WO2019127389A1 - Epoxy resin composition, prepreg, laminate and printed circuit board - Google Patents
Epoxy resin composition, prepreg, laminate and printed circuit board Download PDFInfo
- Publication number
- WO2019127389A1 WO2019127389A1 PCT/CN2017/119904 CN2017119904W WO2019127389A1 WO 2019127389 A1 WO2019127389 A1 WO 2019127389A1 CN 2017119904 W CN2017119904 W CN 2017119904W WO 2019127389 A1 WO2019127389 A1 WO 2019127389A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- epoxy resin
- compound
- resin composition
- substituted
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 183
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 183
- 239000000203 mixture Substances 0.000 title claims abstract description 108
- -1 maleimide compound Chemical class 0.000 claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims description 74
- 239000011347 resin Substances 0.000 claims description 74
- 150000002148 esters Chemical class 0.000 claims description 62
- 229920003986 novolac Polymers 0.000 claims description 52
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 125000000732 arylene group Chemical group 0.000 claims description 21
- 125000001624 naphthyl group Chemical group 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 19
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 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 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000004957 naphthylene group Chemical group 0.000 claims description 15
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 15
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004643 cyanate ester Substances 0.000 claims description 11
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 229930003836 cresol Natural products 0.000 claims description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 6
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 33
- 238000010521 absorption reaction Methods 0.000 abstract description 28
- 230000009477 glass transition Effects 0.000 abstract description 13
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 91
- 239000011521 glass Substances 0.000 description 32
- 239000000843 powder Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 15
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 14
- 239000011342 resin composition Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000003292 glue Substances 0.000 description 13
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 229910002113 barium titanate Inorganic materials 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 5
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000005350 fused silica glass Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 3
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 3
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
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- 239000007822 coupling agent Substances 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000002648 laminated material Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
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- 239000004843 novolac epoxy resin Substances 0.000 description 2
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- RNIPJYFZGXJSDD-UHFFFAOYSA-N 2,4,5-triphenyl-1h-imidazole Chemical compound C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 RNIPJYFZGXJSDD-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-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
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 108091063785 miR-3000 stem-loop Proteins 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- 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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- 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
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
Definitions
- the present invention relates to the field of electronic product technology, and in particular to an epoxy resin composition and a prepreg, a laminate and a printed circuit board using the same.
- the metal foil-clad laminate for producing a printed wiring board has more excellent heat and humidity resistance, a low coefficient of thermal expansion, a dielectric constant, and a low water absorption rate.
- Epoxy resin has excellent mechanical properties and processability. It is a commonly used matrix resin in the production of metal foil laminates for high-end printed wiring boards. Prepregs and laminates are widely used as a A variety of modified raw materials are used in high performance printed circuit board materials.
- the epoxy resin composition has excellent flexibility, chemical resistance, adhesion, and the like.
- the cured product has a problem of high water absorption and insufficient heat and humidity resistance, and cannot satisfy the performance requirements of the high-end substrate.
- Cipheral Patent Application No. CN106103534 to Japanese Pharmaceuticals discloses an aromatic amine resin having a low content of diphenylamine, a maleimide resin derived therefrom, and curing using the aromatic amine resin and the maleimide resin
- the resin composition and the cured product which are excellent in heat resistance, low moisture absorption, low dielectric property, flame retardance, and toughness obtained by curing the curable resin composition.
- these resins have the disadvantage of having a large water absorption rate.
- an object of the present invention to provide an epoxy resin composition and a prepreg, a laminate (including a metal foil-clad laminate) and a printed wiring board which are produced using the same, which have a low dielectric Constant (Dk) / dielectric loss tangent (Df), high glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and heat and humidity resistance.
- Dk dielectric Constant
- Df dielectric loss tangent
- Tg high glass transition temperature
- CTE coefficient of thermal expansion
- the inventors of the present application conducted intensive studies to achieve the above object, and as a result, found that the above object can be attained by using a composition comprising an epoxy resin and a specific structure of maleimide and an active ester compound, particularly a significant reduction. Water absorption rate; Moreover, by adding an active ester compound, the problem that the maleimide is poorly dissolved in a solvent for an epoxy resin and it is difficult to prepare a glue is solved, thereby avoiding a complicated glue mixing process and greatly simplifying The production process improves production efficiency.
- One aspect of the invention relates to an epoxy resin composition characterized in that the epoxy resin composition comprises an epoxy resin (A), a maleimide compound (B) having a structure of the formula (I), Active ester compound (C),
- R is a group, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms
- R 1 is an arylene group having 6 to 18 carbon atoms
- R 2 and R 3 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms
- n is an integer of 1 to 20.
- n in the maleimide compound (B) having the structure of formula (I) is an integer from 1 to 15, preferably n is an integer from 1 to 10;
- R is a group or a hydrogen atom
- R 1 is a phenylene group, a naphthylene group or a biphenylylene group, and further preferably R 1 is a biphenylylene group;
- R 2 and R 3 are a hydrogen atom.
- the epoxy resin (A) is contained in a molecular structure Group, Group, Group, Group, Group or a compound of a group; and/or the active ester compound (C) is contained in a molecular structure Group, Group, Group, Group, Group or a compound of a group.
- the epoxy resin (A) is a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol type epoxy resin, a naphthol novolac type epoxy resin, a fluorene type epoxy Resin, dicyclopentadiene type epoxy resin, dicyclopentadiene novolac type epoxy resin, phenolphthalein type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin Any one or a mixture of at least two kinds of epoxy resins having an arylene ether structure in the molecule; more preferably, the epoxy resin (A) is a novolac type epoxy resin, and a cresol novolac type epoxy resin , naphthol type epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, fluorene type epoxy resin, dicyclopentadiene Any one or
- the active ester compound (C) is at least one selected from the group consisting of:
- an active ester obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acidic halogenated product, and a monohydroxy compound
- the amount of the difunctional carboxylic acid aromatic compound or acid halide in the active ester (1) is 1 mol
- the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol
- the amount of the monohydroxy compound is 0.25 ⁇ . 0.95mol
- the active ester (1) has the following structural formula:
- X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25;
- the styrene-containing active ester (2) has the following structure:
- the imide-modified active ester (3) has the structure represented by the formula (i):
- R is Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group;
- X is an arylene group, an arylene group substituted by a bromine compound, and is substituted by a phosphorus compound.
- Y is phenylene, naphthylene, phenylene substituted by C1-C4 alkyl or naphthylene substituted by C1-C4 alkyl;
- n represents average degree of polymerization , is 0.05-10;
- the imide-modified active ester has the structure represented by formula (ii):
- Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group; and X is an arylene group and an arylene group substituted by a bromine compound.
- Y is a phenylene group, a naphthylene group, a phenylene group substituted by a C1-C4 alkyl group or a naphthylene group substituted by a C1-C4 alkyl group;
- n represents the average degree of polymerization, which is 0.05-10;
- the imide-modified active ester has the structure represented by formula (iii):
- R is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1-C8 alkyl group; n 1 represents an average degree of polymerization, and is 0.05 to 5.0;
- the double-end polyfunctional active ester (4) containing a PPO backbone has a structure represented by the following formula:
- R 1 is R 2 is a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl, allyl or isoallyl group;
- R 3 is H, allyl or isoallyl;
- R 4 , R 5 , R 6 And R 7 is independently selected from H, a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl group, allyl, isoallyl or -OR 8 ;
- R 8 is a substituted or unsubstituted C1- a linear alkyl or branched alkyl group of C3 or a substituted or unsubstituted phenyl group;
- n1, n2 are positive integers greater than 0, and satisfy 4 ⁇ n1+n2 ⁇ 25;
- n3, n4 are equal or unequal, independently It is 1, 2 or 3, preferably independently 2 or 3, more preferably n3, n4 are equal and 2 or 3.
- the content of each component in the epoxy resin composition is as follows: the total amount of the organic solids of the resin component in the epoxy resin composition is 100 parts by weight, the epoxy resin (A) is 20 to 60 parts by weight, the maleimide compound (B) is 10 to 50 parts by weight, and the active ester compound (C) is 10 to 50 parts by weight.
- the epoxy resin composition further comprises a cyanate compound (D); preferably, in the case of the cyanate-containing compound (D), the resin in the epoxy resin composition
- the total amount of the organic solids of the component is 100 parts by weight, and the amount of the cyanate compound (D) in the epoxy resin composition is 10 to 50 parts by weight; more preferably, the active ester compound (C) and The ratio of the cyanate compound (D) is from 1:5 to 5:1.
- the epoxy resin composition further includes an inorganic filler (E), preferably, based on 100 parts by weight of the total amount of the organic solids of the resin component in the epoxy resin composition, The amount of the inorganic filler (E) in the epoxy resin composition is 20 to 300 parts by weight.
- Another aspect of the invention relates to the use of the above epoxy resin composition, comprising a prepreg using the epoxy resin composition, a laminate comprising the prepreg, and a printed wiring board comprising the prepreg.
- the epoxy resin composition of the present invention and prepregs, laminates (including metal foil-clad laminates) and printed wiring boards produced therefrom may have a low dielectric constant (Dk) / dielectric loss tangent (Df), High glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and heat and humidity resistance, especially with significantly reduced water absorption.
- Dk dielectric constant
- Df dielectric loss tangent
- Tg High glass transition temperature
- CTE coefficient of thermal expansion
- excellent heat resistance and heat and humidity resistance especially with significantly reduced water absorption.
- the problem of poor solubility of maleimide in a solvent for an epoxy resin is solved by adding an active ester compound, and the epoxy resin composition can be formulated into a glue, thereby It greatly simplifies the production process and improves production efficiency. Further, by blending the active ester compound (C) with the cyanate compound (D), the water absorption rate is lowered while improving the adhesion to the copper foil.
- One aspect of the invention relates to an epoxy resin composition
- an epoxy resin composition comprising an epoxy resin (A), a maleimide compound (B) having a structure of the formula (I), and an active ester compound (C)
- the following optional components may also be included: cyanate ester compound (D), inorganic filler (E), curing accelerator (G), solvent (H), and other additives (I).
- cyanate ester compound (D) inorganic filler
- E curing accelerator
- H solvent
- other additives I
- the epoxy resin (A) is one of the main components of the epoxy resin composition of the present invention.
- the epoxy resin (A) according to the present invention is not particularly limited, and is selected from organic compounds having at least two epoxy groups in a molecular structure, and may be selected from bisphenol A type epoxy resins and bisphenol F type rings.
- the epoxy resin of the present invention is preferably an epoxy resin having the following groups in its molecular structure:
- novolac type epoxy resins cresol novolac type epoxy resins, naphthol type epoxy resins, naphthol novolac type epoxy resins, fluorene type epoxy resins, dicyclopentadiene type epoxy resins, dicyclopentadiene Ethyl phenol epoxy resin, phenolphthalein epoxy resin, biphenyl epoxy resin, aralkyl epoxy resin, aralkyl phenolic epoxy resin, epoxy resin containing arylene ether structure in the molecule Any one or a mixture of at least two.
- the epoxy resin (A) is a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol type epoxy resin, a naphthol novolac type epoxy resin, a biphenyl type epoxy resin, an aralkyl group Base type epoxy resin, aralkyl novolac type epoxy resin, fluorene type epoxy resin, dicyclopentadiene type epoxy resin, biscyclopentadiene novolac type epoxy resin, ring containing arylene ether structure in the molecule Any one or a mixture of at least two of oxygen resins.
- the epoxy resin may be used singly or in combination of at least two epoxy resins as needed.
- the biphenyl aralkyl type epoxy compound is not particularly limited, and may, for example, be a compound represented by the following formula (IV).
- a biphenyl aralkyl type epoxy resin By using such a biphenyl aralkyl type epoxy resin, the flame retardancy and curability of the resin composition can be improved.
- n represents an integer of 1 or more.
- the upper limit of n is usually 50, preferably 1 to 20.
- the content of the epoxy resin (A) is not particularly limited, and the organic solid content of the resin component in the epoxy resin composition is from the viewpoints of flame retardancy, glass transition temperature, water absorption, and elastic modulus.
- the total amount of the particles may be 10 to 70 parts by mass, preferably 20 to 60 parts by mass, more preferably 30 to 60 parts by mass.
- the maleimide compound (B) used in the present invention has the structure of the formula (I):
- R is a group, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms
- R 1 is an arylene group having 6 to 18 carbon atoms
- R 2 and R 3 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms
- n is an integer of 1 to 20.
- n is an integer of from 1 to 15, preferably n is an integer of from 1 to 10;
- R is a group or a hydrogen atom
- R 1 is a phenylene group, a naphthylene group or a biphenylylene group, and further preferably R 1 is a biphenylylene group;
- R 2 and R 3 are a hydrogen atom.
- the maleimide compound having a structure of the formula (I) can be obtained by reacting maleic anhydride with an amine compound having at least two primary amino groups in one molecule. This reaction is preferably carried out in an organic solvent.
- an organic solvent As a specific example, MIR-3000 manufactured by Nippon Kayaku Co., Ltd. is available. Since the compound has a biphenyl structure, the cured product is excellent in flame retardancy, and since the compound has a novolak-like structure and a large number of crosslinking points, the glass transition temperature of the cured product can be effectively increased.
- the content of the maleimide compound is not particularly limited, and the total amount of the organic solid matter of the resin component in the epoxy resin composition is 100 parts by weight from the viewpoint of glass transition temperature and water absorption.
- the amount of the maleimide compound may be in the range of 5 to 60 parts by mass, preferably 10 to 50 parts by mass.
- active ester compound (C) which can be used in the present invention, the following active ester compounds can be selected
- an active ester obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acidic halogenated product, and a monohydroxy compound
- the amount of the difunctional carboxylic acid aromatic compound or acid halide in the active ester (1) is 1 mol
- the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol
- the amount of the monohydroxy compound is 0.25 ⁇ . 0.95mol
- the difunctional carboxylic acid aromatic compound has one of the following structural formulas:
- X is an alkylene group having 1 to 5 carbon atoms
- the phenolic compound linked by the aliphatic cyclic hydrocarbon structure has one of the following structural formulas:
- p is an integer from 1 to 5;
- the active ester (1) has the following structural formula:
- X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25;
- the styrene-containing active ester (2) has the following structure:
- the imide-modified active ester (3) has the structure represented by the formula (i):
- R is Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group;
- X is an arylene group, an arylene group substituted by a bromine compound, and is substituted by a phosphorus compound.
- Y is phenylene, naphthylene, phenylene substituted by C1-C4 alkyl or naphthylene substituted by C1-C4 alkyl;
- n represents average degree of polymerization , is 0.05-10;
- the imide-modified active ester has the structure represented by formula (ii):
- Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group; and X is an arylene group and an arylene group substituted by a bromine compound.
- Y is a phenylene group, a naphthylene group, a phenylene group substituted by a C1-C4 alkyl group or a naphthylene group substituted by a C1-C4 alkyl group;
- n represents the average degree of polymerization, which is 0.05-10;
- the imide-modified active ester has the structure represented by formula (iii):
- R is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1-C8 alkyl group; n 1 represents an average degree of polymerization, and is 0.05 to 5.0;
- the double-end polyfunctional active ester (4) containing a PPO backbone has a structure represented by the following formula:
- R 1 is R 2 is a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl, allyl or isoallyl group;
- R 3 is H, allyl or isoallyl;
- R 4 , R 5 , R 6 And R 7 is independently selected from H, a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl group, allyl, isoallyl or -OR 8 ;
- R 8 is a substituted or unsubstituted C1- a linear alkyl or branched alkyl group of C3 or a substituted or unsubstituted phenyl group;
- n1, n2 are positive integers greater than 0, and satisfy 4 ⁇ n1+n2 ⁇ 25;
- n3, n4 are equal or unequal, independently It is 1, 2 or 3, preferably independently 2 or 3, more preferably n3, n4 are equal and 2 or 3.
