CN104845365B - A kind of halogen-free resin composition and application thereof - Google Patents
A kind of halogen-free resin composition and application thereof Download PDFInfo
- Publication number
- CN104845365B CN104845365B CN201410052010.XA CN201410052010A CN104845365B CN 104845365 B CN104845365 B CN 104845365B CN 201410052010 A CN201410052010 A CN 201410052010A CN 104845365 B CN104845365 B CN 104845365B
- Authority
- CN
- China
- Prior art keywords
- halogen
- free resin
- resin composition
- weight portions
- allyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 37
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 37
- 239000000945 filler Substances 0.000 claims abstract description 22
- 239000003063 flame retardant Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000012779 reinforcing material Substances 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 8
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000007792 addition Methods 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 229910002113 barium titanate Inorganic materials 0.000 claims description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 5
- 229910017083 AlN Inorganic materials 0.000 claims description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 150000001451 organic peroxides Chemical group 0.000 claims description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims 1
- JIRSPIOGCUEDAI-UHFFFAOYSA-N NCC(C=CC=C1CN)=C1P Chemical compound NCC(C=CC=C1CN)=C1P JIRSPIOGCUEDAI-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 239000005062 Polybutadiene Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 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 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- -1 brominated Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000007342 radical addition reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SHKKTLSDGJRCTR-UHFFFAOYSA-N 1,2-dibromoethylbenzene Chemical compound BrCC(Br)C1=CC=CC=C1 SHKKTLSDGJRCTR-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical class CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical class CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([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
- 239000002994 raw material Substances 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses a kind of halogen-free resin composition and with prepreg made by which and laminate, in terms of organic solid content weight portion, the halogen-free resin composition is included：（A）Pi-allyl modifying benzoxazine resin, 40～80 weight portions；（B）Hydrocarbon resin, 20～60 weight portions；（C）Initiator, 0.01～3 weight portion；（D）Filler, 10～100 weight portions, and（E）Phosphonium flame retardant, 0～80 weight portion.With prepreg and laminate made by the halogen-free resin composition, which has relatively low dielectric constant and a dielectric loss tangent value, higher peel strength, excellent heat resistance, preferable flame retardant effect.
Description
Technical field
The invention belongs to copper-clad laminate preparing technical field, is related to a kind of halogen-free resin composition and application thereof, tool
A kind of body is related to halogen-free resin composition, prepared using the halogen-free resin composition resin adhesive liquid, prepreg, laminate and
Copper-clad laminate.
Background technology
Traditional printed circuit copper-clad laminate, mainly using brominated epoxy resin, realizes sheet material by bromine
Anti-flaming function.But Er Evil are verified in the combustion product of the waste electrical and electronic equipment of the halogens such as brominated, chlorine in recent years,
The carcinogens such as English, dibenzofurans, and halogen product is possible to discharge extremely toxic substance hydrogen halides in combustion.This
Outward, on July 1st, 2006, two parts of environmental protection instructions of European Union《With regard to scrapping electric/electronic device instruction》With《With regard in electric and electronic
Limit using some Hazardous Substances Directives in equipment》It is formal to implement.Due to not environmentally property and the Europe of halogen-containing product combustion product
The enforcement of two parts of environmental protection instructions of alliance so that the focus for being developed into industry of halogen-free flameproof copper-clad laminate, respectively covers Copper Foil
Laminate producer all releases the halogen-free flameproof copper-clad laminate of oneself one after another.
In recent years, with computer and the development of information communication device high performance, multifunction and networking, in order to
High-speed transfer and process Large Copacity information, operation signal is intended to high frequency, thus proposes requirement to the material of circuit substrate.
In the existing material for tellite, the excellent epoxy resin of adhesion properties is widely used.However, epoxy resin is electric
The general dielectric constant of base board and dielectric loss angle tangent are higher（Dielectric constant is more than 4, dielectric loss angle tangent 0.02 or so）,
High frequency characteristics is insufficient, it is impossible to adapt to the requirement of signal high frequency.Therefore the excellent resin of dielectric property, i.e. dielectric must be developed
The low resin of constant and dielectric loss angle tangent.Those skilled in the art is heat cured well to dielectric properties for a long time
Polybutadiene or polybutadiene are studied with cinnamic copolymer resin.
Tetramers of the WO97/38564 using nonpolar styrene with butadiene and divinylbenzene adds aluminosilicate magnesium
Filler, using circuit substrate made by glass fabric as reinforcing material, although dielectric properties are excellent, but the heat resistance of substrate
Very poor, glass transition temperature only has 100 DEG C or so, and thermal coefficient of expansion is very big, it is difficult to meet the unleaded processing procedure of PCB manufacturing process
High temperature（More than 240 DEG C）Require.
