroxide whisker)、氧化镁晶须(magnesium oxide whisker)、氧化钙晶须(calcium oxide whisker)、纳米碳管、纳米级二氧化硅及其相关无机粉体、或具有有机核外层壳为绝缘体修饰的粉体粒子,且无机填充物可为球型、纤维状、板状、粒状、片状或针须状,并可视需要对填料进行表面处理,例如但不限于使用硅烷改质剂(包括但不限于硅氧烷改质剂)、氟硅烷改质剂、钛酸酯偶合剂等对填料进行表面处理。
于本发明中,任何可增进本发明树脂组合物固化速率的硬化促进剂皆可使用。以100重量份的树脂为基础,硬化促进剂的含量可介于0.01重量份至10重量份之间。本发明所述的树脂组合物可选择性添加一种或多种硬化促进剂以增进树脂的固化速率。所述硬化促进剂可包括路易斯碱或路易斯酸等催化剂。其中,路易斯碱可包括咪唑、三氟化硼胺复合物、乙基三苯基氯化鏻、2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、三苯基膦与4-二甲基胺基吡啶的其中至少一种。路易斯酸可包括金属盐类化合物,如锰、铁、钴、镍、铜和锌的金属盐化合物的其中至少一种,优选为辛酸锌、辛酸钴、乙酰丙酮钴或乙酰丙酮锌等金属催化剂。另外,所述硬化促进剂还包括可产生自由基的过氧化物硬化促进剂,例如包括但不限于:过氧化二异丙苯、叔丁基过氧化苯甲酸酯、2,5-二甲基-2,5-二(叔丁基过氧基)-3-己炔及双(叔丁基过氧异丙基)苯或上述的组合。
于本发明中,添加溶剂的主要用途在于改变树脂组合物的固含量,并调整树脂组合物的粘度,以100重量份的反应性材料为基础,溶剂的用量可以是30重量份至300重量份。若未特别指明,本发明采用的溶剂并不特别限制,且可为任一种或多种适用于溶解或稀释前述树脂组合物的溶剂,具体实施例包括但不限于:甲醇、乙醇、乙二醇单甲醚、丙酮、丁酮(又称为甲基乙基酮)、甲基异丁基酮、环己酮、甲苯、γ-丁内酯、二甲苯、甲氧基乙基乙酸酯、乙氧基乙基乙酸酯、丙氧基乙基乙酸酯、N-甲基吡咯烷酮(N-methyl-pyrrolidone,NMP)、乙酸乙酯、二甲基甲酰胺、二甲基乙酰胺、丙二醇甲基醚等溶剂或其混合物。
若未特别指明,本发明采用的硅烷偶合剂并不特别限制,且可为任一种或多种适用于半固化片、树脂膜、积层板或印刷电路板制作的硅烷偶合剂。硅烷偶联剂可包含硅烷化合物(silane,例如但不限于硅氧烷化合物(siloxane)),依官能基种类又可分为胺基硅烷化合物(amino silane)、环氧基硅烷化合物(epoxide silane)、乙烯基硅烷化合物、酯基硅烷化合物、羟基硅烷化合物、异氰酸酯基硅烷化合物、甲基丙烯酰氧基硅烷化合物及丙烯酰氧基硅烷化合物。
添加表面活性剂主要可提供润湿、抗粘、增溶或分散等作用,使无机填充物可以均匀分散于树脂组合物中。前述染色剂可包含但不限于染料(dye)或颜料(pigment)。添加增韧剂的主要作用,在于改善树脂组合物的韧性。其中,增韧剂可包含但不限于橡胶(rubber)树脂、端羧基丁腈橡胶(carboxyl-terminated butadiene acrylonitrile rubber,CTBN)、核壳橡胶(core-shell rubber)等化合物或其任一种组合。
树脂组合物制成的物品
前述树脂组合物可通过各种加工方式制成各种物品,例如适用于各类电子产品中的组件,其包括但不限于半固化片、树脂膜、积层板或印刷电路板。