- the active ester compound (C) is contained in a molecular structure Group, Group, Group, Group or a compound of a group.
- the active ester compound comprises an active ester of the structure:
- X is a phenyl or naphthyl group, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25.
- the rigid structure such as phenyl, naphthyl or cyclopentadiene imparts high heat resistance to the active ester, and at the same time, due to the regularity of the structure and the reaction with the epoxy resin The secondary hydroxyl group is produced, giving it good electrical properties and low water absorption.
- the content of the active ester compound (C) is not particularly limited, and the organic solid content of the resin component in the epoxy resin composition is from the viewpoints of flame retardancy, glass transition temperature, water absorption, and dielectric properties.
- the total amount of the particles is preferably from 10 to 70 parts by mass, more preferably from 10 to 50 parts by mass, per 100 parts by weight.
- the epoxy resin composition of the present invention may further contain a cyanate compound (D).
- a cyanate ester compound (D) As a specific example of the cyanate ester compound (D), a cyanate ester compound known in the art, for example, a cyanate ester monomer or a cyanate ester prepolymer having at least two cyanate groups in a molecular structure may be mentioned.
- a novolac type cyanate resin In order to improve heat resistance and flame retardancy of the cyanate resin composition, a novolac type cyanate resin, a naphthol type cyanate resin, a naphthol novolac type cyanate resin, and a phenolphthalein type cyanate resin are further preferable.
- aralkyl type cyanate resin aralkyl novolac type cyanate resin, novolac type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer Any one or a mixture of at least two of a phenolphthalein type cyanate prepolymer, an aralkyl type cyanate prepolymer or an aralkyl novolac type cyanate prepolymer.
- a novolac type cyanate resin a naphthol novolac type cyanate resin, an aralkyl novolac type cyanate resin, and a novolac type cyanate ester are particularly preferable. Any one or a mixture of at least two of a polymer, a naphthol novolac type cyanate prepolymer or an aralkyl novolac type cyanate prepolymer.
- a bisphenol type cyanate resin an aralkyl type cyanate resin, a dicyclopentadiene type cyanate resin, a bisphenol type cyanate prepolymer, and a aryl group are particularly preferable. Any one or a mixture of at least two of an alkyl type cyanate prepolymer or a dicyclopentadiene type cyanate prepolymer. These cyanate resins may be used singly or in combination of plural kinds as needed.
- the content of the cyanate ester compound (D) is not particularly limited, and the organic component of the resin component in the epoxy resin composition is from the viewpoints of flame retardancy, glass transition temperature, and adhesion of the resin composition.
- the total amount of the solid matter is preferably from 10 to 70 parts by mass, more preferably from 20 to 60 parts by mass, per 100 parts by weight.
- the ratio of the cyanate compound (D) to the active ester compound (C) can be appropriately adjusted so that the comprehensive index of the epoxy resin composition includes (Tg, CTE, and water absorption) ()) is in the preferred range.
- the ratio of the active ester compound (C) to the cyanate compound (D) is from 1:5 to 5:1, preferably from 1:5 to 3:1.
- the epoxy resin composition of the present invention may further contain an inorganic filler (E).
- the inorganic filler (E) mainly serves to improve dielectric properties, lower the coefficient of thermal expansion, improve thermal conductivity, and reduce cost.
- the inorganic filler (E) is not particularly limited and may be selected from the group consisting of silica, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, barium titanate, barium titanate, barium sulfate, boron nitride, and nitrogen.
- fused silica has a characteristic of a low coefficient of thermal expansion, and boehmite is preferred because it is excellent in flame retardancy and heat resistance. More preferably, spherical fused silica, which has characteristics such as a low coefficient of thermal expansion and good dielectric properties, has good dispersibility and fluidity, and is therefore preferred.
- the average particle diameter (d50) of the inorganic filler (E) is not particularly limited, but from the viewpoint of dispersibility, the average particle diameter (d50) is preferably from 0.1 to 10 ⁇ m, for example, 0.2 ⁇ m, 0.8 ⁇ m, 1.5 ⁇ m, 2.1 ⁇ m. 2.6 microns, 3.5 microns, 4.5 microns, 5.2 microns, 5.5 microns, 6 microns, 6.5 microns, 7 microns, 7.5 microns, 8 microns, 8.5 microns, 9 microns, 9.5 microns, more preferably 0.2-5 microns.
- the inorganic fillers of different types, different particle size distributions or different average particle diameters may be used singly or in combination as needed.
- the inorganic filler (E) may be used in combination with a surface treating agent or a wetting agent or a dispersing agent.
- the surface treatment agent is not particularly limited and is selected from surface treatment agents commonly used for inorganic surface treatment. Specific examples thereof include a tetraethyl orthosilicate compound, an organic acid compound, an aluminate compound, a titanate compound, a silicone oligomer, a macromolecular treatment agent, and a silane coupling agent.
- the silane coupling agent is not particularly limited, and is selected from a silane coupling agent commonly used for surface treatment of inorganic materials, and is specifically an aminosilane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, and a phenyl group.
- the wetting agent and the dispersing agent are not particularly limited, and are selected from the group consisting of a wetting agent and a dispersing agent which are commonly used for coating materials.
- the present invention may be used alone or in appropriate combination with different types of surface treating agents or wetting agents and dispersing agents as needed.
- the amount of the inorganic filler (E) to be added is not particularly limited, and the total amount of the organic solids of the resin component in the epoxy resin composition is 100 parts by weight (that is, the components (A) to (C).
- the sum of the added amounts or the sum of the amounts of the components (A) to (D) added is 100 parts by weight, and the inorganic filler (E) may be added in an amount of 0 to 400 parts by weight, preferably 20 to 300 parts by weight. It is further preferably from 50 to 250 parts by weight.
- the cyanate resin composition of the present invention may further comprise an organic filler.
- the organic filler is not particularly limited and is selected from any one or a mixture of at least two of silicone, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber or core-shell rubber, and further preferably silicone powder or/and core shell. rubber.
- the organic filler may be a powder or a granule. Among them, the silicone powder has good flame retardant properties, and the core-shell rubber has a good toughening effect, so it is preferred.
- the epoxy resin composition of the present invention may further contain a curing accelerator (G) which accelerates the curing speed of the resin.
- the curing accelerator is selected from the group consisting of a curing accelerator capable of promoting curing of a cyanate resin, an active ester compound, and an epoxy resin, and is specifically an organic salt of a metal such as copper, zinc, cobalt, nickel or manganese, an imidazole and a derivative thereof. , tertiary amines, etc.
- the curing accelerator may be added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total of the organic solids of the resin component in the epoxy resin composition.
- the epoxy resin composition of the present invention can be formulated into a gel form by using a solvent (H).
- the solvent (H) which can be used in the present invention is not particularly limited as long as it can dissolve various resin components and does not separate upon mixing, and examples thereof include methanol, ethanol, ethylene glycol, acetone, methyl ethyl ketone, and methyl ethyl group.
- One or more solvents can be used.
- the solvent (H) is usually used in an amount of 5 to 50 parts by weight, for example, 10 to 50, 20 to 50, 30 to 40 parts by weight, etc., relative to 100 parts by weight of the epoxy resin composition (excluding the solvent), to facilitate formation.
- a glue of a applied viscosity for example, 300-600 cPa ⁇ s.
- the solids content in the gum may range from 60% to 70% by weight.
- the epoxy resin composition of the present invention may further contain other additives (I) such as a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant or a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds. However, the epoxy resin composition of the present invention preferably does not contain a halogen or a halide. The amount of the other additive (I) can be arbitrarily adjusted within the range not detracting from the effects of the present invention.
- the epoxy resin composition of the present invention may be used in combination with a maleimide compound other than the maleimide compound (B) having a structure of the formula (I) as long as it does not impair the inherent nature of the cyanate resin composition. Performance can be. They can be used singly or in combination of plural kinds as needed.
- the epoxy resin composition of the present invention can also be used in combination with various high polymers as long as it does not impair the inherent properties of the epoxy resin composition.
- it may be a liquid crystal polymer, a thermosetting resin, a thermoplastic resin, a different flame retardant compound or an additive or the like. They can be used singly or in combination of plural kinds as needed.
- Another aspect of the invention relates to a prepreg comprising a substrate and the above epoxy resin composition of the invention adhered to the substrate by impregnation drying.
- the substrate which can be used in the present invention is not particularly limited, and is usually a woven fabric, a nonwoven fabric, a roving, a short fiber, a fiber paper, etc.
- the material may be an inorganic fiber (for example, E glass, D glass, L glass, M glass, Glass fibers such as S glass, T glass, NE glass, and quartz, or organic fibers (for example, polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.) are preferably glass fiber cloth.
- the thickness of the substrate is not particularly limited and may be, for example, about 0.03 to 0.5 mm. From the viewpoint of heat resistance, moisture resistance, and workability, a substrate surface-treated with a silane coupling agent or the like, or a substrate subjected to mechanical fiber opening treatment is preferable.
- the amount of adhesion of the resin composition to the substrate is immersed or applied to the substrate at a resin content of the dried prepreg of 20 to 90% by mass, and usually 1 to 30 at a temperature of 100 to 200 ° C. After heating and drying for a minute, it is semi-cured (B-staged) to obtain a prepreg (also referred to as a prepreg) of the present invention.
- the invention also relates to a laminate comprising at least one prepreg as described above.
- a laminate metal foil-clad laminate
- a laminate can be produced by laminating 1 to 20 prepregs and laminating a metal foil such as copper or aluminum on one or both sides thereof.
- the metal foil is not particularly limited as long as it is used for electrical insulating materials, and examples thereof include metal foils such as copper and aluminum. Among them, a copper foil is preferred. In particular, an electrolytic copper foil, a rolled copper foil, or the like can be suitably used. A known surface treatment such as nickel treatment or cobalt treatment can be applied to the metal foil.
- the thickness of the metal foil can be appropriately adjusted within a range suitable as a material of the printed circuit board, and is preferably 2 to 35 ⁇ m.
- the molding conditions can be applied to laminates and multilayer boards for electrical insulating materials, for example, multi-stage press, multi-stage vacuum press, continuous forming, autoclave molding machine, etc., at a temperature of 100 to 250 ° C and a pressure of 2 to 100 kg/cm 2 .
- the molding is carried out under the conditions of a heating time of 0.1 to 5 hours.
- prepreg and the inner layer wiring board of the present invention may be combined and laminated to form a multilayer board.
- the invention further relates to a printed wiring board comprising at least one prepreg as described above.
- the printed circuit board can be produced by using the above prepreg (or metal foil-clad laminate) as a laminate material. Specifically, a prepreg (or a metal foil-clad laminate) is used as a laminate material, and the prepreg is surface-treated by a conventional method, and a wiring pattern (conductor layer) is formed by plating on the surface of the insulating layer. Thus, the printed circuit board of the present invention can be obtained.
- the epoxy resin composition of the present invention and a prepreg, a laminate (including a metal foil-clad laminate) and a printed wiring board produced therefrom have a low dielectric constant (Dk) / dielectric loss tangent (Df) ), high glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and heat and humidity resistance, especially with significantly reduced water absorption;
- parts by mass of the organic resin are based on parts by mass of the organic solid unless otherwise indicated.
- the epoxy resin, maleimide, active ester, curing accelerator and filler are placed in a container according to the formulation shown in Table 1 and a suitable solvent, stirred and dispersed uniformly to form a glue, and the solution solid is adjusted with a solvent.
- the content is 60%-70% to make a glue, that is, the halogen-free thermosetting resin composition glue is obtained, and the glue is impregnated with 2116 electronic grade fiberglass cloth, baked into a prepreg by an oven, and 4 sheets of 2116 prepreg are taken, and double-sided
- the 18um thick electrolytic copper foil was coated, vacuum laminated on a hot press, cured at 220 ° C / 120 min, and the press pressure was 45 kg / cm 2 to prepare a copper clad plate having a thickness of 0.50 mm.
- the performance test results are shown in Table 2.
- the epoxy resin, maleimide, active ester, cyanate ester, curing accelerator and filler are placed in a container according to the formulation shown in Table 3 and a suitable solvent, and the mixture is stirred and dispersed uniformly to form a glue.
- Solvent adjustment solution solid content to 60%-70% to make a glue, that is, to obtain a halogen-free thermosetting resin composition glue, impregnating the glue with 2116 electronic grade fiberglass cloth, baking into a prepreg through an oven, taking 4 sheets of 2116 prepreg
- the double-sided layer is further coated with 18um thick electrolytic copper foil, vacuum laminated in a hot press, cured at 220 ° C / 120 min, and the press pressure is 45 kg / cm 2 to form a copper clad plate having a thickness of 0.50 mm.
- Table 4 The performance test results are shown in Table 4.
- Dielectric constant (Dk) and dielectric loss tangent (Df) The dielectric constant (Dk) at 1 GHz and the dielectric loss angle were measured according to IPC-TM-650 2.5.5.5 using a strip line resonance method. Tangent value (Df).
- Glass transition temperature (Tg) It was measured by a DMA (Dynamic thermomechanical analysis) test in accordance with the DMA test method specified in IPC-TM-650 2.4.24.
- Sample treatment The sample was dried in an oven at 105-110 ° C for 1 h, taken out, placed in a desiccator and cooled to room temperature, and then weighed immediately after being taken out from the dryer.
- Example 1 is an inventive example of the present patent, and Example 2 and Example 3 were replaced with an epoxy resin and an active ester, respectively, and DK, water absorption.
- the key performance of Z-CTE and the Z-CTE were basically unchanged;
- Example 4 is the invention example after de-filling in Example 1, except that the Z-CTE is increased more, and other key properties are basically unchanged.
- the phenolic resin was used as the curing agent for the epoxy resin, and the DK, water absorption and Z-CTE were significantly increased.
- the Tg was significantly lowered, Z- The CTE was remarkably increased, the water absorbability was also increased, and the heat and humidity resistance could not be passed.
- the maleimide of the other structure was replaced, and the phenomenon of incomplete dissolution and resin precipitation did not occur, and the laminate could not be produced. It can be seen that the epoxy/maleimide/active ester composition of the present invention has low Dk/Df, high glass transition temperature (Tg), low water absorption, low CTE, excellent heat resistance and heat and humidity resistance. Sexual characteristics.
- Example 5 is an inventive example in which a cyanate resin is added in the present patent, and after an epoxy resin and an active ester are replaced by Example 6 and Example 7, respectively.
- the key properties of DK, water absorption and Z-CTE were basically unchanged;
- Example 8 was the inventive example after de-filling in Example 5, except that the Z-CTE was increased more, and other key properties were basically unchanged.
- the phenolic resin was used instead of the active ester as the curing agent for the epoxy resin, and the DK, water absorption and Z-CTE were significantly increased.
- the epoxy/maleimide/active ester/cyanate composition of the present invention has a lower Dk/Df, a higher glass transition temperature (Tg), lower water absorption, lower CTE, and superiority. It is characterized by heat resistance and heat and humidity resistance.