US5571609 using molecular weight less than 5000 low-molecular-weight 1,2- polybutadienes or polyisobutene and
The butadiene of HMW is coordinated with cinnamic copolymer, and adds substantial amounts of silicon powder as filler, with glass fabric
As the circuit substrate that reinforcing material makes, although dielectric properties are excellent, but are because employing HMW in that patent
Composition improving the viscous hand situation of prepreg so that the processing performance for making the process of prepreg is deteriorated；And it is because whole
The ratio of the rigid structure phenyl ring in the molecular resin of individual resin system seldom, and is crosslinked later segment mostly by rigidly very
Low methylene composition, therefore the panel stiffness being fabricated to is bad, bending strength is very low.
Liquid polybutadiene resins of the US6569943 using amino modified of the molecular end with vinyl, addition are a large amount of
Low-molecular-weight the circuit substrate that is fabricated to as curing agent and diluent, impregnated glass fiber cloth of monomer Dowspray 9,
Although dielectric properties very well, are because that resin system is liquid at normal temperatures, it is impossible to be fabricated to tack-free prepreg, because
This sheet material it is compressing when, it is difficult with that general prepreg is folded to foretell technique, technological operation is relatively difficult.
CN1280337C carries the polyphenylene oxide resin of unsaturated double-bond using molecular end, using the low molecule of low-molecular-weight
The vinyl monomer of amount（Such as Dowspray 9）As curing agent, but due to the monomer low boiling point of these low-molecular-weights, in dipping
Can vapor away in the drying course of glass fabric making prepreg, it is difficult to ensure sufficient hardener dose.In addition this
Although bright referring to can adopt polybutadiene resinoid to go the viscosity of modified system, clearly do not propose using with polar group
The polybutadiene resinoid of polybutadiene resinoid and employing with polar group rolled into a ball can improve peel strength.
CN101544841B uses the hydrocarbon resin of molecular weight contents of ethylene more than 60% below 11000 as main body, adopts
The tacky characteristic of prepreg is improved with the phenolic resin that pi-allyl is modified, peel strength has certain lifting, but system solidifies
Heat resistance afterwards is low, and the risk that failure occurs being layered in PCB process in copper-clad laminate is higher.
System based on hydrocarbon resin, which is relatively low with the heat resistance of the bonding force of metal and system, for covering copper
The failure risk of larger probability is brought in the PCB process in plate downstream.
The content of the invention
For the problem in prior art, an object of the present invention is to provide a kind of halogen-free resin composition, is used
Prepreg and laminate prepared by the halogen-free resin composition has relatively low dielectric constant and dielectric loss tangent value, higher
Peel strength, excellent heat resistance and excellent flame retardant effect.
In order to achieve the above object, present invention employs following technical scheme：
A kind of halogen-free resin composition, in terms of organic solid content weight portion, which includes：
（A）Pi-allyl modifying benzoxazine resin, 40～80 weight portions；
（B）Hydrocarbon resin, 20～60 weight portions；
（C）Initiator, 0.01～3 weight portion.
In the resin system, pi-allyl modifying benzoxazine resin is mainly system and contributes excellent heat resistance and bonding
Property, but its dielectric properties is relatively poor；And hydrocarbon resin is then mainly system and contributes excellent dielectric properties；But which is heat-resisting
Property and cohesive are relatively poor.The present invention using pi-allyl modifying benzoxazine resin for system provide excellent heat resistance and
Excellent cohesive, coordinates the hydrocarbon resin of excellent electrical property, further improves the electrical property of curing system.Pi-allyl is modified benzene
Carbon-carbon double bond in Bing oxazines resin and hydrocarbon resin Jing Radical Additions in the presence of initiator, shoot up composition
The huge crosslinked resin network of son amount, the cured product for obtaining have excellent heat resistance, cohesive and dielectric properties.
The component（A）The content of pi-allyl modifying benzoxazine resin is, for example, 42 weight portions, 44 weight portions, 46 weight
Part, 48 weight portions, 50 weight portions, 52 weight portions, 54 weight portions, 56 weight portions, 58 weight portions, 60 weight portions, 62 weight portions, 64
Weight portion, 66 weight portions, 68 weight portions, 70 weight portions, 72 weight portions, 74 weight portions, 76 weight portions or 78 weight portions.
The component（B）The content of hydrocarbon resin be, for example, 22 weight portions, 24 weight portions, 26 weight portions, 28 weight portions, 30
Weight portion, 32 weight portions, 34 weight portions, 36 weight portions, 38 weight portions, 40 weight portions, 42 weight portions, 44 weight portions, 46 weight
Part, 48 weight portions, 50 weight portions, 52 weight portions, 54 weight portions, 56 weight portions or 58 weight portions.
The component（C）The content of initiator is, for example, 0.03 weight portion, 0.05 weight portion, 0.08 weight portion, 0.1 weight
Part, 0.4 weight portion, 0.7 weight portion, 1 weight portion, 1.3 weight portions, 1.5 weight portions, 1.7 weight portions, 1.9 weight portions, 2.1 weights
Amount part, 2.3 weight portions, 2.5 weight portions, 2.7 weight portions or 2.9 weight portions.
