CN117736504A - Resin composition, circuit material containing same and printed circuit board - Google Patents
Resin composition, circuit material containing same and printed circuit board Download PDFInfo
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- CN117736504A CN117736504A CN202311858311.7A CN202311858311A CN117736504A CN 117736504 A CN117736504 A CN 117736504A CN 202311858311 A CN202311858311 A CN 202311858311A CN 117736504 A CN117736504 A CN 117736504A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 73
- 239000011347 resin Substances 0.000 claims abstract description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000945 filler Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 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 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 15
- 239000011324 bead Substances 0.000 claims abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- -1 compound free radical Chemical class 0.000 claims abstract description 13
- 150000003254 radicals Chemical class 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 29
- 229920002857 polybutadiene Polymers 0.000 claims description 29
- 239000012779 reinforcing material Substances 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 229920006026 co-polymeric resin Polymers 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 229920000359 diblock copolymer Polymers 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 2
- WQJUBZMZVKITBU-UHFFFAOYSA-N (3,4-dimethyl-4-phenylhexan-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(CC)C(C)(CC)C1=CC=CC=C1 WQJUBZMZVKITBU-UHFFFAOYSA-N 0.000 claims description 2
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 claims description 2
- DTVHTGANUBTKPO-UHFFFAOYSA-N 1-[2,3-dimethyl-3-(4-methylphenyl)butan-2-yl]-4-methylbenzene Chemical compound C1=CC(C)=CC=C1C(C)(C)C(C)(C)C1=CC=C(C)C=C1 DTVHTGANUBTKPO-UHFFFAOYSA-N 0.000 claims description 2
- QZSVMKVOLCRBKZ-UHFFFAOYSA-N 1-[2,3-dimethyl-3-(4-propan-2-ylphenyl)butan-2-yl]-4-propan-2-ylbenzene Chemical compound C1=CC(C(C)C)=CC=C1C(C)(C)C(C)(C)C1=CC=C(C(C)C)C=C1 QZSVMKVOLCRBKZ-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
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 claims description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000011152 fibreglass Substances 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000004891 communication Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 1
- GXIPHHIBYMWSMN-UHFFFAOYSA-N 6-phenylbenzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=CC=CC=C1 GXIPHHIBYMWSMN-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VMCRDONCOBHEHW-UHFFFAOYSA-N [2,6-bis(2,6-dimethylphenyl)phenyl]phosphane Chemical compound CC1=CC=CC(C)=C1C1=CC=CC(C=2C(=CC=CC=2C)C)=C1P VMCRDONCOBHEHW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a resin composition, a circuit material containing the same and a printed circuit board. The resin composition comprises the following components: (A) Low molecular weight thermosetting resins with unsaturated double bonds; (B) A thermosetting resin of medium molecular weight having unsaturated double bonds; (C) hollow glass bead filler; (D) a silica filler; (E) a flame retardant; (F) a silane coupling agent; (G) A carbon-based free radical initiator or a compound free radical initiator. The circuit material prepared by designing the specific composition of the resin composition has the comprehensive properties of stable dielectric constant and dielectric loss, higher peel strength, good thickness consistency and the like in a high-temperature and high-humidity environment, has very low water absorption rate, and is suitable for preparing a high-frequency substrate.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a resin composition, a circuit material containing the resin composition and a printed circuit board.
Background
The 5G communication technology is a 5 th generation system of the mobile communication technology, and meets the development requirements of mobile Internet and everything Internet services. Compared with the 4G communication technology, the 5G communication technology has the advantages of faster information transmission rate, stronger spectrum utilization efficiency, lower delay, more reliable information transmission, higher link density and the like. In order to meet the design requirements of the wireless communication products in the 5 th generation of communication age, the product design of the MIMO antenna, the active antenna and the multi-layer board antenna is a necessary trend in the 5G age. For the antenna application field in the 5G communication technology, the substrate used is required to have stable dielectric constant, low dielectric loss, good multilayer PCB processing performance, good mechanical performance, low cost and the like, and brings new opportunities and challenges to the CCL.
