CN109306039A - 一种热固性树脂组合物、由其制作的半固化片、覆金属箔层压板及高频电路板 - Google Patents
一种热固性树脂组合物、由其制作的半固化片、覆金属箔层压板及高频电路板 Download PDFInfo
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- CN109306039A CN109306039A CN201710618306.7A CN201710618306A CN109306039A CN 109306039 A CN109306039 A CN 109306039A CN 201710618306 A CN201710618306 A CN 201710618306A CN 109306039 A CN109306039 A CN 109306039A
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- resin
- phosphorous
- thermosetting
- phenolic
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- 229920005989 resin Polymers 0.000 title claims abstract description 152
- 239000011347 resin Substances 0.000 title claims abstract description 152
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 33
- 239000005011 phenolic resin Substances 0.000 claims description 32
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 31
- 229920001568 phenolic resin Polymers 0.000 claims description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 27
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 238000005937 allylation reaction Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- -1 allyl silanol Chemical compound 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 18
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 235000013824 polyphenols Nutrition 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 150000002989 phenols Chemical class 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 11
- 229920002857 polybutadiene Polymers 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 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 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 8
- 229920003986 novolac Polymers 0.000 claims description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000008707 rearrangement Effects 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 229940106691 bisphenol a Drugs 0.000 claims description 5
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000036961 partial effect Effects 0.000 claims description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims 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 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
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 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
- 229910052786 argon Inorganic materials 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
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- ODJZWVFLHZHURI-UHFFFAOYSA-M [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] Chemical compound [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] ODJZWVFLHZHURI-UHFFFAOYSA-M 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- ZGWCKGWOQADGJX-UHFFFAOYSA-N azanium trimethylazanium bromide chloride Chemical compound [Br-].C[NH+](C)C.[Cl-].[NH4+] ZGWCKGWOQADGJX-UHFFFAOYSA-N 0.000 claims 1