- the copper-clad laminate of the present invention has a high glass transition temperature (Tg) and a lower CTE than the general copper foil substrate, and has outstanding performance in terms of Dk/Df and water absorption. It has excellent heat resistance and heat and humidity resistance, and can meet the requirements of substrate materials for high-density printed wiring boards.
Abstract
The present invention relates to an epoxy resin composition, and a prepreg, a laminate and a printed circuit board using the same. The epoxy resin composition of the present invention comprises an epoxy resin (A), a maleimide compound (B) having the structure as represented by formula (I), and an active ester compound (C). A prepreg, a laminate (comprising a metal foil-clad laminate) and a printed wiring board produced by using the epoxy resin composition have a low dielectric constant (Dk)/dielectric loss tangent value (Df), high glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and heat and humidity resistance, and like features.
Description
本发明涉及电子产品技术领域，特别涉及一种环氧树脂组合物以及使用它的预浸料、层压板和印制电路板。The present invention relates to the field of electronic product technology, and in particular to an epoxy resin composition and a prepreg, a laminate and a printed circuit board using the same.
随着电子工业的飞速发展，电子产品向轻、薄、短小、高密度化、安全化、高功能化发展，要求电子元件有更高的布线密度、高集成度可靠性、这就要求用于制作印刷线路板的覆金属箔层压材料具有更优异的耐湿热性，低的热膨胀系数、介电常数和低的吸水率。With the rapid development of the electronics industry, electronic products are becoming lighter, thinner, shorter, more dense, safer, and more functional. It requires higher wiring density and high integration reliability of electronic components, which is required for The metal foil-clad laminate for producing a printed wiring board has more excellent heat and humidity resistance, a low coefficient of thermal expansion, a dielectric constant, and a low water absorption rate.
环氧树脂具有优异的力学性能和工艺加工性，其在制作高端印刷线路板用覆金属箔层压材料中是一种常用的基体树脂，制作的预浸料和层压材料，广泛的作为一种改性原材料应用在高性能印刷线路板材料中。Epoxy resin has excellent mechanical properties and processability. It is a commonly used matrix resin in the production of metal foil laminates for high-end printed wiring boards. Prepregs and laminates are widely used as a A variety of modified raw materials are used in high performance printed circuit board materials.
环氧树脂组合物具有优异的柔韧性、耐化学性、粘合性等，但是，其固化物存在吸水率高，耐湿热性不足的问题，不能满足高端基板的性能需求。The epoxy resin composition has excellent flexibility, chemical resistance, adhesion, and the like. However, the cured product has a problem of high water absorption and insufficient heat and humidity resistance, and cannot satisfy the performance requirements of the high-end substrate.
日本化药的中国专利申请CN106103534公开了二苯胺的含量低的芳香族胺树脂、由其衍生的马来酰亚胺树脂、使用所述芳香族胺树脂和所述马来酰亚胺树脂的固化性树脂组合物和通过将所述固化性树脂组合物固化而得到的耐热性、低吸湿性、低介电特性、阻燃性、韧性优异的固化物。但在实际中发现，这些树脂存在吸水率偏大的缺点。Chinese Patent Application No. CN106103534 to Japanese Pharmaceuticals discloses an aromatic amine resin having a low content of diphenylamine, a maleimide resin derived therefrom, and curing using the aromatic amine resin and the maleimide resin The resin composition and the cured product which are excellent in heat resistance, low moisture absorption, low dielectric property, flame retardance, and toughness obtained by curing the curable resin composition. However, in practice, it has been found that these resins have the disadvantage of having a large water absorption rate.
发明内容Summary of the invention
针对以上现有技术的不足，本发明的目的在于提供一种环氧树脂组合物及使用其制作的预浸料、层压板(包括覆金属箔层压板)以及印刷线路板，其具有低介电常数(Dk)/介质损耗角正切值(Df)，高玻璃化转变温度(Tg)、低吸水率、低热膨胀系数(CTE)、优异的耐热性和耐湿热性等特点。In view of the above deficiencies of the prior art, it is an object of the present invention to provide an epoxy resin composition and a prepreg, a laminate (including a metal foil-clad laminate) and a printed wiring board which are produced using the same, which have a low dielectric Constant (Dk) / dielectric loss tangent (Df), high glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and heat and humidity resistance.
本申请的发明人为实现上述目的进行了反复深入的研究，结果发现：通过使用包含环氧树脂、特定结构的马来酰亚胺与活性酯化合物的组合物，可实现上述目的，尤其是显著降低吸水率；而且，通过添加活性酯化合物，解决了马 来酰亚胺在用于环氧树脂的溶剂中溶解差，难以配制成胶水的问题，从而避免了复杂的胶水混制工艺，极大地简化了生产工艺，提高生产效率。The inventors of the present application conducted intensive studies to achieve the above object, and as a result, found that the above object can be attained by using a composition comprising an epoxy resin and a specific structure of maleimide and an active ester compound, particularly a significant reduction. Water absorption rate; Moreover, by adding an active ester compound, the problem that the maleimide is poorly dissolved in a solvent for an epoxy resin and it is difficult to prepare a glue is solved, thereby avoiding a complicated glue mixing process and greatly simplifying The production process improves production efficiency.
本发明的一个方面涉及一种环氧树脂组合物，其特征在于，所述环氧树脂组合物包括环氧树脂(A)、具有式(Ⅰ)结构的马来酰亚胺化合物(B)、活性酯化合物(C)，One aspect of the invention relates to an epoxy resin composition characterized in that the epoxy resin composition comprises an epoxy resin (A), a maleimide compound (B) having a structure of the formula (I), Active ester compound (C),
R为
基团、氢原子、碳原子数1～6的烷基、碳原子数6～18的芳基或碳原子数7～24的芳烷基，R
1为碳原子数6～18的亚芳基，R
2、R
3为氢原子、碳原子数1～6的烷基、碳原子数6～18的芳基或碳原子数7～24的芳烷基，n为1～20的整数。
R is a group, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and R 1 is an arylene group having 6 to 18 carbon atoms. R 2 and R 3 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and n is an integer of 1 to 20.
在某些实施方案中，所述具有式(Ⅰ)结构的马来酰亚胺化合物(B)中的n为1～15的整数，优选n为1～10的整数；In certain embodiments, n in the maleimide compound (B) having the structure of formula (I) is an integer from 1 to 15, preferably n is an integer from 1 to 10;
优选地，R为
基团或氢原子；
Preferably, R is a group or a hydrogen atom;
优选地，R
1为亚苯基、亚萘基或亚联苯基，进一步优选R
1为亚联苯基；
Preferably, R 1 is a phenylene group, a naphthylene group or a biphenylylene group, and further preferably R 1 is a biphenylylene group;
优选地，R
2、R
3为氢原子。
Preferably, R 2 and R 3 are a hydrogen atom.
在某些实施方案中，所述环氧树脂(A)为分子结构中含有
基团、
基团、
基团、
基团、
基团或
基团的化合物；和/或，所述活性酯化合物(C)为分子结构中含有
基团、
基团、
基团、
基团、
基团或
基团的化合物。
In certain embodiments, the epoxy resin (A) is contained in a molecular structure Group, Group, Group, Group, Group or a compound of a group; and/or the active ester compound (C) is contained in a molecular structure Group, Group, Group, Group, Group or a compound of a group.
在某些实施方案中，所述环氧树脂(A)为线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、萘酚型环氧树脂、萘酚酚醛型环氧树脂、蒽型环氧树脂、双环戊二烯型环氧树脂、双环戊二烯酚醛型环氧树脂、酚酞型环氧树脂、联苯型环氧树脂、芳烷基型环氧树脂、芳烷基酚醛型环氧树脂、分子中含有亚芳基醚结构的环氧树脂中的任意一种或者至少两种的混合物；更优选地，环氧树脂(A)为线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、萘酚型环氧树脂、萘酚酚醛型环氧树脂、联苯型环氧树脂、芳烷基型环氧树脂、芳烷基酚醛型环氧树脂、蒽型环氧树脂、双环戊二烯型环氧树脂、双环戊二烯酚醛型环氧树脂、分子中含 有亚芳基醚结构的环氧树脂中的任意一种或者至少两种的混合物；In certain embodiments, the epoxy resin (A) is a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol type epoxy resin, a naphthol novolac type epoxy resin, a fluorene type epoxy Resin, dicyclopentadiene type epoxy resin, dicyclopentadiene novolac type epoxy resin, phenolphthalein type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin Any one or a mixture of at least two kinds of epoxy resins having an arylene ether structure in the molecule; more preferably, the epoxy resin (A) is a novolac type epoxy resin, and a cresol novolac type epoxy resin , naphthol type epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, fluorene type epoxy resin, dicyclopentadiene Any one or a mixture of at least two types of epoxy resins, biscyclopentadiene novolac type epoxy resins, and epoxy resins having an arylene ether structure in the molecule;
和/或，and / or,
所述活性酯化合物(C)为选自以下的至少一种：The active ester compound (C) is at least one selected from the group consisting of:
(1)由一种通过脂肪环烃结构连接的酚类化合物、二官能度羧酸芳香族化合物或酸性卤代物及一种单羟基化合物反应而得的活性酯，(1) an active ester obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acidic halogenated product, and a monohydroxy compound,
优选地，所述活性酯(1)中二官能羧酸芳香族化合物或酸性卤化物用量为1mol，通过脂肪环烃结构连接的酚类化合物用量为0.05～0.75mol，单羟基化合物用量为0.25～0.95mol；Preferably, the amount of the difunctional carboxylic acid aromatic compound or acid halide in the active ester (1) is 1 mol, the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount of the monohydroxy compound is 0.25 ～. 0.95mol;
优选地，所述活性酯(1)具有以下结构式：Preferably, the active ester (1) has the following structural formula:
X为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25；X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25;
(2)含苯乙烯结构的活性酯，(2) an active ester containing a styrene structure,
优选地，所述含苯乙烯结构的活性酯(2)具有如下结构：Preferably, the styrene-containing active ester (2) has the following structure:
其中A为取代或未取代的苯基、取代或未取代的萘基、C1-C8烷基，m和n为自然数，m/n＝0.8-19；Wherein A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a C1-C8 alkyl group, m and n are natural numbers, m/n = 0.8-19;
(3)酰亚胺改性活性酯，(3) an imide-modified active ester,
优选地，所述酰亚胺改性活性酯(3)具有式(i)所示结构：Preferably, the imide-modified active ester (3) has the structure represented by the formula (i):
式(i)中，R为
Z为苯基、萘基、被C1-C4烷基取代的苯基或被C1-C4烷基取代的萘基；X为亚芳香基、被溴化合物取代的亚芳香基、被磷化合物取代的亚芳香基或C1-C10亚烷基；Y为亚苯基、亚萘基、被C1-C4烷基取代的亚苯基或被C1-C4烷基取代的亚萘基；n表示平均聚合度，为0.05-10；
In formula (i), R is Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group; X is an arylene group, an arylene group substituted by a bromine compound, and is substituted by a phosphorus compound. Arylene or C1-C10 alkylene; Y is phenylene, naphthylene, phenylene substituted by C1-C4 alkyl or naphthylene substituted by C1-C4 alkyl; n represents average degree of polymerization , is 0.05-10;
优选地，所述酰亚胺改性活性酯具有式(ii)所示结构：Preferably, the imide-modified active ester has the structure represented by formula (ii):
式(ii)中，Z为苯基、萘基、被C1-C4烷基取代的苯基或被C1-C4烷基取代的萘基；X为亚芳香基、被溴化合物取代的亚芳香基、被磷化合物取代的亚芳香基或C1-C10亚烷基；Y为亚苯基、亚萘基、被C1-C4烷基取代的亚苯基或被C1-C4烷基取代的亚萘基；n表示平均聚合度，为0.05-10；In the formula (ii), Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group; and X is an arylene group and an arylene group substituted by a bromine compound. An arylene group or a C1-C10 alkylene group substituted by a phosphorus compound; Y is a phenylene group, a naphthylene group, a phenylene group substituted by a C1-C4 alkyl group or a naphthylene group substituted by a C1-C4 alkyl group; ;n represents the average degree of polymerization, which is 0.05-10;
优选地，所述酰亚胺改性活性酯具有式(iii)所示结构：Preferably, the imide-modified active ester has the structure represented by formula (iii):
式(iii)中，R相同或不同，独立地为氢原子、卤素原子或取代或未取代的C1-C8烷基；n
1表示平均聚合度，为0.05-5.0；和
In the formula (iii), R is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1-C8 alkyl group; n 1 represents an average degree of polymerization, and is 0.05 to 5.0;
(4)含有PPO主链的双端基多官能活性酯，(4) a double-ended polyfunctional active ester containing a PPO backbone,
优选地，所述含有PPO主链的双端基多官能活性酯(4)具有下式所示结 构：Preferably, the double-end polyfunctional active ester (4) containing a PPO backbone has a structure represented by the following formula:
式中，R
1为
R
2为
取代或未取代的C1-C3的直链烷基或支链烷基、烯丙基或异烯丙基；R
3为H、烯丙基或异烯丙基；R
4、R
5、R
6、R
7独立选自H、取代或未取代的C1-C3的直链烷基或支链烷基、烯丙基、异烯丙基或-O-R
8；R
8为取代或未取代的C1-C3的直链烷基或支链烷基或取代或未取代的苯基；n1、n2为大于0的正整数，且满足4≤n1+n2≤25；n3、n4相等或不等，独立地为1、2或3，优选独立地为2或3，更优选n3、n4相等且为2或3。
Where R 1 is R 2 is a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl, allyl or isoallyl group; R 3 is H, allyl or isoallyl; R 4 , R 5 , R 6 And R 7 is independently selected from H, a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl group, allyl, isoallyl or -OR 8 ; R 8 is a substituted or unsubstituted C1- a linear alkyl or branched alkyl group of C3 or a substituted or unsubstituted phenyl group; n1, n2 are positive integers greater than 0, and satisfy 4≤n1+n2≤25; n3, n4 are equal or unequal, independently It is 1, 2 or 3, preferably independently 2 or 3, more preferably n3, n4 are equal and 2 or 3.
在某些实施方案中，所述环氧树脂组合物中各组分的含量如下：以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，环氧树脂(A)为20～60重量份，马来酰亚胺化合物(B)为10～50重量份，活性酯化合物(C)为10～50重量份。In certain embodiments, the content of each component in the epoxy resin composition is as follows: the total amount of the organic solids of the resin component in the epoxy resin composition is 100 parts by weight, the epoxy resin (A) is 20 to 60 parts by weight, the maleimide compound (B) is 10 to 50 parts by weight, and the active ester compound (C) is 10 to 50 parts by weight.
在某些实施方案中，所述环氧树脂组合物还包括氰酸酯化合物(D)；优选地，在含有氰酸酯化合物(D)的情况下，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，所述环氧树脂组合物中氰酸酯化合物(D)的量为10～50重量份；更优选地，活性酯化合物(C)与氰酸酯化合物(D)的比例为1:5～5:1。In certain embodiments, the epoxy resin composition further comprises a cyanate compound (D); preferably, in the case of the cyanate-containing compound (D), the resin in the epoxy resin composition The total amount of the organic solids of the component is 100 parts by weight, and the amount of the cyanate compound (D) in the epoxy resin composition is 10 to 50 parts by weight; more preferably, the active ester compound (C) and The ratio of the cyanate compound (D) is from 1:5 to 5:1.