The traditional PTFE substrate has low dielectric constant and low dielectric loss, and has been widely applied to the field of radio frequency microwaves. However, as burrs exist in the drilling process in the PCB processing process of the base material, the sodium treatment is needed in the glue removing process, copper is not easy to be added to the hole wall of the copper precipitation process, green oil bubbles are easy to adhere in the green oil process, burrs exist on the edges of the boards in the routing process, and the alignment of the multilayer boards is offset, the traditional PTFE base material is low in modulus and large in thermal expansion coefficient, so that the phase fluctuation of the PCB is large, the PTFE material cannot meet the design requirements of most antenna products in the 5G age, and the market trend is changing towards thermosetting materials.
In the design of an antenna, the stability and consistency of the dielectric constant and thickness of the dielectric substrate material are important indicators for influencing the gain and other performances of the antenna. Variation in thickness of the dielectric substrate may cause degradation in efficiency of the antenna. In antenna design, the variation in dielectric layer thickness is a factor that affects antenna performance more than the dielectric constant stability. Meanwhile, the thickness deviation can also cause different resin contents, and the stability of the dielectric constant is directly affected by the different resin contents.
In addition, in the end application, the dielectric substrate material is required to maintain stable dielectric constant and dielectric loss in high-temperature and high-humidity environments, so that the antenna substrate can stably transmit signals in various complex environments.
CN111378212a discloses a resin composition, a prepreg comprising the same, and a dielectric substrate for an antenna, the resin composition comprising a thermosetting resin having an unsaturated double bond, a resin melt viscosity adjusting material, an inorganic nano viscosity adjusting material, hollow microspheres without alkali liquor treatment, a non-hollow inorganic filler, a flame retardant, and an initiator, the resin melt viscosity adjusting material having a number average molecular weight of 50000 to 150000 for ensuring a stable thickness and dielectric constant of the dielectric substrate, and the material having such a high molecular weight being used, which causes rapid deterioration of dielectric constant and dielectric loss of the dielectric substrate material in a high-temperature and high-humidity environment.
Therefore, how to provide a resin composition with excellent performance, which can be used for preparing a circuit material with stable dielectric constant and dielectric loss, lower water absorption, higher peeling strength and good thickness consistency in a high-temperature and high-humidity environment, has become a technical problem to be solved at present.
Disclosure of Invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a resin composition, a circuit material and a printed circuit board comprising the same. The circuit material prepared by designing the specific composition of the resin composition has the comprehensive properties of stable dielectric constant and dielectric loss, higher peel strength, good thickness consistency and the like in a high-temperature and high-humidity environment, has very low water absorption rate, and is suitable for preparing a high-frequency substrate.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a resin composition comprising the following components:
(A) A thermosetting resin with unsaturated double bonds and low molecular weight, which is selected from polybutadiene resin and/or polybutadiene copolymer resin, and the number average molecular weight Mn is less than or equal to 5000g/mol;
(B) A thermosetting resin with unsaturated double bonds and a number average molecular weight Mn of 15000-25000 g/mol;
(C) Hollow glass bead filler;
(D) A silica filler;
(E) A flame retardant;
(F) A silane coupling agent;
(G) A carbon-based free radical initiator or a complex free radical initiator;
the component (B) contains 40-60% of butadiene structure in mole ratio, and the mole ratio content of butadiene added at 1,2 positions in the butadiene molecular structure is more than or equal to 80%;
the sum of the parts by weight of the component (A) and the component (B) is 20-30 parts by weight based on 100 parts by weight of the resin composition;
the weight part of the component (C) is 6-10 parts based on 100 parts of the weight part of the resin composition;
the weight part of the component (D) is 50 to 60 parts based on 100 parts by weight of the resin composition.