- XYHUIOCRXXWEAX-UHFFFAOYSA-N cyclopenta-1,3-diene;phenol Chemical compound C1C=CC=C1.OC1=CC=CC=C1 XYHUIOCRXXWEAX-UHFFFAOYSA-N 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims 1
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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 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 16
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-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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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 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
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- OQRWAMBQGTYSRD-UHFFFAOYSA-N dipotassium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[K+].[K+].[Ti+4].[Ti+4].[Ti+4].[Ti+4] OQRWAMBQGTYSRD-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 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
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 235000012254 magnesium hydroxide Nutrition 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
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
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- 229920006393 polyether sulfone Polymers 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000010703 silicon Substances 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
- 238000005476 soldering Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 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
- 235000019352 zinc silicate Nutrition 0.000 description 1
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Classifications
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- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- 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
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
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- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
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- C08G8/36—Chemically modified polycondensates by etherifying
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Abstract
本发明提供一种热固性树脂组合物、由其制作的半固化片、覆金属箔层压板及高频电路板,所述热固性树脂组合物包含热固性成分,所述热固性成分包含含磷单体或含磷树脂以及含有不饱和基团的其他热固性树脂,所述含磷单体或含磷树脂具有如式I所示的结构,利用含磷单体或含磷树脂作为含有不饱和基团的其他热固性树脂的交联剂,通过树脂中大量的不饱和双键进行交联反应来提供电路基板所需要的高频介电性能和耐高温性能。
Description
技术领域
本发明属于覆铜板技术领域,涉及一种热固性树脂组合物、由其制作的半固化片、覆金属箔层压板及高频电路板。
背景技术
近年来,随着信息通信设备高性能化、高功能化以及网络化的发展,为了传输及处理大容量信息,操作信号趋向于高频化,因而对电路基板的材料提出了要求。
现有的用于印制电路基板的材料中,广泛使用粘接特性优异的环氧树脂,然而,环氧树脂电路基板一般介电常数和介质损耗角正切较高(介电常数大于4,介质损耗角正切0.02左右),高频特性不充分,不能适应信号高频化的要求。因此必须研制介电特性优异的树脂,即介电常数和介质损耗角正切低的树脂。长期以来本领域的技术人员对介电性能很好的热固性的聚丁二烯或聚丁二烯与苯乙烯的共聚物树脂进行了研究,以下就这些研究成果进行进一步的探讨。
欧洲专利申请WO97/38564中公开了采用非极性的苯乙烯与丁二烯和二乙烯基苯的四聚物添加硅铝酸镁填料,以玻璃纤维布作为增强材料制成的电路基板,虽然介电性能优异,但是基板的耐热性很差,玻璃化转变温度只有100℃左右,热膨胀系数很大,很难满足PCB制作过程无铅化制程的高温(240℃以上)要求。