在某些实施方案中，所述环氧树脂组合物还包括无机填料(E)，优选地，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，所述环氧树脂组合物中无机填料(E)的量为20～300重量份。In certain embodiments, the epoxy resin composition further includes an inorganic filler (E), preferably, based on 100 parts by weight of the total amount of the organic solids of the resin component in the epoxy resin composition, The amount of the inorganic filler (E) in the epoxy resin composition is 20 to 300 parts by weight.
本发明的另一个方面涉及上述环氧树脂组合物的用途，包括使用所述环氧 树脂组合物的预浸料，包括该预浸料的层压板、以及包括该预浸料的印刷线路板。Another aspect of the invention relates to the use of the above epoxy resin composition, comprising a prepreg using the epoxy resin composition, a laminate comprising the prepreg, and a printed wiring board comprising the prepreg.
本发明的环氧树脂组合物及使用其制作的预浸料、层压板(包括覆金属箔层压板)以及印刷线路板可以具有低介电常数(Dk)/介质损耗角正切值(Df)，高玻璃化转变温度(Tg)、低吸水率、低热膨胀系数(CTE)、优异的耐热性和耐湿热性等特点，尤其是具有显著降低的吸水率。The epoxy resin composition of the present invention and prepregs, laminates (including metal foil-clad laminates) and printed wiring boards produced therefrom may have a low dielectric constant (Dk) / dielectric loss tangent (Df), High glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and heat and humidity resistance, especially with significantly reduced water absorption.
在本发明的环氧树脂组合物中，通过添加活性酯化合物，解决了马来酰亚胺在用于环氧树脂的溶剂中溶解差的问题，可以将环氧树脂组合物配制成胶水，从而极大地简化了生产工艺，提高生产效率。另外，通过活性酯化合物(C)与氰酸酯化合物(D)的调配，在提高与铜箔的粘附性的同时，降低其吸水率。In the epoxy resin composition of the present invention, the problem of poor solubility of maleimide in a solvent for an epoxy resin is solved by adding an active ester compound, and the epoxy resin composition can be formulated into a glue, thereby It greatly simplifies the production process and improves production efficiency. Further, by blending the active ester compound (C) with the cyanate compound (D), the water absorption rate is lowered while improving the adhesion to the copper foil.
下面通过具体实施方式来进一步说明本发明的技术方案。The technical solution of the present invention will be further described below by way of specific embodiments.
本发明的一个方面涉及环氧树脂组合物，所述环氧树脂组合物包括环氧树脂(A)、具有式(Ⅰ)结构的马来酰亚胺化合物(B)、活性酯化合物(C)，还可以包括以下任选组分：氰酸酯化合物(D)、无机填料(E)、固化促进剂(G)、溶剂(H)和其他添加剂(I)。以下将详细描述本发明的环氧树脂组合物的各个组分。One aspect of the invention relates to an epoxy resin composition comprising an epoxy resin (A), a maleimide compound (B) having a structure of the formula (I), and an active ester compound (C) The following optional components may also be included: cyanate ester compound (D), inorganic filler (E), curing accelerator (G), solvent (H), and other additives (I). The respective components of the epoxy resin composition of the present invention will be described in detail below.
-环氧树脂(A)--Epoxy resin (A)-
环氧树脂(A)是本发明的环氧树脂组合物的主要组分之一。对本发明所述的环氧树脂(A)并没有特别的限制，其选自分子结构中含有至少两个环氧基的有机化合物，可以选自双酚A型环氧树脂、双酚F型环氧树脂、线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、双酚A酚醛型环氧树脂、四甲基双酚F型环氧树脂、双酚M型环氧树脂、双酚S型环氧树脂、双酚E型环氧树脂、双酚P型环氧树脂、三官能酚型环氧树脂、四官能酚型环氧树脂、萘型环氧树脂、萘酚型环氧树脂、萘酚酚醛型环氧树脂、蒽型环氧树脂、酚酞型环氧树脂、苯氧基型环氧树脂、降冰片烯型环氧树脂、金刚烷型环氧树脂、芴型环氧树脂、联苯型环氧树脂、双环戊二烯型环氧树脂、双环戊二烯酚醛型环氧树脂、芳烷基型环氧树脂、芳烷基酚醛型环氧树脂、分子中含有亚芳基醚结构的环氧树脂、脂环族环氧树脂、多元醇型环氧树脂、含硅环氧树脂、含氮环氧树脂、缩水甘 油胺环氧树脂、缩水甘油酯环氧树脂以及向这些中导入卤素、磷化合物的含卤素、磷环氧树脂等。The epoxy resin (A) is one of the main components of the epoxy resin composition of the present invention. The epoxy resin (A) according to the present invention is not particularly limited, and is selected from organic compounds having at least two epoxy groups in a molecular structure, and may be selected from bisphenol A type epoxy resins and bisphenol F type rings. Oxygen resin, novolac epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, tetramethyl bisphenol F epoxy resin, bisphenol M epoxy resin, bisphenol S type Epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthalene Phenolic novolac type epoxy resin, bismuth type epoxy resin, phenolphthalein type epoxy resin, phenoxy type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, biphenyl Type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene novolac type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, arylene ether structure in molecule Epoxy resin, cycloaliphatic epoxy resin, polyol epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy Aliphatic, glycidyl amine epoxy resins, glycidyl ester epoxy resin, and introducing a halogen into these, halogen-containing, phosphorus-phosphorus compound such as epoxy resin.
为了提高环氧树脂组合物的耐热性、阻燃性，降低树脂组合物的热膨胀系数、介电特性，本发明所述的环氧树脂优选为分子结构中含有以下基团的环氧树脂：In order to improve the heat resistance and flame retardancy of the epoxy resin composition, and to lower the thermal expansion coefficient and dielectric properties of the resin composition, the epoxy resin of the present invention is preferably an epoxy resin having the following groups in its molecular structure:
进一步优选线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、萘酚型环氧树脂、萘酚酚醛型环氧树脂、蒽型环氧树脂、双环戊二烯型环氧树脂、双环戊二烯酚醛型环氧树脂、酚酞型环氧树脂、联苯型环氧树脂、芳烷基型环氧树脂、芳烷基酚醛型环氧树脂、分子中含有亚芳基醚结构的环氧树脂中的任意一种或者至少两种的混合物。Further preferred are novolac type epoxy resins, cresol novolac type epoxy resins, naphthol type epoxy resins, naphthol novolac type epoxy resins, fluorene type epoxy resins, dicyclopentadiene type epoxy resins, dicyclopentadiene Ethyl phenol epoxy resin, phenolphthalein epoxy resin, biphenyl epoxy resin, aralkyl epoxy resin, aralkyl phenolic epoxy resin, epoxy resin containing arylene ether structure in the molecule Any one or a mixture of at least two.
更优选地，环氧树脂(A)为线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、萘酚型环氧树脂、萘酚酚醛型环氧树脂、联苯型环氧树脂、芳烷基型环氧树脂、芳烷基酚醛型环氧树脂、蒽型环氧树脂、双环戊二烯型环氧树脂、双环戊二烯酚醛型环氧树脂、分子中含有亚芳基醚结构的环氧树脂中的任意一种或者至少两种的混合物。环氧树脂可以单独使用，也可以根据需要将至少两种环氧树脂混合使用。More preferably, the epoxy resin (A) is a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol type epoxy resin, a naphthol novolac type epoxy resin, a biphenyl type epoxy resin, an aralkyl group Base type epoxy resin, aralkyl novolac type epoxy resin, fluorene type epoxy resin, dicyclopentadiene type epoxy resin, biscyclopentadiene novolac type epoxy resin, ring containing arylene ether structure in the molecule Any one or a mixture of at least two of oxygen resins. The epoxy resin may be used singly or in combination of at least two epoxy resins as needed.
作为联苯芳烷基型环氧化合物，没有特别的限制，例如可以为下述式(Ⅳ)表示的化合物。通过使用这样的联苯芳烷基型环氧树脂，可以提高树脂组合物的阻燃性以及固化性。The biphenyl aralkyl type epoxy compound is not particularly limited, and may, for example, be a compound represented by the following formula (IV). By using such a biphenyl aralkyl type epoxy resin, the flame retardancy and curability of the resin composition can be improved.
上述式(Ⅳ)中，n表示1以上的整数。n的上限值通常为50，优选为1～20。In the above formula (IV), n represents an integer of 1 or more. The upper limit of n is usually 50, preferably 1 to 20.
对环氧树脂(A)的含量没有特别的限定，从阻燃性、玻璃化转变温度、吸水率和弹性模量的观点来看，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，可以为10～70质量份，优选为20～60质量份，更优选30～60质量份。The content of the epoxy resin (A) is not particularly limited, and the organic solid content of the resin component in the epoxy resin composition is from the viewpoints of flame retardancy, glass transition temperature, water absorption, and elastic modulus. The total amount of the particles may be 10 to 70 parts by mass, preferably 20 to 60 parts by mass, more preferably 30 to 60 parts by mass.
-具有式(Ⅰ)结构的马来酰亚胺化合物(B)-- Maleimide compound (B) having the structure of formula (I) -
用于本发明的马来酰亚胺化合物(B)具有式(Ⅰ)结构：The maleimide compound (B) used in the present invention has the structure of the formula (I):
其中R为
基团、氢原子、碳原子数1～6的烷基、碳原子数6～18的芳基或碳原子数7～24的芳烷基，R
1为碳原子数6～18的亚芳基，R
2、R
3为氢原子、碳原子数1～6的烷基、碳原子数6～18的芳基或碳原子数7～24的芳烷基，n为1～20的整数。
Where R is a group, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and R 1 is an arylene group having 6 to 18 carbon atoms. R 2 and R 3 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and n is an integer of 1 to 20.
优选地，在所述具有式(Ⅰ)结构的马来酰亚胺化合物中，n为1～15的整数，优选n为1～10的整数；Preferably, in the maleimide compound having the structure of the formula (I), n is an integer of from 1 to 15, preferably n is an integer of from 1 to 10;
优选地，R为
基团或氢原子；
Preferably, R is a group or a hydrogen atom;
优选地，R
1为亚苯基、亚萘基或亚联苯基，进一步优选R
1为亚联苯基；
Preferably, R 1 is a phenylene group, a naphthylene group or a biphenylylene group, and further preferably R 1 is a biphenylylene group;
优选地，R
2、R
3为氢原子。
Preferably, R 2 and R 3 are a hydrogen atom.
具有式(Ⅰ)结构的马来酰亚胺化合物可以由马来酸酐与1分子中具有至少2个伯胺基的胺类化合物反应而得到。该反应优选在有机溶剂中进行。作为具体实例，有日本化药株式会社制造的MIR-3000。该化合物由于具有联苯结构而使固化物阻燃性优异，同时该化合物由于具有类酚醛清漆结构，交联点多，可以有效提高固化物的玻璃化转变温度。The maleimide compound having a structure of the formula (I) can be obtained by reacting maleic anhydride with an amine compound having at least two primary amino groups in one molecule. This reaction is preferably carried out in an organic solvent. As a specific example, MIR-3000 manufactured by Nippon Kayaku Co., Ltd. is available. Since the compound has a biphenyl structure, the cured product is excellent in flame retardancy, and since the compound has a novolak-like structure and a large number of crosslinking points, the glass transition temperature of the cured product can be effectively increased.
对马来酰亚胺化合物的含量没有特别的限定，从玻璃化转变温度和吸水率的观点来看，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，马来酰亚胺化合物的量可以为5～60质量份的范围、优选为10～50质量份。The content of the maleimide compound is not particularly limited, and the total amount of the organic solid matter of the resin component in the epoxy resin composition is 100 parts by weight from the viewpoint of glass transition temperature and water absorption. The amount of the maleimide compound may be in the range of 5 to 60 parts by mass, preferably 10 to 50 parts by mass.
-活性酯化合物(C)--Active ester compound (C)-
作为可用于本发明的活性酯化合物(C)，可以选择以下活性酯化合物As the active ester compound (C) which can be used in the present invention, the following active ester compounds can be selected
(1)由一种通过脂肪环烃结构连接的酚类化合物、二官能度羧酸芳香族化合物或酸性卤代物及一种单羟基化合物反应而得的活性酯，(1) an active ester obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acidic halogenated product, and a monohydroxy compound,
优选地，所述活性酯(1)中二官能羧酸芳香族化合物或酸性卤化物用量为1mol，通过脂肪环烃结构连接的酚类化合物用量为0.05～0.75mol，单羟基化合物用量为0.25～0.95mol；Preferably, the amount of the difunctional carboxylic acid aromatic compound or acid halide in the active ester (1) is 1 mol, the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount of the monohydroxy compound is 0.25 ～. 0.95mol;
优选地，二官能羧酸芳香族化合物具有以下结构式之一：Preferably, the difunctional carboxylic acid aromatic compound has one of the following structural formulas:
式中X为碳原子数为1-5的亚烃基；Wherein X is an alkylene group having 1 to 5 carbon atoms;
优选地，通过脂肪环烃结构连接的酚类化合物具有以下结构式之一：Preferably, the phenolic compound linked by the aliphatic cyclic hydrocarbon structure has one of the following structural formulas:
式中p为1-5的整数；Where p is an integer from 1 to 5;
优选地，所述活性酯(1)具有以下结构式：Preferably, the active ester (1) has the following structural formula:
X为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25；X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25;
(2)含苯乙烯结构的活性酯，(2) an active ester containing a styrene structure,
优选地，所述含苯乙烯结构的活性酯(2)具有如下结构：Preferably, the styrene-containing active ester (2) has the following structure:
其中A为取代或未取代的苯基、取代或未取代的萘基、C1-C8烷基，m和n为自然数，m/n＝0.8-19；Wherein A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a C1-C8 alkyl group, m and n are natural numbers, m/n = 0.8-19;
(3)酰亚胺改性活性酯，(3) an imide-modified active ester,
优选地，所述酰亚胺改性活性酯(3)具有式(i)所示结构：Preferably, the imide-modified active ester (3) has the structure represented by the formula (i):
式(i)中，R为
Z为苯基、萘基、被C1-C4烷基取代的苯基或被C1-C4烷基取代的萘基；X为亚芳香基、被溴化合物取代的亚芳香基、被磷化合物取代的亚芳香基或C1-C10亚烷基；Y为亚苯基、亚萘基、被C1-C4烷基取代的亚苯基或被C1-C4烷基取代的亚萘基；n表示平均聚合度，为0.05-10；
In formula (i), R is Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group; X is an arylene group, an arylene group substituted by a bromine compound, and is substituted by a phosphorus compound. Arylene or C1-C10 alkylene; Y is phenylene, naphthylene, phenylene substituted by C1-C4 alkyl or naphthylene substituted by C1-C4 alkyl; n represents average degree of polymerization , is 0.05-10;
优选地，所述酰亚胺改性活性酯具有式(ii)所示结构：Preferably, the imide-modified active ester has the structure represented by formula (ii):
式(ii)中，Z为苯基、萘基、被C1-C4烷基取代的苯基或被C1-C4烷基取代的萘基；X为亚芳香基、被溴化合物取代的亚芳香基、被磷化合物取代的亚芳香基或C1-C10亚烷基；Y为亚苯基、亚萘基、被C1-C4烷基取代的亚苯基或被C1-C4烷基取代的亚萘基；n表示平均聚合度，为0.05-10；In the formula (ii), Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group; and X is an arylene group and an arylene group substituted by a bromine compound. An arylene group or a C1-C10 alkylene group substituted by a phosphorus compound; Y is a phenylene group, a naphthylene group, a phenylene group substituted by a C1-C4 alkyl group or a naphthylene group substituted by a C1-C4 alkyl group; ;n represents the average degree of polymerization, which is 0.05-10;
优选地，所述酰亚胺改性活性酯具有式(iii)所示结构：Preferably, the imide-modified active ester has the structure represented by formula (iii):
式(iii)中，R相同或不同，独立地为氢原子、卤素原子或取代或未取代的C1-C8烷基；n
1表示平均聚合度，为0.05-5.0；和
In the formula (iii), R is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1-C8 alkyl group; n 1 represents an average degree of polymerization, and is 0.05 to 5.0;
(4)含有PPO主链的双端基多官能活性酯，(4) a double-ended polyfunctional active ester containing a PPO backbone,
优选地，所述含有PPO主链的双端基多官能活性酯(4)具有下式所示结构：Preferably, the double-end polyfunctional active ester (4) containing a PPO backbone has a structure represented by the following formula:
式中，R
1为
R
2为
取代或未取代的C1-C3的直链烷基或支链烷基、烯丙基或异烯丙基；R
3为H、烯丙基或异烯丙基；R
4、R
5、R
6、R
7独立选自H、取代或未取代的C1-C3的直链烷基或支链烷基、烯丙基、异烯丙基或-O-R
8；R
8为取代或未取代的C1-C3的直链烷基或支链烷基或取代或未取代的苯基；n1、n2为大于0的正整数，且满足4≤n1+n2≤25；n3、n4相等或不等，独立地为1、2或3，优选独立地为2或3，更优选n3、n4相等且为2或3。
Where R 1 is R 2 is a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl, allyl or isoallyl group; R 3 is H, allyl or isoallyl; R 4 , R 5 , R 6 And R 7 is independently selected from H, a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl group, allyl, isoallyl or -OR 8 ; R 8 is a substituted or unsubstituted C1- a linear alkyl or branched alkyl group of C3 or a substituted or unsubstituted phenyl group; n1, n2 are positive integers greater than 0, and satisfy 4≤n1+n2≤25; n3, n4 are equal or unequal, independently It is 1, 2 or 3, preferably independently 2 or 3, more preferably n3, n4 are equal and 2 or 3.