具体而言,本发明提供一种半固化片,其具有一补强材及设置于补强材上的绝缘层,该绝缘层由如前述树脂组合物经高温加热形成半固化态(B-stage)而成,制作半固化片的烘烤温度为例如100℃至190℃之间。该补强材可为织布或无纺布,所述织布可为例如纤维材料,纤维材料包括玻璃纤维布、天然纤维布或有机纤维布等,以增加该半固化片的机械强度。所述有机纤维布可包括液晶聚合物树脂织布,例如聚酯织布或聚氨酯织布等,且不限于此。玻璃纤维布的种类并无特别限制,可为市售可用于各种印刷电路板的玻璃纤维布,例如E型玻布、D型玻布、S型玻布、T型玻布、L型玻布或NE玻布,其中纤维的种类包括纱和粗纱等,形式则可包括开纤或不开纤。所述无纺布包括液晶聚合物树脂无纺布,例如聚酯无纺布或聚氨酯无纺布等,且不限于此。优选地,该补强材可选择性进行预处理,例如但不限于使用硅烷改质剂、氟硅烷改质剂、钛酸酯偶合剂等进行表面处理。
由所述树脂组合物制成的物品可为树脂膜,其由所述树脂组合物经由如烘烤加热后半固化而得到。所述树脂组合物可被选择性地涂布于聚对苯二甲酸乙二酯膜(PET膜)、聚酰亚胺膜(PI膜)、液晶聚合物树脂膜、铜箔或背胶铜箔(RCC)上,再经由烘烤加热后半固化所述树脂组合物而形成树脂膜。
本发明各实施方式的树脂组合物可制成积层板(laminate,又称覆铜板,例如铜箔基板),其包括至少二层金属箔层及一层绝缘层,该绝缘层设置于该等金属箔之间,且该绝缘层可由前述树脂组合物在高温、高压下所固化而成,可适用的固化温度例如介于150℃至220℃之间,优选的固化温度介于190℃至210℃之间,固化时间为90至180分钟,较佳为120至150分钟。所述绝缘层可为前述半固化片或树脂膜;该金属箔的材质可为铜、铝、镍、铂、银、金或其合金,例如铜箔。
前述积压板可进一步依照本领域已知的各种电路板制造工艺加工形成印刷电路板。例如,印刷电路板可以使用厚度为28密耳(mil)且具有1oz(盎司)HTE(HighTemperature Elongation)铜箔的双面覆铜板(例如产品EM-827,可购自台光电子材料),钻孔后进行电镀,从而使上层铜箔和底层铜箔之间形成电导通。再对上层铜箔和底层铜箔进行蚀刻,从而形成内层电路。对内层电路进行棕化粗化处理,从而在表面形成凹凸结构以增加粗糙度。然后,将附载体超薄铜箔、前述半固化片、前述内层电路、前述半固化片、附载体超薄铜箔依序堆叠,再使用真空层压装置通过195℃加热75分钟以对半固化片的绝缘层材料进行固化。移除附载体超薄铜箔的载体后,在最外表面的超薄铜箔上进行黑化处理、钻孔、镀铜等本领域已知的各种电路板制造工艺加工,可获得印刷电路板。
本发明公开的树脂组合物与由其制备而得的各种物品,具有以下特性的任何一种或其任何组合:
(1)参考IPC-TM-650 2.4.24.4所述方法测量而得的玻璃转化温度大于或等于235℃,例如大于或等于240℃,例如介于235℃及250℃之间;
(2)参考IPC-TM-650 2.4.24.5所述方法以TMA仪器测量而得的Z轴热膨胀率较小。例如Z轴热膨胀率小于或等于2.10%,例如小于或等于2.03%;
(3)参考IPC-TM-650 2.4.8进行量测得到的铜箔拉力大于或等于4.30lb/inch,例如大于或等于4.50lb/inch,例如铜箔拉力介于4.30lb/inch及5.00lb/inch之间;
(4)参考IPC-TM-650 2.6.16.1及IPC-TM-650 2.4.23所述方法测试吸湿5小时后未发生爆板,耐热性较高;
(5)于10GHz频率、70%树脂含量条件下参考JIS C2565所述方法测量而得的介电常数小于或等于3.60,例如小于或等于3.55;
(6)于10GHz频率、70%树脂含量条件下参考JIS C2565所述方法测量而得的介电损耗小于或等于0.0050,例如小于或等于0.0045;以及
(7)阻燃性达到UL94标准的V0或V1等级,例如V0等级。
采用以下来源的各种原料,依照表1至表3的用量分别调配本发明实施例及本发明比较例的树脂组合物,并进一步制作成各类测试样本或物品。实施例及比较例的测试结果如下表1至表3所示。