US5571609中公开了采用分子量小于5000的低分子量的1,2-聚丁二烯树脂或聚异丁二烯,和高分子量的丁二烯与苯乙烯的共聚物配合,并加入大量的硅微粉作为填料,以玻璃纤维布作为增强材料制作的电路基板,虽然介电性能优异,但是因为在该专利中采用了高分子量的成分来改善半固化片粘手状况,使得制作半固化片的过程的工艺性能变差;而且因为整个树脂体系的树脂分子中的刚性结构苯环的比例很少,而且交联以后的链段大都由刚性很低的亚甲基组成,因此制作成的板材刚性不好,弯曲强度很低。
US6569943公开了使用分子末端带有乙烯基的胺基改性的液体聚丁二烯树脂,添加低分子量的单体作为固化剂和稀释剂,浸渍玻璃纤维布制作成的电路基板,虽然介电性能很好,但是因为树脂体系在常温下是液体,不能制作成不粘手的半固化片,因此在板材的压制成型时,很难采用通用的半固化片叠卜工艺,工艺操作比较困难。
另外,电子电器设备中使用的印制电路基板材料,要求达到阻燃等级94V-0级,这对高频电路板材料也不例外。US5571609中公开了采用以溴为主的含卤类材料做阻燃剂。虽然含卤类材料阻燃效果较好,但有研究表明,含卤类材料在燃烧时易释放刺激性和有毒性的气体,如卤化氢、二惡英等,使人健康受到危害。在一些电子产品中,已经有禁止使用含卤类的电路板材料。近年来,随着人们环保观念的提高,电子电器中使用的电子材料趋向于无卤化,都在寻求可以替代卤素类阻燃剂的其它类型阻燃剂来满足阻燃的要求。金属氢氧化物阻燃剂虽然不存在含卤阻燃剂那样的毒性问题,但因其阻燃效率差,需要添加更大的量来获得良好的阻燃性能,这会导致树脂混合、成型时的流动性差,使复合材料的加工及机械性能变差;另外由于金属氢氧化物的介电常数大,用其作阻燃剂会带来高频电路基板介电性能的下降。含磷阻燃剂大都具有低烟、无毒的特点,不仅具有良好的阻燃性能,而且能够抑制烟雾和有毒气体的释放,复合添加量少、阻燃效果明显的应用要求。
US2009034058公开了一种无卤高频电路板基材的制作方法,其采用聚丁二烯做主树脂,金属氢氧化物(Mg(OH)3)及含氮的化合物作阻燃剂,采用大量的无机填料作为阻燃剂,不仅存在添加量大导致的成型工艺性能差的问题,而且阻燃效率不高,进而会使介电性能变差等诸多问题。
CN103709718公开了使用集中添加型的含磷阻燃剂作为阻燃材料进行高频覆铜板的制作,但所揭示的几种含磷阻燃剂没有反应基团,不参与复合材料树脂分子间的交联,因其几种含磷阻燃剂的熔点很低(小于200℃),用其制作的高频电路基板材料的耐热性差,不能满足后续电路板元件装配过程高温焊接可靠性的要求。
CN106543228A公开了具有如下结构的树脂:
然而如果将这样的树脂应用于覆铜板的制备,则由于其结构中含有羟基极性基团会使得制备得到的覆铜板的介电性能不能满足要求。
CN106366128公开了一种具有如下结构的膦菲类化合物:
然而如果将该化合物用于覆铜板的制备,则会由于其结构中存在的烯丙基醚结构而在加工过程中发生重排反应,导致产生二次羟基极性基团,同样会使得制备得到的覆铜板的介电性能不能满足要求。
因此,在本领域其中,期望开发一种既能够保证具有良好的阻燃性能,又能够在介电性能、耐热性能等多个方面取得良好效果的热固性树脂组合物。
发明内容
针对现有技术的不足,本发明的目的在于提供一种热固性树脂组合物、由其制作的半固化片、覆金属箔层压板及高频电路板,本发明的热固性树脂组合物不含有极性基团(例如羟基)、分子极性低、反应活性高,降低其固化物的介电常数和损耗,并且能够保证固化物具有良好的阻燃性能、良好的机械强度以及良好的耐高温等性能。
为达到此发明目的,本发明采用以下技术方案:
一方面,本发明提供一种热固性树脂组合物,所述热固性树脂组合物包含热固性成分,所述热固性成分包含含磷单体或含磷树脂以及其他含有不饱和基团的热固性树脂,所述含磷单体或含磷树脂具有如式I所示的结构:
其中,R为直链或支链烷基, X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合;A为含磷封端基团,n为1-20的整数。
在本发明所述热固性树脂组合物中,所述含磷单体或含磷树脂具有低极性的特征,所述低极性是指不含有极性基团,尤其是不含有羟基基团,使得树脂具有较低的极性,克服了通用热固性树脂极性大导致的高频介电常数和损耗高的缺陷,同时可通过该结构中的烯丙基结构实现交联固化,保证固化后的力学强度,并使得固化物具有优良的耐热性能,同时,该树脂中含有阻燃性含磷结构,使其具有很好的本征阻燃效果。
在本发明中,所述含磷单体或含磷树脂能够很好地与其他含有不饱和基团的热固性树脂进行配合,一同提升树脂组合物的耐高温以及耐湿热性能,在具备较好阻燃性的同时,使得由该树脂组合物制备得到的固化物具有良好的耐热性以及介电性能。
优选地,所述R为C1-C6(例如C1、C2、C3、C4、C5或C6)的直链烷基或C3-C6(例如C3、C4、C5或C6)支链烷基,具体地可以为-CH2-、 等。
优选地,R为-CH2-、 n为1-20的整数,X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合,A为含磷封端基团。
在本发明中,n为1-20的整数,例如n可以为1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20。
优选地,X和Y独立地为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)的直链烷基或C3-C21(例如C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20或C21)支链烷基。
优选地,A为含有DOPO结构的基团,优选 中的任意一种。
优选地,所述含磷单体或含磷树脂为磷含量大于3%的磷单体或含磷树脂,更优选量大于5%磷单体或含磷树脂,进一步优选磷量大于8%的磷单体或含磷树脂。含磷量越大,可提供热固性树脂组合物良好的阻燃性能。
优选地,所述含磷单体或含磷树脂为具有如下式A-式E所示结构的化合物中的任意一种或至少两种的组合:
其中n为1-20的整数。
优选地,所述含磷单体或含磷树脂通过如下制备方法制备得到,所述方法包括以下步骤:
(1)式II所示酚类化合物或酚类树脂与烯丙基化试剂反应得到式III所示烯丙基醚化树脂,示例反应式如下:
(2)在保护性气体保护下,将式III所示烯丙基醚化树脂加热,发生分子内重排反应得到式IV所示烯丙基化酚类树脂;