优选地，活性酯化合物(C)为分子结构中含有
基团、
基团、
基团、
基团、
基团或
基团的化合物。
Preferably, the active ester compound (C) is contained in a molecular structure Group, Group, Group, Group, Group or a compound of a group.
更优选地，活性酯化合物包括如下结构的活性酯：More preferably, the active ester compound comprises an active ester of the structure:
X为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25。X is a phenyl or naphthyl group, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25.
由于该活性酯的特殊结构，其中的苯基、萘基、环戊二烯等刚性结构赋予该活性酯高的耐热性，同时由于其结构的规整性及与环氧树脂反应过程中无二次羟基产生，赋予其良好的电性能和低吸水性。Due to the special structure of the active ester, the rigid structure such as phenyl, naphthyl or cyclopentadiene imparts high heat resistance to the active ester, and at the same time, due to the regularity of the structure and the reaction with the epoxy resin The secondary hydroxyl group is produced, giving it good electrical properties and low water absorption.
对活性酯化合物(C)的含量没有特别的限定，从阻燃性、玻璃化转变温度、吸水率和介电特性的观点来看，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，优选为10～70质量份、更优选为10～50质量份。The content of the active ester compound (C) is not particularly limited, and the organic solid content of the resin component in the epoxy resin composition is from the viewpoints of flame retardancy, glass transition temperature, water absorption, and dielectric properties. The total amount of the particles is preferably from 10 to 70 parts by mass, more preferably from 10 to 50 parts by mass, per 100 parts by weight.
-氰酸酯化合物(D)--Cyanate ester compound (D)-
本发明的环氧树脂组合物中还可以含有氰酸酯化合物(D)。作为氰酸酯化合物(D)的具体实例，可以列举本领域已知的氰酸酯化合物，例如，分子结构中含有至少两个氰酸酯基的氰酸酯单体或氰酸酯预聚物，优选为自双酚A型氰酸酯树脂、双酚F型氰酸酯树脂、四甲基双酚F型氰酸酯树脂、双酚M型氰酸酯树脂、双酚S型氰酸酯树脂、双酚E型氰酸酯树脂、双酚P型氰酸酯树脂、线性酚醛型氰酸酯树脂、甲酚酚醛型氰酸酯树脂、萘酚型氰酸酯树脂、萘酚酚醛型氰酸酯树脂、双环戊二烯型氰酸酯树脂、酚酞型氰酸酯树脂、芳烷基型氰酸酯树脂、芳烷基酚醛型氰酸酯树脂、双酚A型氰酸酯预聚物、双酚F型氰酸酯预聚物、四甲基双酚F型氰酸酯预聚物、双酚M型氰酸酯预聚物、双酚S型氰酸酯预聚物、双酚E型氰酸酯预聚物、双酚P型氰酸酯预聚物、线性酚醛型氰酸酯预聚物、甲酚酚醛型氰酸酯预聚物、萘酚型氰酸酯预聚物、萘酚酚醛型氰酸酯预聚物、双环戊二烯型氰酸酯预聚物、酚酞型氰酸酯预聚物、芳烷基型氰酸酯预聚物或芳烷基酚醛型氰酸酯预聚物中的任意一种或者至少两种的混合物，所述混合物例如双酚A型氰酸酯树脂和双酚F型氰酸酯树脂的混合物，四 甲基双酚F型氰酸酯树脂和双酚M型氰酸酯树脂的混合物，双酚S型氰酸酯树脂和双酚E型氰酸酯树脂的混合物，双酚P型氰酸酯树脂和线性酚醛型氰酸酯树脂的混合物，甲酚酚醛型氰酸酯树脂和萘酚酚醛型氰酸酯树脂的混合物，双环戊二烯型氰酸酯树脂和酚酞型氰酸酯树脂的混合物，芳烷基型氰酸酯树脂和芳烷基酚醛型氰酸酯树脂的混合物，线性酚醛型氰酸酯树脂和双酚A型氰酸酯预聚物的混合物，双酚A型氰酸酯预聚物和双酚F型氰酸酯预聚物的混合物，四甲基双酚F型氰酸酯预聚物和双酚M型氰酸酯预聚物的混合物，双酚S型氰酸酯预聚物和双酚E型氰酸酯预聚物的混合物，双酚P型氰酸酯预聚物和线性酚醛型氰酸酯预聚物的混合物，甲酚酚醛型氰酸酯预聚物和萘酚酚醛型氰酸酯预聚物的混合物，双环戊二烯型氰酸酯预聚物、酚酞型氰酸酯预聚物、芳烷基型氰酸酯预聚物和芳烷基酚醛型氰酸酯预聚物的混合物。为了提高氰酸酯树脂组合物的耐热性、阻燃性，进一步优选线性酚醛型氰酸酯树脂、萘酚型氰酸酯树脂、萘酚酚醛型氰酸酯树脂、酚酞型氰酸酯树脂、芳烷基型氰酸酯树脂、芳烷基酚醛型氰酸酯树脂、线性酚醛型氰酸酯预聚物、萘酚型氰酸酯预聚物、萘酚酚醛型氰酸酯预聚物、酚酞型氰酸酯预聚物、芳烷基型氰酸酯预聚物或芳烷基酚醛型氰酸酯预聚物中的任意一种或者至少两种的混合物。从更好耐热性和阻燃性的角度考虑，特别优选线性酚醛型氰酸酯树脂、萘酚酚醛型氰酸酯树脂、芳烷基酚醛型氰酸酯树脂、线性酚醛型氰酸酯预聚物、萘酚酚醛型氰酸酯预聚物或芳烷基酚醛型氰酸酯预聚物中的任意一种或者至少两种的混合物。从更好介电性能的角度考虑，特别优选双酚型氰酸酯树脂、芳烷基型氰酸酯树脂、双环戊二烯型氰酸酯树脂、双酚型氰酸酯预聚物、芳烷基型氰酸酯预聚物或双环戊二烯型氰酸酯预聚物中的任意一种或者至少两种的混合物。这些氰酸酯树脂可以根据需要单独使用或多种组合使用。The epoxy resin composition of the present invention may further contain a cyanate compound (D). As a specific example of the cyanate ester compound (D), a cyanate ester compound known in the art, for example, a cyanate ester monomer or a cyanate ester prepolymer having at least two cyanate groups in a molecular structure may be mentioned. Preferred from self-bisphenol A type cyanate resin, bisphenol F type cyanate resin, tetramethyl bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol S type cyanate Resin, bisphenol E type cyanate resin, bisphenol P type cyanate resin, novolac type cyanate resin, cresol novolac type cyanate resin, naphthol type cyanate resin, naphthol novolac type cyanide Acid ester resin, dicyclopentadiene type cyanate resin, phenolphthalein type cyanate resin, aralkyl type cyanate resin, aralkyl novolac type cyanate resin, bisphenol A type cyanate prepolymer , bisphenol F type cyanate prepolymer, tetramethyl bisphenol F type cyanate prepolymer, bisphenol M type cyanate prepolymer, bisphenol S type cyanate prepolymer, bisphenol E-type cyanate prepolymer, bisphenol P type cyanate prepolymer, novolac type cyanate prepolymer, cresol novolac type cyanate prepolymer, naphthol type cyanate prepolymer Naphthol Aldehyde type cyanate prepolymer, dicyclopentadiene type cyanate prepolymer, phenolphthalein type cyanate prepolymer, aralkyl type cyanate prepolymer or aralkyl novolac type cyanate pre Any one or a mixture of at least two of, such as a mixture of a bisphenol A type cyanate resin and a bisphenol F type cyanate resin, a tetramethyl bisphenol F type cyanate resin and a mixture of a bisphenol M type cyanate resin, a mixture of a bisphenol S type cyanate resin and a bisphenol E type cyanate resin, a mixture of a bisphenol P type cyanate resin and a novolac type cyanate resin, Mixture of cresol novolac type cyanate resin and naphthol novolac type cyanate resin, mixture of dicyclopentadiene type cyanate resin and phenolphthalein type cyanate resin, aralkyl type cyanate resin and aralkyl Mixture of phenolic type cyanate resin, mixture of novolac type cyanate resin and bisphenol A type cyanate prepolymer, bisphenol A type cyanate prepolymer and bisphenol F type cyanate pre Mixture of polymers, mixture of tetramethyl bisphenol F type cyanate prepolymer and bisphenol M type cyanate prepolymer, bisphenol S type Mixture of acid ester prepolymer and bisphenol E type cyanate prepolymer, mixture of bisphenol P type cyanate prepolymer and novolac type cyanate prepolymer, cresol novolac type cyanate pre Mixture of a polymer and a naphthol novolac type cyanate prepolymer, a dicyclopentadiene type cyanate prepolymer, a phenolphthalein type cyanate prepolymer, an aralkyl type cyanate prepolymer and an aralkyl A mixture of phenolic type cyanate prepolymers. In order to improve heat resistance and flame retardancy of the cyanate resin composition, a novolac type cyanate resin, a naphthol type cyanate resin, a naphthol novolac type cyanate resin, and a phenolphthalein type cyanate resin are further preferable. , aralkyl type cyanate resin, aralkyl novolac type cyanate resin, novolac type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer Any one or a mixture of at least two of a phenolphthalein type cyanate prepolymer, an aralkyl type cyanate prepolymer or an aralkyl novolac type cyanate prepolymer. From the viewpoint of better heat resistance and flame retardancy, a novolac type cyanate resin, a naphthol novolac type cyanate resin, an aralkyl novolac type cyanate resin, and a novolac type cyanate ester are particularly preferable. Any one or a mixture of at least two of a polymer, a naphthol novolac type cyanate prepolymer or an aralkyl novolac type cyanate prepolymer. From the viewpoint of better dielectric properties, a bisphenol type cyanate resin, an aralkyl type cyanate resin, a dicyclopentadiene type cyanate resin, a bisphenol type cyanate prepolymer, and a aryl group are particularly preferable. Any one or a mixture of at least two of an alkyl type cyanate prepolymer or a dicyclopentadiene type cyanate prepolymer. These cyanate resins may be used singly or in combination of plural kinds as needed.
对氰酸酯化合物(D)的含量没有特别的限定，从阻燃性、玻璃化转变温度和树脂组合物粘附性的观点来看，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，优选为10～70质量份、更优选为20～60质量份。The content of the cyanate ester compound (D) is not particularly limited, and the organic component of the resin component in the epoxy resin composition is from the viewpoints of flame retardancy, glass transition temperature, and adhesion of the resin composition. The total amount of the solid matter is preferably from 10 to 70 parts by mass, more preferably from 20 to 60 parts by mass, per 100 parts by weight.
另外，在本发明的环氧树脂组合物中，可以适当调节氰酸酯化合物(D)与活性酯化合物(C)的比例，使得环氧树脂组合物的综合指标，包括(Tg、CTE和吸水性)处于优选的范围。例如，活性酯化合物(C)与氰酸酯化合物 (D)的比例为1:5～5:1，优选1:5～3:1。Further, in the epoxy resin composition of the present invention, the ratio of the cyanate compound (D) to the active ester compound (C) can be appropriately adjusted so that the comprehensive index of the epoxy resin composition includes (Tg, CTE, and water absorption) ()) is in the preferred range. For example, the ratio of the active ester compound (C) to the cyanate compound (D) is from 1:5 to 5:1, preferably from 1:5 to 3:1.
-无机填料(E)--Inorganic filler (E)-
本发明的环氧树脂组合物中还可以含有无机填料(E)。无机填料(E)主要起改善介电性能、降低热膨胀系数、改善导热性及降低成本之作用。The epoxy resin composition of the present invention may further contain an inorganic filler (E). The inorganic filler (E) mainly serves to improve dielectric properties, lower the coefficient of thermal expansion, improve thermal conductivity, and reduce cost.