1.末端甲基丙烯酸酯的聚苯醚树脂(methacrylate-terminated polyphenyleneether resin),商品名为SA-9000,购自Sabic公司。
2.末端乙烯苄基的联苯聚苯醚树脂(vinylbenzyl-terminated biphenylpolyphenylene ether resin),商品名为OPE-2st,购自三菱瓦斯化学。
3.苯乙烯-丁二烯共聚物,商品名为Ricon 100,购自Cray Valley公司。
4.双酚A氰酸酯树脂(bisphenol A cyanate ester resin),商品名为BA-230S,购自Lonza公司。
5.氰酸酯树脂(cyanate ester resin),商品名为BTP-6020S,购自Lonza公司。
6.苯甲烷马来酰亚胺聚合物(polyphenylmethane maleimide),商品名为BMI-2300,购自大和化成公司。
7.2,5-二甲基-2,5-二(叔丁基过氧基)-3-己炔(2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne),商品名为25B,购自日本油脂。
8.磷腈化合物(phosphazene),商品名为SPB-100,购自大塚化学。
9.间苯二酚双(二2,6-二甲基苯基磷酸盐)(resorcinol bis[di(2,6-dimethylphenyl)phosphate]),商品名为PX-200,购自日本大八化学。
10.双酚A双二苯基磷酸酯,商品名为CR-741,购自日本大八化学。
11.熔融态二氧化硅,购自硅比科公司。
12.辛酸锌,购自勤裕公司。
13.Di-DOPO含磷高熔点阻燃剂,如式(X)所示,参考中国专利号CN105936745A方法自行制造。
14.乙烯基化-THCPO反应型含磷阻燃剂,如式(XI)所示,参考中国专利号CN106366128A方法自行制造。
[表1]实施例树脂组合物的组成(单位:重量份)与性质测试结果
[表2]实施例树脂组合物的组成(单位:重量份)与性质测试结果
[表3]比较例树脂组合物的组成(单位:重量份)与性质测试结果
性质测试的待测样品的制备:
前述性质测试是分别选用E1至E15和C1至C5的树脂组合物,将树脂组合物分别于搅拌槽中混合均匀,置入一含浸槽中,再将玻璃纤维布(规格为2116的E-玻璃纤维布(E-glass fiber fabric),购自Asahi)浸入上述含浸槽,使树脂组合物附着于玻璃纤维布上,再于120至160℃下进行加热烘烤成半固化态,得到各半固化片,可用于制成以下待测样品。
1.含铜基板(五片半固化片压合而成):
准备两张0.5盎司(厚度为18微米)的RTF铜箔(reverse treated copper foil)以及五张各待测样品所制得的半固化片(2116E-玻璃纤维布),每一张半固化片的树脂含量约为55%。依照铜箔、五片半固化片及铜箔的顺序进行叠合,于真空条件、195℃下压合2小时形成含铜箔基板样品。其中,五张相互叠合的半固化片会固化形成两铜箔间的绝缘材料层,绝缘材料层的树脂含量约为55%。
2.不含铜基板(五片半固化片压合而成):
将上述含铜基板经蚀刻去除两铜箔,以获得不含铜基板,不含铜基板是由五片半固化片所压合而成,其树脂含量约为55%。
3、不含铜基板(两片半固化片压合而成):
准备两张0.5盎司的RTF铜箔以及两张各待测样品所制得的半固化片(1080E-玻璃纤维布),每一张半固化片的树脂含量约为70%。依照铜箔、两片半固化片及铜箔的顺序进行叠合,于真空条件、195℃下压合2小时形成含铜箔基板。接着,将所得到的含铜基板经蚀刻去除两铜箔,以获得不含铜基板(两片半固化片压合而成),其树脂含量约为70%。
4、不含铜基板(八片半固化片压合而成):