(3)式III所示烯丙基化酚类树脂与含磷封端试剂发生反应,得到式I所示含磷单体或含磷树脂;
其中,R1为直链或支链烷基, R2为直链或支链烷基, R3为直链或支链烷基, R为直链或支链烷基,或X和Y独立地为氢、烯丙基、直链烷基或支链烷基中的任意一种或至少两种的组合;A为含磷封端基团,n为1-20的整数。
在本发明中,步骤(2)的重排步骤中,当R2为或时,包括其中的烯丙醚基会发生重排的情况,导致在式IV所示烯丙基化酚类树脂的中间单元R3中含有由于重排而产生烯丙基,进而在产物式I所示低极性树脂的R单元中包括由于重排而产生的烯丙基,本发明中为了表述的简单未将该烯丙基直接表示至R3和R的相应结构中,而仅仅由X来代表了苯环上所有的取代基,然而在此明确此处X包含由于重排而产生的烯丙基,如果在重排反应前R2为或苯环上带有其他取代基X,在步骤(2)的重排反应后,则在R3的结构中X可以表示重排产生的烯丙基和反应前的其他取代基的组合。当然在步骤(2)的重排步骤中,也包括R2为时,R2单元中烯丙醚基不发生重排反应的情况,此时,反应后R3以及产物R中的X与反应前式III所示烯丙基醚化树脂中R2中的X基团相同。
优选地,步骤(1)所述酚类化合物或酚类树脂为酚、二元酚、多元酚或它们的衍生树脂,优选为苯酚、邻甲酚、双酚A、双酚F、四甲基双酚A、酚醛树脂、邻甲酚酚醛树脂或环戊二烯酚醛树脂中的任意一种或至少两种的组合。
优选地,所述烯丙基化试剂为烯丙基硅醇、烯丙基氯、烯丙基溴、烯丙基碘或烯丙基胺中的任意一种或至少两种的组合。
优选地,所述酚类化合物或酚类树脂中酚羟基与烯丙基化试剂中烯丙基的摩尔比为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。
优选地,步骤(1)所述反应在碱性物质存在下进行,所述碱性物质优选氢氧化钠、氢氧化钾、碳酸钠或碳酸钾中的任意一种或至少两种的组合。
优选地,所述碱性物质与步骤(1)所述酚类化合物或酚类树脂中所含酚羟基的摩尔比为(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。
优选地,步骤(1)所述反应在相转移催化剂存在下进行。
优选地,所述相转移催化剂为季铵盐类相转移催化剂,优选四丁基氯化铵、四丁基溴化铵、苄基三乙基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵或十四烷基溴三甲基氯化铵中的任意一种或至少两种的组合。
优选地,所述相转移催化剂的加入量为步骤(1)所述酚类化合物或酚类树脂质量的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%。
优选地,步骤(1)所述反应的溶剂为醇类溶剂、芳香烃溶剂或酮类溶剂中的任意一种或至少两种的组合,优选为乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一种或至少两种的组合。
优选地,所述溶剂的加入量为步骤(1)所述酚类化合物或酚类树脂质量的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。
优选地,步骤(1)所述反应的温度为60-90℃,例如60℃、63℃、65℃、68℃、70℃、75℃、78℃、80℃、85℃、88℃或90℃。
优选地,步骤(1)所述反应的时间为4-6小时,例如4小时、4.3小时、4.5小时、4.8小时、5小时、5.2小时、5.5小时、5.8小时或6小时。
优选地,步骤(2)所述保护性气体为氮气或氩气。
优选地,步骤(2)所述加热为加热至180-220℃,例如180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃。
优选地,步骤(2)所述反应的时间为4-6小时,例如4小时、4.3小时、4.5小时、4.8小时、5小时、5.2小时、5.5小时、5.8小时或6小时。
优选地,步骤(3)所述含磷封端试剂为9,10-二氢-9-氧杂-10-膦菲-10-氧化物、9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-1,4-对苯二酚、2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-4-苯酚、2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-3-苯酚、2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-4-苯甲醇或2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-3-苯甲醇中的任意一种或至少两种的组合。
优选地,步骤(3)所述式III所示烯丙基化酚类树脂中酚羟基与含磷封端试剂中含磷封端基的摩尔比为1:(1~1.2),例如1:1、1:1.05、1:1.1、1:1.15或1:1.2。使得反应得到的树脂分子结构中酚羟基均被含磷封端基封端,从而使树脂中无极性羟基基团。
优选地,步骤(3)所述反应在碱性物质存在下进行。
优选地,所述碱性物质为无机碱或有机碱,优选氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、三乙胺或吡啶中的任意一种或至少两种的组合。
优选地,所述碱性物质与式III所示烯丙基化酚类树脂中酚羟基的摩尔比为(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。
优选地,步骤(3)所述反应在四氯化碳存在下进行。
优选地,所述四氯化碳与步骤(3)所述式III所示烯丙基化酚类树脂中酚羟基摩尔比为(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。
优选地,步骤(3)所述反应的溶剂为卤代烃类溶剂,优选为一氯甲烷、二氯甲烷、三氯甲烷或二氯乙烷中的任意一种或至少两种的组合。
优选地,所述溶剂的加入量为步骤(3)所述烯丙基化酚类树脂质量的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。
优选地,步骤(3)所述反应的温度为0-30℃,例如0℃、3℃、5℃、8℃、10℃、15℃、18℃、20℃、25℃、28℃或30℃,优选10℃。