The thermosetting resin with unsaturated double bonds in the medium molecular weight has the number average molecular weight Mn of 15000-25000 g/mol, when the number average molecular weight Mn is smaller than 15000g/mol, the bonding sheet has slight hand adhesion, the gummosis is larger when the sheet is pressed, and the consistency of the thickness and the dielectric constant of the sheet is poorer. When the number average molecular weight Mn is more than 25000g/mol, the adhesive flow of the adhesive sheet pressing plate is reduced, the adhesion between layers is affected, more internal micro defects can be generated, the plate structure is not compact, the water absorption rate of the final plate is higher, and the dielectric constant and dielectric loss of the dielectric substrate material in a high-temperature high-humidity environment can be deteriorated.
In the invention, the sum of the parts by weight of the component (A) and the component (B) is 20-30 parts, the part by weight of the component (C) is 6-10 parts, and the part by weight of the component (D) is 50-60 parts, based on 100 parts by weight of the resin composition, the proportion of the resin (component (A) and the component (B)) and the proportion of the filler (component (C) and the component (D)) are the result of the formula integrating the dielectric property and the production manufacturability of the product. If the proportion of the resin is too small, the resin cannot fill gaps among the fillers, so that voids are easy to form, the plate is low in peeling strength and high in water absorption rate, and the voids also cause poor thickness consistency and overall plate dielectric constant consistency; if the resin proportion is too high, particularly hydrocarbon resin with low molecular weight is used, the bonding sheet can be sticky to affect the production manufacturability, and if the resin proportion is too high, the gummosis is too large, and the thickness consistency of the plate and the dielectric constant consistency of the whole plate are affected.
In the present invention, by controlling the amount of the silica filler within a specific range, a resin composition having a good dielectric property can be prepared.
In the invention, the comprehensive performance of the resin composition can be further improved by controlling the dosage of the hollow glass microspheres within a specific range. If the dosage of the hollow glass beads is too small, the prepared resin composition Dk is higher; if the dosage of the hollow glass beads is too large, df of the prepared resin composition is too high.
In the present invention, the number average molecular weight of the low molecular weight thermosetting resin polybutadiene resin and/or polybutadiene copolymer resin having unsaturated double bonds may be 1000g/mol, 1400g/mol, 1800g/mol, 2200g/mol, 2600g/mol, 3000g/mol, 3500g/mol, 4000g/mol, 4500g/mol, 5000g/mol, or the like.
The number average molecular weight of the thermosetting resin with an unsaturated double bond of the medium molecular weight may be 15000g/mol, 16000g/mol, 17000g/mol, 18000g/mol, 19000g/mol, 20000g/mol, 22000g/mol, 24000g/mol, 25000g/mol, or the like.
The sum of the parts by weight of the component (a) and the component (B) may be 20 parts, 22 parts, 25 parts, 27 parts, 30 parts, or the like.
The weight part of the component (C) may be 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or the like.
The weight part of the component (D) may be 50 parts, 54 parts, 56 parts, 57 parts, 58 parts, 60 parts or the like.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
As a preferable technical scheme of the invention, the mass ratio of the component (A) to the component (B) is 1 (0.5-2), and can be 1:0.5, 1:0.7, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8 or 1:2, for example.
In order to ensure that the high-frequency substrate has better thickness consistency and overall dielectric constant consistency, the thermosetting resin with unsaturated double bonds and medium molecular weight is added into the formula, so that the high-frequency substrate can be ensured to have better thickness consistency and overall dielectric constant consistency. Because the thermosetting resin polybutadiene resin and/or polybutadiene copolymer resin with unsaturated double bonds with low molecular weight flows glue after being heated and pressurized, apparent defects such as ravines and the like are easy to generate, the thickness of the plate edge is thinner, the thickness of the whole plate of the plate is unstable, and the consistency of the dielectric constants of the whole plate is poor. The effect is best when the mass ratio of the low molecular weight thermosetting resin polybutadiene resin with unsaturated double bonds and/or polybutadiene copolymer resin to the middle molecular weight thermosetting resin with unsaturated double bonds is 1 (0.5-2), if the mass ratio of the middle molecular weight thermosetting resin with unsaturated double bonds is too low, the purpose of improving the thickness consistency and the consistency of the dielectric constant of the whole plate is not achieved, if the mass ratio of the middle molecular weight thermosetting resin with unsaturated double bonds is too low, no gummosis easily occurs, the occurrence of voids and the lower peeling strength of the plate are caused, and the consistency of the thickness and the consistency of the dielectric constant of the whole plate are also poor.
