CN112538254A - 一种磁介电树脂组合物、包含其的层压板及其印刷电路板 - Google Patents
一种磁介电树脂组合物、包含其的层压板及其印刷电路板 Download PDFInfo
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- CN112538254A CN112538254A CN202011431355.8A CN202011431355A CN112538254A CN 112538254 A CN112538254 A CN 112538254A CN 202011431355 A CN202011431355 A CN 202011431355A CN 112538254 A CN112538254 A CN 112538254A
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- resin
- resin composition
- magnetic
- titanate
- barium
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- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 239000012762 magnetic filler Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000696 magnetic material Substances 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims abstract description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 3
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000013034 phenoxy resin Substances 0.000 claims description 6
- 229920006287 phenoxy resin Polymers 0.000 claims description 6
- 239000012779 reinforcing material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- CMSBLKQHGOOWBO-UHFFFAOYSA-N 1,1,3-trimethyl-5-(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1CC(C)CC(C)(C)C1 CMSBLKQHGOOWBO-UHFFFAOYSA-N 0.000 claims description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 2
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 claims description 2
- RCDLELXZNBHNBN-UHFFFAOYSA-N 2,3,4-tripentylphenol Chemical compound CCCCCC1=CC=C(O)C(CCCCC)=C1CCCCC RCDLELXZNBHNBN-UHFFFAOYSA-N 0.000 claims description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- LEHNQGSPRXHYRT-UHFFFAOYSA-N 2-dodecyl-1h-imidazole Chemical compound CCCCCCCCCCCCC1=NC=CN1 LEHNQGSPRXHYRT-UHFFFAOYSA-N 0.000 claims description 2
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 claims description 2
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- PBFMRGSHDMCVHH-UHFFFAOYSA-N C(C)(C)(C)OOC1=CC(=CC=C1)C(C)(C)C1=CC=CC=C1 Chemical compound C(C)(C)(C)OOC1=CC(=CC=C1)C(C)(C)C1=CC=CC=C1 PBFMRGSHDMCVHH-UHFFFAOYSA-N 0.000 claims description 2
