TWI650361B - 一種熱固性樹脂組合物、由其製作之半固化片、覆金屬箔層壓板及高頻電路板 - Google Patents
一種熱固性樹脂組合物、由其製作之半固化片、覆金屬箔層壓板及高頻電路板 Download PDFInfo
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- TWI650361B TWI650361B TW106140390A TW106140390A TWI650361B TW I650361 B TWI650361 B TW I650361B TW 106140390 A TW106140390 A TW 106140390A TW 106140390 A TW106140390 A TW 106140390A TW I650361 B TWI650361 B TW I650361B
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- resin
- phosphorus
- resin composition
- thermosetting
- thermosetting resin
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 87
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 12
- 239000002184 metal Substances 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 118
- 239000011347 resin Substances 0.000 claims abstract description 118
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 80
- 239000011574 phosphorus Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000005011 phenolic resin Substances 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 17
- 229920001568 phenolic resin Polymers 0.000 claims description 16
- -1 allyl silanol Chemical compound 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005062 Polybutadiene Substances 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- CYQFCXCEBYINGO-IAGOWNOFSA-N delta1-THC Chemical group C1=C(C)CC[C@H]2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3[C@@H]21 CYQFCXCEBYINGO-IAGOWNOFSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- 238000006462 rearrangement reaction Methods 0.000 claims description 9
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 6
- 239000002174 Styrene-butadiene Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 239000011115 styrene butadiene Substances 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Substances OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 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 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 2
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical group C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000005453 ketone based solvent Substances 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- WTBPWOVBWKJVPF-UHFFFAOYSA-N 3-(2-ethylhexylperoxymethyl)heptane Chemical compound CCCCC(CC)COOCC(CC)CCCC WTBPWOVBWKJVPF-UHFFFAOYSA-N 0.000 claims 1