As a preferred embodiment of the present invention, the polybutadiene resin is selected from any one or a combination of at least two of a 1, 2-polybutadiene resin, a maleic anhydride-modified polybutadiene resin, an acrylate-modified polybutadiene resin, an epoxy-modified polybutadiene resin, an amine-modified polybutadiene resin, a carboxyl-terminated modified polybutadiene resin, and a hydroxyl-terminated modified polybutadiene resin.
Preferably, the polybutadiene copolymer resin is selected from any one or a combination of at least two of polybutadiene-styrene copolymer resin, polybutadiene-styrene-divinylbenzene graft copolymer resin, maleic anhydride-modified styrene-butadiene copolymer resin or acrylate-modified styrene-butadiene copolymer resin.
As a preferred embodiment of the present invention, the thermosetting resin having an unsaturated double bond of a medium molecular weight is selected from any one or a combination of at least two of a styrene-butadiene diblock copolymer, a styrene-butadiene-styrene triblock copolymer, a styrene- (ethylene-butylene) -styrene triblock copolymer, a styrene-isoprene diblock copolymer, a styrene-isoprene-styrene triblock copolymer, a styrene- (ethylene-propylene) -styrene triblock copolymer, and a styrene- (ethylene-butylene) diblock copolymer.
As a preferable technical scheme of the invention, the density of the hollow glass bead filler is 0.2-0.6g/cm 3 For example, it may be 0.2g/cm 3 、0.3g/cm 3 、0.4g/cm 3 、0.5g/cm 3 Or 0.6g/cm 3 Etc.
Preferably, the silica filler is a silica filler which has not been surface-treated or a silica filler which has been surface-treated with a vinyl silane coupling agent, and further preferably a silica filler which has been surface-treated with a vinyl silane coupling agent.
Preferably, the silica filler comprises an angular silica filler and/or a spherical silica filler.
Preferably, the silica filler has a median particle diameter D 50 The particle size may be 3 to 20. Mu.m, for example, 3 μm, 5 μm, 7 μm, 10 μm, 12 μm, 15 μm, 18 μm or 20 μm.
In a preferred embodiment of the present invention, the flame retardant is 5 to 15 parts by weight based on 100 parts by weight of the resin composition, and may be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, or the like.
Preferably, the flame retardant comprises a bromine-containing flame retardant and/or a phosphorus-containing flame retardant.
Preferably, the bromine-containing flame retardant is selected from any one or a combination of at least two of decabromodiphenyl ether, decabromodiphenyl ethane or ethylene bis-tetrabromophthalimide.
Preferably, the phosphorus-containing flame retardant is selected from any one or a combination of at least two of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene or 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
In a preferred embodiment of the present invention, the weight part of the silane coupling agent is 0.1 to 1 part, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, or the like, based on 100 parts by weight of the resin composition.
Preferably, the silane coupling agent is a vinyl silane coupling agent.
In a preferred embodiment of the present invention, the carbon-based free radical initiator or the compound free radical initiator may be, for example, 0.1 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part, 2 parts, or the like, independently of each other, based on 100 parts by weight of the resin composition.
Preferably, the built free radical initiator comprises a combination of at least one organic peroxide free radical initiator and at least one carbon based free radical initiator.
Preferably, the organic peroxide free radical initiator is selected from any one or a combination of at least two of dicumyl peroxide, 1, 3-bis (tert-butylperoxyisopropyl) benzene, 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane, 2, 5-di-tert-butylperoxy-2, 5-dimethylhexyne-3, di-tert-butyl peroxide or tert-butylcumyl peroxide.
Preferably, the carbon-based free radical initiator is selected from any one or a combination of at least two of 2, 3-dimethyl-2, 3-diphenyl butane, 2, 3-dimethyl-2, 3-bis (4-methylphenyl) butane, 2, 3-dimethyl-2, 3-bis (4-isopropylphenyl) butane, 3, 4-dimethyl-3, 4-diphenyl hexane.