- QMQVIEKDJWQHKY-UHFFFAOYSA-N C1(=CC=CC=C1)O.CN(C)CN Chemical compound C1(=CC=CC=C1)O.CN(C)CN QMQVIEKDJWQHKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- OUPYOLABCAXGHH-UHFFFAOYSA-N [Ba].[Rb] Chemical compound [Ba].[Rb] OUPYOLABCAXGHH-UHFFFAOYSA-N 0.000 claims description 2
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 claims description 2
- VNSWULZVUKFJHK-UHFFFAOYSA-N [Sr].[Bi] Chemical compound [Sr].[Bi] VNSWULZVUKFJHK-UHFFFAOYSA-N 0.000 claims description 2
- WVEIBSXNFJMONP-UHFFFAOYSA-N [Ta].[K] Chemical compound [Ta].[K] WVEIBSXNFJMONP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- FWGZLZNGAVBRPW-UHFFFAOYSA-N alumane;strontium Chemical compound [AlH3].[Sr] FWGZLZNGAVBRPW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- IQONKZQQCCPWMS-UHFFFAOYSA-N barium lanthanum Chemical compound [Ba].[La] IQONKZQQCCPWMS-UHFFFAOYSA-N 0.000 claims description 2
- DUPIXUINLCPYLU-UHFFFAOYSA-N barium lead Chemical compound [Ba].[Pb] DUPIXUINLCPYLU-UHFFFAOYSA-N 0.000 claims description 2
- IJBYNGRZBZDSDK-UHFFFAOYSA-N barium magnesium Chemical compound [Mg].[Ba] IJBYNGRZBZDSDK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 2
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002115 bismuth titanate Inorganic materials 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 2
- JXDXDSKXFRTAPA-UHFFFAOYSA-N calcium;barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[Ca+2].[Ti+4].[Ba+2] JXDXDSKXFRTAPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
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- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- BRHAUGJKIFZHDU-UHFFFAOYSA-N tert-butyl octanoate Chemical compound CCCCCCCC(=O)OC(C)(C)C BRHAUGJKIFZHDU-UHFFFAOYSA-N 0.000 claims description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种磁介电树脂组合物、包含其的层压板及其印刷电路板，所述磁介电树脂组合物包括树脂和磁性填料，所述磁性填料包含Fe、Si、M1、M2和M3磁性材料，M1选自ZnO、NiO、MnO、CuO、MgO的任意一种或至少两种的组合，M2选自CaO、SiO、HfO、ZnO、ZrO、V2O5、TiO2、Ta2O5、Co3O4、Nb2O5、La2O3、Ce2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3和Tb2O3、SnO2、BiO、BaTiO3、PbO、SrCO3、CoO、Nb2O中的至少一种。该磁介电树脂组合物制备的板材磁导率高、磁损耗低、电阻率高、介电损耗角正切低。
Description
技术领域
本发明属于层压板技术领域，涉及一种磁介电树脂组合物、包含其的层压板及其印刷电路板。
背景技术