准备两张0.5盎司的HTE铜箔以及八张各待测样品所制得的半固化片(7628E-玻璃纤维布),每一张半固化片的树脂含量约为45%。依照铜箔、八片半固化片及铜箔的顺序进行叠合,于真空条件、195℃下压合2小时形成含铜箔基板。接着,将所得到的含铜基板经蚀刻去除两铜箔,以获得不含铜基板(八片半固化片压合而成),其树脂含量约为45%。
对于前述待测样品,依照下述方式进行性质测试。
1.玻璃转化温度(glass transition temperature,Tg):
于玻璃转化温度的量测中,选用不含铜基板(五片半固化片压合而成)作为待测样品。采用动态机械分析仪(dynamic mechanical analyzer,DMA),参考IPC-TM-6502.4.24.4 Glass Transition and Modulus of Materials Used in High DensityInterconnection(HDI)and Microvias-DMA Method所述方法测量各待测样品。
2.热膨胀率(thermal expansion ratio,z-axis):
在热膨胀率的量测中,选用不含铜基板(五片半固化片压合而成)作为待测样品进行热机械分析(thermal mechanical analysis,TMA)。以温升速率每分钟10℃加热样品,由50℃升温至260℃的温度,参照IPC-TM-650 2.4.24.5所述方法测量各待测样品的尺寸胀缩率(单位为%),其尺寸胀缩百分比越低越佳。
3.铜箔拉力(peel strength,P/S)
选用上述含铜基板(五片半固化片压合而成)为待测样品,使用万能拉伸强度试验机,依IPC-TM-650 2.4.8所述方法测量其铜箔拉力(单位为lb/inch)。
4.吸湿后耐热性测试(PCT):
选用不含铜基板(五片半固化片压合而成),参照IPC-TM-650 2.6.16.1所述的方法经压力蒸煮测试(pressure cooking test,PCT)在相对湿度100%环境下进行吸湿5小时测试后,使用上述吸湿后的不含铜基板,将各待测样品分别浸入恒温设定于288℃的锡炉内20秒,取出后观察是否发生爆板(爆板即未通过测试),例如绝缘层与绝缘层间是否造成层间剥离,层间剥离即基板任意层间发生起泡分离的现象。
5.介电常数(dielectric constant,Dk)及介电损耗(dissipation factor,Df):
于介电常数及介电损耗的量测中,选用上述不含铜基板(两片半固化片压合而成)为待测样品,采用微波介电常数分析仪(microwave dielectrometer,购自日本AET公司),参考JIS C2565Measuring methods for ferrite cores for microwave device所述方法,于10GHz的频率下测量各待测样品。介电常数越低、介电损耗越低代表待测样品的介电特性越佳。Dk值的差异大于0.05代表不同基板的介电常数之间存在显着差异。在10GHz的量测频率下且Df值小于0.005以下的范围,Df值的差异大于0.0001代表不同基板的介电损耗之间存在显著差异(存在显著的技术困难度)。
6.阻燃性(flame retardancy):
在阻燃测试中,使用125毫米×13毫米的不含铜基板(八片半固化片压合而成)为待测样品;根据UL94规范方法进行测量,阻燃性分析结果以V-0、V-1、V-2等级表示,其中V-0的阻燃性优于V-1的阻燃性,V-1的阻燃性优于V-2的阻燃性,样品燃尽则为最差。
除此之外,采用以下方法比较本发明阻燃剂对于极性树脂及非极性树脂的增溶作用。