优选地,步骤(3)所述反应的时间为4-6小时,例如4小时、4.3小时、4.5小时、4.8小时、5小时、5.2小时、5.5小时、5.8小时或6小时。
通过本发明的方法制备得到的树脂中不含有极性的羟基、并且分子结构稳定,具有分子极性低、反应活性高的特点,在其应用的加工过程中也不会产生极性羟基,避免了产生的二次羟基对于其产物的性能的影响,并且以含磷封端基封端,赋予树脂组合物以本征阻燃性能。
在本发明中,所述含磷单体或含磷树脂中的杂质或副产物含量少,杂质或副产物含量少,可以提供热固性树脂组合物良好的介电性能和耐热性。优选的所述含磷单体或含磷树脂的介质损耗角正切小于等于0.0025(1GHz)。
优选地,所述其他含有不饱和基团的热固性树脂为含有双键或叁键的热固性树脂,优选烯丙基封端的聚苯醚树脂、丙烯酸酯封端的聚苯醚树脂、乙烯基封端的聚苯醚树脂、热固性聚丁二烯树脂、热固性聚丁二烯与苯乙烯的共聚树脂(丁苯树脂)、双马来酰亚胺树脂、氰酸酯树脂、烯丙基化的酚醛树脂、烯丙基化的邻甲酚酚醛树脂或乙烯基封端的硅氧烷树脂中的任意一种或至少两种的组合。以上虽列举但不局限于以上列举的树脂,所述树脂可以是一种,也可以是两种以上配合使用。
优选地,所述其他含有不饱和基团的热固性树脂为分子量在11000以下(例如11000、10000、9000、8000、7000、6000、5000、4000、3000、2000、1000等)由碳氢元素组成的含有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与苯乙烯的共聚物树脂为基础的热固性树脂,更优选地分子量小于8000。在本发明中此处所述热固性树脂在室温下是液体,液体树脂的粘度很低,因而有利于后面的浸渍工艺操作。
在本发明中,所述含磷单体或含磷树脂可作为上述其他含有不饱和基团的热固性树脂的交联剂,用于交联固化上述其他含有不饱和基团的热固性树脂。
优选地,所述热固性成分在所述热固性树脂组合物中所占的重量百分比为5-90%,例如5%、8%、10%、15%、18%、20%、25%、30%、40%、50%、60%、70%、80%或90%。
优选地,所述含磷单体或含磷树脂占其他含有不饱和基团的热固性树脂和含磷单体或含磷树脂的总重量的20~75%,例如20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%或75%。
优选地,所述热固性树脂组合物还包括粉末填料,以重量含量计,所述粉末填料在热固性树脂组合物中的含量为0%~50%,例如0%、1%、5%、10%、20%、30%、40%或50%。
优选地,所述粉末填料包括结晶型二氧化硅、熔融型二氧化硅、球型二氧化硅、二氧化钛、钛酸锶、钛酸钡、钛酸锶钡、硅酸锌、硅酸镁、氮化铝、氮化硼、氮化硅、碳化硅、氧化铝、氧化镁、氧化锆、氧化铍、氢氧化铝、氢氧化镁、高岭土、滑石粉、水滑石、硅酸钙、剥离粉、熔融硅微粉、洁净硅微粉、球形硅微粉、硼酸锌、莫来石、金红石型二氧化钛、锐钛型二氧化钛、中空玻璃微珠、钛酸钾纤维、聚四氟乙烯粉末、聚苯硫醚粉末、苯乙烯粉末、玻璃纤维、聚四氟乙烯、聚苯硫醚或聚醚砜中的任意一种或至少两种的组合。以上填料可以单独使用或混合使用,其中,最佳填料是二氧化硅,可采用的二氧化硅填料如CE44I(CE minerals公司)、FB-35(Denka公司)、525(Sibelco公司)。
优选地,所述粉末填料的粒径中度值为1-15μm,例如1μm、3μm、5μm、7μm、9μm、10μm、12μm或15μm,优选粉末填料的粒径中度值为1-10μm,位于该粒径段的填料在树脂液中具有良好的分散性。
优选地,所述热固性树脂组合物还包括固化引发剂。
固化引发剂选自可产生自由基的材料。固化引发剂起到加速固化交联反应的作用,本发明的热固性树脂组合物被加热时,固化引发剂分解产生自由基,引发热固性树脂和含磷交联剂的分子链发生交联。
优选地,所述固化引发剂在所述热固性树脂组合物中的质量百分比为0.3-6%,例如0.3%、0.5%、0.8%、1%、2%、3%、4%、5%或6%。
优选地,所述固化引发剂为过氧化苯甲酰、过氧化二异丙苯、过氧化苯甲酸叔丁酯或2,5-二(2-乙基己酰过氧)-2,5-二甲基己烷中的任意一种或至少两种的组合。以上虽列举但不局限于以上列举的材料,只要是能产生自由基的材料,都可以作为固化引发剂使用。
优选地,所述热固性树脂组合物还包括助交联剂,所述助交联剂包括分子结构中带有不饱和双键或不饱和叁键的单体或低分子共聚物。在本发明中,添加一定量助交联剂可以提高交联密度。
优选地,所述助交联剂为三烯丙基三聚异氰酸酯、三烯丙基三聚氰酸酯、二乙烯基苯、多官能丙烯酸酯或双马来酰亚胺中的任意一种或至少两种的组合。
另一方面,本发明提供一种树脂胶液,所述树脂胶液是将本发明所述的热固性树脂组合物溶解或分散在溶剂中得到。
优选地,所述溶剂为酮类、烃类、醚类、酯类或非质子溶剂中的一种或者至少两种的组合,优选丙酮、甲基乙基酮、甲基异丁基酮、甲苯、二甲苯、甲醇、乙醇、伯醇、乙二醇单甲醚、丙二醇单甲醚、丙二醇甲醚醋酸酯、乙酸乙酯、N,N-二甲基甲酰胺或N,N-二乙基甲酰胺中的一种或者至少两种的混合物。所述溶剂可单独使用,也可混合使用。溶剂的添加量可由本领域技术人员根据所选用树脂的粘度来确定,使得到树脂胶液的粘度适中,便于固化,本发明对此不作限定。
另一方面,本发明提供一种半固化片,所述半固化片包括增强材料以及通过含浸干燥后附着其上的如上所述的热固性树脂组合物。
在本发明中,所述增强材料为编织纤维布,优选编织玻璃纤维布。可列举的有E-glass玻璃纤维布、NE-glass玻璃纤维布、Q-glass玻璃纤维布等,型号包括7628型、2116型、1080型、106型、104型,市售的玻璃布规格和型号皆可用于本发明所述树脂组合物的制作,不局限于以上可列举的玻璃布型号。编织纤维布还可以包括有机纤维编织的布,可列举的有PTFE纤维布、芳纶纤维编织布等。
另一方面,本发明提供一种层压板,所述层压板包括至少一张如上所述的半固化片。
另一方面,本发明提供一种覆金属箔层压板,所述覆金属箔层压板包括一张或至少两张叠合的如上所述的半固化片,以及位于叠合后的半固化片的一侧或两侧的金属箔。
另一方面,本发明提供一种高频电路板,所述高频电路板包括一张或至少两张叠合的如上所述的半固化片。
在本发明中,所述覆金属箔层压板可以示例性地有以下方法制备:将上述的半固化片数张相叠合,上下各压覆一张铜箔,放进压机进行固化制得所述覆金属箔层压板,本步骤的固化温度为150℃~300℃(例如150℃、160℃、180℃、200℃、230℃、250℃、280℃或300℃),固化压力为25~70kg/cm2(例如25kg/cm2、30kg/cm2、35kg/cm2、40kg/cm2、50kg/cm2、60kg/cm2或70kg/cm2)。