随着微电子、微机械等新兴微加工技术的发展，在以高密度安装技术为背景的潮流中，驱动电容器、集成电路、电路模块、天线射频模块等不断往小型化方向发展。作为雷达和现代无线通信系统中的关键组件，作为小型化的瓶颈，天线尺寸减小已引起人们极大关注。减小天线尺寸之一的办法是使用高介电材料，专利CN103101252A、CN103351578A公开了一种高介电常数板材，这种板材可以减小天线尺寸，但是这种办法会减小天线的增益、降低天线综合性能。
减小天线尺寸的另一条办法是采用磁介电材料作为基板，如公式1所示，(εrμr)1/2是小型化因子，介电常数越高、磁导率越大，小型化因子越高，越有利于小型化。在介电常数不能改变的情况、提高磁导率就能有效减小天线尺寸，同时保持或提高天线增益和带宽。
λ＝c/f(εrμr)1/2 (1)
尖晶石铁氧体具有高磁导率值，例如NiZn、MnZn铁氧体，但是，这些尖晶石铁氧体截止频率的截止频率低，在300MHz以上难以使用。平面六角铁氧体具有高的截止频率，例如Co2Z六角铁氧体，但是磁导率低，难以大幅度降低天线尺寸。
CN109553955A公开了一种磁介电树脂组合物，磁导率高、电阻率高，但是研究板材的磁损耗角正切。CN101589443公开一种金属磁性粉末的树脂组合物，磁损耗高、绝缘性也会受影响；CN1246500公开了一种软磁填料树脂组合物，但是磁损耗高，也没有研究绝缘性性能。
因此，在本领域，期望开发一种成本低并且磁导率高、磁损耗低的磁介电材料。
发明内容
针对现有技术的不足，本发明的目的在于提供一种磁介电树脂组合物、包含其的层压板及其印刷电路板。
为达此目的，本发明采用以下技术方案：
一方面，本发明提供一种磁介电树脂组合物，所述磁介电树脂组合物包括树脂和磁性填料，所述磁性填料包含Fe、Si、M1、M2磁性材料，M1选自ZnO、NiO、MnO、CuO、MgO的任意一种或至少两种的组合，M2选自CaO、SiO、HfO、ZnO、ZrO、V2O5、TiO2、Ta2O5、Co3O4、Nb2O5、La2O3、Ce2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3和Tb2O3、SnO2、BiO、BaTiO3、PbO、SrCO3、CoO、Nb2O中的任意一种或至少两种的组合。
在本发明中通过在磁介电树脂组合物中使用所述磁性填料，该磁性材料中Fe、Si、M1、M2和M3的结合，使得磁介电树脂组合物制备的板材具有磁导率高、磁损耗低、电阻率高、介电损耗角正切低等优异综合性能。
优选地，所述磁性填料占磁介电树脂组合物的重量百分比为20wt％～90wt％；例如可以是20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％、85wt％或90wt％等。磁性填料含量小于20wt％会导致磁导率太低，达不到使用要求，磁性填料含量大于9020wt％会导致工艺性差、无法加工制备；
优选地，所述磁性填料的粒径为0.1μm～30μm，例如0.1μm、2μm、5μm、8μm、10μm、13μm、16μm、19μm、22μm、25μm、28μm、30μm。
优选地，所述树脂选自环氧树脂、氰酸酯树脂、聚苯醚树脂、聚丁二烯树脂、丁苯树脂、双马来酰亚胺-三嗪树脂、双马来酰亚胺树脂、聚四氟乙烯树脂、聚酰亚胺树脂、酚醛树脂、丙烯酸树脂、液晶树脂、苯并恶嗪树脂、酚氧树脂、丁腈橡胶、端羧基丁腈橡胶或端羟基丁腈橡胶中的任意一种或者至少两种的混合物。
优选地，所述树脂在磁介电树脂组合物中的重量百分比为10wt％～80wt％，例如10wt％、15wt％、20wt％、30wt％、40wt％、50wt％、60wt％、70wt％或80wt％。
优选地，所述磁介电树脂组合物还包括非磁性填料和促进剂。
优选地，所述的非磁性填料选自二氧化硅、二氧化钛、钛酸钡、钛酸锶、钛酸镁、钛酸钙、钛酸锶钡、钙钛酸钡、钛酸铅、锆钛酸铅、锆钛酸镧铅、钛酸镧钡、钛酸锆钡、二氧化铪、铌镁酸铅、铌镁酸钡、铌酸锂、铌酸钾、钽酸铝锶、铌酸钽钾、铌酸锶钡、铌酸钡铅、铌酸钛钡、钽酸铋锶、钛酸铋、钛酸钡铷、钛酸铜或钛酸铅-铌镁酸铅中的任意一种或者至少两种的混合物。
优选地，所述促进剂为2-甲基咪唑、2-乙基-4甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、2-十七烷基咪唑、2-异丙基咪唑、2-苯基-4-甲基咪唑、2-十二烷基咪唑或1-氰乙基-2-甲基咪唑中的任意一种或者至少两种的混合物。
优选地，所述磁介电树脂组合物还包括引发剂。
优选地，所述引发剂选自a,a'-二(叔丁基过氧化间异丙苯)苯、过氧化二异丙苯、叔丁基过氧化异丙苯、1,1-双(叔己基过氧化)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己-3-炔、辛酸叔丁酯、过氧化苯甲酸叔丁酯，三乙级胺及其盐类、四级胺盐化合物、2,4,6-三(二甲胺基甲胺)苯酚、苄基二甲胺、咪唑类、三戊基酚酸胺、单酚化合物\多酚化合物、三氟化硼、三氟化硼有机物的配合物、磷酸或亚磷酸三苯酯中的任意一种或者至少两种的混合。
优选地，所述磁介电树脂组合物还包括交联剂；