It is to be noted that the resin composition of the present invention can also be used in combination with other various polymers, as long as they do not impair the inherent properties of the resin composition, and the other various polymers illustratively include, but are not limited to: liquid crystal polymers, thermoplastic resins, different flame retardant compounds or additives, etc.; and may be used alone or in combination of plural kinds as needed.
Meanwhile, the preparation method of the resin composition is not limited in any particular way, and the preparation methods commonly used in the art are applicable, and exemplary include, but are not limited to: the components of the resin composition are stirred and mixed to obtain the resin composition.
In the invention, the particle size test method of the filler adopts a Markov 3000 laser particle size analyzer for testing; the density of hollow glass beads was measured by the gas displacement method (JC/T2285-2014); the number average molecular weight Mn of the thermosetting resin was measured by gel permeation chromatography based on polystyrene calibration using GB/T21863-2008.
In a second aspect, the present invention provides a circuit material including a dielectric substrate layer and conductive metal layers stacked on one side or both sides of the dielectric substrate layer;
the dielectric substrate layer comprises a reinforcing material and the resin composition according to the first aspect coated on the reinforcing material.
Preferably, the reinforcing material is an electronic grade glass fiber cloth.
Preferably, the reinforcing material is glass fiber cloth surface-treated by vinyl silane coupling agent.
Preferably, the conductive metal layer is copper foil.
Preferably, the copper foil has a thickness of 9 to 150 μm, for example, 9 μm, 20 μm, 30 μm, 40 μm, 50 μm, 70 μm, 90 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, or the like.
It should be noted that, in the present invention, there is no specific limitation on the preparation method of the circuit material, and the preparation method of the circuit material includes the following steps:
(1) Dissolving or dispersing the resin composition in a solvent to obtain a resin glue solution, impregnating the reinforcing material with the resin glue solution, drying, and removing the solvent to obtain a prepreg;
(2) Laminating at least one piece of prepreg together, arranging a conductive metal layer on one side or two sides of the surface of the prepreg, and then placing the prepreg into a laminating machine to prepare the circuit material through hot press curing.
It should be noted that the solvent in step (1) is not particularly limited, and organic solvents commonly used in the art are suitable, and exemplary solvents include, but are not limited to: alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, diethylene glycol diethyl ether and diethylene glycol butyl ether, ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, esters such as ethoxyethyl acetate and ethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone. The above solvents may be used singly or in combination of two or more.
The solvent may be 60 to 120 parts by weight, for example, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, or the like based on 100 parts by weight of the resin composition.
In a third aspect, the present invention provides a printed circuit board comprising the circuit material as described in the second aspect.
Preferably, the printed circuit board is a high frequency substrate.
In the present invention, the high-frequency substrate refers to a special circuit board with high electromagnetic frequency, and specifically is defined as a substrate with a frequency of more than 1 GHz.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention designs the specific composition of the resin composition, takes the hollow glass beads and the silicon dioxide as the fillers, and simultaneously controls the dosage of the hollow glass beads and the dosage proportion of the fillers and the resin within a specific range, so that the prepared circuit material can meet the requirements of stable dielectric constant and dielectric loss, lower water absorption, higher peeling strength and good thickness consistency in a high-temperature and high-humidity environment, has good Dk consistency, has the dielectric constant (Dk, 10 GHz) of 3.10-3.25, the dielectric loss (Df, 10 GHz) of 0.0032-0.0039, the peeling strength of more than or equal to 0.81N/mm, the DeltaDk (10 GHz) of less than or equal to 0.04, and the DeltaDf (10 GHz) of less than or equal to 0.0033.
(2) According to the invention, the thermosetting resin with unsaturated double bonds in medium molecular weight and the thermosetting resin polybutadiene resin and/or polybutadiene copolymer resin with unsaturated double bonds in low molecular weight are compounded and used, the mass ratio of the thermosetting resin with unsaturated double bonds and the polybutadiene resin is controlled within a specific range, the high-frequency substrate is ensured to have better thickness consistency and overall dielectric constant consistency, and the peeling strength of the plate is higher.