举例而言,将10重量份的丁二烯聚合物(Ricon100)及50重量份的双马来酰亚胺树脂(BMI-2300),分别加入单一溶剂或混合溶剂中,例如丁酮(60重量份)、环己酮(60重量份)、混合溶剂1(含有40重量份的丁酮及20重量份的甲苯)、混合溶剂2(含有40重量份的二甲基乙酰胺及20重量份的甲苯)或混合溶剂3(含有40重量份的丁酮及20重量份的二甲基乙酰胺)中,或者以混合溶剂1、混合溶剂2或混合溶剂3包含的两种溶剂分别将丁二烯聚合物和双马来酰亚胺树脂溶解后再混合,会出现丁二烯聚合物析出,明显出现树脂分层现象(分层标示为O、无分层标示为╳),如样本编号A。之后加入10重量份的本发明阻燃剂(式(II)、式(III)或式(IV))或其他阻燃剂并搅拌均匀,静置24小时后,观察混合物胶液的分层现象。若无分层现象,代表所添加的阻燃剂有起到增溶的作用。结果如下表4所示。
[表4]增溶测试结果
由表1至表4的分析结果可知,采用本发明的式(I)化合物作为阻燃剂的样品在玻璃转化温度、热膨胀率、铜箔拉力、耐热性、介电常数、介电损耗、阻燃性等一个或多个方面得到改善,例如可同时满足Z轴热膨胀率小于或等于2.10%以及介电损耗小于或等于0.0045。更为意外的发现,本发明的式(I)化合物还可提高极性树脂及非极性树脂的相容性,起到显著的增溶作用。
以上实施方式本质上仅为辅助说明,且并不欲用以限制申请标的的实施例或这些实施例的应用或用途。在本文中,用语“例示性”代表“作为一个实例、范例或说明”。本文中任一种例示性的实施形态并不必然可解读为相对于其他实施形态而言为优选或较有利者。
此外,尽管已于前述实施方式中提出至少一例示性实施例或比较例,但应了解本发明仍可存在大量的变化。同样应了解的是,本文所述的实施例并不欲用以通过任何方式限制所请求的申请标的的范围、用途或组态。相反的,前述实施方式将可提供本领域技术人员一种简便的指引以实施所述的一种或多种实施例。再者,可对要素的功能与排列进行各种变化而不脱离权利要求所界定的范围,且权利要求包含已知的均等物及在本专利申请案提出申请时的所有可预见均等物。
Claims (14)
2.根据权利要求1所述的化合物,其中X代表共价键、-C(CH3)2-、-CH(CH3)-或-CH2-。
4.根据权利要求1所述的化合物,其磷含量介于6.0%及9.0%之间。
5.一种权利要求1所述的化合物的制造方法,包括:将含有磷原子的阻燃性官能基团的化合物与含有C=C不饱和键的双酚类化合物进行反应。
6.一种将权利要求1所述的化合物用作树脂组合物的交联剂与阻燃剂的用途。
7.一种树脂组合物,包括权利要求1所述的化合物及树脂。
8.根据权利要求7所述的树脂组合物,其中所述树脂为含不饱和键树脂。
9.根据权利要求8所述的树脂组合物,其中所述含不饱和键树脂包含一个或多个碳-碳双键、碳-氮双键或碳-氮三键。
10.根据权利要求8所述的树脂组合物,其中所述含不饱和键树脂包含聚烯烃、氰酸酯树脂、马来酰亚胺树脂、乙烯基聚苯醚树脂或其组合。
11.根据权利要求7所述的树脂组合物,其中所述树脂包含极性树脂及非极性树脂,且所述化合物用于提高极性树脂及非极性树脂的相容性,其中所述极性树脂包括环氧树脂、聚苯醚树脂、苯并噁嗪树脂、马来酰亚胺树脂、氰酸酯树脂或马来酸酐化苯乙烯-丁二烯共聚物,所述非极性树脂包括聚丁二烯均聚物、苯乙烯丁二烯共聚物、氢化苯乙烯丁二烯共聚物、苯乙烯-丁二烯-二乙烯基苯三元聚合物或苯乙烯异戊二烯共聚物。
12.根据权利要求7所述的树脂组合物,其中相较于100重量份的树脂,所述化合物的含量介于1及100重量份之间。
13.一种由权利要求7所述的树脂组合物制成的物品,其包括半固化片、树脂膜、积层板或印刷电路板。
14.如权利要求13所述的物品,其具有以下特性的至少一种:
以TMA仪器参考IPC-TM-650 2.4.24.5所述方法测量而得的Z轴热膨胀率小于或等于2.10%;以及
参考JIS C2565所述方法在10GHz的频率下测量而得的介电损耗小于或等于0.0045。
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