Preferably, on the basis of the technical scheme that the present invention is provided, a kind of halogen-free resin composition, with organic solid content
Weight portion meter, which includes：
（A）Pi-allyl modifying benzoxazine resin, 40～80 weight portions；
（B）Hydrocarbon resin, 20～60 weight portions；
（C）Initiator, 0.01～3 weight portion；
Wherein, content of the content of pi-allyl modifying benzoxazine resin more than hydrocarbon resin.
In the resin system, pi-allyl modifying benzoxazine resin is mainly system and contributes excellent heat resistance and bonding
Property, but its dielectric properties is relatively poor；And hydrocarbon resin is then mainly system and contributes excellent dielectric properties；But which is heat-resisting
Property and cohesive are relatively poor.With pi-allyl modifying benzoxazine resin as matrix resin, which provides excellent for system to the present invention
Heat resistance and excellent cohesive, coordinate excellent electrical property hydrocarbon resin, further improve the electrical property of curing system.
And, the Jing free radical additions in the presence of initiator of the carbon-carbon double bond in pi-allyl modifying benzoxazine resin and hydrocarbon resin
Reaction, shoots up into the huge crosslinked resin network of molecular weight, as pi-allyl modifying benzoxazine resin is matrix resin,
Therefore the heat resistance of system and cohesive are significantly increased compared with hydrocarbon resin, while the electrical property of cured product has obtained preferable guarantor
Hold.
Preferably, on the basis of the technical scheme that the present invention is provided, a kind of halogen-free resin composition, with organic solid content
Weight portion meter, which includes：
（A）Pi-allyl modifying benzoxazine resin, 40～80 weight portions；
（B）Hydrocarbon resin, 20～60 weight portions；
（C）Initiator, 0.01～3 weight portion；
Wherein, content of the content of hydrocarbon resin more than pi-allyl modifying benzoxazine resin.
In copper-clad plate field for the copper-clad plate of different purposes has not to the heat resistance of system, cohesive and dielectric properties
Same stresses demand, so for for the copper-clad plate of the special-purpose for having requirements at the higher level to the dielectric properties of system, Ke Yi
It is appropriate in certain limit to reduce to, when copper-clad plate heat resistance and caking property requirement, the present invention be big by adjusting hydrocarbon resin content
Realize in pi-allyl modifying benzoxazine resin.
Preferably, on the basis of the technical scheme that the present invention is provided, a kind of halogen-free resin composition, with organic solid content
Weight portion meter, which includes：
（A）Pi-allyl modifying benzoxazine resin, 60～80 weight portions；
（B）Hydrocarbon resin, 40～50 weight portions；
（C）Initiator, 0.01～3 weight portion.
Preferably, on the basis of the technical scheme that the present invention is provided, the component（A）Pi-allyl modified benzoxazine tree
Fat is modified selected from pi-allyl modified bisphenol A type benzoxazine colophony, pi-allyl modified bisphenol F type benzoxazine colophonies, pi-allyl
Dicyclopentadiene phenolic benzoxazine colophony, pi-allyl modified bisphenol S types benzoxazine colophony or two amine type benzoxazine colophonies
In any one or at least two mixture.The mixture such as pi-allyl modified bisphenol A type benzoxazine colophony
With the mixture of pi-allyl modified bisphenol F type benzoxazine colophonies, the modified dicyclopentadiene phenolic benzoxazine colophony of pi-allyl
With the mixture of pi-allyl modified bisphenol S type benzoxazine colophonies, two amine type benzoxazine colophonies, pi-allyl modified bisphenol A type
The mixture of benzoxazine colophony and pi-allyl modified bisphenol F type benzoxazine colophonies, the modified dicyclopentadiene phenolic of pi-allyl
The mixture of benzoxazine colophony, pi-allyl modified bisphenol S types benzoxazine colophony and two amine type benzoxazine colophonies.
Preferably, on the basis of the technical scheme that the present invention is provided, the hydrocarbon resin is number-average molecular weight 11000
It is more than 60% by the contents of ethylene that hydrocarbon two kinds of elements are constituted below, is the hydrocarbon resin of liquid at room temperature, preferred number is divided equally
Less than 7000 and 1, the contents of ethylene of 2 additions is more than 70% to son amount, is the hydrocarbon resin of liquid at room temperature.
Preferably, on the basis of the technical scheme that the present invention is provided, the initiator is to decompose under the action of heat
Go out the material of free radical, selected from organic peroxide, preferred cumyl peroxide, peroxidized t-butyl perbenzoate or 2,5- bis-
In (2- ethyihexanoylperoxies) -2,5- dimethylhexanes any one or at least two mixture.The mixture is for example
The mixture of cumyl peroxide and peroxidized t-butyl perbenzoate, 2,5- bis- (2- ethyihexanoylperoxies) -2,5- dimethyl
The mixture of hexane and cumyl peroxide, bis- (2- ethyihexanoylperoxies) -2,5- of peroxidized t-butyl perbenzoate and 2,5-
The mixture of dimethylhexane, cumyl peroxide, peroxidized t-butyl perbenzoate and 2,5- bis- (2- ethyihexanoylperoxies)-
The mixture of 2,5- dimethylhexanes.