无机填料(E)没有特别的限制，可以选自二氧化硅、金属水合物、氧化钼、钼酸锌、氧化钛、氧化锌、钛酸锶、钛酸钡、硫酸钡、氮化硼、氮化铝、碳化硅、氧化铝、硼酸锌、锡酸锌、粘土、高岭土、滑石、云母、复合硅微粉、E玻璃粉、D玻璃粉、L玻璃粉、M玻璃粉、S玻璃粉、T玻璃粉、NE玻璃粉、Q玻璃粉、石英玻璃粉、短玻璃纤维或空心玻璃中的任意一种或者至少两种的混合物，优选结晶型二氧化硅、熔融二氧化硅、无定形二氧化硅、球形二氧化硅、空心二氧化硅、氢氧化铝、勃姆石、氢氧化镁、氧化钼、钼酸锌、氧化钛、氧化锌、钛酸锶、钛酸钡、硫酸钡、氮化硼、氮化铝、碳化硅、氧化铝、硼酸锌、锡酸锌、粘土、高岭土、滑石、云母、复合硅微粉、E玻璃粉、D玻璃粉、L玻璃粉、M玻璃粉、S玻璃粉、T玻璃粉、NE玻璃粉、Q玻璃粉、石英玻璃粉、短玻璃纤维或空心玻璃中的任意一种或者至少两种的混合物，所述混合物例如结晶型二氧化硅和熔融二氧化硅的混合物，无定形二氧化硅和球形二氧化硅的混合物，空心二氧化硅和氢氧化铝的混合物，勃姆石和氢氧化镁的混合物，氧化钼和钼酸锌的混合物，氧化钛、氧化锌、钛酸锶和钛酸钡的混合物，硫酸钡、氮化硼和氮化铝的混合物，碳化硅、氧化铝、硼酸锌和锡酸锌的混合物，复合硅微粉、E玻璃粉、D玻璃粉、L玻璃粉和M玻璃粉的混合物，S玻璃粉、T玻璃粉、NE玻璃粉和石英玻璃粉的混合物，粘土、高岭土、滑石和云母的混合物，短玻璃纤维和空心玻璃的混合物，进一步优选熔融二氧化硅或/和勃姆石。其中，熔融二氧化硅具有低热膨胀系数的特性，勃姆石的阻燃性和耐热性优异，故优选之。更优选球形熔融二氧化硅，球形熔融二氧化硅具有低热膨胀系数和良好的介电性能等特性的同时，又具有良好的分散性、流动性，故优选之。The inorganic filler (E) is not particularly limited and may be selected from the group consisting of silica, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, barium titanate, barium titanate, barium sulfate, boron nitride, and nitrogen. Aluminum, silicon carbide, aluminum oxide, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silicon powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass Any one or a mixture of at least two of powder, NE glass powder, Q glass powder, quartz glass powder, short glass fiber or hollow glass, preferably crystalline silica, fused silica, amorphous silica, Spherical silica, hollow silica, aluminum hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, barium titanate, barium titanate, barium sulfate, boron nitride, Aluminum nitride, silicon carbide, aluminum oxide, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silicon powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T Glass powder, NE glass powder, Q glass powder, quartz glass powder, short Any one or a mixture of at least two of glass fibers or hollow glass, such as a mixture of crystalline silica and fused silica, a mixture of amorphous silica and spherical silica, hollow dioxide a mixture of silicon and aluminum hydroxide, a mixture of boehmite and magnesium hydroxide, a mixture of molybdenum oxide and zinc molybdate, a mixture of titanium oxide, zinc oxide, barium titanate and barium titanate, barium sulfate, boron nitride and nitrogen a mixture of aluminum, a mixture of silicon carbide, aluminum oxide, zinc borate and zinc stannate, a mixture of composite silicon micropowder, E glass powder, D glass powder, L glass powder and M glass powder, S glass powder, T glass powder, A mixture of NE glass frit and quartz glass frit, a mixture of clay, kaolin, talc and mica, a mixture of short glass fibers and hollow glass, further preferably fused silica or/and boehmite. Among them, fused silica has a characteristic of a low coefficient of thermal expansion, and boehmite is preferred because it is excellent in flame retardancy and heat resistance. More preferably, spherical fused silica, which has characteristics such as a low coefficient of thermal expansion and good dielectric properties, has good dispersibility and fluidity, and is therefore preferred.
对无机填料(E)的平均粒径(d50)没有特别的限定，但从分散性角度考虑，平均粒径(d50)优选为0.1-10微米，例如0.2微米、0.8微米、1.5微米、2.1微米、2.6微米、3.5微米、4.5微米、5.2微米、5.5微米、6微米、6.5微米、7微米、7.5微米、8微米、8.5微米、9微米、9.5微米，更优选为0.2-5微米。可以根据 需要单独使用或多种组合使用不同类型、不同颗粒大小分布或不同平均粒径的无机填料。The average particle diameter (d50) of the inorganic filler (E) is not particularly limited, but from the viewpoint of dispersibility, the average particle diameter (d50) is preferably from 0.1 to 10 μm, for example, 0.2 μm, 0.8 μm, 1.5 μm, 2.1 μm. 2.6 microns, 3.5 microns, 4.5 microns, 5.2 microns, 5.5 microns, 6 microns, 6.5 microns, 7 microns, 7.5 microns, 8 microns, 8.5 microns, 9 microns, 9.5 microns, more preferably 0.2-5 microns. The inorganic fillers of different types, different particle size distributions or different average particle diameters may be used singly or in combination as needed.
为了提高无机填料(E)与树脂组合物的相容性，可以结合表面处理剂或润湿剂、分散剂一起使用。对表面处理剂没有特别的限定，其选自无机物表面处理常用的表面处理剂。其具体为正硅酸乙酯类化合物、有机酸类化合物、铝酸酯类化合物、钛酸酯类化合物、有机硅低聚物、大分子处理剂、硅烷偶联剂等。对硅烷偶联剂没有特别的限制，其选自无机物表面处理常用的硅烷偶联剂，其具体为氨基硅烷偶联剂、环氧基硅烷偶联剂、乙烯基硅烷偶联剂、苯基硅烷偶联剂、阳离子硅烷偶联剂、巯基硅烷偶联剂等。对润湿剂、分散剂没有特别的限制，其选自常用于涂料的润湿剂、分散剂。本发明可以根据需要单独使用或适当组合使用不同类型的表面处理剂或润湿剂、分散剂。In order to improve the compatibility of the inorganic filler (E) with the resin composition, it may be used in combination with a surface treating agent or a wetting agent or a dispersing agent. The surface treatment agent is not particularly limited and is selected from surface treatment agents commonly used for inorganic surface treatment. Specific examples thereof include a tetraethyl orthosilicate compound, an organic acid compound, an aluminate compound, a titanate compound, a silicone oligomer, a macromolecular treatment agent, and a silane coupling agent. The silane coupling agent is not particularly limited, and is selected from a silane coupling agent commonly used for surface treatment of inorganic materials, and is specifically an aminosilane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, and a phenyl group. A silane coupling agent, a cationic silane coupling agent, a mercaptosilane coupling agent, and the like. The wetting agent and the dispersing agent are not particularly limited, and are selected from the group consisting of a wetting agent and a dispersing agent which are commonly used for coating materials. The present invention may be used alone or in appropriate combination with different types of surface treating agents or wetting agents and dispersing agents as needed.
无机填料(E)的添加量并无特别限定，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计(即，以组分(A)～(C)的添加量之和或组分(A)～(D)的添加量之和为100重量份计)，无机填料(E)的添加量可以为0～400重量份，优选20～300重量份，进一步优选为50-250重量份。The amount of the inorganic filler (E) to be added is not particularly limited, and the total amount of the organic solids of the resin component in the epoxy resin composition is 100 parts by weight (that is, the components (A) to (C). The sum of the added amounts or the sum of the amounts of the components (A) to (D) added is 100 parts by weight, and the inorganic filler (E) may be added in an amount of 0 to 400 parts by weight, preferably 20 to 300 parts by weight. It is further preferably from 50 to 250 parts by weight.
本发明所述的氰酸酯树脂组合物还可以包括有机填料。对有机填料没有特别的限定，选自有机硅、液晶聚合物、热固性树脂、热塑性树脂、橡胶或核壳橡胶中的任意一种或者至少两种的混合物，进一步优选有机硅粉末或/和核壳橡胶。所述有机填料可以为粉末或颗粒。其中，有机硅粉末具有良好的阻燃特性，核壳橡胶具有良好的增韧效果，故优选之。The cyanate resin composition of the present invention may further comprise an organic filler. The organic filler is not particularly limited and is selected from any one or a mixture of at least two of silicone, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber or core-shell rubber, and further preferably silicone powder or/and core shell. rubber. The organic filler may be a powder or a granule. Among them, the silicone powder has good flame retardant properties, and the core-shell rubber has a good toughening effect, so it is preferred.
-固化促进剂(G)-- curing accelerator (G) -
本发明的环氧树脂组合物中还可以含有固化促进剂(G)，其加快树脂固化速度。固化促进剂选自可以促进氰酸酯树脂、活性酯化合物、环氧树脂固化的固化促进剂，其具体为铜、锌、钴、镍、锰之类的金属的有机盐、咪唑及其衍生物、叔胺等。The epoxy resin composition of the present invention may further contain a curing accelerator (G) which accelerates the curing speed of the resin. The curing accelerator is selected from the group consisting of a curing accelerator capable of promoting curing of a cyanate resin, an active ester compound, and an epoxy resin, and is specifically an organic salt of a metal such as copper, zinc, cobalt, nickel or manganese, an imidazole and a derivative thereof. , tertiary amines, etc.
优选地，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，固化促进剂的添加量可以为0.01～5重量份。Preferably, the curing accelerator may be added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total of the organic solids of the resin component in the epoxy resin composition.
-溶剂(H)--Solvent (H)-
本发明的环氧树脂组合物的一个突出的优点在于，可以通过使用溶剂(H)将环氧树脂组合物配制成胶水形式。作为可用于本发明的溶剂(H)，只要能使 各种树脂组分溶解、且混合时不发生分离即可，可以列举：甲醇、乙醇、乙二醇、丙酮、丁酮、甲基乙基甲酮、环己酮、甲苯、二甲苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、醋酸乙酯、乙二醇甲醚(MC)，丙二醇甲醚(PM)、丙二醇甲醚醋酸酯(PMA)等。可以使用一种或多种溶剂。An outstanding advantage of the epoxy resin composition of the present invention is that the epoxy resin composition can be formulated into a gel form by using a solvent (H). The solvent (H) which can be used in the present invention is not particularly limited as long as it can dissolve various resin components and does not separate upon mixing, and examples thereof include methanol, ethanol, ethylene glycol, acetone, methyl ethyl ketone, and methyl ethyl group. Methyl ketone, cyclohexanone, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, ethyl acetate, ethylene glycol methyl ether (MC), propylene glycol methyl ether (PM), propylene glycol methyl ether acetate (PMA), and the like. One or more solvents can be used.
相对于100重量份的环氧树脂组合物(溶剂除外)，溶剂(H)的用量一般为5-50重量份，例如10-50，20-50，30-40重量份等，以形成具有便于涂覆的粘度(例如300-600cPa·s)的胶液。胶液中的固体含量可以为60重量％-70重量％。The solvent (H) is usually used in an amount of 5 to 50 parts by weight, for example, 10 to 50, 20 to 50, 30 to 40 parts by weight, etc., relative to 100 parts by weight of the epoxy resin composition (excluding the solvent), to facilitate formation. A glue of a applied viscosity (for example, 300-600 cPa·s). The solids content in the gum may range from 60% to 70% by weight.
-其他添加剂(I)--Other Additives (I)-
本发明的环氧树脂组合物还可以包含其他添加剂(I)，例如阻燃剂，抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。但是，本发明的环氧树脂组合物优选不含卤素或卤化物。其他添加剂(I)的量可以在不损失本发明的效果的范围内任意调节。The epoxy resin composition of the present invention may further contain other additives (I) such as a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant or a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds. However, the epoxy resin composition of the present invention preferably does not contain a halogen or a halide. The amount of the other additive (I) can be arbitrarily adjusted within the range not detracting from the effects of the present invention.
本发明的环氧树脂组合物还可以结合具有式(Ⅰ)结构的马来酰亚胺化合物(B)以外的马来酰亚胺化合物一起使用，只要其不损害氰酸酯树脂组合物的固有性能即可。它们可以根据需要单独使用或多种组合使用。The epoxy resin composition of the present invention may be used in combination with a maleimide compound other than the maleimide compound (B) having a structure of the formula (I) as long as it does not impair the inherent nature of the cyanate resin composition. Performance can be. They can be used singly or in combination of plural kinds as needed.
本发明所述的环氧树脂组合物还可以结合各种高聚物一起使用，只要其不损害环氧树脂组合物的固有性能。具体例如可以为液晶聚合物、热固性树脂、热塑性树脂、不同的阻燃化合物或添加剂等。它们可以根据需要单独使用或多种组合使用。The epoxy resin composition of the present invention can also be used in combination with various high polymers as long as it does not impair the inherent properties of the epoxy resin composition. Specifically, for example, it may be a liquid crystal polymer, a thermosetting resin, a thermoplastic resin, a different flame retardant compound or an additive or the like. They can be used singly or in combination of plural kinds as needed.
本发明的另一个方面涉及一种预浸料，其包括基材及通过含浸干燥后附着基材上的本发明的上述环氧树脂组合物。Another aspect of the invention relates to a prepreg comprising a substrate and the above epoxy resin composition of the invention adhered to the substrate by impregnation drying.
对可用于本发明的基材没有特别的限制，通常是纺织物、无纺布、粗纱、短纤维、纤维纸等，材质可以是无机纤维(例如E玻璃、D玻璃、L玻璃、M玻璃、S玻璃、T玻璃、NE玻璃、石英等玻璃纤维)或有机纤维(例如聚酰亚胺、聚酰胺、聚酯、聚苯醚、液晶聚合物等)，优选玻璃纤维布。The substrate which can be used in the present invention is not particularly limited, and is usually a woven fabric, a nonwoven fabric, a roving, a short fiber, a fiber paper, etc., and the material may be an inorganic fiber (for example, E glass, D glass, L glass, M glass, Glass fibers such as S glass, T glass, NE glass, and quartz, or organic fibers (for example, polyimide, polyamide, polyester, polyphenylene ether, liquid crystal polymer, etc.) are preferably glass fiber cloth.
对基材的厚度没有特别限制，可以为例如约0.03～0.5mm。从耐热性、耐湿性、加工性的方面考虑，优选用硅烷偶联剂等表面处理的基材或实施了机械 开纤处理的基材。树脂组合物相对于该基材的附着量以干燥后的预浸料的树脂含有率为20～90质量％浸渍或涂敷到基材后，通常在100～200℃的温度下进行1～30分钟加热干燥，使其半固化(B阶化)，得到本发明的预浸料(也称为半固化片)。The thickness of the substrate is not particularly limited and may be, for example, about 0.03 to 0.5 mm. From the viewpoint of heat resistance, moisture resistance, and workability, a substrate surface-treated with a silane coupling agent or the like, or a substrate subjected to mechanical fiber opening treatment is preferable. The amount of adhesion of the resin composition to the substrate is immersed or applied to the substrate at a resin content of the dried prepreg of 20 to 90% by mass, and usually 1 to 30 at a temperature of 100 to 200 ° C. After heating and drying for a minute, it is semi-cured (B-staged) to obtain a prepreg (also referred to as a prepreg) of the present invention.
本发明还涉及一种层压板，其包括至少一张如上所述的预浸料。例如可通过使1～20片预浸料重叠，并用在其单面或两面配置了铜及铝等金属箔的构成层压成形，从而制造层压板(覆金属箔层压板)。The invention also relates to a laminate comprising at least one prepreg as described above. For example, a laminate (metal foil-clad laminate) can be produced by laminating 1 to 20 prepregs and laminating a metal foil such as copper or aluminum on one or both sides thereof.
金属箔只要是电气绝缘材料用途中使用的材料则没有特别限制，例如可列举出铜、铝等的金属箔。其中优选为铜箔。尤其可适合地使用电解铜箔、压延铜箔等。可以对金属箔实施例如镍处理、钴处理等公知的表面处理。金属箔的厚度可以在适合作为印刷电路板的材料的范围内适当调整，优选为2～35μm。The metal foil is not particularly limited as long as it is used for electrical insulating materials, and examples thereof include metal foils such as copper and aluminum. Among them, a copper foil is preferred. In particular, an electrolytic copper foil, a rolled copper foil, or the like can be suitably used. A known surface treatment such as nickel treatment or cobalt treatment can be applied to the metal foil. The thickness of the metal foil can be appropriately adjusted within a range suitable as a material of the printed circuit board, and is preferably 2 to 35 μm.