- 239000004342 Benzoyl peroxide Substances 0.000 claims 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 238000005937 allylation reaction Methods 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000004744 fabric Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 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 15
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- 239000007864 aqueous solution Substances 0.000 description 3
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- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 229910052582 BN Inorganic materials 0.000 description 1
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- ZEIAMUWWPWYCDI-UHFFFAOYSA-N C=CCOC1=C[I]=CC=C1 Chemical compound C=CCOC1=C[I]=CC=C1 ZEIAMUWWPWYCDI-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- MEYBPUZOYCHPIG-UHFFFAOYSA-N benzoic acid;2-tert-butylperoxy-2-methylpropane Chemical compound OC(=O)C1=CC=CC=C1.CC(C)(C)OOC(C)(C)C MEYBPUZOYCHPIG-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
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- 230000001146 hypoxic effect Effects 0.000 description 1
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- 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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Classifications
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- 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
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- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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Abstract
本發明提供一種熱固性樹脂組合物、由其製作之半固化片、覆金屬箔層壓板及高頻電路板,前述熱固性樹脂組合物包含熱固性成分,前述熱固性成分包含含磷單體或含磷樹脂以及含有不飽和基團的其他熱固性樹脂,前述含磷單體或含磷樹脂具有如式I所示的結構,利用含磷單體或含磷樹脂作為含有不飽和基團的其他熱固性樹脂的交聯劑,藉由樹脂中大量的不飽和雙鍵進行交聯反應來提供電路基板所必須的高頻介電性能和耐高溫性能。
Description
本發明屬於覆銅板技術領域,關於一種熱固性樹脂組合物、由其製作之半固化片、覆金屬箔層壓板及高頻電路板。
近年來,隨著資訊通訊設備高性能化、高功能化以及網路化的發展,為了傳輸及處理大容量訊息,操作訊號趨向於高頻化,因而對電路基板的材料提出了要求。
現有之用於印製電路基板的材料中,廣泛使用黏接特性優異之環氧樹脂,然而,環氧樹脂電路基板一般介電常數和介質損耗角正切較高(介電常數大於4,介質損耗角正切0.02左右),高頻特性不充分,不能適應訊號高頻化的要求。因此必須研製介電特性優異之樹脂,即介電常數和介質損耗角正切低的樹脂。長期以來所屬領域中具有通常知識者對介電性能良好之熱固性的聚丁二烯或聚丁二烯與苯乙烯之共聚物樹脂進行研究,以下就這些研究成果進行進一步的探討。
歐洲專利申請WO97/38564中公開了採用非極性的苯乙烯與丁二烯和二乙烯基苯的四聚物添加矽鋁酸鎂填料,以玻璃纖維布作為增強材料製成的電路基板,雖然介電性能優異,但是基板的耐熱性很差,玻
璃轉化溫度只有100℃左右,熱膨脹係數很大,很難滿足PCB製作過程無鉛化製程的高溫(240℃以上)要求。
US5571609中公開採用分子量小於5000的低分子量的1,2-聚丁二烯樹脂或聚異丁二烯,和高分子量的丁二烯與苯乙烯的共聚物配合,並加入大量的矽微粉作為填料,以玻璃纖維布作為增強材料製作的電路基板,雖然介電性能優異,但是因為在該專利中採用了高分子量的成分來改善半固化片黏手狀況,使得製作半固化片的過程的工藝性能變差;而且因為整個樹脂體系的樹脂分子中的剛性結構苯環的比例很少,而且交聯以後的鏈段大都由剛性很低的亞甲基組成,因此製作成的板材剛性不佳,彎曲強度很低。
US6569943公開使用分子末端帶有乙烯基的胺基改性的液體聚丁二烯樹脂,添加低分子量的單體作為固化劑和稀釋劑,浸漬玻璃纖維布製作成的電路基板,雖然介電性能良好,但是因為樹脂體系在常溫下係液體,不能製作成不黏手的半固化片,因此在板材的壓製成型時,很難採用通用的半固化片疊箔工藝,工藝操作比較困難。