优选地，所述交联剂选自异氰脲酸三烯丙酯、聚异氰脲酸三烯丙酯、三烯丙酯三聚氰酸酯、三甲基丙烯酸、邻苯二甲酸二烯丙酯、二乙烯基苯或多官能的丙烯酸酯中的任意一种或者至少两种的混合。
另一方面，本发明提供一种树脂胶液，所述树脂胶液中含有如上所述的磁介电树脂组合物和溶剂。
优选地，所述溶剂为醚类、酮类、芳香族烃类、酯类或含氮类溶剂中的任意一种或至少两种的组合。
优选地，所述溶剂选自甲醇、乙醇、丁醇、乙基溶纤剂、丁基溶纤剂、乙二醇甲醚、二乙二醇乙醚、二乙二醇丁醚等醚类，或丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮、甲苯、二甲苯、均三甲苯、乙氧基乙基乙酸酯、醋酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基-2-吡咯烷中的任意一种或至少两种的组合。
另一方面，本发明提供一种预浸料，所述预浸料包括增强材料及通过含浸干燥后附着其上的如上所述的磁介电树脂组合物。
优选地，所述增强材料包括玻璃纤维布。
另一方面，本发明提供一种覆金属箔层压板，所述覆金属箔层压板包括至少一张如上所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。
另一方面，本发明提供一种印刷电路板，所述印刷电路板包括至少一张如上所述的预浸料或至少一张如上所述的覆金属箔层压板。
相对于现有技术，本发明具有以下有益效果：
在本发明中通过在磁介电树脂组合物中使用所述磁性填料，该磁性材料中Fe、Si、M1、M2和M3的结合，使得磁介电树脂组合物制备的板材具有磁导率高、磁损耗低、电阻率高、介电损耗角正切低等优异综合性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
以下实施例和对比例中所用到的材料具体如下：
聚苯醚树脂：沙比克SA9000；
溴化环氧树脂：台湾长春BEB531A80P；
酚氧树脂：新日铁YP-50EK35；
邻甲酚线型酚醛树脂：KOLON KCE-F2118；
2-MI：巴斯夫(德国)2MI；
本发明以下实施例和对比例中所使用的磁性填料的组分及其性能如表1所示；表1中，各组分的含量为摩尔百分含量(其中所述磁导率为相对磁导率)。
表1
磁性填料的制备方法如下：
按照表1所示的配方，按照摩尔比例称取各原料组分，物理干法混合1h，制备成环状胚体，然后1300℃烧结4h；得到的烧结产物为环形样品(内径3.04mm、外径6.96mm、厚度3mm)；将烧结产物在球磨机中湿法球磨粉碎，转速为3000转/min，时间为1～5h，锆珠的粒径为1～10mm复配；球磨后干燥，得到磁性填料；通过球磨时间的控制实现不同粒径的制备。
表1中，磁导率和温漂系数的测试方法为：
(1)样品制备：将各原料组分物理干法混合后，制备成环状胚体，1300℃烧结4h，得到的烧结产物为成环形样品(内径3.04mm、外径6.96mm、厚度3mm)，测试烧结产物的磁导率和温漂系数；
(2)磁导率、截止频率测试：采用阻抗分析仪测试材料0.1～1GHz的磁导率，测试仪器为是德科技E5071C网络分析仪+N1500测试系统；
实施例1
将25g溴化环氧树脂B、15g酚氧树脂C、40g聚苯醚树脂SA9000，溶解在溶剂乙二醇甲醚中；再加入磁性填料，磁性填料的种类为C5200、磁导率为200、粒径为0.1μm，加入量为20g；在室温下混合得到胶液。
使用增强材料浸渍上述胶液，然后在155℃的烘箱中烘烤5分钟固化为B阶段，得到增强材料预浸料。将制作的预浸料放在铜箔之间，在压机中于210℃层压并固化，得到覆铜板后测量介电常数、磁导率、电阻率等性能，具体性能测试结果见表2。
实施例2
本实施例与实施例1的区别在于：制备原料包括：4g环氧树脂A、5g溴化环氧树脂B、1g酚氧树脂C，磁性填料的种类为C-150、磁导率为150、粒径为10μm，加入量为90g。
将本实施例制备的磁介电树脂组合物制备覆铜板，所制备的覆铜板的性能见表2。
实施例3
本实施例与实施例1的区别在于：制备原料包括：20g环氧树脂A、25g溴化环氧树脂B、5g酚氧树脂C，磁性填料的种类为C-75、磁导率为75、粒径为30μm，加入量为50g。
将本实施例制备的磁介电树脂组合物制备覆铜板，所制备的覆铜板的性能见表2。
实施例4
本实施例与实施例3的区别在于：还包括10g的硅微粉。
将本实施例制备的磁介电树脂组合物制备覆铜板，所制备的覆铜板的性能见表2。
对比例1
提供一种覆铜箔层压板，与实施例1的区别在于，磁性填料的粒径为0.05μm。填料分散性差、粘度大，无法制备出合格覆铜板。
对比例2
提供一种覆铜箔层压板，与实施例1的区别在于，磁性填料加入量为10g。
对比例3
提供一种覆铜箔层压板，与实施例2的区别在于，磁性填料加入量为95g。填料分散性差、粘度大，无法制备出合格覆铜板。
对比例4
提供一种覆铜箔层压板，与实施例1的区别在于，磁性填料使用C220。填料分散性差、粘度大，无法制备出合格覆铜板。