成形条件可以应用电气绝缘材料用层压板及多层板的手法，例如可使用多段冲压、多段真空冲压、连续成形、高压釜成形机等，在温度100～250℃、压力2～100kg/cm
2、加热时间0.1～5小时的范围的条件下进行成形。
The molding conditions can be applied to laminates and multilayer boards for electrical insulating materials, for example, multi-stage press, multi-stage vacuum press, continuous forming, autoclave molding machine, etc., at a temperature of 100 to 250 ° C and a pressure of 2 to 100 kg/cm 2 . The molding is carried out under the conditions of a heating time of 0.1 to 5 hours.
另外，也可以组合本发明的预浸料与内层用布线板，进行层压成形制造多层板。Further, the prepreg and the inner layer wiring board of the present invention may be combined and laminated to form a multilayer board.
本发明还涉及一种印刷线路板，其包括至少一张如上所述的预浸料。The invention further relates to a printed wiring board comprising at least one prepreg as described above.
所述印刷电路板可以将上述预浸料(或覆金属箔层压板)用作积层材料来制作。具体而言，将预浸料(或覆金属箔层压板)用作积层材料，通过常规方法，对该预浸料进行表面处理，通过镀覆在绝缘层表面来形成布线图案(导体层)，从而可以得到本发明的印刷电路板。The printed circuit board can be produced by using the above prepreg (or metal foil-clad laminate) as a laminate material. Specifically, a prepreg (or a metal foil-clad laminate) is used as a laminate material, and the prepreg is surface-treated by a conventional method, and a wiring pattern (conductor layer) is formed by plating on the surface of the insulating layer. Thus, the printed circuit board of the present invention can be obtained.
本发明可以具有以下优点中的至少一种：The invention may have at least one of the following advantages:
(1)本发明的环氧树脂组合物及使用其制作的预浸料、层压板(包括覆金属箔层压板)以及印刷线路板具有低介电常数(Dk)/介质损耗角正切值(Df)，高玻璃化转变温度(Tg)、低吸水率、低热膨胀系数(CTE)、优异的耐热性和耐湿热性等特点，尤其是具有显著降低的吸水率；(1) The epoxy resin composition of the present invention and a prepreg, a laminate (including a metal foil-clad laminate) and a printed wiring board produced therefrom have a low dielectric constant (Dk) / dielectric loss tangent (Df) ), high glass transition temperature (Tg), low water absorption, low coefficient of thermal expansion (CTE), excellent heat resistance and heat and humidity resistance, especially with significantly reduced water absorption;
(2)通过添加活性酯化合物，解决了马来酰亚胺在用于环氧树脂的溶剂中 溶解差的问题，可以将环氧树脂组合物配制成胶水，从而极大地简化了生产工艺，提高生产效率。(2) By adding an active ester compound, the problem of poor solubility of maleimide in a solvent for an epoxy resin is solved, and the epoxy resin composition can be formulated into a glue, thereby greatly simplifying the production process and improving Productivity.
(3)通过活性酯化合物(C)与氰酸酯化合物(D)的调配，在提高与铜箔的粘附性的同时，降低其吸水率。(3) By blending the active ester compound (C) with the cyanate compound (D), the water absorption rate is lowered while improving the adhesion to the copper foil.
实施例Example
下面通过实施例来进一步说明本发明的技术方案，但是这些实施例不以任何方式限制本发明的范围。The technical solutions of the present invention are further illustrated by the following examples, but these examples are not intended to limit the scope of the invention in any way.
在以下实施例中，除非另外指出，有机树脂的质量份按有机固形物质量份计。In the following examples, parts by mass of the organic resin are based on parts by mass of the organic solid unless otherwise indicated.
实施例1-4和比较例1-3Examples 1-4 and Comparative Examples 1-3
将环氧树脂、马来酰亚胺、活性酯、固化促进剂、填料按照表1所示的配方及合适溶剂放入容器中，搅拌使其混合分散均匀，制成胶水，用溶剂调整溶液固体含量至60％-70％而制成胶液，即得到无卤热固性树脂组合物胶液，用2116电子级玻纤布浸渍胶水，经烘箱烘烤成半固化片，取4张2116半固化片，双面再覆上18um厚电解铜箔，在热压机作真空层压，固化220℃/120min，压机压力45kg/cm
2，制成厚度为0.50mm覆铜板。性能测试结果如表2所示。
The epoxy resin, maleimide, active ester, curing accelerator and filler are placed in a container according to the formulation shown in Table 1 and a suitable solvent, stirred and dispersed uniformly to form a glue, and the solution solid is adjusted with a solvent. The content is 60%-70% to make a glue, that is, the halogen-free thermosetting resin composition glue is obtained, and the glue is impregnated with 2116 electronic grade fiberglass cloth, baked into a prepreg by an oven, and 4 sheets of 2116 prepreg are taken, and double-sided The 18um thick electrolytic copper foil was coated, vacuum laminated on a hot press, cured at 220 ° C / 120 min, and the press pressure was 45 kg / cm 2 to prepare a copper clad plate having a thickness of 0.50 mm. The performance test results are shown in Table 2.
实施例及比较例中所用各组分详述如下：The components used in the examples and comparative examples are detailed as follows:
(A)环氧树脂(A) Epoxy resin
(A-1)联苯型环氧树脂：NC-3000-H(日本化药)(A-1) Biphenyl type epoxy resin: NC-3000-H (Japanese medicine)
(A-2)双环戊二烯型环氧树脂：HP-7200H(日本DIC)(A-2) Dicyclopentadiene type epoxy resin: HP-7200H (Japan DIC)
(B)马来酰亚胺：(B) Maleimide:
(B-1)MIR-3000-70MT(日本化药)(B-1) MIR-3000-70MT (Japanese medicine)
(B-2)BMI-70(KI化学)(B-2) BMI-70 (KI Chemistry)
(C)活性酯：(C) Active ester:
(C-1)HPC-8000-65T(日本DIC，符合更优选的活性酯通式，X为萘环)(C-1) HPC-8000-65T (Japan DIC, which conforms to the more preferred active ester formula, X is a naphthalene ring)
(C-2)HPC-8000L-65MT(日本DIC)(C-2) HPC-8000L-65MT (Japan DIC)
(D)氰酸酯：BA-3000S(Lonza，双酚A型氰酸酯)(D) Cyanate ester: BA-3000S (Lonza, bisphenol A type cyanate)
(E)填料：球形二氧化硅SC-2500SQ(ADMATECHS)(E) Filler: Spherical Silica SC-2500SQ (ADMATECHS)
(F)线性酚醛树脂：HF-4M(日本明和)(F) Novolac resin: HF-4M (Mingwa, Japan)
(G)固化促进剂(G) curing accelerator
(G-1)：DMAP(4-二甲氨基吡啶)(G-1): DMAP (4-dimethylaminopyridine)
(G-2)：2P4MHZ-PW(2-苯基-4-甲基-5羟甲基咪唑)(G-2): 2P4MHZ-PW (2-phenyl-4-methyl-5-hydroxymethylimidazole)
(G-3)：异辛酸锌(G-3): Zinc isooctanoate
(G-4)：2,4,5-三苯基咪唑(G-4): 2,4,5-triphenylimidazole
表1.树脂组合物配方(重量份)Table 1. Resin composition formula (parts by weight)
表2.基材特性值Table 2. Substrate property values
实施例5-8和比较例4-6Examples 5-8 and Comparative Examples 4-6
将环氧树脂、马来酰亚胺、活性酯、氰酸酯、固化促进剂、填料按照表3所示的配方及合适溶剂放入容器中，搅拌使其混合分散均匀，制成胶水，用溶剂调整溶液固体含量至60％-70％而制成胶液，即得到无卤热固性树脂组合物胶液，用2116电子级玻纤布浸渍胶水，经烘箱烘烤成半固化片，取4张2116半固化片，双面再覆上18um厚电解铜箔，在热压机作真空层压，固化220℃/120min，压机压力45kg/cm
2，制成厚度为0.50mm覆铜板。性能测试结果如表4所示。
The epoxy resin, maleimide, active ester, cyanate ester, curing accelerator and filler are placed in a container according to the formulation shown in Table 3 and a suitable solvent, and the mixture is stirred and dispersed uniformly to form a glue. Solvent adjustment solution solid content to 60%-70% to make a glue, that is, to obtain a halogen-free thermosetting resin composition glue, impregnating the glue with 2116 electronic grade fiberglass cloth, baking into a prepreg through an oven, taking 4 sheets of 2116 prepreg The double-sided layer is further coated with 18um thick electrolytic copper foil, vacuum laminated in a hot press, cured at 220 ° C / 120 min, and the press pressure is 45 kg / cm 2 to form a copper clad plate having a thickness of 0.50 mm. The performance test results are shown in Table 4.
表3.树脂组合物配方(重量份)Table 3. Resin composition formula (parts by weight)
表4.基材特性值Table 4. Substrate characteristic values
以上特性的测试方法如下：The test methods for the above characteristics are as follows:
(1)介电常数(Dk)与介质损耗角正切值(Df)：使用条状线的共振法，按照IPC-TM-650 2.5.5.5测定1GHz下的介电常数(Dk)与介质损耗角正切值(Df)。(1) Dielectric constant (Dk) and dielectric loss tangent (Df): The dielectric constant (Dk) at 1 GHz and the dielectric loss angle were measured according to IPC-TM-650 2.5.5.5 using a strip line resonance method. Tangent value (Df).
(2)玻璃化转变温度(Tg)：使用DMA(Dynamic thermomechanical analysis)测试，按照IPC-TM-650 2.4.24所规定的DMA测试方法进行测定。(2) Glass transition temperature (Tg): It was measured by a DMA (Dynamic thermomechanical analysis) test in accordance with the DMA test method specified in IPC-TM-650 2.4.24.
(3)热膨胀系数(Z-CTE)：使用热机械分析仪(TMA)测试，按照IPC-TM-6502.4.24.1所规定的TMA测试方法进行测定。(3) Thermal expansion coefficient (Z-CTE): The test was carried out using a thermomechanical analyzer (TMA) according to the TMA test method specified in IPC-TM-6502.4.24.1.
(4)吸水性：按照IPC-TM-650 2.6.2.1所规定的测试方法进行测定，具体步骤如下：(4) Water absorption: According to the test method specified in IPC-TM-650 2.6.2.1, the specific steps are as follows:
1、试样处理：试样放在烘箱内于105-110℃干燥1h，取出后放入干燥器中冷至室温，从干燥器中取出后立即称重。1. Sample treatment: The sample was dried in an oven at 105-110 ° C for 1 h, taken out, placed in a desiccator and cooled to room temperature, and then weighed immediately after being taken out from the dryer.
2、称重：每一个烘过的试样分别称重并记录为m
1，准确至0.1mg。
2. Weighing: Each dried sample was weighed and recorded as m 1 , accurate to 0.1 mg.
3、浸水：处理过的试样放入盛有蒸馏水的容器中，所有边缘应完全浸入水中，试样应在容器中分开放置，不得叠合或表面与表面相互接触。水温保持在23±1℃，经24+0.5/-0h后，从水中取出试样，用干布擦除去表面水分后立即称重，记录为m
2，准确至0.1mg。
3. Immersion: The treated sample is placed in a container containing distilled water. All edges should be completely immersed in water. The samples should be placed separately in the container, and should not be overlapped or the surface and surface should be in contact with each other. The water temperature was maintained at 23 ± 1 ° C. After 24 + 0.5 / -0 h, the sample was taken out from the water, and the surface moisture was wiped off with a dry cloth and weighed immediately, and recorded as m 2 , accurate to 0.1 mg.
4、计算按如下公式计算每块试样的吸水率，准确至0.01％。4. Calculate the water absorption rate of each sample according to the following formula, accurate to 0.01%.
吸水率％＝(m
2-m
1)/m
1×100
Water absorption %=(m 2 -m 1 )/m 1 ×100
(5)耐湿热性评价：将覆铜板表面的铜箔蚀刻后，评价基板；将基板放置压力锅中，在120℃、105KPa条件下处理4小时后浸渍在288℃的锡炉中；当基板在锡炉中超过5min还没出现起泡或分层时即可结束评价。(5) Evaluation of moisture and heat resistance: After etching the copper foil on the surface of the copper clad laminate, the substrate was evaluated; the substrate was placed in a pressure cooker, treated at 120 ° C, 105 KPa for 4 hours, and then immersed in a tin furnace at 288 ° C; The evaluation can be ended when there is no blistering or delamination in the tin furnace for more than 5 minutes.
从表1的物性数据和表2的基材特性值可知，实施例1为本专利的发明例，实施例2和实施例3分别更换一种环氧树脂和活性酯后，其DK、吸水性和Z-CTE的关键性能基本没有变化；实施例4为实施例1去填料后的发明例，除Z-CTE升高较多外，其它关键性能基本没有变化。比较例1采用酚醛树脂代替活性酯作为环氧树脂的固化剂，其DK、吸水性和Z-CTE都有明显升高；比较例2去除马来酰亚胺后，其Tg明显降低、Z-CTE明显升高，吸水性也有所上升，而且耐湿热性无法通过；比较例3更换另外1种结构的马来酰亚胺后，出现无法完全溶解和树脂析出的现象，无法制作层压板。可见本发明的环氧/马来酰亚胺/活性酯的组合物具有低Dk/Df，较高的玻璃化转变温度(Tg)、低吸水率、低CTE、优异的耐热性和耐湿热性的特点。From the physical property data of Table 1 and the substrate property values of Table 2, Example 1 is an inventive example of the present patent, and Example 2 and Example 3 were replaced with an epoxy resin and an active ester, respectively, and DK, water absorption. The key performance of Z-CTE and the Z-CTE were basically unchanged; Example 4 is the invention example after de-filling in Example 1, except that the Z-CTE is increased more, and other key properties are basically unchanged. In Comparative Example 1, the phenolic resin was used as the curing agent for the epoxy resin, and the DK, water absorption and Z-CTE were significantly increased. After the removal of the maleimide in Comparative Example 2, the Tg was significantly lowered, Z- The CTE was remarkably increased, the water absorbability was also increased, and the heat and humidity resistance could not be passed. In Comparative Example 3, the maleimide of the other structure was replaced, and the phenomenon of incomplete dissolution and resin precipitation did not occur, and the laminate could not be produced. It can be seen that the epoxy/maleimide/active ester composition of the present invention has low Dk/Df, high glass transition temperature (Tg), low water absorption, low CTE, excellent heat resistance and heat and humidity resistance. Sexual characteristics.