另外,電子電器設備中使用的印製電路基板材料,要求達到阻燃等級94V-0級,這對高頻電路板材料也不例外。US5571609中公開了採用以溴為主的含鹵類材料做阻燃劑。雖然含鹵類材料阻燃效果較佳,但有研究表明,含鹵類材料在燃燒時易釋放刺激性和有毒性的氣體,如鹵化氫、戴奧辛等,使人健康受到危害。在一些電子產品中,已有禁止使用含鹵類的電路板材料。近年來,隨著人們環保觀念的提高,電子電器中使用的電子材料趨向於無鹵化,皆在尋求可以替代鹵素類阻燃劑的其他類型阻
燃劑來滿足阻燃的要求。金屬氫氧化物阻燃劑雖然不存在含鹵阻燃劑如此之毒性問題,但因其阻燃效率差,必須添加更大的量來獲得良好的阻燃性能,如此會導致樹脂混合、成型時的流動性差,使複合材料的加工及機械性能變差;另外由於金屬氫氧化物之介電常數大,用其作阻燃劑會帶來高頻電路基板介電性能之下降。含磷阻燃劑大都具有低煙、無毒之特點,不僅具有良好的阻燃性能,此外能夠抑製煙霧和有毒氣體的釋放,符合添加量少、阻燃效果明顯的應用要求。
US2009034058公開一種無鹵高頻電路板基材的製作方法,其採用聚丁二烯做主樹脂,金屬氫氧化物(Mg(OH)3)及含氮的化合物作阻燃劑,採用大量的無機填料作為阻燃劑,不僅存在添加量大導致的成型工藝性能差的問題,而且阻燃效率不高,進而會使介電性能變差等諸多問題。
CN103709718公開使用集中添加型的含磷阻燃劑作為阻燃材料進行高頻覆銅板的製作,但所揭示的幾種含磷阻燃劑沒有反應基團,不參與複合材料樹脂分子間的交聯,由於此等含磷阻燃劑的熔點很低(小於200℃),用其製作的高頻電路基板材料的耐熱性差,無法滿足後續電路板元件裝配過程高溫焊接可靠性的要求。
CN106543228A公開具有如下結構的樹脂:
,然而若將此種樹脂應用於覆銅板之製備,則由於其結構中含有羥基極性基團會使得製備得到的覆銅板之介電性能無法滿足要求。
CN106366128公開了一種具有如下結構的膦菲類化合物:,然而若將該化合物用於覆銅板之製備,則會由於其結構中存在的烯丙基醚結構而在加工過程中發生重排反應,導致產生二次羥基極性基團,同樣會使得製備得到的覆銅板之介電性能無法滿足要求。
因此,在所屬技術領域之中,期望開發一種既能夠保證具有良好的阻燃性能,又能夠在介電性能、耐熱性能等多個方面取得良好效果之熱固性樹脂組合物。
針對先前技術的不足,本發明之目的係提供一種熱固性樹脂組合物、由其製作之半固化片、覆金屬箔層壓板及高頻電路板,本發明之熱固性樹脂組合物不含有極性基團(例如羥基)、分子極性低、反應活性高,降低其固化物之介電常數和損耗,此外能夠保證固化物具有良好的阻燃性能、良好的機械強度以及良好的耐高溫等性能。
為達到此發明目的,本發明採用以下技術手段:一方面,本發明提供一種熱固性樹脂組合物,前述熱固性樹脂組合物包含熱固性成分,前述熱固性成分包含含磷單體或含磷樹脂以及其他含有不飽和基團之熱固性樹脂,前述含磷單體或含磷樹脂具有如式I所示的結構:
其中,R為直鏈或支鏈烷基、、-O-、
或,X和Y獨立地為氫、烯丙基、直鏈烷基、支鏈烷基中的任意一種或至少兩種的組合;A為含磷封端基團,n為1-20的整數。
在本發明所記載之熱固性樹脂組合物中,前述含磷單體或含
磷樹脂具有低極性的特徵,前述低極性係指不含有極性基團,尤其是不含有羥基基團,使得樹脂具有較低的極性,克服習知之熱固性樹脂極性大導致的高頻介電常數和損耗高之缺陷,同時可藉由該結構中之烯丙基結構實現交聯固化,保證固化後之力學強度,此外使得固化物具有優良的耐熱性能,同時,該樹脂中含有阻燃性含磷結構,使其具有良好之本徵阻燃效果。
在本發明中,前述含磷單體或含磷樹脂能夠良好地與其他含有不飽和基團的熱固性樹脂進行配合,一同提升樹脂組合物的耐高溫以及耐濕熱性能,在具備較佳阻燃性的同時,使得由該樹脂組合物製備得到的固化物具有良好的耐熱性以及介電性能。
理想地,前述R為C1-C6(例如C1、C2、C3、C4、C5或C6)的直鏈烷基或C3-C6(例如C3、C4、C5或C6)支鏈烷基,具體而言可以為-CH2-、或等。
理想地,R為-CH2-、、-O-、
或,n為1-20的整數,X和Y獨立地為氫、烯丙基、直鏈烷基、支鏈烷基中的任意一種或至少兩種的組合,A為含磷封端基團。
在本發明中,n為1-20的整數,例如n可以為1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20。
理想地,X和Y獨立地為C1-C21(例如C1、C2、C3、C4、
C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20或C21)的直鏈烷基或C3-C21(例如C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20或C21)支鏈烷基。
理想地,A為含有DOPO結構之基團,理想為 或中之任意一種。
理想地,前述含磷單體或含磷樹脂為磷含量大於3%之含磷單體或含磷樹脂,更理想為磷含量大於5%之含磷單體或含磷樹脂,進一步理想為磷含量大於8%之含磷單體或含磷樹脂。含磷量越大,可提供熱固性樹脂組合物良好的阻燃性能。
理想地,前述含磷單體或含磷樹脂為具有如下式A至式D所示結構之化合物中的任意一種或至少兩種的組合:
其中n為1-20的整數。
理想地,前述含磷單體或含磷樹脂藉由如下製備方法製備得
到,所記載之方法包含以下步驟:
(1)式II所示酚類化合物或酚類樹脂與烯丙基化試劑反應得到式III所示烯丙基醚化樹脂,示例反應式如下:
(2)在保護性氣體保護下,將式III所示烯丙基醚化樹脂加熱,發生分子內重排反應得到式IV所示烯丙基化酚類樹脂;
(3)式III所示烯丙基化酚類樹脂與含磷封端試劑發生反應,得到式I所示含磷單體或含磷樹脂;