将本对比例制备的磁介电树脂组合物制备覆铜板，所制备的覆铜板的性能见表2(表2中1.4012E+11表示1.4012×1011)。
表2
上述实施例和对比例中板材的磁导率、磁损耗角正切采用空气同轴传输线法测试；
从上述实施例和对比例的可以看出，实施例1到实施例4制备的覆铜板的磁导率高、距离温度高等综合性能较好。
对比例2中使用磁性填料占树脂组合的质量百分比小于20wt％，与实施例1相比，制备的覆铜板的磁导率低，只有1.4；
对比例4中使用不含si元素的磁性填料，导致板材介电损耗高、电阻率低。
综上述结果可知，本发明制备的树脂组合物制备的覆铜板具有磁导率高、磁介比小、介电损耗角正切小等优良综合性能，可以满足磁介电基板的性能要求。
申请人声明，本发明通过上述实施例来说明本发明的磁介电树脂组合物、包含其的层压板及其印刷电路板，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种磁介电树脂组合物，其特征在于，所述磁介电树脂组合物包括树脂和磁性填料，所述磁性填料包含Fe、Si、M1、M2磁性材料，M1选自ZnO、NiO、MnO、CuO、MgO的任意一种或至少两种的组合，M2选自CaO、SiO、HfO、ZnO、ZrO、V2O5、TiO2、Ta2O5、Co3O4、Nb2O5、La2O3、Ce2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3和Tb2O3、SnO2、BiO、BaTiO3、PbO、SrCO3、CoO、Nb2O中的任意一种或至少两种的组合。
2.根据权利要求1所述的磁介电树脂组合物，其特征在于，所述磁性填料占磁介电树脂组合物的重量百分比为20wt％～90wt％；
优选地，所述磁性填料的粒径为0.1μm～30μm。
3.根据权利要求1或2所述的磁介电树脂组合物，其特征在于，所述树脂选自环氧树脂、氰酸酯树脂、聚苯醚树脂、聚丁二烯树脂、丁苯树脂、双马来酰亚胺-三嗪树脂、双马来酰亚胺树脂、聚四氟乙烯树脂、聚酰亚胺树脂、酚醛树脂、丙烯酸树脂、液晶树脂、苯并恶嗪树脂、酚氧树脂、丁腈橡胶、端羧基丁腈橡胶或端羟基丁腈橡胶中的任意一种或者至少两种的混合物；
优选地，所述树脂在磁介电树脂组合物中的重量百分比为10wt％～80wt％。
4.根据权利要求1-3中任一项所述的磁介电树脂组合物，其特征在于，所述磁介电树脂组合物还包括非磁性填料和促进剂；
优选地，所述的非磁性填料选自二氧化硅、二氧化钛、钛酸钡、钛酸锶、钛酸镁、钛酸钙、钛酸锶钡、钙钛酸钡、钛酸铅、锆钛酸铅、锆钛酸镧铅、钛酸镧钡、钛酸锆钡、二氧化铪、铌镁酸铅、铌镁酸钡、铌酸锂、铌酸钾、钽酸铝锶、铌酸钽钾、铌酸锶钡、铌酸钡铅、铌酸钛钡、钽酸铋锶、钛酸铋、钛酸钡铷、钛酸铜或钛酸铅-铌镁酸铅中的任意一种或者至少两种的混合物；
优选地，所述促进剂为2-甲基咪唑、2-乙基-4甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、2-十七烷基咪唑、2-异丙基咪唑、2-苯基-4-甲基咪唑、2-十二烷基咪唑或1-氰乙基-2-甲基咪唑中的任意一种或者至少两种的混合物。
5.根据权利要求1-4中任一项所述的磁介电树脂组合物，其特征在于，所述磁介电树脂组合物还包括引发剂；
优选地，所述引发剂选自a,a'-二(叔丁基过氧化间异丙苯)苯、过氧化二异丙苯、叔丁基过氧化异丙苯、1,1-双(叔己基过氧化)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己-3-炔、辛酸叔丁酯、过氧化苯甲酸叔丁酯，三乙级胺及其盐类、四级胺盐化合物、2,4,6-三(二甲胺基甲胺)苯酚、苄基二甲胺、咪唑类、三戊基酚酸胺、单酚化合物\多酚化合物、三氟化硼、三氟化硼有机物的配合物、磷酸或亚磷酸三苯酯中的任意一种或者至少两种的混合。
6.根据权利要求1-5中任一项所述的磁介电树脂组合物，其特征在于，所述磁介电树脂组合物还包括交联剂；
优选地，所述交联剂选自异氰脲酸三烯丙酯、聚异氰脲酸三烯丙酯、三烯丙酯三聚氰酸酯、三甲基丙烯酸、邻苯二甲酸二烯丙酯、二乙烯基苯或多官能的丙烯酸酯中的任意一种或者至少两种的混合。
7.一种树脂胶液，其特征在于，所述树脂胶液中含有如权利要求1-6中任一项所述的磁介电树脂组合物和溶剂。
8.一种预浸料，其特征在于，所述预浸料包括增强材料及通过含浸干燥后附着其上的如权利要求1-6中任一项所述的磁介电树脂组合物；
优选地，所述增强材料包括玻璃纤维布。
9.一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括至少一张如权利要求8所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。
10.一种印刷电路板，其特征在于，所述印刷电路板包括至少一张如权利要求8所述的预浸料或至少一张如权利要求9所述的覆金属箔层压板。
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