从表3的物性数据和表4的基材特性值可知，实施例5为本专利添加氰酸酯树脂的发明例，实施例6和实施例7分别更换一种环氧树脂和活性酯后，其DK、吸水性和Z-CTE的关键性能基本没有变化；实施例8为实施例5去填料后的发明例，除Z-CTE升高较多外，其它关键性能基本没有变化。比较例4采用酚醛树脂代替活性酯作为环氧树脂的固化剂，其DK、吸水性和Z-CTE都有明显升高；比较例5去除马来酰亚胺后，其Tg明显降低、Z-CTE明显升高，吸水性也有所上升，而且耐湿热性无法通过；比较例6更换另外1种结构的马来酰亚胺后，出现无法完全溶解和树脂析出的现象，无法制作层压板。可见本发明的环氧/马来酰亚胺/活性酯/氰酸酯的组合物具有较低Dk/Df，更高的玻璃化转变温度(Tg)、较低吸水率、更低CTE、优异的耐热性和耐湿热性的特点。From the physical property data of Table 3 and the substrate property values of Table 4, Example 5 is an inventive example in which a cyanate resin is added in the present patent, and after an epoxy resin and an active ester are replaced by Example 6 and Example 7, respectively. The key properties of DK, water absorption and Z-CTE were basically unchanged; Example 8 was the inventive example after de-filling in Example 5, except that the Z-CTE was increased more, and other key properties were basically unchanged. In Comparative Example 4, the phenolic resin was used instead of the active ester as the curing agent for the epoxy resin, and the DK, water absorption and Z-CTE were significantly increased. After the removal of the maleimide in Comparative Example 5, the Tg was significantly lowered, Z- The CTE was remarkably increased, the water absorbability was also increased, and the heat and humidity resistance could not be passed. When the maleimide of the other structure was replaced in Comparative Example 6, the phenomenon of incomplete dissolution and resin precipitation did not occur, and the laminate could not be produced. It can be seen that the epoxy/maleimide/active ester/cyanate composition of the present invention has a lower Dk/Df, a higher glass transition temperature (Tg), lower water absorption, lower CTE, and superiority. It is characterized by heat resistance and heat and humidity resistance.
综上所述，与一般的铜箔基板相比，本发明的覆铜箔层压板具有高玻璃化转变温度(Tg)和更低CTE，在Dk/Df、吸水性方面也有突出的表现，并具备优异的耐热性和耐湿热性等性能，能满足制作高密度印刷线路板的基板材料的要求。In summary, the copper-clad laminate of the present invention has a high glass transition temperature (Tg) and a lower CTE than the general copper foil substrate, and has outstanding performance in terms of Dk/Df and water absorption. It has excellent heat resistance and heat and humidity resistance, and can meet the requirements of substrate materials for high-density printed wiring boards.
当然，以上所述之实施例，只是本发明的较佳实例而已。申请人声明，本发明通过上述实施例来说明本发明的详细组成，但本发明并不局限于上述详细组成，即不意味着本发明必须依赖上述详细组成才能实施。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。Of course, the embodiments described above are only preferred examples of the present invention. The Applicant declares that the present invention is described in detail by the above-described embodiments, but the present invention is not limited to the above-described detailed composition, and does not mean that the present invention must be implemented by relying on the above detailed composition. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.
Claims (11)
- 一种环氧树脂组合物，其特征在于，所述环氧树脂组合物包括环氧树脂(A)、具有式(Ⅰ)结构的马来酰亚胺化合物(B)、活性酯化合物(C)，An epoxy resin composition comprising an epoxy resin (A), a maleimide compound (B) having a structure of the formula (I), and an active ester compound (C) ,
R为基团、氢原子、碳原子数1～6的烷基、碳原子数6～18的芳基或碳原子数7～24的芳烷基，R 1为碳原子数6～18的亚芳基，R 2、R 3为氢原子、碳原子数1～6的烷基、碳原子数6～18的芳基或碳原子数7～24的芳烷基，n为1～20的整数。 R is
a group, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and R 1 is an arylene group having 6 to 18 carbon atoms. R 2 and R 3 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and n is an integer of 1 to 20. - 如权利要求1所述的环氧树脂组合物，其特征在于，在所述具有式(Ⅰ)结构的马来酰亚胺化合物(B)中，n为1～15的整数，优选n为1～10的整数；The epoxy resin composition according to claim 1, wherein in the maleimide compound (B) having the structure of the formula (I), n is an integer of from 1 to 15, preferably n is 1 An integer of ～10;优选地，R为基团或氢原子； Preferably, R is
a group or a hydrogen atom;优选地，R 1为亚苯基、亚萘基或亚联苯基，进一步优选R 1为亚联苯基； Preferably, R 1 is a phenylene group, a naphthylene group or a biphenylylene group, and further preferably R 1 is a biphenylylene group;优选地，R 2、R 3为氢原子。 Preferably, R 2 and R 3 are a hydrogen atom. - 如权利要求1或2所述的环氧树脂组合物，其特征在于，所述环氧树脂(A)为分子结构中含有基团、
基团、
基团、
基团、
基团或
基团的化合物；和/或，所述活性酯化合物(C)为分子结构中含有
基团、
基团、
基团、
基团、
基团或
基团的化合物。 The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin (A) is contained in a molecular structure
Group,Group,Group,Group,Group ora compound of a group; and/or the active ester compound (C) is contained in a molecular structureGroup,Group,Group,Group,Group ora compound of a group. - 如权利要求1-3之一所述的环氧树脂组合物，其特征在于，所述环氧树脂(A)为线性酚醛型环氧树脂、甲酚酚醛型环氧树脂、萘酚型环氧树脂、萘酚酚醛型环氧树脂、联苯型环氧树脂、蒽型环氧树脂、双环戊二烯型环氧树脂、双环戊二烯酚醛型环氧树脂、芳烷基型环氧树脂、芳烷基酚醛型环氧树脂、分子中含有亚芳基醚结构的环氧树脂中的至少一种；The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin (A) is a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol type epoxy resin. Resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene novolac type epoxy resin, aralkyl type epoxy resin, At least one of an aralkyl phenolic epoxy resin and an epoxy resin having an arylene ether structure in its molecule;和/或，and / or,所述活性酯化合物(C)为选自以下的至少一种：The active ester compound (C) is at least one selected from the group consisting of:(1)由一种通过脂肪环烃结构连接的酚类化合物、二官能度羧酸芳香族化合物或酸性卤代物及一种单羟基化合物反应而得的活性酯，(1) an active ester obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acidic halogenated product, and a monohydroxy compound,优选地，所述活性酯(1)中二官能羧酸芳香族化合物或酸性卤化物用量为1mol，通过脂肪环烃结构连接的酚类化合物用量为0.05～0.75mol，单羟基化合物用量为0.25～0.95mol；Preferably, the amount of the difunctional carboxylic acid aromatic compound or acid halide in the active ester (1) is 1 mol, the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount of the monohydroxy compound is 0.25 ～. 0.95mol;优选地，所述活性酯(1)具有以下结构式：Preferably, the active ester (1) has the following structural formula:
X为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25；X is phenyl or naphthyl, j is 0 or 1, k is 0 or 1, and n represents a repeating unit of 0.25 to 1.25;(2)含苯乙烯结构的活性酯，(2) an active ester containing a styrene structure,优选地，所述含苯乙烯结构的活性酯(2)具有如下结构：Preferably, the styrene-containing active ester (2) has the following structure:
其中A为取代或未取代的苯基、取代或未取代的萘基、C1-C8烷基，m和n为自然数，m/n＝0.8-19；Wherein A is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a C1-C8 alkyl group, m and n are natural numbers, m/n = 0.8-19;(3)酰亚胺改性活性酯，(3) an imide-modified active ester,优选地，所述酰亚胺改性活性酯(3)具有式(i)所示结构：Preferably, the imide-modified active ester (3) has the structure represented by the formula (i):
式(i)中，R为
Z为苯基、萘基、被C1-C4烷基取代的苯基或被C1-C4烷基取代的萘基；X为亚芳香基、被溴化合物取代的亚芳香基、被磷化合物取代的亚芳香基或C1-C10亚烷基；Y为亚苯基、亚萘基、被C1-C4烷基取代的亚苯基或被C1-C4烷基取代的亚萘基；n表示平均聚合度，为0.05-10； In formula (i), R is
Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group; X is an arylene group, an arylene group substituted by a bromine compound, and is substituted by a phosphorus compound. Arylene or C1-C10 alkylene; Y is phenylene, naphthylene, phenylene substituted by C1-C4 alkyl or naphthylene substituted by C1-C4 alkyl; n represents average degree of polymerization , is 0.05-10;优选地，所述酰亚胺改性活性酯具有式(ii)所示结构：Preferably, the imide-modified active ester has the structure represented by formula (ii):
式(ii)中，Z为苯基、萘基、被C1-C4烷基取代的苯基或被C1-C4烷基取代的萘基；X为亚芳香基、被溴化合物取代的亚芳香基、被磷化合物取代的亚芳香基或C1-C10亚烷基；Y为亚苯基、亚萘基、被C1-C4烷基取代的亚苯基或被C1-C4烷基取代的亚萘基；n表示平均聚合度，为0.05-10；In the formula (ii), Z is a phenyl group, a naphthyl group, a phenyl group substituted by a C1-C4 alkyl group or a naphthyl group substituted by a C1-C4 alkyl group; and X is an arylene group and an arylene group substituted by a bromine compound. An arylene group or a C1-C10 alkylene group substituted by a phosphorus compound; Y is a phenylene group, a naphthylene group, a phenylene group substituted by a C1-C4 alkyl group or a naphthylene group substituted by a C1-C4 alkyl group; ;n represents the average degree of polymerization, which is 0.05-10;优选地，所述酰亚胺改性活性酯具有式(iii)所示结构：Preferably, the imide-modified active ester has the structure represented by formula (iii):
式(iii)中，R相同或不同，独立地为氢原子、卤素原子或取代或未取代的C1-C8烷基；n 1表示平均聚合度，为0.05-5.0；和 In the formula (iii), R is the same or different and is independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1-C8 alkyl group; n 1 represents an average degree of polymerization, and is 0.05 to 5.0;(4)含有PPO主链的双端基多官能活性酯，(4) a double-ended polyfunctional active ester containing a PPO backbone,优选地，所述含有PPO主链的双端基多官能活性酯(4)具有下式所示结构：Preferably, the double-end polyfunctional active ester (4) containing a PPO backbone has a structure represented by the following formula:
式中，R 1为
R 2为
取代或未取代的C1-C3的直链烷基或支链烷基、烯丙基或异烯丙基；R 3为H、烯丙基或异烯丙基；R 4、R 5、R 6、R 7独立选自H、取代或未取代的C1-C3的直链烷基或支链烷基、烯丙基、异烯丙基或-O-R 8；R 8为取代或未取代的C1-C3的直链烷基或支链烷基或取代或未取代的苯基；n1、n2为大于0的正整数，且满足4≤n1+n2≤25；n3、n4相等或不等，独立地为1、2或3，优选独立地为2或3，更优选n3、n4相等且为2或3。 Where R 1 is
R 2 isa substituted or unsubstituted C1-C3 linear alkyl or branched alkyl, allyl or isoallyl group; R 3 is H, allyl or isoallyl; R 4 , R 5 , R 6 And R 7 is independently selected from H, a substituted or unsubstituted C1-C3 linear alkyl or branched alkyl group, allyl, isoallyl or -OR 8 ; R 8 is a substituted or unsubstituted C1- a linear alkyl or branched alkyl group of C3 or a substituted or unsubstituted phenyl group; n1, n2 are positive integers greater than 0, and satisfy 4≤n1+n2≤25; n3, n4 are equal or unequal, independently It is 1, 2 or 3, preferably independently 2 or 3, more preferably n3, n4 are equal and 2 or 3. - 如权利要求1-4之一所述的环氧树脂组合物，其特征在于，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，各组分的含量如下：环氧树脂(A)为20～60重量份，马来酰亚胺化合物(B)为10～50重量份，活性酯化合物(C)为10～50重量份。The epoxy resin composition according to any one of claims 1 to 4, wherein the total amount of the organic solids of the resin component in the epoxy resin composition is 100 parts by weight, of each component The content is as follows: the epoxy resin (A) is 20 to 60 parts by weight, the maleimide compound (B) is 10 to 50 parts by weight, and the active ester compound (C) is 10 to 50 parts by weight.
- 如权利要求1-5之一所述的环氧树脂组合物，其特征在于，所述环氧树脂组合物还包括氰酸酯化合物(D)；优选地，以所述环氧树脂组合物中树脂组分的有机固形物的总量为100重量份计，所述环氧树脂组合物中氰酸酯化合物(D)的量为10～50重量份；更优选地，活性酯化合物(C)与氰酸酯化合物(D)的比例为1:5～5:1。The epoxy resin composition according to any one of claims 1 to 5, wherein the epoxy resin composition further comprises a cyanate compound (D); preferably, in the epoxy resin composition The total amount of the organic solids of the resin component is 100 parts by weight, and the amount of the cyanate compound (D) in the epoxy resin composition is 10 to 50 parts by weight; more preferably, the active ester compound (C) The ratio to the cyanate ester compound (D) is from 1:5 to 5:1.
- 如权利要求1-6之一所述的环氧树脂组合物，其特征在于，所述环氧树脂组合物还包括无机填料(E)，优选地，以所述环氧树脂组合物中树脂组分的 有机固形物的总量为100重量份计，所述环氧树脂组合物中无机填料(E)的量为20～300重量份。The epoxy resin composition according to any one of claims 1 to 6, wherein the epoxy resin composition further comprises an inorganic filler (E), preferably, a resin group in the epoxy resin composition The total amount of the organic solids is 100 parts by weight, and the amount of the inorganic filler (E) in the epoxy resin composition is 20 to 300 parts by weight.
- 一种预浸料，其特征在于，所述预浸料包括基材及通过含浸干燥后附着基材上的如权利要求1-7之一所述的环氧树脂组合物。A prepreg characterized in that the prepreg comprises a substrate and the epoxy resin composition according to any one of claims 1 to 7 adhered to the substrate by impregnation and drying.
- 一种层压板，其特征在于，所述层压板包括至少一张如权利要求8所述的预浸料。A laminate characterized in that the laminate comprises at least one prepreg according to claim 8.
- 如权利要求9所述的层压板，其特征在于，所述层压板为覆金属箔层压板，优选地，所述覆金属箔层压板包括至少一张如权利要求8所述的预浸料及覆于预浸料一侧或两侧的金属箔。The laminate according to claim 9, wherein said laminate is a metal foil-clad laminate, preferably said metal foil-clad laminate comprises at least one prepreg and coating according to claim 8. A metal foil on one or both sides of the prepreg.
- 一种印刷线路板，其特征在于，所述印刷线路板包括至少一张如权利要求8所述的预浸料。A printed wiring board characterized in that the printed wiring board comprises at least one prepreg according to claim 8.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2017/119904 WO2019127389A1 (en) | 2017-12-29 | 2017-12-29 | Epoxy resin composition, prepreg, laminate and printed circuit board |
| KR1020207012853A KR20200055795A (en) | 2017-12-29 | 2017-12-29 | Epoxy resin composition, prepreg, laminated board and printed circuit board |
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2017/119904 WO2019127389A1 (en) | 2017-12-29 | 2017-12-29 | Epoxy resin composition, prepreg, laminate and printed circuit board |
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| WO2019127389A1 true WO2019127389A1 (en) | 2019-07-04 |
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| CN112250994A (en) * | 2020-10-15 | 2021-01-22 | 常熟生益科技有限公司 | Resin composition, and prepreg, laminated board and printed circuit board prepared from resin composition |
| CN114685935A (en) * | 2020-12-25 | 2022-07-01 | 衡所华威电子有限公司 | Low-dielectric-constant resin composition and preparation method and application thereof |
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- 2017-12-29 KR KR1020207012853A patent/KR20200055795A/en not_active IP Right Cessation
- 2017-12-29 WO PCT/CN2017/119904 patent/WO2019127389A1/en active Application Filing
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| JP2013234328A (en) * | 2013-06-18 | 2013-11-21 | Ajinomoto Co Inc | Epoxy resin composition |
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