Preferably, on the basis of the technical scheme that the present invention is provided, the halogen-free resin composition also includes（D）Fill out
Material.
Preferably, on the basis of the technical scheme that the present invention is provided, the content of described filler is 1～100 weight portion, example
Such as 5 weight portions, 10 weight portions, 15 weight portions, 20 weight portions, 25 weight portions, 30 weight portions, 35 weight portions, 40 weight portions, 45
Weight portion, 50 weight portions, 55 weight portions, 60 weight portions, 65 weight portions, 70 weight portions, 75 weight portions, 80 weight portions, 85 weight
Part, 90 weight portions or 95 weight portions, preferably 10～100 weight portions.
Preferably, the present invention provide technical scheme on the basis of, described filler selected from silica, titanium dioxide,
In strontium titanates, barium titanate, boron nitride, aluminium nitride, carborundum or aluminum oxide any one or at least two mixture, it is excellent
Select powdered quartz, amorphous silica, preparing spherical SiO 2, titanium dioxide, strontium titanates, barium titanate, boron nitride, nitrogen
Change aluminium, in carborundum or aluminum oxide any one or at least two mixture, the mixture such as crystal type dioxy
The mixture of the mixture of SiClx and amorphous silica, preparing spherical SiO 2 and titanium dioxide, strontium titanates and barium titanate
The mixture of the mixture of mixture, boron nitride and nitridation, carborundum and aluminum oxide, powdered quartz, amorphous dioxy
The mixture of SiClx and preparing spherical SiO 2, the mixture of titanium dioxide, strontium titanates and barium titanate, boron nitride, aluminium nitride, carbonization
The mixture of silicon and aluminum oxide.
Preferably, on the basis of the technical scheme that the present invention is provided, described filler is silica.
Preferably, on the basis of the technical scheme that the present invention is provided, in the particle diameter of described filler, angle value is 1～15 μm,
Such as 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm or 14 μm, enter by preferably 1～10 μm
Preferably 1～5 μm of one step.Filler positioned at the particle diameter section has good dispersiveness in resin adhesive liquid.
Preferably, on the basis of the technical scheme that the present invention is provided, the halogen-free resin composition also includes（E）It is phosphorous
Fire retardant.
Preferably, on the basis of the technical scheme that the present invention is provided, the content of the phosphonium flame retardant is 0～80 weight
Part, not including 0, such as 0.05 weight portion, 1 weight portion, 3 weight portions, 5 weight portions, 10 weight portions, 15 weight portions, 20 weight portions,
25 weight portions, 30 weight portions, 35 weight portions, 40 weight portions, 45 weight portions, 50 weight portions, 55 weight portions, 60 weight portions, 65 weights
Amount part, 70 weight portions, 72 weight portions, 74 weight portions, 76 weight portions or 78 weight portions.
Preferably, on the basis of the technical scheme that the present invention is provided, the phosphonium flame retardant is three (2,6- dimethyl benzenes
Base) phosphine, the miscellaneous -10- phosphines phenanthrene -10- oxides of 10- (2,5- dihydroxy phenyls) -9,10- dihydro-9-oxies, bis- (2,6- diformazans of 2,6-
Base phenyl) phosphino- benzene, the miscellaneous -10- phosphines phenanthrene -10- oxides of 10- phenyl -9,10- dihydro-9-oxies or polyphenylene oxide phosphonitrile and its spread out
In biology any one or at least two mixture.
Preferably, on the basis of the technical scheme that the present invention is provided, the content of halogen of the halogen-free resin composition exists
Below 0.09 weight %, such as 0.01 weight %, 0.02 weight %, 0.03 weight %, 0.04 weight %, 0.05 weight %, 0.06 weight
Amount %, 0.07 weight % or 0.08 weight %.
A kind of exemplary halogen-free resin composition, in terms of organic solid content weight portion, which includes：
（A）Pi-allyl modifying benzoxazine resin, 40～80 weight portions；
（B）Hydrocarbon resin, 20～60 weight portions；
（C）Initiator, 0.01～3 weight portion；
（D）Filler, 1～100 weight portion；
（E）Phosphonium flame retardant, 0～80 weight portion, not including 0.
A kind of exemplary halogen-free resin composition, in terms of organic solid content weight portion, which includes：
（A）Pi-allyl modifying benzoxazine resin, 40～80 weight portions；
（B）Hydrocarbon resin, 20～60 weight portions；
（C）Initiator, 0.01～3 weight portion；
（D）Filler, 1～100 weight portion；
（E）Phosphonium flame retardant, 0～80 weight portion, not including 0；
Wherein, content of the content of pi-allyl modifying benzoxazine resin more than hydrocarbon resin.
A kind of exemplary halogen-free resin composition, in terms of organic solid content weight portion, which includes：
（A）Pi-allyl modifying benzoxazine resin, 60～80 weight portions；
（B）Hydrocarbon resin, 40～50 weight portions；
（C）Initiator, 0.01～3 weight portion；
（D）Filler, 1～100 weight portion；
（E）Phosphonium flame retardant, 0～80 weight portion, not including 0.