(3) The invention ensures that the high-frequency substrate has better consistency of thickness and dielectric constant by controlling the number average molecular weight of the thermosetting resin with unsaturated double bonds in the medium molecular weight within a specific range under the condition of ensuring that the bonding sheet is not sticky, and has stable dielectric constant and dielectric loss in a high-temperature and high-humidity environment, and the water absorption rate is less than or equal to 0.09 percent.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The sources of some of the components in the examples and comparative examples are shown in Table 1 below:
TABLE 1
Examples 1 to 14
Examples 1 to 14 respectively provide a resin composition and a circuit material, the specific composition of the resin composition and the specific composition of the circuit material are shown in the following tables 2 and 3, the resin compositions in tables 2 and 3 are used in parts by weight, the reinforcing material is in number of sheets, and the conductive metal layer is in number of sheets.
The circuit material comprises a dielectric substrate layer, a conductive metal layer and conductive metal layers on two sides of the dielectric substrate layer;
the dielectric substrate layer includes a reinforcing material and a resin composition overlying the reinforcing material.
The preparation method of the circuit material comprises the following steps:
(1) Dissolving or dispersing the resin composition in xylene (100 parts) to obtain a resin glue solution, impregnating the reinforcing material with the resin glue solution, drying, and removing solvent xylene to obtain a bonding sheet;
(2) Laminating multiple bonding sheets, respectively coating copper foil on two side surfaces, placing in laminating machine, and heating at 245 deg.C under 60Kg/cm 2 And performing hot press curing to obtain the circuit material.
Comparative examples 1 to 7
Comparative examples 1 to 7 respectively provide a resin composition and a circuit material, the specific composition of the resin composition and the specific composition materials of the circuit material are shown in the following Table 3, and the unit of use of the resin composition in Table 3 is parts by weight.
The circuit materials described in comparative examples 1 to 7 can be prepared by referring to the preparation methods provided in the above examples.
TABLE 2
TABLE 3 Table 3
The performance of the circuit materials (boards) provided in the above examples and comparative examples was tested as follows:
(1) Dielectric constant (Dk) and dielectric loss (Df): testing the dielectric constant (Dk) and dielectric loss (Df) of the plate at 10GHz frequency by adopting an SPDR method;
(2) Peel Strength (PS): according to the experimental condition of 'after thermal stress' in the IPC-TM-650.2.4.8 method, the peel strength of the plate is tested, and the unit of the peel strength is N/mm;
(3) Water absorption rate: the determination was carried out according to the IPC-TM-650.2.6.2.1 method;
(4) Thickness uniformity: taking five samples at four corners of the plate and the middle position of the plate to test the thickness of the plate, wherein if the thickness of the plate meets the three-level tolerance of the copper-clad plate, the thickness consistency is good, and if the thickness of the plate can not meet the three-level tolerance of the copper-clad plate, the thickness consistency is poor;
(5) Dk consistency: taking five samples at four corners of the plate and the middle position of the plate to test Dk of the plate, wherein if Dk of the plate is extremely poor to be less than or equal to 0.05, dk consistency is good, and if Dk of the plate is extremely poor to be greater than 0.05, dk consistency is poor;
(6) Dielectric constant change value (Δdk) after high temperature and high humidity: adopting an SPDR method, testing the dielectric constant (Dk 1) of the plate in a receiving state at the frequency of 10GHz, then treating the plate for 15 days at the temperature of 85% RH and the high temperature and the high humidity of 85 ℃, and then testing the dielectric constant (Dk 2) after the high temperature and the high humidity, wherein the dielectric constant change value delta Dk=Dk2-Dk1 after the high temperature and the high humidity;
(7) Dielectric loss change value (Δdf) after high temperature and high humidity: the SPDR method is adopted, dielectric loss (Df 1) of the plate in a receiving state is tested at the frequency of 10GHz, then the plate is treated for 15 days at the temperature of 85% RH and the temperature of 85 ℃, dielectric loss (Df 2) after high temperature and high humidity is tested, and dielectric loss change value delta Df=Df2-Df1 after high temperature and high humidity is tested.