与现有技术相比,本发明具有如下有益效果:
(1)本发明的含磷单体或含磷树脂中不含有极性的羟基、并且分子结构稳定,具有分子极性低、反应活性高的特点,在其应用的加工过程中也不会产生极性羟基,避免了产生的二次羟基对于其产物的性能的影响,因此该树脂在提高介电性能同时,依旧带有可交联反应基团,使得固化后耐高温性能无显著变化,引入含磷封端基团,使得树脂具有本征阻燃性能,而且所述的含磷单体或含磷树脂具有良好溶解性能、较低的熔融粘度,赋予了热固性树脂组合物良好的工艺加工性能。
(2)采用介电性能优异含磷单体或含磷树脂作为热固性树脂组合物的组分,可赋予热固性树脂组合物良好的介电性能,所述含磷单体或含磷树脂可作为含有不饱和基团的其他热固性树脂的交联剂,用于交联固化上述含有不饱和基团的其他热固性树脂,通过树脂中大量的不饱和双键进行交联反应来提供电路基板所需要的高频介电性能和耐高温性能。
(3)利用本发明的热固性树脂组合物制作半固化片较容易,用其制作的层压板或覆金属箔层压板,介电常数和介质损耗角正切低,工艺操作方便,因此本发明的复合材料适合于制作高频电子设备的电路基板。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
本发明实施例所选取的树脂组合物中的组成物来源如下表1:
表1
制备例1
三口反应瓶中加入188g丙酮,将228g双酚A加入反应瓶中,搅拌溶解后,加入106g碳酸钠。缓慢滴加153g氯丙烯溶液,然后升温反应4小时后停止反应。过滤,除去大部分溶剂,洗涤,再除去残留的溶剂和水,即得到双酚A二烯丙基醚。
将制备的134g双酚A二烯丙基醚放入反应瓶中,加热进行重排反应6小时,降温出料,得到棕色粘稠液体即二烯丙基双酚A。
三口瓶中通惰性气体保护,加入300g二氯甲烷,将制备的134g二烯丙基双酚A放入反应瓶中,搅拌溶解后,加入40g氢氧化钠,并加入152g四氯化碳。缓慢滴加230g 2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-4-苯酚,反应4小时,停止反应,加入氢氧化钠水溶液洗涤至中性,再洗涤数次,除去残留的溶剂和水,即得到含磷酯化二烯丙基双酚A,其结构如下所示:
制备例2
三口反应瓶中加入300g正丁醇,将114g线型酚醛树脂加入反应瓶中,搅拌溶解后,加入56g氢氧化钾。缓慢滴加153g溴丙烯溶液,然后升温反应4小时后停止反应。过滤,洗涤,再除去残留的溶剂和水,即得到烯丙基醚化酚醛树脂。
将制备的141g烯丙基醚化酚醛树脂放入反应瓶中,加热进行重排反应4小时,降温出料,得到棕色粘稠液体即烯丙基酚醛树脂。
三口瓶中通惰性气体保护,加入350g二氯甲烷,将制备的141g二烯丙基双酚A放入反应瓶中,搅拌溶解后,加入72g三乙胺,并加入152g四氯化碳。待温度降至30℃以下后,缓慢滴加230g 2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-4-苯酚,反应4小时,停止反应,加入氢氧化钠水溶液洗涤至中性,再洗涤数次,除去残留的溶剂和水,即得到含磷酯化烯丙基酚醛树脂,其Mn为1300,其结构如下所示:
制备例3
三口反应瓶中加入250g甲苯,将118g邻甲酚酚醛树脂加入反应瓶中,搅拌溶解后,加入100g氢氧化钠水溶液(浓度40%),再加入1g四丁基溴化铵。待温度恒定后,缓慢滴加153g氯丙烯溶液,然后升温反应4小时后停止反应,洗涤,再除去溶剂,即得到烯丙基醚化邻甲酚酚醛树脂。
将制备的159g烯丙基醚化邻甲酚酚醛树脂放入反应瓶中,加热进行重排反应4小时,降温出料,得到深棕色半固体为烯丙基邻甲酚酚醛树脂。
三口瓶中通惰性气体保护,加入350g二氯甲烷,将制备的159g二烯丙基双酚A放入反应瓶中,搅拌溶解后,加入103g吡啶,并加入152g四氯化碳。缓慢滴加230g 2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-3-苯酚,反应4小时,停止反应,加入氢氧化钠水溶液洗涤至中性,再洗涤数次,除去残留的溶剂和水,即得到含磷酯化烯丙基邻甲酚酚醛树脂,Mn为1200,结构如下所示:
实施例1
将80重量份的液体丁苯树脂Ricon100,20重量份的制备例1制作的含磷酯化二烯丙基双酚A,85重量份的二氧化硅(525),6.5重量份的引发剂DCP混合,用溶剂甲苯调至合适的粘度,搅拌混合均匀,使填料均一的分散在树脂中,制得胶液。用1080玻璃纤维布浸渍以上胶液,然后烘干去掉溶剂后制得半固化片。将八张已制成的半固化片相叠合,在其两侧压覆1oz(盎司)厚度的铜箔,在压机中进行2小时固化,固化压力为50kg/cm2,固化温度为190℃,物性数据如表2所示。
实施例2
制作工艺和实施例1相同,改变热固性树脂组合物成分的配比,其成分配比以及制备得到的覆铜板的性能数据如表2所示。
实施例3-4
制作工艺和实施例1相同,加入助交联剂双马来酰亚胺,其树脂组合物的成分配比以及制备得到的覆铜板的性能数据如表2所示。
实施例5
将80重量份的液体丁苯树脂Ricon100,20重量份的制备例2制作的含磷酯化烯丙基酚醛树脂,85重量份的二氧化硅(525),6.5重量份的引发剂DCP混合,用溶剂甲苯调至合适的粘度,搅拌混合均匀,使填料均一的分散在树脂中,制得胶液。用1080玻璃纤维布浸渍以上胶液,然后烘干去掉溶剂后制得半固化片。将八张已制成的半固化片相叠合,在其两侧压覆1oz(盎司)厚度的铜箔,在压机中进行2小时固化,固化压力为50kg/cm2,固化温度为190℃,物性数据如表2所示。
实施例6
将80重量份的液体丁苯树脂Ricon100,20重量份的制备例3制作的含磷酯化烯丙基邻甲酚酚醛树脂,85重量份的二氧化硅(525),6.5重量份的引发剂DCP混合,用溶剂甲苯调至合适的粘度,搅拌混合均匀,使填料均一的分散在树脂中,制得胶液。用1080玻璃纤维布浸渍以上胶液,然后烘干去掉溶剂后制得半固化片。将八张已制成的半固化片相叠合,在其两侧压覆1oz(盎司)厚度的铜箔,在压机中进行2小时固化,固化压力为50kg/cm2,固化温度为190℃,物性数据如表2所示。
实施例7-8
制作工艺和实施例1相同,改变热固性树脂组合物成分的配比,其成分配比以及制备得到的覆铜板的性能数据如表2所示。
比较例1-2
制作工艺和实施例1相同,配比以及制备得到的覆铜板的性能数据如表2所示。
表2
表3