" including " of the present invention, it is intended which can also include other components, these other components in addition to the component
Give the halogen-free resin composition different characteristics.In addition, " including " of the present invention, may be replaced by closing
" being " of formula or " by ... constitute ".
For example, the halogen-free resin composition can also contain various additives, as concrete example, can enumerate antioxygen
Agent, heat stabilizer, antistatic additive, ultra-violet absorber, pigment, colouring agent or lubricant etc..These various additives can be single
Solely use, it is also possible to which two kinds two or more are used in mixed way.
The second object of the present invention is to provide a kind of resin adhesive liquid, and which is will be halogen-free resin composition as above molten
Solution or dispersion are obtained in a solvent.
As the solvent in the present invention, be not particularly limited, as concrete example, can enumerate acetone, butanone, cyclohexanone,
In EGME, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, benzene, toluene and dimethylbenzene at least any one or
At least two mixture, its consumption can as needed depending on, be not especially limited, so as to get resin adhesive liquid reach and be suitable to make
Viscosity.
The conventional preparation method of exemplary halogen-free resin composition glue is：First the solid content in said components is put
Enter in appropriate container, then solubilizer, after stirring is until be completely dissolved, adds appropriate filler, be eventually adding liquid tree
Fat and initiator, continue to stir.The solids content 65～75% of solution can suitably be adjusted with solvent during use and be made
Glue.
The third object of the present invention is to provide a kind of prepreg, and which includes reinforcing material and adheres to after impregnation is dried
Halogen-free resin composition as above on reinforcing material.The prepreg its there is relatively low dielectric constant and dielectric to damage
Consumption tangent value, higher peel strength, excellent heat resistance, preferable flame retardant effect.
The reinforcing material is the reinforcing material disclosed in prior art, such as adhesive-bonded fabric or braided fabric, exemplary
Such as natural fiber, organic synthetic fibers and inorfil, preferably electronic-grade glass fiber cloth.
Above-mentioned resin adhesive liquid is impregnated with using the fabrics such as reinforcing material glass fabric or organic fabric, by the enhancing being impregnated with
Material is dried 5～8 minutes in 170 DEG C of baking oven makes printed circuit prepreg.
The fourth object of the present invention is to provide a kind of laminate, and the laminate contains at least one as above in advance
Leaching material.
The fifth object of the present invention is to provide a kind of copper-clad laminate, and the copper-clad laminate includes at least one
The prepreg as above for overlapping and the Copper Foil of the one or both sides for covering the prepreg after overlapping.The copper foil covered pressure
Plate, which has relatively low dielectric constant and a dielectric loss tangent value, higher peel strength, excellent heat resistance, preferably hinders
Fuel efficiency fruit.
The preparation method of exemplary copper-clad laminate is：Using one ounce of above-mentioned prepreg 4 and two panels（35μm
It is thick）Copper Foil be superimposed together, by hot press be laminated, so as to be pressed into doublesided copperclad laminate；Described covers Copper Foil
Lamination need to meet claimed below：1st, the heating rate of lamination, generally in 80～220 DEG C of material temperature, controls at 1.0～3.0 DEG C/minute
Clock；2nd, the pressure of lamination is arranged, and outer layer material temperature applies full pressure at 80～100 degrees Celsius, and full pressure pressure is 300psi or so；3、
During solidification, control material temperature is at 220 DEG C, and is incubated 120 minutes；The metal forming for being covered can also be nickel foil, aluminium foil in addition to Copper Foil
And SUS paper tinsels etc., its material is not limited.
Compared with the prior art, the present invention has the advantages that：
The present invention provides excellent heat resistance and excellent for system based on pi-allyl modifying benzoxazine resin
Electrical property, coordinates the hydrocarbon resin of excellent electrical property, further improves the electrical property of curing system.In the present invention, pi-allyl changes
Property benzoxazine colophony and hydrocarbon resin in carbon-carbon double bond in the presence of initiator Jing Radical Additions, shoot up
Into the huge crosslinked resin network of molecular weight, as pi-allyl modifying benzoxazine resin is matrix resin, therefore system is heat-resisting
Property and cohesive are significantly increased compared with hydrocarbon resin, while the electrical property of cured product has obtained preferable holding.Using this
Prepreg made by bright halogen-free resin composition has relatively low dielectric constant and dielectric loss tangent value, and higher stripping is strong
Degree, excellent heat resistance, preferable flame retardant effect；Using copper-clad laminate made by the prepreg, which has relatively low dielectric
Constant and dielectric loss tangent value, higher peel strength, excellent heat resistance, preferable flame retardant effect.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
The example composition formula is shown in Table 1.Using the copper foil covered pressure of use in printed circuit board made by said method
The physical datas such as plate, its dielectric constant, dielectric dissipation factor and anti-flammability are shown in Table 2.