The results of the above performance tests are detailed in table 4 below:
TABLE 4 Table 4
From the above, it is known that the resin composition with excellent performance is prepared by designing the specific composition of the resin composition, compounding the thermosetting resin with unsaturated double bonds in medium molecular weight with the thermosetting resin with unsaturated double bonds in low molecular weight, using hollow glass beads and silicon dioxide as fillers, controlling the dosage of the hollow glass bead fillers within a specific range, and the prepared circuit material has stable dielectric constant, low dielectric loss, higher peel strength, better PCB drilling processability and other comprehensive performances, and also has very low water absorption rate, is suitable for preparing high-frequency substrates, has dielectric constant (Dk, 10 GHz) of 3.10-3.25, dielectric loss (Df, 10 GHz) of 0.0032-0.0039, peel Strength (PS) of 0.81-0.91N/mm, water absorption rate of 0.05-0.09%, good thickness consistency, and delta Dk consistency of 0.03-0.04 GHz and delta Df of 0.0032-3.0023.
As is clear from the comparison of the data of examples 1 to 12 and examples 13 to 14, the present invention further improves the properties of the resin composition by controlling the mass ratio of the thermosetting resin having an unsaturated double bond in the medium molecular weight to the thermosetting resin having an unsaturated double bond in the low molecular weight within a specific range, and a circuit material excellent in properties is produced.
As is clear from the comparison of the data of examples 1 to 12 and comparative examples 1 to 2, the circuit material with excellent performance is prepared by using the thermosetting resin with unsaturated double bond and medium molecular weight and the thermosetting resin with unsaturated double bond with low molecular weight.
As can be seen from the comparison of the data of examples 1-12 and comparative examples 3-5, the present invention uses hollow glass beads and silica as fillers, and controls the amount of the hollow glass beads as fillers within a specific range, thus preparing a circuit material with excellent performance.
As is clear from comparison of the data concerning examples 1 to 12 and comparative examples 6 to 7, the overall performance of the circuit material can be further improved by controlling the ratio of the resin and the filler in the resin composition within a specific range in the present invention.
In summary, the resin composition with excellent performance is prepared by designing the specific composition of the resin composition, so that the prepared circuit material has the comprehensive properties of stable dielectric constant, low dielectric loss, high peel strength, good PCB drilling processability and the like, has very low water absorption rate, and is suitable for preparing high-frequency substrates.
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A resin composition, characterized in that the resin composition comprises the following components:
(A) A thermosetting resin with unsaturated double bonds and low molecular weight, which is selected from polybutadiene resin and/or polybutadiene copolymer resin, and the number average molecular weight Mn is less than or equal to 5000g/mol;
(B) A thermosetting resin with unsaturated double bonds and a number average molecular weight Mn of 15000-25000 g/mol;
(C) Hollow glass bead filler;
(D) A silica filler;
(E) A flame retardant;
(F) A silane coupling agent;
(G) A carbon-based free radical initiator or a complex free radical initiator;
the component (B) contains 40-60% of butadiene structure in mole ratio, and the mole ratio content of butadiene added at 1,2 positions in the butadiene molecular structure is more than or equal to 80%;
the sum of the parts by weight of the component (A) and the component (B) is 20-30 parts by weight based on 100 parts by weight of the resin composition;
the weight part of the component (C) is 6-10 parts based on 100 parts of the weight part of the resin composition;
the weight part of the component (D) is 50 to 60 parts based on 100 parts by weight of the resin composition.
2. The resin composition according to claim 1, wherein the mass ratio of the component (A) to the component (B) is 1 (0.5-2).