物性分析
从表2和表3的物性数据结果可以看出,实施例1-4制作的电路基板材料比比较例1和比较例2具有更好的耐热性能和阻燃性能,并且实施例2、4、7与实施例1、3、5、6、8的对比也可以看出在所述含磷单体或含磷树脂占其他含有不饱和基团的热固性树脂和含磷单体或含磷树脂的总重量的20~75%时组分间配合更加优化,能够使得覆铜板获得更好的阻燃性以及耐热性。
从表2的物性数据结果可以看出,当在本发明配比范围内加入双马来酰亚胺,可以获得更好的耐热性。
过上述实施例来说明本发明的热固性树脂组合物、由其制作的半固化片、覆金属箔层压板及高频电路基板,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种热固性树脂组合物,其特征在于,所述热固性树脂组合物包含热固性成分,所述热固性成分包含含磷单体或含磷树脂以及其他含有不饱和基团的热固性树脂,所述含磷单体或含磷树脂具有如式I所示的结构:
其中,R为直链或支链烷基,-O-、 X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合;A为含磷封端基团,n为1-20的整数。
2.根据权利要求1所述的热固性树脂组合物,其特征在于,所述R为-CH2-、-O-、n为1-20的整数,X和Y独立地为氢、烯丙基、直链烷基、支链烷基中的任意一种或至少两种的组合;A为含磷封端基团;
优选地,A为含有DOPO结构的基团,优选 中的任意一种;
优选地,所述含磷单体或含磷树脂为磷含量大于3%的磷单体或含磷树脂,更优选量大于5%磷单体或含磷树脂,进一步优选磷量大于8%的磷单体或含磷树脂;
优选地,所述含磷单体或含磷树脂为具有如下式A-式D所示结构的化合物中的任意一种或至少两种的组合:
其中n为1-20的整数。
3.根据权利要求1或2所述的热固性树脂组合物,其特征在于,所述含磷单体或含磷树脂通过如下制备方法制备得到,所述方法包括以下步骤:
(1)式II所示酚类化合物或酚类树脂与烯丙基化试剂反应得到式III所示烯丙基醚化树脂,示例反应式如下:
(2)在保护性气体保护下,将式III所示烯丙基醚化树脂加热,发生分子内重排反应得到式IV所示烯丙基化酚类树脂;
(3)式III所示烯丙基化酚类树脂与含磷封端试剂发生反应,得到式I所示含磷单体或含磷树脂;
其中,R1为直链或支链烷基,-O-、 R2为直链或支链烷基,-O-、R3为直链或支链烷基, -O-、R为直链或支链烷基,-O-、 X和Y独立地为氢、烯丙基、直链烷基或支链烷基中的任意一种或至少两种的组合;A为含磷封端基团,n为1-20的整数;
优选地,步骤(1)所述酚类化合物或酚类树脂为酚、二元酚、多元酚或它们的衍生树脂,优选为苯酚、邻甲酚、双酚A、双酚F、四甲基双酚A、酚醛树脂、邻甲酚酚醛树脂或环戊二烯酚醛树脂中的任意一种或至少两种的组合;
优选地,所述烯丙基化试剂为烯丙基硅醇、烯丙基氯、烯丙基溴、烯丙基碘或烯丙基胺中的任意一种或至少两种的组合;
优选地,所述酚类化合物或酚类树脂中酚羟基与烯丙基化试剂中烯丙基的摩尔比为1:(0.3~1.2);
优选地,步骤(1)所述反应在碱性物质存在下进行,所述碱性物质优选氢氧化钠、氢氧化钾、碳酸钠或碳酸钾中的任意一种或至少两种的组合;
优选地,所述碱性物质与步骤(1)所述酚类化合物或酚类树脂中所含酚羟基的摩尔比为(0.3~1.4):1;
优选地,步骤(1)所述反应在相转移催化剂存在下进行;
优选地,所述相转移催化剂为季铵盐类相转移催化剂,优选四丁基氯化铵、四丁基溴化铵、苄基三乙基氯化铵、四丁基硫酸氢铵、三辛基甲基氯化铵、十二烷基三甲基氯化铵或十四烷基溴三甲基氯化铵中的任意一种或至少两种的组合;
优选地,所述相转移催化剂的加入量为步骤(1)所述酚类化合物或酚类树脂质量的0.1-5%;
优选地,步骤(1)所述反应的溶剂为醇类溶剂、芳香烃溶剂或酮类溶剂中的任意一种或至少两种的组合,优选为乙醇、丙醇、丁醇、甲苯或二甲苯中的任意一种或至少两种的组合;
优选地,所述溶剂的加入量为步骤(1)所述酚类化合物或酚类树脂质量的2-5倍;
优选地,步骤(1)所述反应的温度为60-90℃;
优选地,步骤(1)所述反应的时间为4-6小时;
优选地,步骤(2)所述保护性气体为氮气或氩气;
优选地,步骤(2)所述加热为加热至180-220℃;
优选地,步骤(2)所述反应的时间为4-6小时;
优选地,步骤(3)所述含磷封端试剂为9,10-二氢-9-氧杂-10-膦菲-10-氧化物、9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-1,4-对苯二酚、2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-4-苯酚、2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-3-苯酚、2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-4-苯甲醇或2-(6H-二苯并(c,e)(1,2)-5-氧杂-6-膦酰杂-6-苯基-3-苯甲醇中的任意一种或至少两种的组合;
优选地,步骤(3)所述式III所示烯丙基化酚类树脂中酚羟基与含磷封端试剂中含磷封端基的摩尔比为1:(1~1.2);
优选地,步骤(3)所述反应在碱性物质存在下进行;
优选地,所述碱性物质为无机碱或有机碱,优选氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、三乙胺或吡啶中的任意一种或至少两种的组合;
优选地,所述碱性物质与式III所示烯丙基化酚类树脂中酚羟基的摩尔比为(1~1.4):1;
优选地,步骤(3)所述反应在四氯化碳存在下进行;
优选地,所述四氯化碳与步骤(3)所述式III所示烯丙基化酚类树脂中酚羟基摩尔比为(1-2):1;
优选地,步骤(3)所述反应的溶剂为卤代烃类溶剂,优选为一氯甲烷、二氯甲烷、三氯甲烷或二氯乙烷中的任意一种或至少两种的组合;
优选地,所述溶剂的加入量为步骤(3)所述烯丙基化酚类树脂质量的2-5倍;
优选地,步骤(3)所述反应的温度为0-30℃,优选10℃;
优选地,步骤(3)所述反应的时间为4-6小时。
4.根据权利要求1-3中任一项所述的热固性树脂组合物,其特征在于,所述其他含有不饱和基团的热固性树脂为含有双键或叁键的热固性树脂,优选烯丙基封端的聚苯醚树脂、丙烯酸酯封端的聚苯醚树脂、乙烯基封端的聚苯醚树脂、热固性聚丁二烯树脂、热固性聚丁二烯与苯乙烯的共聚树脂(丁苯树脂)、双马来酰亚胺树脂、氰酸酯树脂、烯丙基化的酚醛树脂或乙烯基封端的硅氧烷树脂中的任意一种或至少两种的组合;