The concrete component of the halogen-free resin composition is as follows：
（A）Pi-allyl modifying benzoxazine resin
A-1 pi-allyl modified bisphenol A type benzoxazine colophonies
The modified dicyclopentadiene phenolic benzoxazine colophony of A-2 pi-allyls
A-3 pi-allyl modified bisphenol F type benzoxazine colophonies
（B）Hydrocarbon resin
B-1 butadiene styrene resins（Marque Ricon104H, Sartomer）
B-2 butadiene styrene resins（Marque Ricon153H, Sartomer）
B-3 butadiene styrene resins（Marque Ricon100, Sartomer）
（C）Initiator：Cumyl peroxide（Shanghai Gaoqiao）
（D）Filler：Ball-shaped silicon micro powder（Trade name SFP-30M, Deuki Kagaku Kogyo Co., Ltd）
（E）Phosphonium flame retardant：Polyphenylene oxide phosphazene compound, SPB-100（Ben Otsuka Chemical Co., Ltd trade name）.
The formula composition of 1. each embodiment of table and comparative example
Note：1st, in table all in terms of solid constituent weight portion.
2nd, comparative example 1*With the modified dicyclopentadiene phenolic benzoxazine colophony curing reaction of phenolic resin and pi-allyl.
3rd, comparative example 2**Also include that another kind of component is middle low-molecular-weight and the solid styrene base containing unsaturated double-bond
Resin.
4th, comparative example 3***Also include pi-allyl phenol-formaldehyde resin modified, while which uses bromide fire retardant fire-retardant.
The physical data of 2. each embodiment of table and comparative example
The method of testing of above characteristic is as follows：
Glass transition temperature (Tg)：According to differential scanning calorimetry（DSC）, according to IPC-TM-6502.4.25 defineds
DSC method be measured.
Peel strength（PS）：" after thermal stress " experiment condition according to IPC-TM-6502.4.8 methods, tests crown cap
The peel strength of layer.
Flammability：Determine according to UL94 vertical combustions.
Thermally stratified layer time T-288：It is measured according to IPC-TM-6502.4.24.1 methods.
Thermal coefficient of expansion Z axis CTE（TMA）：It is measured according to IPC-TM-6502.4.24. methods.
Heat decomposition temperature Td：It is measured according to IPC-TM-6502.4.26 methods.
Water imbibition：It is measured according to IPC-TM-6502.6.2.1 methods.
Dielectric loss angle tangent, dielectric constant：According to the resonance method using stripline runs, according to IPC-TM-6502.5.5.9
Determine the dielectric loss angle tangent under 10GHz.
（10）Content of halogen is tested：It is measured according to IPC-TM-6502.3.41 methods.
Physical Property Analysis
Understand that copper-clad laminate made by embodiment 1-4 has excellent dielectric properties, higher from the physical data of table 2
Glass transition temperature.
Compared with comparative example 1, with the addition of hydrocarbon resin, the dielectric properties of system are obviously improved embodiment, and
The heat resistance of system has obtained preferable holding with peel strength.Embodiment compared with comparative example 2, with the modified benzo of pi-allyl
The addition of oxazine resin, the peel strength and heat resistance of system are obviously improved, while the dielectric properties of system obtain maximum
The holding of limit.Compared with comparative example 3, the addition of pi-allyl modifying benzoxazine resin significantly improves system to embodiment
Tg, while realizing halogen-free flameproof realizes environmental protection.
, compared with comparative example 4, in comparative example 4, the ratio of hydrocarbon resin is very big, and after curing reaction, system possesses more for embodiment
Low dielectric loss and dielectric constant, but there is significantly decline in the Tg of system, cohesive, heat resistance and flammability.
The V-0 standards in flame retardancy test UL94 can be reached in JPCA Halogen standard claimed ranges, thermal coefficient of expansion is low,
The stable height of thermal decomposition, water imbibition is low, and content of halogen is below 0.09%, reaches the requirement of environmental protection.
In sum, halogen-free resin composition of the present invention extraordinary benzoxazine colophony, polyphenylene oxide resin, hydrocarbon
Resin, curing agent and other components are allowed to good cooperative characteristics, and outside fire-retardant using P elements, content of halogen exists
Less than 0.09%, so as to reach environmental protection standard.And had using bonding sheet made by the halogen-free resin composition excellent electrical
Energy, higher glass transition temperature, excellent heat resistance, preferable flame retardant effect and relatively low water imbibition.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary element of each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (23)
1. a kind of halogen-free resin composition, it is characterised in that in terms of organic solid content weight portion, which includes：
(A) pi-allyl modifying benzoxazine resin, 72～80 weight portions；
(B) hydrocarbon resin, 20～30 weight portions；
(C) initiator, 0.01～3 weight portion.
2. halogen-free resin composition as claimed in claim 1, it is characterised in that the pi-allyl modifying benzoxazine resin choosing
It is modified from pi-allyl modified bisphenol A type benzoxazine colophony, pi-allyl modified bisphenol F type benzoxazine colophonies, pi-allyl bicyclic
The modified two amine type benzene of pentadiene phenolic benzoxazine colophony, pi-allyl modified bisphenol S types benzoxazine colophony or pi-allyl Evil
In piperazine resin any one or at least two mixture.