3. The resin composition according to claim 1 or 2, wherein the polybutadiene resin is selected from any one or a combination of at least two of a 1, 2-polybutadiene resin, a maleic anhydride modified polybutadiene resin, an acrylate modified polybutadiene resin, an epoxy modified polybutadiene resin, an amine modified polybutadiene resin, a carboxyl-terminated modified polybutadiene resin, or a hydroxyl-terminated modified polybutadiene resin;
preferably, the polybutadiene copolymer resin is selected from any one or a combination of at least two of polybutadiene-styrene copolymer resin, polybutadiene-styrene-divinylbenzene graft copolymer resin, maleic anhydride-modified styrene-butadiene copolymer resin or acrylate-modified styrene-butadiene copolymer resin.
4. A resin composition according to any one of claims 1 to 3, wherein the thermosetting resin with unsaturated double bonds of medium molecular weight is selected from any one or a combination of at least two of styrene-butadiene diblock copolymer, styrene-butadiene-styrene triblock copolymer, styrene- (ethylene-butylene) -styrene triblock copolymer, styrene-isoprene diblock copolymer, styrene-isoprene-styrene triblock copolymer, styrene- (ethylene-propylene) -styrene triblock copolymer or styrene- (ethylene-butylene) diblock copolymer.
5. The resin composition according to any one of claims 1 to 4, wherein the hollow glass bead filler has a density of 0.2 to 0.6g/cm 3 ；
Preferably, the silica filler is a silica filler which is not surface-treated or a silica filler which is surface-treated with a vinyl silane coupling agent, and further preferably a silica filler which is surface-treated with a vinyl silane coupling agent;
preferably, the silica filler comprises an angular silica filler and/or a spherical silica filler;
preferably, the silica filler has a median particle diameter D 50 3-20 μm.
6. The resin composition according to any one of claims 1 to 5, wherein the flame retardant is 5 to 15 parts by weight based on 100 parts by weight of the resin composition;
preferably, the flame retardant comprises a bromine-containing flame retardant and/or a phosphorus-containing flame retardant.
7. The resin composition according to any one of claims 1 to 6, wherein the weight part of the silane coupling agent is 0.1 to 1 part based on 100 parts by weight of the resin composition;
preferably, the silane coupling agent is a vinyl silane coupling agent.
8. The resin composition according to any one of claims 1 to 7, wherein the weight parts of the carbon-based radical initiator or the compound radical initiator are each independently 0.1 to 2 parts based on 100 parts by weight of the resin composition;
preferably, the built free radical initiator comprises a combination of at least one organic peroxide free radical initiator and at least one carbon-based free radical initiator;
preferably, the organic peroxide free radical initiator is selected from any one or a combination of at least two of dicumyl peroxide, 1, 3-bis (tert-butylperoxyisopropyl) benzene, 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane, 2, 5-di-tert-butylperoxy-2, 5-dimethylhexyne-3, di-tert-butyl peroxide or tert-butylcumyl peroxide;
preferably, the carbon-based free radical initiator is selected from any one or a combination of at least two of 2, 3-dimethyl-2, 3-diphenyl butane, 2, 3-dimethyl-2, 3-bis (4-methylphenyl) butane, 2, 3-dimethyl-2, 3-bis (4-isopropylphenyl) butane, 3, 4-dimethyl-3, 4-diphenyl hexane.
9. A circuit material, characterized in that the circuit material comprises a dielectric substrate layer and conductive metal layers laminated on one side or both sides of the dielectric substrate layer;
the dielectric substrate layer comprising a reinforcing material and the resin composition of any one of claims 1-8 overlying the reinforcing material;
preferably, the reinforcing material is electronic grade glass fiber cloth;
preferably, the reinforcing material is a surface-treated open-fiber glass fiber cloth of a vinyl silane coupling agent;
preferably, the conductive metal layer is copper foil.
10. A printed circuit board, characterized in that the printed circuit board comprises the circuit material according to claim 9;
preferably, the printed circuit board is a high frequency substrate.
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| CN202311858311.7A CN117736504A (en) | 2023-12-29 | 2023-12-29 | Resin composition, circuit material containing same and printed circuit board |
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| CN202311858311.7A CN117736504A (en) | 2023-12-29 | 2023-12-29 | Resin composition, circuit material containing same and printed circuit board |
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