其中,R1為直鏈或支鏈烷基、、-O-、或;R2為直鏈或支鏈烷基、、-O-、或;R3為直鏈或支鏈烷基、
、-O-、或
R為直鏈或支鏈烷基、、-O-、或
;X和Y獨立地為氫、烯丙基、直鏈烷基或支鏈烷基中的任意一種或至少兩種的組合;A為含磷封端基團,n為1-20的整數。
在本發明中,步驟(2)的重排步驟中,當R2為或時,包含其中的烯丙醚基會發生重排之情況,導致在式IV所示烯丙基化酚類樹脂的中間單元R3中含有由於重排而產生烯丙基,進而在產物式I所示低極性樹脂的R單元中包含由於重排而產生的烯丙基,本發明中為了表述簡潔未將該烯丙基直接表示至R3和R的相應結構中,而僅僅由X來代表了苯環上所有的取代基,然而在此明確此處X包含由於重排而產生的烯丙基,若在重排反應前R2為或,苯環上帶有其他取代基X,在步驟(2)的重排反應後,則在R3的結構或
中X可以表示重排產生之烯丙基和反應前之其他取代基的組合。當然在步驟(2)的重排步驟中,亦包含R2為或時,R2單元中烯丙醚基不發生重排反應之情況,此時,反應後R3以及產物R中的X與反應前式III所示烯丙基醚化樹脂中R2中的X基團相同。
理想地,步驟(1)所記載之酚類化合物或酚類樹脂為酚、二元酚、多元酚或它們的衍生樹脂,理想為苯酚、鄰甲酚、雙酚A、雙酚F、四甲基雙酚A、酚醛樹脂、鄰甲酚酚醛樹脂或環戊二烯酚醛樹脂中的任意一種或至少兩種的組合。
理想地,前述烯丙基化試劑為烯丙基矽醇、烯丙基氯、烯丙基溴、烯丙基碘或烯丙基胺中的任意一種或至少兩種的組合。
理想地,前述酚類化合物或酚類樹脂中酚羥基與烯丙基化試劑中烯丙基之莫耳比為1:(0.3~1.2),例如1:0.3、1:0.4、1:0.5、1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:1.1或1:1.2。
理想地,步驟(1)所記載之反應在鹼性物質存在下進行,前述鹼性物質理想為氫氧化鈉、氫氧化鉀、碳酸鈉或碳酸鉀中的任意一種或至少兩種的組合。
理想地,前述鹼性物質與步驟(1)所記載之酚類化合物或酚類樹脂中所含酚羥基之莫耳比為(0.3~1.4):1,例如0.3:1、0.4:1、0.5:1、0.6:1、
0.7:1、0.8:1、0.9:1、1:1、1.1:1、1.2:1、1.3:1或1.4:1。
理想地,步驟(1)所記載之反應在相轉移催化劑存在下進行。
理想地,前述相轉移催化劑為季銨鹽類相轉移催化劑,理想為四丁基氯化銨、四丁基溴化銨、苄基三乙基氯化銨、四丁基硫酸氫銨、三辛基甲基氯化銨、十二烷基三甲基氯化銨或十四烷基溴三甲基氯化銨中的任意一種或至少兩種的組合。
理想地,前述相轉移催化劑的加入量為步驟(1)所記載之酚類化合物或酚類樹脂質量的0.1-5%,例如0.1%、0.3%、0.5%、0.8%、1%、1.3%、1.5%、1.8%、2%、2.3%、2.5%、2.8%、3%、3.3%、3.5%、3.8%、4%、4.3%、4.5%、4.8%或5%。
理想地,步驟(1)所記載之反應的溶劑為醇類溶劑、芳香烴溶劑或酮類溶劑中的任意一種或至少兩種的組合,理想為乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一種或至少兩種的組合。
理想地,前述溶劑之加入量為步驟(1)所記載之酚類化合物或酚類樹脂質量的2-5倍,例如2倍、2.3倍、2.5倍、2.8倍、3倍、3.3倍、3.5倍、3.8倍、4倍、4.3倍、4.5倍、4.8倍或5倍。
理想地,步驟(1)所記載之反應的溫度為60-90℃,例如60℃、63℃、65℃、68℃、70℃、75℃、78℃、80℃、85℃、88℃或90℃。
理想地,步驟(1)所記載之反應的時間為4-6小時,例如4小時、4.3小時、4.5小時、4.8小時、5小時、5.2小時、5.5小時、5.8小時或6小時。
理想地,步驟(2)所記載之保護性氣體為氮氣或氬氣。
理想地,步驟(2)所記載之加熱為加熱至180-220℃,例如180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃。
理想地,步驟(2)所記載之反應的時間為4-6小時,例如4小時、4.3小時、4.5小時、4.8小時、5小時、5.2小時、5.5小時、5.8小時或6小時。
理想地,步驟(3)所記載之含磷封端試劑為9,10-二氫-9-氧雜-10-膦菲-10-氧化物、9,10-二氫-9-氧雜-10-膦菲-10-氧化物、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-1,4-對苯二酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯甲醇或2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯甲醇中的任意一種或至少兩種的組合。
理想地,步驟(3)所記載之式III所示烯丙基化酚類樹脂中酚羥基與含磷封端試劑中含磷封端基之莫耳比為1:(1~1.2),例如1:1、1:1.05、1:1.1、1:1.15或1:1.2。使得反應得到的樹脂分子結構中酚羥基均被含磷封端基封端,從而使樹脂中無極性羥基基團。
理想地,步驟(3)所記載之反應在鹼性物質存在下進行。
理想地,前述鹼性物質為無機堿或有機堿,理想為氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙胺或吡啶中的任意一種或至少兩種的組合。
理想地,前述鹼性物質與式III所示烯丙基化酚類樹脂中酚
羥基之莫耳比為(1~1.4):1,例如1:1、1.05:1、1.1:1、1.15:1、1.2:1、1.25:1、1.3:1、1.35:1或1.4:1。
理想地,步驟(3)所記載之反應在四氯化碳存在下進行。