3. halogen-free resin composition as claimed in claim 1, it is characterised in that the hydrocarbon resin exists for number-average molecular weight
Less than 11000 are more than 60% by the contents of ethylene that hydrocarbon two kinds of elements are constituted, and are the hydrocarbon resin of liquid at room temperature.
4. halogen-free resin composition as claimed in claim 3, it is characterised in that the hydrocarbon resin is less than for number-average molecular weight
7000 and 1, the contents of ethylene of 2 additions is more than 70%, is the hydrocarbon resin of liquid at room temperature.
5. halogen-free resin composition as claimed in claim 1, it is characterised in that the initiator is selected from organic peroxide.
6. halogen-free resin composition as claimed in claim 5, it is characterised in that the initiator is selected from peroxidating diisopropyl
In benzene, peroxidized t-butyl perbenzoate or 2,5- bis- (2- ethyihexanoylperoxies) -2,5- dimethylhexanes any one or
At least two mixture.
7. halogen-free resin composition as claimed in claim 1, it is characterised in that the halogen-free resin composition also includes (D)
Filler.
8. halogen-free resin composition as claimed in claim 7, it is characterised in that the content of described filler is 1～100 weight
Part.
9. halogen-free resin composition as claimed in claim 7, it is characterised in that the content of described filler is 10～100 weight
Part.
10. halogen-free resin composition as claimed in claim 7, it is characterised in that described filler is selected from silica, titanium dioxide
In titanium, strontium titanates, barium titanate, boron nitride, aluminium nitride, carborundum or aluminum oxide any one or at least two mixing
Thing.
11. halogen-free resin compositions as claimed in claim 7, it is characterised in that described filler selected from powdered quartz,
Amorphous silica, preparing spherical SiO 2, titanium dioxide, strontium titanates, barium titanate, boron nitride, aluminium nitride, carborundum or oxidation
In aluminium any one or at least two mixture.
12. halogen-free resin compositions as claimed in claim 7, it is characterised in that described filler is silica.
13. halogen-free resin compositions as claimed in claim 7, it is characterised in that angle value is 1～15 in the particle diameter of described filler
μm。
14. halogen-free resin compositions as claimed in claim 13, it is characterised in that in the particle diameter of described filler angle value be 1～
10μm。
15. halogen-free resin compositions as claimed in claim 14, it is characterised in that angle value is 1～5 in the particle diameter of described filler
μm。
16. halogen-free resin compositions as claimed in claim 1, it is characterised in that the halogen-free resin composition also includes (E)
Phosphonium flame retardant.
17. halogen-free resin compositions as claimed in claim 16, it is characterised in that the content of the phosphonium flame retardant be 0～
80 weight portions, not including 0.
18. halogen-free resin compositions as claimed in claim 16, it is characterised in that the phosphonium flame retardant is three (2,6- bis-
Aminomethyl phenyl) phosphine, the miscellaneous -10- phosphines phenanthrene -10- oxides of 10- (2,5- dihydroxy phenyls) -9,10- dihydro-9-oxies, 2,6- bis- (2,
6- 3,5-dimethylphenyls) phosphino- benzene, the miscellaneous -10- phosphines phenanthrene -10- oxides of 10- phenyl -9,10- dihydro-9-oxies or polyphenylene oxide phosphonitrile
And its in derivative any one or at least two mixture.
19. halogen-free resin compositions as claimed in claim 1, it is characterised in that the halogen of the halogen-free resin composition contains
Amount is below 0.09 weight %.
20. a kind of resin adhesive liquids, it is characterised in which is will be the halogen-free resin composition as described in one of claim 1-19 molten
Solution or dispersion are obtained in a solvent.
21. a kind of prepregs, it is characterised in which includes reinforcing material and is attached on reinforcing material after impregnation is dried
Halogen-free resin composition as described in one of claim 1-19.
22. a kind of laminates, it is characterised in that the laminate contains at least one prepreg as claimed in claim 21.