优选地,所述其他含有不饱和基团的热固性树脂为分子量在11000以下由碳氢元素组成的含有60%以上乙烯基的聚丁二烯或聚丁二烯与苯乙烯的共聚物树脂为基础的热固性树脂,更优选地分子量小于8000;
优选地,所述热固性成分在所述热固性树脂组合物中所占的重量百分比为5-90%;
优选地,所述含磷单体或含磷树脂占其他含有不饱和基团的热固性树脂和含磷单体或含磷树脂的总重量的20~75%。
5.根据权利要求1-4中任一项所述的热固性树脂组合物,其特征在于,所述热固性树脂组合物还包括粉末填料;
优选地,所述粉末填料的粒径中度值为1-15μm,优选粉末填料的粒径中度值为1-10μm;
优选地,所述粉末填料在热固性树脂组合物中的重量百分含量为0%~50%;
优选地,所述热固性树脂组合物还包括固化引发剂;
优选地,所述固化引发剂的用量为热固性树脂组合物中的质量百分比为0.3-6%;
优选地,所述固化引发剂为过氧化苯甲酰、过氧化二异丙苯、过氧化苯甲酸叔丁酯或2,5-二(2-乙基己酰过氧)-2,5-二甲基己烷中的任意一种或至少两种的组合;
优选地,所述热固性树脂组合物还包括助交联剂,所述助交联剂包括分子结构中带有不饱和双键或不饱和叁键的单体或低分子共聚物;
优选地,所述助交联剂为三烯丙基三聚异氰酸酯、三烯丙基三聚氰酸酯、二乙烯基苯、多官能丙烯酸酯或双马来酰亚胺中的任意一种或至少两种的组合。
6.一种树脂胶液,其特征在于,所述树脂胶液是将如权利要求1-5中任一项所述的热固性树脂组合物溶解或分散在溶剂中得到。
7.一种半固化片,其特征在于,所述半固化片包括增强材料以及通过含浸干燥后附着其上的如权利要求1-5中任一项所述的热固性树脂组合物。
8.一种层压板,其特征在于,所述层压板包括至少一张如权利要求7所述的半固化片。
9.一种覆金属箔层压板,其特征在于,所述覆金属箔层压板包括一张或至少两张叠合的如权利要求7所述的半固化片,以及位于叠合后的半固化片的一侧或两侧的金属箔。
10.一种高频电路板,其特征在于,所述高频电路板包括一张或至少两张叠合的如权利要求7所述的半固化片。
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CN201710618306.7A CN109306039A (zh) | 2017-07-26 | 2017-07-26 | 一种热固性树脂组合物、由其制作的半固化片、覆金属箔层压板及高频电路板 |
KR1020207001410A KR102282600B1 (ko) | 2017-07-26 | 2017-11-02 | 열경화성 수지 조성물, 이로 제조된 프리프레그, 금속박 적층판 및 고주파 회로기판 |
PCT/CN2017/109051 WO2019019465A1 (zh) | 2017-07-26 | 2017-11-02 | 一种热固性树脂组合物、由其制作的半固化片、覆金属箔层压板及高频电路板 |
EP17918939.4A EP3660026A4 (en) | 2017-07-26 | 2017-11-02 | COMPOSITION OF THERMOSETTING RESIN, PRE-IMPREGNATED MADE FROM IT, LAMINATE COATED WITH METAL SHEET, AND PRINTED HIGH FREQUENCY CIRCUIT BOARD |
JP2019557756A JP6815539B2 (ja) | 2017-07-26 | 2017-11-02 | 熱硬化性樹脂組成物、それにより製造されたプリプレグ、金属箔張積層板および高周波配線基板 |
US16/633,012 US11319397B2 (en) | 2017-07-26 | 2017-11-02 | Thermosetting resin composition, prepreg made therefrom, laminate clad with metal foil, and high-frequency circuit board |
TW106140390A TWI650361B (zh) | 2017-07-26 | 2017-11-21 | 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 |
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JP (1) | JP6815539B2 (zh) |
KR (1) | KR102282600B1 (zh) |
CN (1) | CN109306039A (zh) |
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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 |
KR20220121549A (ko) * | 2021-02-25 | 2022-09-01 | 주식회사 신아티앤씨 | 비닐계 화합물 제조방법 |
CN116330807A (zh) * | 2023-02-20 | 2023-06-27 | 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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TWI650361B (zh) | 2019-02-11 |
KR20200021079A (ko) | 2020-02-27 |
EP3660026A4 (en) | 2021-04-28 |
JP6815539B2 (ja) | 2021-01-20 |
US20200207899A1 (en) | 2020-07-02 |
KR102282600B1 (ko) | 2021-07-29 |
US11319397B2 (en) | 2022-05-03 |
WO2019019465A1 (zh) | 2019-01-31 |
EP3660026A1 (en) | 2020-06-03 |
TW201910413A (zh) | 2019-03-16 |
JP2020517792A (ja) | 2020-06-18 |
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