理想地,前述四氯化碳與步驟(3)所記載之式III所示烯丙基化酚類樹脂中酚羥基莫耳比為(1-2):1,例如1:1、1.1:1、1.2:1、1.3:1、1.4:1、1.5:1、1.6:1、1.7:1、1.8:1、1.9:1或2:1。
理想地,步驟(3)所記載之反應的溶劑為鹵代烴類溶劑,理想為一氯甲烷、二氯甲烷、三氯甲烷或二氯乙烷中的任意一種或至少兩種的組合。
理想地,前述溶劑的加入量為步驟(3)所記載之烯丙基化酚類樹脂質量的2-5倍,例如2倍、2.3倍、2.5倍、2.8倍、3倍、3.3倍、3.5倍、3.8倍、4倍、4.3倍、4.5倍、4.8倍或5倍。
理想地,步驟(3)所記載之反應的溫度為0-30℃,例如0℃、3℃、5℃、8℃、10℃、15℃、18℃、20℃、25℃、28℃或30℃,理想為10℃。
理想地,步驟(3)所記載之反應的時間為4-6小時,例如4小時、4.3小時、4.5小時、4.8小時、5小時、5.2小時、5.5小時、5.8小時或6小時。
藉由本發明之方法製備得到的樹脂中不含有極性的羥基、此外分子結構穩定,具有分子極性低、反應活性高的特點,在其應用的加工過程中也不會產生極性羥基,避免產生的二次羥基對於其產物之性能的影響,此外以含磷封端基封端,賦予樹脂組合物以本徵阻燃性能。
在本發明中,前述含磷單體或含磷樹脂中的雜質或副產物含量少,雜質或副產物含量少,可以提供熱固性樹脂組合物良好之介電性能和耐熱性。理想的前述含磷單體或含磷樹脂的介質損耗角正切小於等於0.0025(1GHz)。
理想地,前述其他含有不飽和基團的熱固性樹脂為含有雙鍵或三鍵的熱固性樹脂,理想為烯丙基封端的聚苯醚樹脂、丙烯酸酯封端的聚苯醚樹脂、乙烯基封端的聚苯醚樹脂、熱固性聚丁二烯樹脂、熱固性聚丁二烯與苯乙烯的共聚樹脂(丁苯樹脂)、雙馬來醯亞胺樹脂、氰酸酯樹脂、烯丙基化的酚醛樹脂、烯丙基化的鄰甲酚酚醛樹脂或乙烯基封端的矽氧烷樹脂中的任意一種或至少兩種的組合。以上雖列舉但不侷限於以上列舉的樹脂,前述樹脂可以是一種,也可以是兩種以上配合使用。
理想地,前述其他含有不飽和基團的熱固性樹脂為分子量在11000以下(例如11000、10000、9000、8000、7000、6000、5000、4000、3000、2000、1000等)由碳氫元素組成的含有60%以上(例如60%、65%、70%、75%、80%、85%甚至更高)乙烯基的聚丁二烯或聚丁二烯與苯乙烯的共聚物樹脂為基礎的熱固性樹脂,更理想地分子量小於8000。在本發明中此處前述熱固性樹脂在室溫下係液體,液體樹脂的黏度很低,因而有利於後面的浸漬工藝操作。
在本發明中,前述含磷單體或含磷樹脂可作為上述其他含有不飽和基團的熱固性樹脂的交聯劑,用於交聯固化上述其他含有不飽和基團的熱固性樹脂。
理想地,前述熱固性成分在前述熱固性樹脂組合物中所占的
重量百分比為5-90%,例如5%、8%、10%、15%、18%、20%、25%、30%、40%、50%、60%、70%、80%或90%。
理想地,前述含磷單體或含磷樹脂占其他含有不飽和基團的熱固性樹脂和含磷單體或含磷樹脂之總重量的20~75%,例如20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%或75%。
理想地,前述熱固性樹脂組合物亦包含粉末填料,以重量含量計,前述粉末填料在熱固性樹脂組合物中之含量為0%~50%,例如0%、1%、5%、10%、20%、30%、40%或50%。
理想地,前述粉末填料包含結晶型二氧化矽、熔融型二氧化矽、球型二氧化矽、二氧化鈦、鈦酸鍶、鈦酸鋇、鈦酸鍶鋇、矽酸鋅、矽酸鎂、氮化鋁、氮化硼、氮化矽、碳化矽、氧化鋁、氧化鎂、氧化鋯、氧化鈹、氫氧化鋁、氫氧化鎂、高嶺土、滑石粉、水滑石、矽酸鈣、玻璃粉、熔融矽微粉、潔淨矽微粉、球形矽微粉、硼酸鋅、莫來石、金紅石型二氧化鈦、銳鈦型二氧化鈦、中空玻璃微珠、鈦酸鉀纖維、聚四氟乙烯粉末、聚苯硫醚粉末、苯乙烯粉末、玻璃纖維、聚四氟乙烯、聚苯硫醚或聚醚碸中的任意一種或至少兩種的組合。以上填料可以單獨使用或混合使用,其中,最佳填料係二氧化矽,可採用的二氧化矽填料如CE44I(CE minerals公司)、FB-35(Denka公司)、525(Sibelco公司)。
理想地,前述粉末填料之粒徑中度值為1-15μm,例如1μm、3μm、5μm、7μm、9μm、10μm、12μm或15μm,理想的粉末填料之粒徑中度值為1-10μm,位於該粒徑段的填料在樹脂液中具有良好的分散性。
理想地,前述熱固性樹脂組合物亦包含固化引發劑。
固化引發劑選自可產生自由基之材料。固化引發劑起到加速固化交聯反應的作用,本發明的熱固性樹脂組合物被加熱時,固化引發劑分解產生自由基,引發熱固性樹脂和含磷交聯劑的分子鏈發生交聯。
理想地,前述固化引發劑在前述熱固性樹脂組合物中之質量百分比為0.3-6%,例如0.3%、0.5%、0.8%、1%、2%、3%、4%、5%或6%。
理想地,前述固化引發劑為過氧化苯甲醯、過氧化二異丙苯、過氧化苯甲酸叔丁酯或2,5-二(2-乙基己醯過氧)-2,5-二甲基己烷中的任意一種或至少兩種的組合。以上雖列舉但不侷限於以上列舉的材料,只要是能產生自由基的材料,都可以作為固化引發劑使用。
理想地,前述熱固性樹脂組合物亦包含助交聯劑,前述助交聯劑包含分子結構中帶有不飽和雙鍵或不飽和三鍵的單體或低分子共聚物。在本發明中,添加一定量助交聯劑可以提高交聯密度。
理想地,前述助交聯劑為三烯丙基三聚異氰酸酯、三烯丙基三聚氰酸酯、二乙烯基苯、多官能丙烯酸酯或雙馬來醯亞胺中的任意一種或至少兩種的組合。
另一方面,本發明提供一種樹脂膠液,前述樹脂膠液係將本發明前述的熱固性樹脂組合物溶解或分散在溶劑中得到。
理想地,前述溶劑為酮類、烴類、醚類、酯類或非質子溶劑中的一種或者至少兩種的組合,理想為丙酮、甲基乙基酮、甲基異丁基酮、甲苯、二甲苯、甲醇、乙醇、伯醇、乙二醇單甲醚、丙二醇單甲醚、丙二醇甲醚醋酸酯、乙酸乙酯、N,N-二甲基甲醯胺或N,N-二乙基甲醯胺中的一種或者至少兩種的混合物。前述溶劑可單獨使用,也可混合使用。溶劑的
添加量可由所屬領域具有通常知識者根據所選用樹脂的黏度來確定,使得到樹脂膠液的黏度適中,便於固化,本發明對此不作限定。
另一方面,本發明提供一種半固化片,前述半固化片包含增強材料以及藉由含浸乾燥後附著其上的如上前述的熱固性樹脂組合物。
在本發明中,前述增強材料為編織纖維布,理想為編織玻璃纖維布。可列舉的有E-glass玻璃纖維布、NE-glass玻璃纖維布、Q-glass玻璃纖維布等,型號包含7628型、2116型、1080型、106型、104型,市售的玻璃布規格和型號皆可用於本發明前述樹脂組合物的製作,不侷限於以上可列舉的玻璃布型號。編織纖維布進一步可以包含有機纖維編織的布,可列舉的有PTFE纖維布、芳綸纖維編織布等。
另一方面,本發明提供一種層壓板,前述層壓板包含至少一張如上述之半固化片。
另一方面,本發明提供一種覆金屬箔層壓板,前述覆金屬箔層壓板包含一張或至少兩張疊合的如上述之半固化片,以及位於疊合後之半固化片的一側或兩側的金屬箔。
另一方面,本發明提供一種高頻電路板,前述高頻電路板包含一張或至少兩張疊合的如上述之半固化片。
在本發明中,前述覆金屬箔層壓板可以示例性地由以下方法製備:將上述之半固化片數張相疊合,上下各壓覆一張銅箔,放進壓機進行固化製得前述覆金屬箔層壓板,本步驟之固化溫度為150℃~300℃(例如150℃、160℃、180℃、200℃、230℃、250℃、280℃或300℃),固化壓力為25~70kg/cm2(例如25kg/cm2、30kg/cm2、35kg/cm2、40kg/cm2、50
kg/cm2、60kg/cm2或70kg/cm2)。
與先前技術相比,本發明至少具有如下功效:
(1)本發明的含磷單體或含磷樹脂中不含有極性的羥基、此外分子結構穩定,具有分子極性低、反應活性高的特點,在其應用之加工過程中也不會產生極性羥基,避免了產生的二次羥基對於其產物之性能的影響,因此該樹脂在提高介電性能同時,依舊帶有可交聯反應基團,使得固化後耐高溫性能無顯著變化,引入含磷封端基團,使得樹脂具有本徵阻燃性能,而且前述的含磷單體或含磷樹脂具有良好溶解性能、較低的熔融黏度,賦予了熱固性樹脂組合物良好的工藝加工性能。
(2)採用介電性能優異含磷單體或含磷樹脂作為熱固性樹脂組合物的組分,可賦予熱固性樹脂組合物良好的介電性能,前述含磷單體或含磷樹脂可作為含有不飽和基團的其他熱固性樹脂的交聯劑,用於交聯固化上述含有不飽和基團的其他熱固性樹脂,藉由樹脂中大量的不飽和雙鍵進行交聯反應來提供電路基板所必須之高頻介電性能和耐高溫性能。
(3)利用本發明之熱固性樹脂組合物製作半固化片較容易,用其製作的層壓板或覆金屬箔層壓板,介電常數和介質損耗角正切低,工藝操作方便,因此本發明的複合材料適合於製作高頻電子設備的電路基板。
下面藉由具體實施方式來進一步說明本發明的技術手段。所屬技術領域中具有通常知識者應該明瞭,下述實施例僅僅係幫助理解本發明,不應視為對本發明之具體限制。
本發明實施例所選取之樹脂組合物中的組成物來源如下表1:
製備例1
三口反應瓶中加入188g丙酮,將228g雙酚A加入反應瓶中,攪拌溶解後,加入106g碳酸鈉。緩慢滴加153g氯丙烯溶液,接著升溫反應4小時後停止反應。過濾,除去大部分溶劑,洗滌,再除去殘留的溶劑和水,即得到雙酚A二烯丙基醚。
將製備的134g雙酚A二烯丙基醚放入反應瓶中,加熱進行重排反應6小時,降溫出料,得到棕色黏稠液體即二烯丙基雙酚A。
三口瓶中通惰性氣體保護,加入300g二氯甲烷,將製備的134g二烯丙基雙酚A放入反應瓶中,攪拌溶解後,加入40g氫氧化鈉,並加入152g四氯化碳。緩慢滴加230g2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯酚,反應4小時,停止反應,加入氫氧化鈉水溶液洗滌至中性,再洗滌數次,除去殘留的溶劑和水,即得到含磷酯化二烯丙基雙酚A,其結構如下所示:
製備例2
三口反應瓶中加入300g正丁醇,將114g線型酚醛樹脂加入反應瓶中,攪拌溶解後,加入56g氫氧化鉀。緩慢滴加153g溴丙烯溶液,接著升溫反應4小時後停止反應。過濾,洗滌,再除去殘留的溶劑和水,即得到烯丙基醚化酚醛樹脂。
將製備的141g烯丙基醚化酚醛樹脂放入反應瓶中,加熱進行重排反應4小時,降溫出料,得到棕色黏稠液體即烯丙基酚醛樹脂。
三口瓶中通惰性氣體保護,加入350g二氯甲烷,將製備的141g烯丙基酚醛樹脂放入反應瓶中,攪拌溶解後,加入72g三乙胺,並加入152g四氯化碳。待溫度降至30℃以下後,緩慢滴加230w2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯酚,反應4小時,停止反應,加入氫氧化鈉水溶液洗滌至中性,再洗滌數次,除去殘留的溶劑和水,即得到含磷酯化烯丙基酚醛樹脂,其Mn為1300,其結構如下所示:
製備例3
三口反應瓶中加入250g甲苯,將118g鄰甲酚酚醛樹脂加入反應瓶中,攪拌溶解後,加入100g氫氧化鈉水溶液(濃度40%),再加入1g四丁基溴化銨。待溫度恒定後,緩慢滴加153g氯丙烯溶液,接著升溫反應4小時後停止反應,洗滌,再除去溶劑,即得到烯丙基醚化鄰甲酚酚醛樹脂。
將製備的159g烯丙基醚化鄰甲酚酚醛樹脂放入反應瓶中,加熱進行重排反應4小時,降溫出料,得到深棕色半固體為烯丙基鄰甲酚酚醛樹脂。
三口瓶中通惰性氣體保護,加入350g二氯甲烷,將製備的159g烯丙基鄰甲酚酚醛樹脂放入反應瓶中,攪拌溶解後,加入103g吡啶,並加入152g四氯化碳。緩慢滴加230g 2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯酚,反應4小時,停止反應,加入氫氧化鈉水溶液洗滌至中性,再洗滌數次,除去殘留的溶劑和水,即得到含磷酯化烯丙基鄰甲酚酚醛樹脂,Mn為1200,結構如下所示:
實施例1
將80重量份的液體丁苯樹脂Ricon100,20重量份的製備例1製作的含磷酯化二烯丙基雙酚A,85重量份的二氧化矽(525),6.5重量份的引發劑DCP混合,用溶劑甲苯調至合適的黏度,攪拌混合均勻,使填料均一的分
散在樹脂中,製得膠液。用1080玻璃纖維布浸漬以上膠液,接著烘乾去掉溶劑後製得半固化片。將八張已製成的半固化片相疊合,在其兩側壓覆1oz(盎司)厚度的銅箔,在壓機中進行2小時固化,固化壓力為50kg/cm2,固化溫度為190℃,物性資料如表2所示。
實施例2
製作工藝和實施例1相同,改變熱固性樹脂組合物成分的配比,其成分配比以及製備得到的覆銅板的性能資料如表2所示。
實施例3-4
製作工藝和實施例1相同,加入助交聯劑雙馬來醯亞胺,其樹脂組合物的成分配比以及製備得到的覆銅板的性能資料如表2所示。
實施例5
將80重量份的液體丁苯樹脂Ricon100,20重量份的製備例2製作的含磷酯化烯丙基酚醛樹脂,85重量份的二氧化矽(525),6.5重量份的引發劑DCP混合,用溶劑甲苯調至合適的黏度,攪拌混合均勻,使填料均一的分散在樹脂中,製得膠液。用1080玻璃纖維布浸漬以上膠液,接著烘乾去掉溶劑後製得半固化片。將八張已製成的半固化片相疊合,在其兩側壓覆1oz(盎司)厚度的銅箔,在壓機中進行2小時固化,固化壓力為50kg/cm2,固化溫度為190℃,物性資料如表2所示。
實施例6
將80重量份的液體丁苯樹脂Ricon100,20重量份的製備例3製作的含磷酯化烯丙基鄰甲酚酚醛樹脂,85重量份的二氧化矽(525),6.5重量份的引發劑DCP混合,用溶劑甲苯調至合適的黏度,攪拌混合均勻,使填料
均一的分散在樹脂中,製得膠液。用1080玻璃纖維布浸漬以上膠液,接著烘乾去掉溶劑後製得半固化片。將八張已製成的半固化片相疊合,在其兩側壓覆1oz(盎司)厚度的銅箔,在壓機中進行2小時固化,固化壓力為50kg/cm2,固化溫度為190℃,物性資料如表2所示。
實施例7-8
製作工藝和實施例1相同,改變熱固性樹脂組合物成分的配比,其成分配比以及製備得到的覆銅板的性能資料如表2所示。
比較例1-2
製作工藝和實施例1相同,配比以及製備得到的覆銅板的性能資料如表2所示。
物性分析
從表2和表3的物性資料結果可以看出,實施例1-4製作的電路基板材料比比較例1和比較例2具有更佳的耐熱性能和阻燃性能,此外實施例2、4、7與實施例1、3、5、6、8的對比也可以看出在前述含磷單體或含磷樹脂占其他含有不飽和基團的熱固性樹脂和含磷單體或含磷樹脂的總重量的20~75%時組分間配合更加優化,能夠使得覆銅板獲得更佳的阻燃性以及耐熱性。
從表2的物性資料結果可以看出,當在本發明配比範圍內加入雙馬來醯亞胺,可以獲得更佳的耐熱性。
藉由上述實施例來說明本發明的熱固性樹脂組合物、由其製作的半固化片、覆金屬箔層壓板及高頻電路基板,但本發明並不侷限於上述實施例,即不意味著本發明必須依賴上述實施例才能實施。所屬技術領域中具有通常知識者應該明瞭,對本發明的任何改進,對本發明所選用原
料的均等置換及輔助成分的添加、具體方式的選擇等,均落在本發明的保護範圍和公開範圍之內。
Claims (20)
- 如申請專利範圍第1項所記載之熱固性樹脂組合物,其中,A為含有DOPO結構的基團。
- 如申請專利範圍第1項所記載之熱固性樹脂組合物,其中,前述含磷單體或含磷樹脂為磷含量大於3%之含磷單體或含磷樹脂。
- 如申請專利範圍第1或2項所記載之熱固性樹脂組合物,其中,前述含磷單體或含磷樹脂藉由如下製備方法製備得到,前述方法包含以下步驟:(1)式II所示酚類化合物或酚類樹脂與烯丙基化試劑反應得到式III所示烯丙基醚化樹脂,示例反應式如下:(2)在保護性氣體保護下,將式III所示烯丙基醚化樹脂加熱,發生分子內重排反應得到式IV所示烯丙基化酚類樹脂;(3)式IV所示烯丙基化酚類樹脂與含磷封端試劑發生反應,得到式I所示含磷單體或含磷樹脂;且,R1為直鏈或支鏈烷基、、、-O-、或;R2為直鏈或支鏈烷基、、、-O-、或;R3為直鏈或支鏈烷基、、、-O-、或;R為直鏈或支鏈烷基、、、-O-、或;X和Y獨立地為氫、烯丙基、直鏈烷基或支鏈烷基中的任意一種或至少兩種的組合;A為含磷封端基團,n為1-20的整數。
- 如申請專利範圍第5項所記載之熱固性樹脂組合物,其中,步驟(1)所記載之酚類化合物或酚類樹脂為酚、二元酚、多元酚或其等之衍生樹脂;前述烯丙基化試劑為烯丙基矽醇、烯丙基氯、烯丙基溴、烯丙基碘或烯丙基胺中的任意一種或至少兩種的組合;前述酚類化合物或酚類樹脂中酚羥基與烯丙基化試劑中烯丙基的莫耳比為1:(0.3~1.2)。
- 如申請專利範圍第5項所記載之熱固性樹脂組合物,其中,步驟(1)所記載之反應在鹼性物質存在下進行;前述鹼性物質與步驟(1)所記載之酚類化合物或酚類樹脂中所含酚羥基之莫耳比為(0.3~1.4):1;及步驟(1)所記載之反應在相轉移催化劑存在下進行;前述相轉移催化劑為季銨鹽類相轉移催化劑;前述相轉移催化劑的加入量為步驟(1)所記載之酚類化合物或酚類樹脂質量的0.1-5%。
- 如申請專利範圍第5項所記載之熱固性樹脂組合物,其中,步驟(1)所記載之反應的溶劑為醇類溶劑、芳香烴溶劑或酮類溶劑中的任意一種或至少兩種的組合;前述溶劑的加入量為步驟(1)所記載之酚類化合物或酚類樹脂質量的2-5倍。
- 如申請專利範圍第5項所記載之熱固性樹脂組合物,其中,步驟(3)所記載之含磷封端試劑為9,10-二氫-9-氧雜-10-膦菲-10-氧化物、9,10-二氫-9-氧雜-10-膦菲-10-氧化物、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-1,4-對苯二酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯酚、2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-4-苯甲醇或2-(6H-二苯並(c,e)(1,2)-5-氧雜-6-膦醯雜-6-苯基-3-苯甲醇中的任意一種或至少兩種的組合;步驟(3)所記載之式IV所示烯丙基化酚類樹脂中酚羥基與含磷封端試劑中含磷封端基之莫耳比為1:(1~1.2);步驟(3)所記載之反應在鹼性物質存在下進行;前述鹼性物質與式III所示烯丙基化酚類樹脂中酚羥基之莫耳比為(1~1.4):1;及步驟(3)所記載之反應在四氯化碳存在下進行;前述四氯化碳與步驟(3)所記載之式III所示烯丙基化酚類樹脂中酚羥基莫耳比為(1-2):1;步驟(3)所記載之反應的溶劑為鹵代烴類溶劑;前述溶劑的加入量為步驟(3)所記載之烯丙基化酚類樹脂質量的2-5倍。
- 如申請專利範圍第1至3項中任一項所記載之熱固性樹脂組合物,其中,前述其他含有不飽和基團的熱固性樹脂為烯丙基封端的聚苯醚樹脂、丙烯酸酯封端的聚苯醚樹脂、乙烯基封端的聚苯醚樹脂、熱固性聚丁二烯樹脂、熱固性聚丁二烯與苯乙烯的共聚樹脂(丁苯樹脂)、雙馬來醯亞胺樹脂、氰酸酯樹脂、烯丙基化的酚醛樹脂或乙烯基封端的矽氧烷樹脂中的任意一種或至少兩種的組合;前述其他含有不飽和基團的熱固性樹脂為分子量在11000以下由碳氫元素組成的含有60%以上乙烯基的聚丁二烯或聚丁二烯與苯乙烯的共聚物樹脂為基礎的熱固性樹脂。
- 如申請專利範圍第1項所記載之熱固性樹脂組合物,其中,前述熱固性成分在前述熱固性樹脂組合物中所占的重量百分比為5-90%。
- 如申請專利範圍第1至4項中任一項所記載之熱固性樹脂組合物,其中,前述熱固性樹脂組合物亦包含粉末填料;前述粉末填料的粒徑中度值為1-15μm;前述粉末填料在熱固性樹脂組合物中的重量百分含量為0%~50%。
- 如申請專利範圍第1至4項中任一項所記載之熱固性樹脂組合物,其中,前述熱固性樹脂組合物亦包含固化引發劑;前述固化引發劑的用量為熱固性樹脂組合物中的質量百分比為0.3-6%;前述固化引發劑為過氧化苯甲醯、過氧化二異丙苯、過氧化苯甲酸叔丁酯或2,5-二(2-乙基己醯過氧)-2,5-二甲基己烷中的任意一種或至少兩種的組合。
- 如申請專利範圍第1至4項中任一項所記載之熱固性樹脂組合物,其中,前述熱固性樹脂組合物亦包含助交聯劑,前述助交聯劑包含分子結構中帶有不飽和雙鍵或不飽和三鍵的單體或低分子共聚物。
- 如申請專利範圍第14項所記載之熱固性樹脂組合物,其中,前述助交聯劑為三烯丙基三聚異氰酸酯、三烯丙基三聚氰酸酯、二乙烯基苯、多官能丙烯酸酯或雙馬來醯亞胺中的任意一種或至少兩種的組合。
- 一種樹脂膠液,其特徵係,前述樹脂膠液係將如申請專利範圍第1至15項中任一項所記載之熱固性樹脂組合物溶解或分散在溶劑中得到。
- 一種半固化片,其特徵係,前述半固化片包含增強材料以及藉由含浸乾燥後附著其上的如申請專利範圍第1至15項中任一項所記載之熱固性樹脂組合物。
- 一種層壓板,其特徵係,前述層壓板包含至少一張如申請專利範圍第17項所記載之半固化片。
- 一種覆金屬箔層壓板,其特徵係,前述覆金屬箔層壓板包含一張或至少兩張疊合的如申請專利範圍第17項所記載之半固化片,以及位於疊合後的半固化片的一側或兩側的金屬箔。
- 一種高頻電路板,其特徵係,前述高頻電路板包含一張或至少兩張疊合的如申請專利範圍第17項所記載之半固化片。
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CN110938234B (zh) * | 2018-09-25 | 2021-06-08 | 中山台光电子材料有限公司 | 阻燃性化合物、其制造方法、树脂组合物及其制品 |
CN112679911B (zh) * | 2020-12-22 | 2022-12-09 | 常熟生益科技有限公司 | 改性环氧树脂组合物及应用其制备的半固化片和层压板 |
KR102677600B1 (ko) * | 2021-02-25 | 2024-06-20 | 주식회사 신아티앤씨 | 수지 조성물 |
KR102700757B1 (ko) * | 2021-02-25 | 2024-08-30 | 주식회사 신아티앤씨 | 비닐계 화합물 제조방법 |
CN116330807B (zh) * | 2023-02-20 | 2024-05-28 | 江苏奇安特节能科技有限公司 | 一种高阻燃夹筋铝箔贴面及其制备方法 |
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JP2020517792A (ja) | 2020-06-18 |
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US20200207899A1 (en) | 2020-07-02 |
US11319397B2 (en) | 2022-05-03 |
JP6815539B2 (ja) | 2021-01-20 |
KR20200021079A (ko) | 2020-02-27 |
TW201910413A (zh) | 2019-03-16 |
CN109306039A (zh) | 2019-02-05 |
WO2019019465A1 (zh) | 2019-01-31 |
EP3660026A1 (en) | 2020-06-03 |
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