A kind of 23. copper-clad laminates, it is characterised in that the copper-clad laminate include at least one overlapping as right will
Seek the prepreg described in 21 and cover the Copper Foil of the one or both sides of the prepreg after overlapping.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052010.XA CN104845365B (en) | 2014-02-14 | 2014-02-14 | A kind of halogen-free resin composition and application thereof |
| TW103110692A TW201531524A (en) | 2014-02-14 | 2014-03-21 | A halogen-free resin composition and its application |
| PCT/CN2014/073839 WO2015120651A1 (en) | 2014-02-14 | 2014-03-21 | Halogen-free resin composition and use for same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052010.XA CN104845365B (en) | 2014-02-14 | 2014-02-14 | A kind of halogen-free resin composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104845365A CN104845365A (en) | 2015-08-19 |
| CN104845365B true CN104845365B (en) | 2017-04-05 |
Family
ID=53799541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410052010.XA Active CN104845365B (en) | 2014-02-14 | 2014-02-14 | A kind of halogen-free resin composition and application thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN104845365B (en) |
| TW (1) | TW201531524A (en) |
| WO (1) | WO2015120651A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6350889B2 (en) * | 2015-12-08 | 2018-07-04 | Dic株式会社 | Oxazine compound, composition and cured product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544841A (en) * | 2009-04-10 | 2009-09-30 | 广东生益科技股份有限公司 | Composite material and high-frequency circuit board made of same |
| CN101684191A (en) * | 2009-08-27 | 2010-03-31 | 广东生益科技股份有限公司 | Halogen-free high-frequency resin composition and prepreg and laminated board prepared from same |
| CN102093666A (en) * | 2010-12-23 | 2011-06-15 | 广东生益科技股份有限公司 | Halogen-free resin composition and manufacturing method of halogen-free copper-clad laminate using same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161823B (en) * | 2010-07-14 | 2012-09-26 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit substrate therefrom and manufacture method thereof |
| CN102977551B (en) * | 2011-09-02 | 2014-12-10 | 广东生益科技股份有限公司 | Halogen-free resin composition and method for preparing copper-clad plate from the halogen-free resin composition |
| CN102850726A (en) * | 2012-09-07 | 2013-01-02 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit substrate made therefrom and method for making same |
| CN103265791B (en) * | 2013-05-29 | 2015-04-08 | 苏州生益科技有限公司 | Thermosetting resin composition for integrated circuit as well as prepreg and laminated board both fabricated by using composition |
-
2014
- 2014-02-14 CN CN201410052010.XA patent/CN104845365B/en active Active
- 2014-03-21 TW TW103110692A patent/TW201531524A/en not_active IP Right Cessation
- 2014-03-21 WO PCT/CN2014/073839 patent/WO2015120651A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544841A (en) * | 2009-04-10 | 2009-09-30 | 广东生益科技股份有限公司 | Composite material and high-frequency circuit board made of same |
| CN101684191A (en) * | 2009-08-27 | 2010-03-31 | 广东生益科技股份有限公司 | Halogen-free high-frequency resin composition and prepreg and laminated board prepared from same |
| CN102093666A (en) * | 2010-12-23 | 2011-06-15 | 广东生益科技股份有限公司 | Halogen-free resin composition and manufacturing method of halogen-free copper-clad laminate using same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201531524A (en) | 2015-08-16 |
| TWI506090B (en) | 2015-11-01 |
| WO2015120651A1 (en) | 2015-08-20 |
| CN104845365A (en) | 2015-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104845363B (en) | A kind of halogen-free resin composition and application thereof | |
| CN104845366B (en) | A kind of halogen-free resin composition and application thereof | |
| CN104892902B (en) | A kind of compositions of thermosetting resin and application thereof | |
| CN104371273B (en) | Halogen-free resin composition and prepreg and laminate prepared therefrom | |
| CN104974520B (en) | A kind of halogen-free resin composition and application thereof | |
| CN104448702B (en) | Halogen-free resin composition as well as prepreg and laminated board made of halogen-free resin composition | |
| CN106700424B (en) | A kind of low-loss resin combination, prepreg and laminate | |
| CN103980704B (en) | Halogen-free resin composition, prepreg and laminate for high-frequency high-speed substrate | |
| CN105778412B (en) | A kind of composition epoxy resin and use its prepreg and laminate | |
| CN105585808A (en) | Low-dielectric-loss high-heat-conductivity resin composition and preparation method thereof, and prepreg and laminated board prepared from resin composition | |
| CN106349442B (en) | A kind of compositions of thermosetting resin and prepreg and laminate using its making | |
| CN109777123A (en) | Resin combination, preliminary-dip piece used for printed circuit and metal-coated laminated board | |
| CN106750260A (en) | A kind of modified polyphenylene ether resin and its application | |
| CN113088061A (en) | Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same | |
| CN103724936B (en) | Improve the Halogen-free low dielectric epoxy resin composition of shock resistance | |
| CN106893258A (en) | A kind of composition epoxy resin and the prepreg containing it, laminate and printed circuit board | |
| CN105801814A (en) | Halogen-free thermosetting resin composition and prepreg and printed circuit laminated board using the same | |
| CN106749952A (en) | Resin combination and the prepreg, laminate and the interlayer dielectric that are made using it | |
| CN104845364B (en) | A kind of halogen-free resin composition and application thereof | |
| CN106280387A (en) | There are halogen fire-proof resin composition and the resin using it to make, laminate | |
| CN104845365B (en) | A kind of halogen-free resin composition and application thereof | |
| CN106751821A (en) | A kind of halogen-free flame resistance resin composite and use its bonding sheet and copper-clad laminate | |
| CN109370141A (en) | The electronics composite substrate that a kind of thermosetting property electronics composite material and preparation method are prepared with it | |
| CN108192281A (en) | A kind of halogen-free thermosetting resin composite and use its prepreg, laminate, metal-clad laminate and printed circuit board | |
| CN108047647A (en) | A kind of halogen-free thermosetting resin composite and use its prepreg, laminate, metal-clad laminate and printed circuit board (PCB) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |