JP2017020011A - Resin composition, copper-clad laminate and printed circuit sheet using the same - Google Patents
Resin composition, copper-clad laminate and printed circuit sheet using the same Download PDFInfo
- Publication number
- JP2017020011A JP2017020011A JP2016134078A JP2016134078A JP2017020011A JP 2017020011 A JP2017020011 A JP 2017020011A JP 2016134078 A JP2016134078 A JP 2016134078A JP 2016134078 A JP2016134078 A JP 2016134078A JP 2017020011 A JP2017020011 A JP 2017020011A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- epoxy resin
- bisphenol
- resin composition
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 58
- 239000003822 epoxy resin Substances 0.000 claims abstract description 77
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 77
- 229920005989 resin Polymers 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 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 abstract description 28
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005011 phenolic resin Substances 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 24
- 239000003063 flame retardant Substances 0.000 claims abstract description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 35
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 27
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 21
- -1 m-benzylphosphine Chemical compound 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 239000004843 novolac epoxy resin Substances 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 11
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 5
- LLVVSBBXENOOQY-UHFFFAOYSA-N 1,2,3,4,5-pentabromobenzene Chemical compound BrC1=CC(Br)=C(Br)C(Br)=C1Br LLVVSBBXENOOQY-UHFFFAOYSA-N 0.000 claims description 4
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 4
- QRFTXHFUNIFHST-UHFFFAOYSA-N 4,5,6,7-tetrabromoisoindole-1,3-dione Chemical compound BrC1=C(Br)C(Br)=C2C(=O)NC(=O)C2=C1Br QRFTXHFUNIFHST-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- 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 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 3
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 28
- 230000002787 reinforcement Effects 0.000 abstract 1
- 239000011889 copper foil Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002079 cooperative effect Effects 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QMAQLCVJIYANPZ-UHFFFAOYSA-N 2-propoxyethyl acetate Chemical compound CCCOCCOC(C)=O QMAQLCVJIYANPZ-UHFFFAOYSA-N 0.000 description 1
- HRCSALDOULKIIP-UHFFFAOYSA-N 3-methyl-2,4-dioxa-3$l^{5}-phosphabicyclo[3.3.1]nona-1(9),5,7-triene 3-oxide Chemical compound C1=CC(OP(C)(=O)O2)=CC2=C1 HRCSALDOULKIIP-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 208000037427 Beta-propeller protein-associated neurodegeneration Diseases 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ASONQZPECNCPCA-UHFFFAOYSA-N P(=O)(OC1(C(C=CC=C1)C)C)(OC1(C(C=CC=C1)C)C)OC1=CC(O)=CC=C1 Chemical compound P(=O)(OC1(C(C=CC=C1)C)C)(OC1(C(C=CC=C1)C)C)OC1=CC(O)=CC=C1 ASONQZPECNCPCA-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UFZOLVFGAOAEHD-UHFFFAOYSA-N benzaldehyde;phenol Chemical compound OC1=CC=CC=C1.O=CC1=CC=CC=C1 UFZOLVFGAOAEHD-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- MWVJKIZKNCNWHE-UHFFFAOYSA-N bis(1,6-dimethylcyclohexa-2,4-dien-1-yl) hydrogen phosphate Chemical compound C1(C(C=CC=C1)C)(C)OP(OC1(C(C=CC=C1)C)C)(O)=O MWVJKIZKNCNWHE-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 201000007614 neurodegeneration with brain iron accumulation 5 Diseases 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 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
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000011678 thiamine pyrophosphate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明は、樹脂組成物、特に銅張積層板およびプリント回路板に使用される樹脂組成物に関する。 The present invention relates to a resin composition, particularly a resin composition used for copper-clad laminates and printed circuit boards.
既存技術では、DICYをエポキシ樹脂の硬化剤として使用するが、Tgが低下し（DSC測定でTg＝140℃）、基板PCTの耐熱性がよくない場合がある。 In existing technology, DICY is used as a curing agent for epoxy resin, but Tg decreases (Tg = 140 ° C. in DSC measurement), and the heat resistance of the substrate PCT may be poor.
既存技術では、ベンゾオキサジン（Benzoxazine、Bz）樹脂をエポキシ樹脂の硬化剤として使用するが、ベンゾオキサジン樹脂では、共硬化剤でベンゾオキサジンを開環させた後、エポキシ樹脂と架橋する必要がある。日立化成（CN1088727C）では、フェノールノボラック樹脂を用いてBz樹脂と協同作用させるが、フェノールノボラック樹脂を使用すると、誘電率特性が高くなりすぎるため（Dk：約4.4、Df：約0.014@2GHｚ）、低誘電率の銅張積層板としての要求に満足できない。 In existing technology, benzoxazine (Bz) resin is used as a curing agent for epoxy resin. However, in benzoxazine resin, benzoxazine must be ring-opened with a co-curing agent and then crosslinked with epoxy resin. Hitachi Chemical (CN1088727C) uses phenol novolac resin to cooperate with Bz resin, but when phenol novolac resin is used, the dielectric constant characteristics become too high (Dk: about 4.4, Df: about 0.014@2 GHz). Unsatisfied with the requirements for a low dielectric constant copper clad laminate.
既有技術では、銅張積層板の低誘電率特性（Dk≦4.1、Df≦0.01@2GHｚ）のため、通常、原料のコストが高価のシアネート樹脂を使用するが、シアネート樹脂は、原料コストがエポキシ樹脂の約8倍以上であるため、高いコストによって、製品の競争力が低い。 In existing technology, due to the low dielectric constant characteristics of copper-clad laminates (Dk ≤ 4.1, Df ≤ 0.01 @ 2 GHz), usually cyanate resins with high raw material costs are used, but cyanate resins have low raw material costs. Because it is more than about 8 times that of epoxy resin, its competitiveness is low due to its high cost.
以上のように、本分野で、シアネート樹脂を使用しなくても、低誘電率特性が実現でき、且つ基板の高耐熱特性を兼ね持つ樹脂組成物が欠けている。 As described above, in this field, there is a lack of a resin composition that can realize a low dielectric constant characteristic without using a cyanate resin and also has a high heat resistance characteristic of a substrate.
そのため、本分野で、シアネート樹脂を使用しなくても、低誘電率特性が実現でき、且つ基板の高耐熱特性を兼ね持つ樹脂組成物の開発が切望されている。 Therefore, in this field, development of a resin composition that can realize a low dielectric constant characteristic without using a cyanate resin and also has a high heat resistance characteristic of a substrate is eagerly desired.
本発明の第一の目的は、このコストの難題を克服するため、本発明は、シアネート樹脂を使用しなくても、低誘電率特性が実現でき且つ基板の高耐熱特性を兼ね持つ樹脂組成物を開示することにある。 The first object of the present invention is to overcome this cost problem. Therefore, the present invention can realize a low dielectric constant characteristic without using a cyanate resin and also has a high heat resistance characteristic of a substrate. Is to disclose.
本発明の第二の目的は、本発明の樹脂組成物を使用したプリプレグを得ることにある。
本発明の第三の目的は、本発明の樹脂組成物を使用した銅張積層板を得ることにある。
The second object of the present invention is to obtain a prepreg using the resin composition of the present invention.
The third object of the present invention is to obtain a copper-clad laminate using the resin composition of the present invention.
本発明の第四の目的は、本発明の樹脂組成物を使用したプリント回路板を得ることにある。 The fourth object of the present invention is to obtain a printed circuit board using the resin composition of the present invention.
本発明の第一は、
（Ａ）100重量部のエポキシ樹脂と、
（Ｂ）10〜80重量部のベンゾオキサジン樹脂と、
（Ｃ）10〜50重量部のジシクロペンタジエン・フェノール樹脂と、
（Ｄ）0.5〜5重量部のアミン系硬化剤と、
を含む樹脂組成物を提供する。
The first of the present invention is
(A) 100 parts by weight of epoxy resin;
(B) 10 to 80 parts by weight of a benzoxazine resin;
(C) 10 to 50 parts by weight of dicyclopentadiene / phenol resin;
(D) 0.5 to 5 parts by weight of an amine curing agent,
The resin composition containing this is provided.
前述樹脂組成物には、ジアリルビスフェノールA（DABPA）が含まれない。
本発明の一つの具体的な実施形態において、前述ジシクロペンタジエン・フェノール樹脂は、以下のような構造式の化合物から選ばれる。
The resin composition does not contain diallyl bisphenol A (DABPA).
In one specific embodiment of the present invention, the dicyclopentadiene / phenol resin is selected from compounds having the following structural formula.
ただし、nは1〜5の正整数で、Zは、-H、-CH3から選ばれる一つまたはその組合わせである。 However, n is a positive integer of 1 to 5, and Z is one selected from —H and —CH 3 or a combination thereof.
本発明の一つの具体的な実施形態において、前述アミン系硬化剤は、ジアミノジフェニルスルホン、ジアミノジフェニルメタン、ジアミノジフェニルエーテル、ジアミノジフェニルスルフィドおよびジシアンジアミドからなる群から選ばれる少なくとも一つである。 In one specific embodiment of the present invention, the amine-based curing agent is at least one selected from the group consisting of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, and dicyandiamide.
本発明の一つの好適な実施形態において、前述アミン系硬化剤は、ジシアンジアミド（dicy）である。 In one preferred embodiment of the present invention, the amine-based curing agent is dicyandiamide (dicy).
本発明の一つの具体的な実施形態において、前述エポキシ樹脂は、ビスフェノールAエポキシ樹脂、ビスフェノールFエポキシ樹脂、ビスフェノールSエポキシ樹脂、ビスフェノールADエポキシ樹脂、ビスフェノールAノボラックエポキシ樹脂、o-クレゾールノボラックエポキシ樹脂、3官能団エポキシ樹脂、4官能団エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、DOPOを含有するエポキシ樹脂、DOPO-HQを含有するエポキシ樹脂、p-キシレンエポキシ樹脂、ナフタレン型エポキシ樹脂、ベンゾピラン型エポキシ樹脂、ビフェニルノボラックエポキシ樹脂、イソシアネート改質エポキシ樹脂、フェノール・ベンズアルデヒドエポキシ樹脂およびフェノールアラルキルノボラックエポキシ樹脂からなる群から選ばれる少なくとも一つである。 In one specific embodiment of the present invention, the epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin, Trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin containing DOPO, epoxy resin containing DOPO-HQ, p-xylene epoxy resin, naphthalene type epoxy resin, benzopyran type epoxy resin And at least one selected from the group consisting of a biphenyl novolac epoxy resin, an isocyanate-modified epoxy resin, a phenol-benzaldehyde epoxy resin, and a phenol aralkyl novolac epoxy resin.
本発明の一つの具体的な実施形態において、前述ベンゾオキサジン樹脂は、ビスフェノールA型ベンゾオキサジン樹脂、ビスフェノールF型ベンゾオキサジン樹脂、ジアミノジフェニルエーテル型ベンゾオキサジン樹脂およびフェノールフタレイン型ベンゾオキサジン樹脂からなる群から選ばれる少なくとも一つである。 In one specific embodiment of the present invention, the benzoxazine resin is selected from the group consisting of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, diaminodiphenyl ether type benzoxazine resin and phenolphthalein type benzoxazine resin. At least one selected.
本発明の一つの具体的な実施形態において、さらに、難燃剤を含み、前述難燃剤は、ビスフェノールジフェニルリン酸塩、ポリリン酸アンモニウム、ヒドロキノン-ビス（ジフェニルリン酸塩）、ビスフェノールA-ビス（ジフェニルリン酸塩）、トリ（2-カルボキシエチル）ホスフィン、トリ（イソプロピルクロリド）リン酸塩、トリメチルリン酸塩、ジメチル-メチルリン酸塩、レゾルジノールジキシレニルリン酸塩、ホスファゼン、m-ベンジルホスフィン、ポリリン酸メラミン、メラミンシアヌレートおよびトリ（ヒドロキシエチル）イソシアヌレート、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキシド(DOPO)、DOPO含有フェノール樹脂、エチル-ビス(テトラブロモフタルイミド)、エタン-1,2-ビス(ペンタブロモベンゼン)および2,4,6-トリ(2,4,6-トリブロモフェノキシ)-1,3,5-トリアジンから選ばれる無ハロゲン難燃剤およびハロゲン系難燃剤の少なくとも一つである。 In one specific embodiment of the present invention, it further comprises a flame retardant, said flame retardant being bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis (diphenyl phosphate), bisphenol A-bis (diphenyl). Phosphate), tri (2-carboxyethyl) phosphine, tri (isopropyl chloride) phosphate, trimethyl phosphate, dimethyl-methyl phosphate, resordinol dixylenyl phosphate, phosphazene, m-benzylphosphine Melamine polyphosphate, melamine cyanurate and tri (hydroxyethyl) isocyanurate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), DOPO-containing phenolic resin, ethyl-bis (tetra Bromophthalimide), ethane-1,2-bis (pentabromobenzene) and 2,4,6-to At least one of (2,4,6-tribromophenoxy) halogen-free flame retardants and halogenated flame retardants selected from 1,3,5-triazine.
本発明の一つの具体的な実施形態において、前述難燃剤は、物理的混合または化学的方法によって成分（Ａ）のエポキシ樹脂、または他の樹脂に架橋することができる。例えば、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキシド(DOPO)は、エポキシ樹脂に架橋し、DOPO含有エポキシ樹脂を形成することができる。 In one specific embodiment of the present invention, the flame retardant can be cross-linked to the component (A) epoxy resin or other resin by physical mixing or chemical methods. For example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) can be cross-linked to an epoxy resin to form a DOPO-containing epoxy resin.
本発明の第二は、本発明に係る樹脂組成物を含むプリプレグを提供する。
本発明の第三は、本発明に係るプリプレグを含む銅張積層板を提供する。
The second of the present invention provides a prepreg comprising the resin composition according to the present invention.
3rd of this invention provides the copper clad laminated board containing the prepreg which concerns on this invention.
本発明の第四は、本発明に係る銅張積層板を含むプリント回路板を提供する。
本発明の最良の実施形態
本発明者は、幅広く深く研究した結果、製造プロセスの改善によって、シアネート樹脂を使用しなくても、低誘電率特性が実現でき、且つ基板の高耐熱特性を兼ね持つ樹脂組成物を得たため、シアネートの使用量を減少し、ひいては使用せずに済む。これに基づき、本発明を完成させた。
A fourth aspect of the present invention provides a printed circuit board including the copper clad laminate according to the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION As a result of extensive and extensive research, the present inventor can realize a low dielectric constant characteristic without using a cyanate resin by improving a manufacturing process, and also has a high heat resistance characteristic of a substrate. Since the resin composition is obtained, the amount of cyanate used is reduced, so that it is not necessary to use it. Based on this, the present invention was completed.
本発明は、コスト低下のため、シアネート樹脂を使用しなくても、低誘電率および高耐熱性の要求に満足できるが、本発明では、シアネート樹脂を配合から除外するわけではない。 Although the present invention can satisfy the requirements for low dielectric constant and high heat resistance without using cyanate resin due to cost reduction, in the present invention, cyanate resin is not excluded from the blending.
本発明において、用語の「含有」または「含む」は、各種の成分が一緒に本発明の混合物或いは組成物に用いられることを指す。そのため、用語の「主に〜からなる」と「〜からなる」は、用語の「含有」または「含む」に含まれる。 In the present invention, the terms “containing” or “including” indicate that various components are used together in the mixture or composition of the present invention. Therefore, the terms “consisting mainly of” and “consisting of” are included in the terms “containing” or “including”.
本発明の発想は、以下の通りである。
本発明では、ベンゾオキサジン、ジシクロペンタジエンフェノール樹脂およびアミン系硬化剤をエポキシ樹脂の硬化剤として使用し、且つジアリルビスフェノールAを含有せず、エポキシ樹脂と三種の硬化剤の協同作用によって、本発明の樹脂組成物に低誘電率および高基板耐熱性を与える。
The idea of the present invention is as follows.
In the present invention, benzoxazine, dicyclopentadiene phenol resin, and amine curing agent are used as a curing agent for epoxy resin, and do not contain diallyl bisphenol A. A low dielectric constant and high substrate heat resistance are imparted to the resin composition.
以下、本発明の各方面について詳細に説明する。
概要
本発明は、
（Ａ）100重量部のエポキシ樹脂と、
（Ｂ）10〜80重量部のベンゾオキサジン樹脂と、
（Ｃ）10〜50重量部のジシクロペンタジエン・フェノール樹脂と、
（Ｄ）0.5〜5重量部のアミン系硬化剤と、
を含む樹脂組成物を提供する。
前述樹脂組成物には、ジアリルビスフェノールA（DABPA）が含まれない。
Hereinafter, each aspect of the present invention will be described in detail.
Overview The present invention
(A) 100 parts by weight of epoxy resin;
(B) 10 to 80 parts by weight of a benzoxazine resin;
(C) 10 to 50 parts by weight of dicyclopentadiene / phenol resin;
(D) 0.5 to 5 parts by weight of an amine curing agent,
The resin composition containing this is provided.
The resin composition does not contain diallyl bisphenol A (DABPA).
本発明は、樹脂成分（Ａ）のエポキシ樹脂と樹脂成分（Ｂ）のベンゾオキサジン樹脂、樹脂成分（Ｃ）のジシクロペンタジエン・フェノール樹脂および樹脂成分（Ｄ）のアミン系硬化剤の間の協同作用を利用し、低誘電率特性および基板の高耐熱特性を兼ね持つ樹脂組成物を得る。前述樹脂成分には、ジアリルビスフェノールA（DABPA）が含まれない。そうではないと、基板の耐熱性（T288）が低下するおそれがある。 The present invention provides cooperation between the epoxy resin of the resin component (A) and the benzoxazine resin of the resin component (B), the dicyclopentadiene / phenol resin of the resin component (C) and the amine-based curing agent of the resin component (D). By using the action, a resin composition having both low dielectric constant characteristics and high heat resistance characteristics of the substrate is obtained. The resin component does not contain diallyl bisphenol A (DABPA). Otherwise, the heat resistance (T288) of the substrate may be reduced.
樹脂成分（Ａ）：エポキシ樹脂
前述のように、本発明は、樹脂成分（Ａ）のエポキシ樹脂、第一の硬化剤成分（Ｂ）のベンゾオキサジン樹脂、第二の硬化剤成分（Ｃ）のジシクロペンタジエン・フェノール樹脂および第三の硬化剤成分（Ｄ）のアミン系硬化剤を樹脂成分とし、その協同作用を利用し、低誘電率特性および高基板耐熱性が実現する。
Resin Component (A): Epoxy Resin As described above, the present invention includes the epoxy resin of the resin component (A), the benzoxazine resin of the first curing agent component (B), and the second curing agent component (C). The dicyclopentadiene / phenol resin and the amine curing agent of the third curing agent component (D) are used as a resin component, and the low dielectric constant characteristics and high substrate heat resistance are realized by utilizing the cooperative action.
通常のエポキシ樹脂は、一般的に、他の成分と協同作用するため、前述エポキシ樹脂に具体的な制限がなく、本発明の目的に支障が生じないものであればよい。 Since an ordinary epoxy resin generally cooperates with other components, there is no specific limitation on the above-mentioned epoxy resin, and any material that does not hinder the object of the present invention may be used.
本発明の樹脂組成物において、前述成分（Ａ）のエポキシ樹脂は、ビスフェノールA(bisphenol A)エポキシ樹脂、ビスフェノールF(bisphenol F)エポキシ樹脂、ビスフェノールS(bisphenol S)エポキシ樹脂、ビスフェノールAD(bisphenol AD)エポキシ樹脂、ビスフェノールAノボラック(bisphenol A novolac)エポキシ樹脂、o-クレゾールノボラック(o-cresol novolac)エポキシ樹脂、3官能団(trifunctional)エポキシ樹脂、4官能団(tetrafunctional)エポキシ樹脂、ジシクロペンタジエン型(dicyclopentadiene type、DCPD type)エポキシ樹脂、DOPOを含有するエポキシ樹脂、DOPO-HQを含有するエポキシ樹脂、p-キシレンエポキシ樹脂(p-xylene epoxy resin)、ナフタレン型エポキシ樹脂、ベンゾピラン(benzopyran)型エポキシ樹脂、ビフェニルノボラック(biphenyl novolac)エポキシ樹脂、イソシアネート改質(isocyanate modified)エポキシ樹脂、フェノール・ベンズアルデヒド(phenol benzaldehyde)エポキシ樹脂およびフェノールアラルキルノボラック(phenol aralkyl novolac)エポキシ樹脂の一つまたはその組合わせである。ここで、DOPOエポキシ樹脂は、DOPO-PNエポキシ樹脂、DOPO-CNEエポキシ樹脂、DOPO-BPNエポキシ樹脂でもよく、DOPO-HQエポキシ樹脂は、DOPO-HQ-PNエポキシ樹脂、DOPO-HQ-CNEエポキシ樹脂、DOPO-HQ-BPNエポキシ樹脂でもよい。 In the resin composition of the present invention, the epoxy resin of component (A) is bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD (bisphenol AD). ) Epoxy resin, bisphenol A novolac epoxy resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene type (dicyclopentadiene type, DCPD type) epoxy resin, epoxy resin containing DOPO, epoxy resin containing DOPO-HQ, p-xylene epoxy resin, naphthalene type epoxy resin, benzopyran type epoxy Resin, biphenyl novolac epoxy resin, isocyanate modified ) One or a combination of epoxy resins, phenol benzaldehyde epoxy resins and phenol aralkyl novolac epoxy resins. Here, the DOPO epoxy resin may be DOPO-PN epoxy resin, DOPO-CNE epoxy resin, DOPO-BPN epoxy resin, DOPO-HQ epoxy resin is DOPO-HQ-PN epoxy resin, DOPO-HQ-CNE epoxy resin DOPO-HQ-BPN epoxy resin may be used.
第一の硬化剤：成分（Ｂ）のベンゾオキサジン樹脂
本発明は三種の硬化剤の間の協同を充分に利用する。具体的に、本発明の樹脂組成物において、前述成分（Ｂ）のベンゾオキサジン樹脂は、ビスフェノールA型ベンゾオキサジン樹脂、ビスフェノールF型ベンゾオキサジン樹脂、ジアミノジフェニルエーテル型ベンゾオキサジン樹脂およびフェノールフタレイン型ベンゾオキサジン樹脂の一つまたはその組合わせである。より具体的に、好ましくは以下の一般式（１）〜（３）から選ばれる少なくとも一つである。
First curing agent: benzoxazine resin of component (B) The present invention fully utilizes the cooperation between the three curing agents. Specifically, in the resin composition of the present invention, the component (B) benzoxazine resin includes bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, diaminodiphenyl ether type benzoxazine resin and phenolphthalein type benzoxazine. One or a combination of resins. More specifically, it is preferably at least one selected from the following general formulas (1) to (3).
ただし、Ｘ1及びＸ2は、それぞれ独立にＲ又はＡｒ又は-SO2-で、Ｒは、-C(CH3)2-、-CH(CH3)-、-CH2-及び置換又は無置換のジシクロペンタジエニルから選ばれ、Ａｒは、置換又は無置換のベンゼン、ビフェニル、ナフタレン、フェノールアルデヒド、ビスフェノールA、ビスフェノールAフェノールアルデヒド、ビスフェノールF官能団から選ばれる。例えば、Huntsmanによって販売される商品名LZ-8270、LZ-8280、LZ-8290、MT 35700、MT 35800が挙げられる。 X 1 and X 2 are each independently R, Ar, or —SO 2 —, and R is —C (CH 3 ) 2 —, —CH (CH 3 ) —, —CH 2 —, and substituted or unsubstituted. Ar is selected from substituted or unsubstituted benzene, biphenyl, naphthalene, phenol aldehyde, bisphenol A, bisphenol A phenol aldehyde, and bisphenol F functional group. For example, trade names LZ-8270, LZ-8280, LZ-8290, MT 35700, MT 35800 sold by Huntsman can be mentioned.
本発明の一つの具体的な実施形態において、前述ベンゾオキサジン樹脂は、ビスフェノールA型ベンゾオキサジン樹脂、ビスフェノールF型ベンゾオキサジン樹脂、ジアミノジフェニルエーテル型ベンゾオキサジン樹脂およびフェノールフタレイン型ベンゾオキサジン樹脂からなる群から選ばれる少なくとも一つである。 In one specific embodiment of the present invention, the benzoxazine resin is selected from the group consisting of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, diaminodiphenyl ether type benzoxazine resin and phenolphthalein type benzoxazine resin. At least one selected.
本発明の樹脂組成物において、100重量部のエポキシ樹脂に対して、10〜80重量部のベンゾオキサジンを添加する。この範囲で添加するベンゾオキサジン樹脂の含有量であれば、当該樹脂組成物を期待の低誘電損失値（Df）にできる。ベンゾオキサジン樹脂が10重量部未満であれば、期待の低誘電損失値にできず、80重量部を超えると、前述樹脂組成物で製造された基板は耐熱性が劣る。 In the resin composition of the present invention, 10 to 80 parts by weight of benzoxazine is added to 100 parts by weight of the epoxy resin. If it is content of the benzoxazine resin added in this range, the said resin composition can be made into the expected low dielectric loss value (Df). If the benzoxazine resin is less than 10 parts by weight, the expected low dielectric loss value cannot be obtained, and if it exceeds 80 parts by weight, the substrate manufactured from the resin composition has poor heat resistance.
第二の硬化剤：成分（Ｃ）のジシクロペンタジエン・フェノール樹脂
本発明の樹脂組成物において、100重量部のエポキシ樹脂に対して、10〜50重量部のジシクロペンタジエン・フェノール樹脂を添加する。この範囲で添加するジシクロペンタジエン・フェノール樹脂の含有量であれば、当該樹脂組成物を期待の誘電率の値（Dk）にできる。ジシクロペンタジエン・フェノール樹脂が10重量部未満であれば、期待の低誘電率値にできず、基板は耐熱性（T288、Tg）が劣る。50重量部を超えると、前述樹脂組成物で製造された基板はガラス転移温度（Tg）が低下する。
Second curing agent: dicyclopentadiene / phenol resin as component (C) In the resin composition of the present invention, 10 to 50 parts by weight of dicyclopentadiene / phenol resin is added to 100 parts by weight of the epoxy resin. . If the content of the dicyclopentadiene / phenol resin added in this range is reached, the resin composition can have an expected dielectric constant (Dk). If the dicyclopentadiene / phenolic resin is less than 10 parts by weight, the expected low dielectric constant cannot be obtained, and the substrate has poor heat resistance (T288, Tg). If it exceeds 50 parts by weight, the glass transition temperature (Tg) of the substrate produced from the resin composition is lowered.
本発明の樹脂組成物において、100重量部のエポキシ樹脂に対して、好ましくは10〜40重量部のジシクロペンタジエン・フェノール樹脂を添加する。 In the resin composition of the present invention, preferably 10 to 40 parts by weight of dicyclopentadiene / phenol resin is added to 100 parts by weight of the epoxy resin.
硬化剤成分におけるジアリルビスフェノールA（DABPA）の除外
前述硬化剤組成物には、ジアリルビスフェノールA（DABPA）が含まれない。
Exclusion of diallyl bisphenol A (DABPA) in the curing agent component The aforementioned curing agent composition does not contain diallyl bisphenol A (DABPA).
発明者は、以前の実験において、エポキシ樹脂にジアリルビスフェノールA（DABPA）樹脂を添加すると、当該樹脂組成物は優れた架橋性に達し、且つTgおよび樹脂と銅箔のピール強度を向上させることを見出した。 The inventors have shown in previous experiments that when diallyl bisphenol A (DABPA) resin is added to an epoxy resin, the resin composition reaches excellent crosslinkability and improves the peel strength of Tg, resin and copper foil. I found it.
しかし、本発明者は、更なる実験において、意外に、前述ジアリルビスフェノールA（DABPA）を除外し、ジシクロペンタジエン・フェノール樹脂だけ使用する場合、逆に基板の耐熱性（T288）の向上により有利であることを見出した。 However, the present inventor unexpectedly excluded the aforementioned diallyl bisphenol A (DABPA) and used only dicyclopentadiene / phenol resin in a further experiment, but on the contrary, it was more advantageous to improve the heat resistance (T288) of the substrate. I found out.
第三の硬化剤：成分（Ｄ）のアミン系硬化剤
本発明の樹脂組成物において、前述成分（Ｄ）のアミン系硬化剤は、官能団のアミノ基（amino）を有する樹脂、好ましくは官能団のジアミノ基（diamino）を有する樹脂である。より具体的に、前述アミン系硬化剤は、ジアミノジフェニルスルホン(diamino diphenyl sulfone)、ジアミノジフェニルメタン(diamino diphenyl methane)、ジアミノジフェニルエーテル(diamino diphenyl ether)、ジアミノジフェニルスルフィド(diamino diphenyl sulfide)、ジシアンジアミド(dicyandiamide、DICY)の一つまたはその組合わせでもよい。中でも、前述アミン系硬化剤は、好ましくは4,4’-ジアミノジフェニルスルホン(4,4’-diamino diphenyl sulfone)、4,4’-ジアミノジフェニルメタン(4,4’-diamino diphenyl methane)、4,4’-ジアミノジフェニルエーテル(4,4’-diamino diphenyl ether)、4,4’-ジアミノジフェニルスルフィド(4,4’-diamino diphenyl sulfide)、ジシアンジアミド(dicyandiamide, DICY)の一つまたはその組合わせである。
Third curing agent: Amine-based curing agent of component (D) In the resin composition of the present invention, the amine-based curing agent of component (D) is a resin having an amino group (amino) of a functional group, preferably a functional group. A resin having a diamino group. More specifically, the amine curing agent includes diamino diphenyl sulfone, diamino diphenyl methane, diamino diphenyl ether, diamino diphenyl sulfide, dicyandiamide, DICY) or a combination thereof. Among these, the amine curing agent is preferably 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, One or a combination of 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, dicyandiamide, DICY .
本発明の一つの具体的な実施形態において、前述アミン系硬化剤は、ジアミノジフェニルスルホン、ジアミノジフェニルメタン、ジアミノジフェニルエーテル、ジアミノジフェニルスルフィドおよびジシアンジアミドからなる群から選ばれる少なくとも一つである。 In one specific embodiment of the present invention, the amine-based curing agent is at least one selected from the group consisting of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, and dicyandiamide.
好適な前述アミン系硬化剤は、ジシアンジアミド（dicy）である。
本発明の樹脂組成物において、100重量部のエポキシ樹脂に対して、0.5〜5重量部のアミン系硬化剤を添加する。この範囲で添加するアミン系硬化剤の含有量であれば、当該樹脂組成物の銅箔のピール強度値を向上させる。アミン系硬化剤が0.5重量部未満であれば、期待のピール強度にできず、5重量部を超えると、前述樹脂組成物で製造された基板は吸湿性が上昇し、基板PCT測定（銅基板を含まない圧力鍋蒸気加熱測定）で基板が剥離する(delamination, fail)。
A suitable such amine based curing agent is dicyandiamide (dicy).
In the resin composition of the present invention, 0.5 to 5 parts by weight of an amine curing agent is added to 100 parts by weight of the epoxy resin. If it is content of the amine hardening | curing agent added in this range, the peel strength value of the copper foil of the said resin composition will be improved. If the amine-based curing agent is less than 0.5 parts by weight, the expected peel strength cannot be obtained, and if it exceeds 5 parts by weight, the substrate manufactured from the resin composition has increased hygroscopicity, and substrate PCT measurement (copper substrate) (Delamination, fail).
本発明の樹脂組成物において、100重量部のエポキシ樹脂に対して、好ましくは0.5〜3重量部のアミン系硬化剤を添加する。 In the resin composition of the present invention, 0.5 to 3 parts by weight of an amine curing agent is preferably added to 100 parts by weight of the epoxy resin.
さらに、本発明の樹脂組成物において、100重量部のエポキシ樹脂に対して、より好ましくは0.5〜3重量部のジシアンジアミドを添加する。 Further, in the resin composition of the present invention, 0.5 to 3 parts by weight of dicyandiamide is more preferably added to 100 parts by weight of the epoxy resin.
三つの成分の協同
三種の硬化剤成分の配合割合は以下の通りである。
The mixing ratio of the three cooperative three kinds of curing agent of component are as follows.
（Ｂ）10〜80重量部のベンゾオキサジン樹脂、
（Ｃ）10〜50重量部のジシクロペンタジエン・フェノール樹脂、
（Ｄ）0.5〜5重量部のアミン系硬化剤。
(B) 10 to 80 parts by weight of a benzoxazine resin,
(C) 10 to 50 parts by weight of dicyclopentadiene / phenol resin,
(D) 0.5 to 5 parts by weight of an amine curing agent.
そのため、三種の成分の配合割合は、順に(10〜80):(10〜50):(0.5〜5)で、より優れた協同効果を得るため、好ましくはベンゾオキサジン樹脂:ジシクロペンタジエン・フェノール樹脂:アミン系硬化剤は、10〜60:15〜35:0.5〜3である。 Therefore, the blending ratio of the three components is (10-80) :( 10-50) :( 0.5-5) in order, and preferably a benzoxazine resin: dicyclopentadiene / phenol in order to obtain a better cooperative effect. Resin: amine curing agent is 10-60: 15-35: 0.5-3.
前述のように、発明者は、前述ジアリルビスフェノールA（DABPA）を除外し、ジシクロペンタジエン・フェノール樹脂だけ使用する場合、逆に前述基板の耐熱性（T288）がさらに向上することを見出した。 As described above, the inventor has found that when the diallyl bisphenol A (DABPA) is excluded and only the dicyclopentadiene / phenol resin is used, the heat resistance (T288) of the substrate is further improved.
さらに、本発明において、第三の硬化剤成分（Ｄ）のDICYと他の硬化剤の組合わせが好適に使用される。既存技術では、DICYをエポキシ樹脂の硬化剤として使用すると、Tgが低下し（DSC測定でTg＝140℃）、基板PCTの耐熱性がよくないと言われている。本発明者は、第一の硬化剤成分（Ｂ）のベンゾオキサジン樹脂、第二の硬化剤成分（Ｃ）のジシクロペンタジエン・フェノール樹脂および第三の硬化剤成分（Ｄ）のDICYの協同作用によって、より優れた効果が得られることを見出した。本発明の実施例E13に示されるように、優れた効果が得られるが、DDSよりDICYを使用する場合の効果が良い。実施例7において、DICYが増加し、ピール強度も向上し、且つTgの要求に満足できた。比較例C14及び実施例E14から、前述ジアリルビスフェノールA（DABPA）を除外し、ジシクロペンタジエン・フェノール樹脂だけ使用する場合、逆に前述銅含有基板の耐熱性（T288）がさらに向上したことがわかる。 Furthermore, in the present invention, a combination of the third curing agent component (D) DICY and another curing agent is preferably used. In the existing technology, it is said that when DICY is used as a curing agent for epoxy resin, Tg is lowered (Tg = 140 ° C. by DSC measurement) and the heat resistance of the substrate PCT is not good. The present inventor made a cooperative action of the first curing agent component (B) benzoxazine resin, the second curing agent component (C) dicyclopentadiene / phenol resin and the third curing agent component (D) DICY. It has been found that a better effect can be obtained. As shown in Example E13 of the present invention, an excellent effect can be obtained, but the effect when using DICY is better than that of DDS. In Example 7, DICY was increased, peel strength was improved, and Tg requirements were satisfied. From Comparative Example C14 and Example E14, when diallylbisphenol A (DABPA) is excluded and only dicyclopentadiene / phenol resin is used, the heat resistance (T288) of the copper-containing substrate is further improved. .
他の成分
本発明の一つの具体的な実施形態において、さらに30〜70重量部の難燃剤を含む。前述難燃剤は、ハロゲン系難燃剤、または無ハロゲン難燃剤から選ばれる。
Other Components In one specific embodiment of the present invention, the composition further comprises 30 to 70 parts by weight of a flame retardant. The flame retardant is selected from a halogen-based flame retardant or a halogen-free flame retardant.
前述ハロゲン系難燃剤は、臭素系難燃剤でもよいが、特に限定されず、好ましくはエチル-ビス(テトラブロモフタルイミド)（例えばAlbemarleから購入のSAYTEX BT-93）、エタン-1,2-ビス(ペンタブロモベンゼン)（例えばAlbemarleから購入のSAYTEX 8010）および2,4,6-トリ(2,4,6-トリブロモフェノキシ)-1,3,5-トリアジン(例えばICL Industrial社から購入のFR-245)から選ばれる少なくとも一つである。 The halogen-based flame retardant may be a brominated flame retardant, but is not particularly limited, and preferably ethyl-bis (tetrabromophthalimide) (for example, SAYTEX BT-93 purchased from Albemarle), ethane-1,2-bis ( Pentabromobenzene) (eg SAYTEX 8010 purchased from Albemarle) and 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine (eg FR- 245).
前述無ハロゲン難燃剤は、窒素含有難燃剤またはリン含有難燃剤を使用してもよいが、ビスフェノールジフェニルリン酸塩(bisphenol diphenyl phosphate)、ポリリン酸アンモニウム(ammonium poly phosphate)、ヒドロキノン-ビス（ジフェニルリン酸塩）(hydroquinone bis-(diphenyl phosphate))、ビスフェノールA-ビス（ジフェニルリン酸塩）(bisphenol A bis-(diphenylphosphate))、トリ（2-カルボキシエチル）ホスフィン(tri(2-carboxyethyl)phosphine、TCEP)、トリ（イソプロピルクロリド）リン酸塩、トリメチルリン酸塩(trimethyl phosphate、TMP)、ジメチル-メチルリン酸塩(dimethyl methyl phosphonate, DMMP)、レゾルジノールジキシレニルリン酸塩(resorcinol bis(dixylenyl phosphate)、RDXP、例えばPX-200)、ホスファゼン(phosphazene、例えばSPB-100)、m-ベンジルホスフィン(m-phenylene methylphosphonate、PMP)、ポリリン酸メラミン(melamine polyphosphate)、メラミンシアヌレート(melamine cyanurate)及びトリ（ヒドロキシエチル）イソシアヌレート(tri-hydroxy ethyl isocyanurate)などの少なくとも一つを選択して添加してもよいが、これらに限定されない。また、無ハロゲン難燃剤は、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキシド(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide、DOPO)、DOPO含有フェノール樹脂（例えばDOPO-HQ、DOPO-PN、DOPO-BPN）なども使用してもよく、ここで、DOPO-BPNは、DOPO-BPAN、DOPO-BPFN、DOPO-BPSNなどのビスフェノール-フェノールアルデヒド化合物であってもいい。 As the halogen-free flame retardant, a nitrogen-containing flame retardant or a phosphorus-containing flame retardant may be used, but bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis (diphenyl phosphorus). Acid salt) (hydroquinone bis- (diphenyl phosphate)), bisphenol A bis- (diphenylphosphate), tri (2-carboxyethyl) phosphine, TCEP), tri (isopropyl chloride) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol dixylenyl phosphate (resorcinol bis (dixylenyl) phosphate), RDXP, e.g. PX-200), phosphazene (e.g. SPB-100), m-benzyl phosphine (m-phenylene methylphosphonate, PMP), polyphosphate melamine Down (melamine polyphosphate), melamine cyanurate (melamine cyanurate) and tri (hydroxyethyl) isocyanurate (tri-hydroxy ethyl isocyanurate) may be added by selecting at least one such as, but not limited to. Halogen-free flame retardants are 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), DOPO Containing phenolic resins (eg DOPO-HQ, DOPO-PN, DOPO-BPN) may also be used, where DOPO-BPN is a bisphenol-phenol aldehyde such as DOPO-BPAN, DOPO-BPFN, DOPO-BPSN It may be a compound.
本発明の樹脂組成物にいて、さらに、無機フィラー（filler）、硬化促進剤(curing accelerator)、シランカップリング剤(silane coupling agent)、強化剤(toughening agent)、溶媒(solvent)の一つまたはその組合わせを含んでもよい。 In the resin composition of the present invention, one or more of an inorganic filler, a curing accelerator, a silane coupling agent, a toughening agent, a solvent, or The combination may be included.
本発明の樹脂組成物にさらに添加される無機フィラーの主な作用は、樹脂組成物の熱伝導性を向上させ、熱膨張性や機械的強度などの特性を改善することで、且つ無機フィラーは、均一に当該樹脂組成物に分布するため、好適である。中でも、無機フィラーは、シリカ（溶融状態、非溶融状態、多孔質または中空型）、水酸化アルミニウム、酸化マグネシウム、水酸化マグネシウム、炭酸カルシウム、窒化ホウ素、炭化アルミニウムケイ素、炭化ケイ素、二酸化チタン、酸化亜鉛、マイカ、ベーマイト(boehmite、AlOOH)、焼成タルク、タルク、窒化ケイ素、焼成カオリンを含む。また、無機フィラーは、球状、繊維状、板状、粒子状、シート状または髭状でもよく、必要によってシランカップリング剤で前処理してもよい。 The main action of the inorganic filler further added to the resin composition of the present invention is to improve the thermal conductivity of the resin composition, to improve properties such as thermal expansion and mechanical strength, and the inorganic filler is , Because it is uniformly distributed in the resin composition. Among them, inorganic fillers are silica (molten, non-molten, porous or hollow), aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, boron nitride, aluminum carbide silicon, silicon carbide, titanium dioxide, oxidation Includes zinc, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, calcined kaolin. The inorganic filler may be spherical, fibrous, plate-like, particle-like, sheet-like or bowl-like, and may be pretreated with a silane coupling agent as necessary.
本発明の樹脂組成物において、100重量部のエポキシ樹脂に対して、10〜150重量部の無機フィラーを添加する。無機フィラーの含有量が10重量部未満の場合、顕著な熱伝導性がなく、且つ熱膨張性および機械的強度などの特性も改善されない。150重量部を超えると、当該樹脂組成物の穴埋めの流動性が劣り、PCBの穴あけプロセスにおけるドリルの摩耗が大きい。より具体的に、本発明の樹脂組成物において、好ましくは30〜70重量部の無機フィラーを添加する。 In the resin composition of the present invention, 10 to 150 parts by weight of an inorganic filler is added to 100 parts by weight of the epoxy resin. When the content of the inorganic filler is less than 10 parts by weight, there is no remarkable thermal conductivity, and properties such as thermal expansion and mechanical strength are not improved. If it exceeds 150 parts by weight, the fluidity of hole filling of the resin composition is inferior, and the wear of the drill in the PCB drilling process is great. More specifically, in the resin composition of the present invention, preferably 30 to 70 parts by weight of an inorganic filler is added.
本発明に係る硬化促進剤は、ルイス塩基またはルイス酸などの触媒(catalyst)を含んでもよい。ここで、ルイス塩基は、イミダゾール(imidazole)、トリフッ化ホウ素-アミン複合体、塩化エチルトリフェニルホスホニウム(ethyltriphenyl phosphonium chloride)、2-メチルイミダゾール(2-methylimidazole、2MI)、2-フェニルイミダゾール(2-phenyl-1H-imidazole、2PZ)、2-エチル-4-メチルイミダゾール(2-ethyl-4-methylimidazole,、2E4MI)、トリフェニルホスフィン(triphenylphosphine, TPP)および4-ジメチルアミノピリジン(4-dimethylaminopyridine、DMAP)の一つまたは複数種を含んでもよい。ルイス酸は、マンガン、鉄、コバルト、ニッケル、銅、亜鉛などの金属塩系化合物、例えばオクタン酸亜鉛、オクタン酸コバルトなどの金属触媒である。 The curing accelerator according to the present invention may contain a catalyst such as Lewis base or Lewis acid. Here, Lewis bases are imidazole, boron trifluoride-amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole, 2MI, 2-phenylimidazole (2- phenyl-1H-imidazole, 2PZ), 2-ethyl-4-methylimidazole, 2E4MI, triphenylphosphine, TPP and 4-dimethylaminopyridine, DMAP ) May be included. The Lewis acid is a metal salt compound such as manganese, iron, cobalt, nickel, copper, or zinc, for example, a metal catalyst such as zinc octoate or cobalt octoate.
本発明に係るシランカップリング剤は、シラン化合物(silane)とシロキサン化合物(siloxane)を含んでもよく、官能団の種類によって、アミノシラン化合物(amino silane)、アミノシロキサン化合物(amino siloxane)、エポキシシラン化合物(epoxy silane)およびエポキシシロキサン化合物(epoxy siloxane)に分かれる。 The silane coupling agent according to the present invention may include a silane compound (silane) and a siloxane compound (siloxane), and depending on the type of functional group, an aminosilane compound (amino silane), an aminosiloxane compound (amino siloxane), and an epoxysilane compound (epoxy silane) and epoxy siloxane compound (epoxy siloxane).
本発明に係る強化剤は、ゴム(rubber)樹脂、カルボキシル基末端ブタジエンアクリルニトリルゴム(carboxyl-terminated butadiene acrylonitrile rubber、CTBN)、コアシェル型ゴム(core-shell rubber)等の添加物から選ばれる。 The reinforcing agent according to the present invention is selected from additives such as rubber resin, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), and core-shell rubber.
本発明に係る溶媒は、メタノール、エタノール、エチレングリコールモノメチルエーテル、アセトン、ブタノン（メチルエチルケトン）、メチルイソブチルケトン、シクロヘキサノン、トルエン、キシレン、酢酸メトキシエチル、酢酸エトキシエチル、酢酸プロポキシエチル、酢酸エチル、ジメチルホルムアミド、プロピレングリコールメチルエーテルなどの溶媒またはその混合溶媒から選ばれる。 Solvents according to the present invention are methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide And a solvent such as propylene glycol methyl ether or a mixed solvent thereof.
本発明に係る樹脂組成物は、さらに、ポリフェニレンエーテル(polyphenylene ether)樹脂、シアネート(cyanate ester)樹脂、イソシアネート(isocyanate ester)樹脂、マレイミド(maleimide)樹脂、ポリエステル(polyester)樹脂、スチレン(styrene)樹脂、ブタジエン(butadiene)樹脂、フェノキシ(phenoxy)樹脂、ポリアミド(polyamide)樹脂、ポリイミド(polyimide)樹脂の一つまたはその組合わせを含んでもよい。 The resin composition according to the present invention further includes a polyphenylene ether resin, a cyanate ester resin, an isocyanate ester resin, a maleimide resin, a polyester resin, and a styrene resin. In addition, one or a combination of butadiene resin, phenoxy resin, polyamide resin, and polyimide resin may be included.
プリプレグ
本発明は、本発明に係る組成物を含むプリプレグを提供する。
Prepreg The present invention provides a prepreg comprising the composition according to the present invention.
本発明のもう一つの目的は、低誘導率、低誘電損失、耐熱や難燃などの特性を有するプリプレグ(prepreg)を開示することにある。これによって、本発明で開示されるプリプレグは、補強材と前述の樹脂組成物を含んでもよいが、当該樹脂組成物を含浸などの方法で当該補強材に付着させ、且つ高温加熱で半硬化状態とする。ここで、補強材は、繊維材料、織布および不織布、例えばガラス繊維布などでもよいが、当該プリプレグの機械的強度を向上させるものである。また、当該補強材は、必要によって、シランカップリング剤またはシロキサンカップリング剤で前処理してもよいが、例えばシランカップリング剤で前処理したガラス繊維布が挙げられる。 Another object of the present invention is to disclose a prepreg having characteristics such as low inductivity, low dielectric loss, heat resistance and flame retardancy. Accordingly, the prepreg disclosed in the present invention may contain a reinforcing material and the above-described resin composition, but the resin composition is attached to the reinforcing material by a method such as impregnation and is semi-cured by high-temperature heating. And Here, the reinforcing material may be a fiber material, a woven fabric, and a non-woven fabric, such as a glass fiber fabric, but improves the mechanical strength of the prepreg. In addition, the reinforcing material may be pretreated with a silane coupling agent or a siloxane coupling agent, if necessary, and examples thereof include a glass fiber cloth pretreated with a silane coupling agent.
前述のプリプレグは、高温加熱または高温・高圧での加熱で硬化して硬化フィルムまたは固体絶縁層を形成するが、樹脂組成物が溶媒を含むと、当該溶媒は高温加熱の中で発揮して除去される。 The above-mentioned prepreg is cured by high-temperature heating or high-temperature / high-pressure heating to form a cured film or a solid insulating layer. When the resin composition contains a solvent, the solvent is exhibited and removed during high-temperature heating. Is done.
銅張積層板
本発明は、本発明に係るプリプレグを含む銅張積層板を提供する。
Copper-clad laminate The present invention provides a copper-clad laminate including the prepreg according to the present invention.
本発明のまた一つの目的は、低誘導率特性、耐熱性、難燃性などの特性を有し、且つ特に高速度で高周波数の信号を伝達する回路板に適する銅張積層板(copper clad laminate)を開示することにある。これによって、本発明は、2枚または2枚以上の銅箔と少なくとも一つの絶縁層とを含む銅張積層板を提供する。ここで、銅箔は、さらに銅とアルミニウム、ニッケル、白金、銀、金などの少なくとも1種との合金を含んでもよい。絶縁層は、前述のプリプレグを高温高圧で硬化させてなるもので、例えば前述プリプレグを2枚の銅箔の間に積層して高温と高圧で圧着してなるものが挙げられる。 Another object of the present invention is a copper clad laminate having characteristics such as low inductivity, heat resistance and flame retardancy, and suitable for circuit boards that transmit high-frequency signals at high speeds. laminate) is disclosed. Accordingly, the present invention provides a copper clad laminate including two or more copper foils and at least one insulating layer. Here, the copper foil may further contain an alloy of copper and at least one of aluminum, nickel, platinum, silver, gold and the like. The insulating layer is formed by curing the above-described prepreg at high temperature and high pressure. For example, the insulating layer may be formed by laminating the above-described prepreg between two copper foils and press-bonding at high temperature and high pressure.
本発明に係る銅張積層板は、低誘電率と低誘電損失、優れた耐熱性および難燃性から選ばれた少なくとも一つの利点を有する。当該銅張積層板は、さらに回路制作などの加工をした後、回路板を形成することができ、且つ当該回路板を電子部材と接合して高温、高湿度などの過酷な環境で操作してもその品質に影響しない。 The copper clad laminate according to the present invention has at least one advantage selected from low dielectric constant and low dielectric loss, excellent heat resistance and flame retardancy. The copper-clad laminate can be processed after circuit processing, etc. to form a circuit board, and the circuit board is joined to an electronic member and operated in a harsh environment such as high temperature and high humidity. Does not affect its quality.
プリント回路板
本発明は、本発明に係る銅張積層板を含むプリント回路板を提供する。
Printed Circuit Board The present invention provides a printed circuit board including the copper clad laminate according to the present invention.
本発明のまた一つの目的は、低誘導率特性、耐熱性や難燃性などの特性を有し、且つ特に高速度で高周波数の信号の伝達に適するプリント回路板(printed circuit board)を開示することにある。ここで、当該回路板は、少なくとも1枚の前述銅張積層板を含み、且つ当該回路板は、既知の制作方法で作られる。 Another object of the present invention is to disclose a printed circuit board that has characteristics such as low inductivity, heat resistance and flame retardancy, and is particularly suitable for high-speed and high-frequency signal transmission. There is to do. Here, the circuit board includes at least one copper-clad laminate, and the circuit board is manufactured by a known production method.
具体的な説明がない場合、本発明の各種の原料はすべて市販品として得られ、または本分野の通常の方法で製造される。特に定義や説明がない限り、本文に用いられるすべての専門用語と科学用語は、本分野の技術者に知られている意味と同様である。また、記載の内容と類似或いは同等の方法及び材料は、いずれも本発明の方法に用いることができる。 If there is no specific explanation, the various raw materials of the present invention are all obtained as commercial products, or are produced by ordinary methods in this field. Unless otherwise defined or explained, all technical and scientific terms used herein have the same meaning as is known to those skilled in the art. In addition, any methods and materials similar or equivalent to those described can be used for the method of the present invention.
本発明の他の主旨は、本文の公開される内容によって、この分野の技術者にとっては明らかになっている。 The other gist of the present invention is made clear to engineers in this field by the published contents of the text.
以下、具体的な実施例によって、さらに本発明を説明する。これらの実施例は本発明を説明するために用いられるものだけで、本発明の範囲の制限にはならないと理解されるものである。以下の実施例において、具体的な条件が記載されていない実験方法は、通常、国家標準に従って測定する。相応の国家標準がない場合、汎用の国際標準、通常の条件、またはメーカーが推薦する条件で行われる。特に説明しない限り、すべての部は重量部で、すべての百分比は重量百分比で、前述の重合体の分子量は数平均分子量である。 Hereinafter, the present invention will be further described with reference to specific examples. It should be understood that these examples are only used to illustrate the invention and do not limit the scope of the invention. In the following examples, experimental methods for which specific conditions are not described are usually measured according to national standards. If there is no corresponding national standard, it will be done under general international standards, normal conditions or conditions recommended by the manufacturer. Unless otherwise stated, all parts are parts by weight, all percentages are percentages by weight, and the molecular weight of the aforementioned polymers is number average molecular weight.
実施例1〜14および比較例1〜11,14
SEC-365：イソシアネート改質エポキシ樹脂、Shin-Aから購入。
Examples 1 to 14 and Comparative Examples 1 to 11, 14
SEC-365: Isocyanate-modified epoxy resin, purchased from Shin-A.
EXA-9900：ナフタレン環含有エポキシ樹脂、大日本インク化学(D.I.C.)から購入。
HP-7200H：ジシクロペンタジエン・フェノールエポキシ樹脂、大日本インク化学(D.I.C.)から購入。
EXA-9900: Naphthalene ring-containing epoxy resin, purchased from Dainippon Ink and Chemicals (DIC).
HP-7200H: Dicyclopentadiene / phenol epoxy resin, purchased from Dainippon Ink and Chemicals (DIC).
NC-3000：ビフェニルエポキシ樹脂、日本化薬(Nippon Kayaku)から購入。
LZ 8280：ビスフェノールF型ベンゾオキサジン樹脂、Huntsmanから購入。
NC-3000: Biphenyl epoxy resin, purchased from Nippon Kayaku.
LZ 8280: Bisphenol F-type benzoxazine resin, purchased from Huntsman.
MT 35700：ビスフェノールA型ベンゾオキサジン樹脂、Huntsmanから購入。
MT 35800：フェノールフタレイン型ベンゾオキサジン樹脂、Huntsmanから購入。
MT 35700: bisphenol A benzoxazine resin, purchased from Huntsman.
MT 35800: Phenophthalein-type benzoxazine resin, purchased from Huntsman.
PF-3500：ジアミノジフェニルエーテル型ベンゾオキサジン樹脂、長春樹脂から購入。
PD-9110：ジシクロペンタジエン・フェノール樹脂、長春プラスチック（Chang Chun Plastics）購入。
PF-3500: Purchased from diaminodiphenyl ether type benzoxazine resin, Changchun resin.
PD-9110: Dicyclopentadiene / phenol resin, Chang Chun Plastics purchased.
Dicy：ジシアンジアミド、勤裕から購入。
DDS：4,4-ジアミノジフェニルスルホン、Atul LTDから購入。
Dicy: Dicyandiamide, purchased from Kunyu.
DDS: 4,4-diaminodiphenyl sulfone, purchased from Atul LTD.
SPB-100：ホスファゼン化合物、大塚化学から購入。
XZ92741：リン含有難燃剤、ダウ・ケミカルから購入。
SPB-100: Phosphazene compound, purchased from Otsuka Chemical.
XZ92741: Phosphorus-containing flame retardant, purchased from Dow Chemical.
PX-200：縮合リン酸エステル、大八化学から購入。
8010：エタン-1,2-ビス（ペンタブロモベンゼン）、Albemarleから購入。
PX-200: Condensed phosphate ester, purchased from Daihachi Chemical.
8010: Ethane-1,2-bis (pentabromobenzene), purchased from Albemarle.
BT-93：エチル-ビス（テトラブロモフタルイミド）、Albemarleから購入。
Fused silica：溶融シリカ、Silicon から購入。
BT-93: Ethyl-bis (tetrabromophthalimide), purchased from Albemarle.
Fused silica: Fused silica, purchased from Silicon.
2PZ：2-フェニルイミダゾール、四国化成から購入。
6020：アミノシラン、ダウコーニングから購入。
2PZ: 2-phenylimidazole, purchased from Shikoku Kasei.
6020: Purchased from Aminosilane, Dow Corning.
前述実施例1〜14および比較例1〜11,14の配合は、以下の表１及び表２に示す。実施例のサンプルは、E1〜E14に、比較例のサンプルは、C1〜11,C14に示す。 The formulations of Examples 1 to 14 and Comparative Examples 1 to 11 and 14 are shown in Tables 1 and 2 below. The sample of an Example is shown to E1-E14, and the sample of a comparative example is shown to C1-11, C14.
前述実施例1〜14及び比較例1〜11,14の樹脂組成物を、バッチで撹拌槽で均一に混合した後、含浸槽に置き、さらにガラス繊維布を前述含浸槽に通らせ、樹脂組成物をガラス繊維布に付着させ、さらに加熱で半硬化状態にしてプリプレグが得られた。 The resin compositions of Examples 1 to 14 and Comparative Examples 1 to 11 and 14 were mixed uniformly in a stirring tank in a batch, and then placed in an impregnation tank. Further, the glass fiber cloth was passed through the impregnation tank, and the resin composition The product was adhered to a glass fiber cloth and further heated to a semi-cured state to obtain a prepreg.
前述バッチで得られたプリプレグを、同じバッチのプリプレグ4枚と18μmの銅箔2枚を取り、銅箔、4枚のプリプレグ、銅箔の順に積層し、さらに真空条件で200℃で2時間圧着して銅張積層板を形成し、4枚のプリプレグが硬化して2枚の銅箔の間の絶縁層となった。 The prepreg obtained in the above batch is taken with 4 pieces of prepreg of the same batch and 2 pieces of 18 μm copper foil, laminated in the order of copper foil, 4 pieces of prepreg and copper foil, and further crimped at 200 ° C for 2 hours under vacuum conditions Thus, a copper clad laminate was formed, and the four prepregs were cured to form an insulating layer between the two copper foils.
前述銅箔含有基板及び銅箔をそれぞれエッチングした銅を含有しない基板を物性量の測定に供し、物性量の測定項目は、ガラス転移温度(Tg、DSC示差走査熱量計、differentialscanning calorimetry)、耐熱性T-288 (銅含有基板テスト、288℃で加熱されて剥離しない時間、熱機械分析装置(Thermomechanical analysis、TMA)によって銅含有基板の288℃における耐熱性を測定し、加熱されて剥離しない時間で耐熱性を評価し、長いほど優れる)、PCT (2atm/3時間) (銅を含有しない基板の圧力鍋蒸気加熱テスト、121℃で高圧で加熱して(pressure cooking at 121℃)3時間吸湿した後はんだ浸漬テストを行い、288℃のはんだ炉内ではんだ浸漬テストを行い、20秒で剥離の有無を観察する)、銅箔と基板のピール強度(peeling strength(剥離強度、テンシロン万能試験機で測定)、P/S、half ounce copper foil(0.5オンス銅箔)、銅箔と基板のピール強度が高いほど優れる)、銅含有基板のはんだ浸漬テスト(solder dip、S/D、288℃、10秒、耐熱回数を測定)、誘電率(dielectric constant、Dk、Dkが低いほど優れるが、AETマイクロ波誘電分析装置で銅を含有しない基板のDk値を測定)、誘電正接(dissipation factor、Df、Dfが低いほど優れるが、AETマイクロ波誘電分析装置で銅を含有しない基板のDf値を測定)、難燃テスト(flaming test、UL94、ここで、グレードの優劣はV-0 > V-1 > V-2の順である)を含む。それぞれ実施例1〜14の樹脂組成物の測定結果を表１に、比較例1〜11,14の樹脂組成物の測定結果を表２に示す。 The copper foil-containing substrate and the copper-free substrate etched with copper are used for the measurement of physical properties, and the measurement items for the physical properties are glass transition temperature (Tg, DSC differential scanning calorimetry, differential scanning calorimetry), heat resistance T-288 (copper-containing board test, time when heated at 288 ° C and not peeled off), heat resistance of copper-containing board at 288 ° C measured by thermomechanical analyzer (TMA), and time when heated and not peeled off PCT (2 atm / 3 hours) (pressure cooker steam heating test of copper-free board, heated at 121 ° C under high pressure (pressure cooking at 121 ° C) and absorbed moisture for 3 hours) Perform post-solder immersion test, perform solder immersion test in a solder furnace at 288 ° C, observe the presence or absence of peeling in 20 seconds), peel strength of copper foil and board (peeling strength, peeling strength, Tensilon universal testing machine) Measurement), P / S, half ounce copper foil (0 .5 ounce copper foil), higher the peel strength between the copper foil and the substrate, the better), the solder immersion test of the copper-containing substrate (solder dip, S / D, 288 ° C, 10 seconds, measured heat resistance), dielectric constant ( The lower the dielectric constant, Dk, and Dk, the better, but the lower the dissipation factor, Df, and Df, the better the AET microwave dielectric. Df value of the substrate not containing copper is measured with an analyzer, and flame retardant test (UL94, where grades are in the order of V-0> V-1> V-2). The measurement results of the resin compositions of Examples 1 to 14 are shown in Table 1, and the measurement results of the resin compositions of Comparative Examples 1 to 11 and 14 are shown in Table 2, respectively.
結論：
実施例1〜14では、ベンゾオキサジン、ジシクロペンタジエン・フェノール樹脂およびアミン系硬化剤を併用し、基板を同時に耐熱(T288、Tg、S/D)、耐湿熱(PCT)、銅箔のピール強度(P/S)、低誘電率(Dk & Df)および難燃性の要求に満足させた。
Conclusion:
In Examples 1 to 14, benzoxazine, dicyclopentadiene / phenol resin and amine curing agent were used in combination, and the substrate was simultaneously heat resistant (T288, Tg, S / D), moisture heat resistant (PCT), and peel strength of the copper foil. (P / S), low dielectric constant (Dk & Df) and flame retardant requirements were satisfied.
実施例E6とE7を比較すると、E7では、より多いdicyを使用し、銅箔のピール強度(P/S)を向上させた。 When Examples E6 and E7 were compared, E7 used more dicy and improved the peel strength (P / S) of the copper foil.
比較例C1〜C2では、ジアリルビスフェノールA樹脂（DABPA）を使用したことで、基板の耐熱性が顕著に低下した（T288）。しかし、実施例E14では、ジアリルビスフェノールA樹脂（DABPA）を含有しなかったため、基板の耐熱性（T288）が比較例C14よりも顕著に優れた。 In Comparative Examples C1 to C2, the heat resistance of the substrate was significantly reduced by using diallyl bisphenol A resin (DABPA) (T288). However, since Example E14 did not contain diallyl bisphenol A resin (DABPA), the heat resistance (T288) of the substrate was significantly superior to Comparative Example C14.
比較例C3〜C11では、配合におけるいずれかの成分が本発明で限定された相応の含有量範囲から離れたため、C3〜C11は同時に耐熱(T288、Tg、S/D)、耐湿熱(PCT)、銅箔のピール強度(P/S)、低誘電率(Dk & Df)および難燃性の要求に満足することができなかった。 In Comparative Examples C3 to C11, since any component in the formulation was separated from the corresponding content range defined in the present invention, C3 to C11 were simultaneously heat resistant (T288, Tg, S / D), heat resistant to moisture (PCT) However, it was not possible to satisfy the requirements of peel strength (P / S), low dielectric constant (Dk & Df) and flame retardancy of copper foil.
以上の説明は本発明の好ましい実施例だけで、本発明の実質の技術内容の範囲を限定するものではなく、本発明の実質の技術内容は広義的に出願の請求の範囲に定義され、他の人が完成した技術実体或いは方法は、出願の請求の範囲に定義されたものとまったく同じものであれば、或いは効果が同等の変更であれば、いずれもその請求の範囲に含まれるとみなされる。 The above description is only a preferred embodiment of the present invention, and does not limit the scope of the substantial technical contents of the present invention. The substantial technical contents of the present invention are broadly defined in the claims of the application, and Any technical entity or method completed by a person is considered to be included in the scope of the claim if it is exactly the same as defined in the scope of the claims of the application, or if the effect is equivalent. It is.
各文献がそれぞれ単独に引用されるように、本発明に係るすべての文献は本出願で参考として引用する。また、本発明の上記の内容を読み終わった後、この分野の技術者が本発明を各種の変動や修正をすることができるが、それらの等価の様態のものは本発明の請求の範囲に含まれることが理解されるべきである。 All documents according to the present invention are cited in this application as a reference, so that each document is individually cited. In addition, after reading the above description of the present invention, engineers in this field can make various changes and modifications to the present invention, but those equivalent aspects are within the scope of the present invention. It should be understood that it is included.
Claims (11)
（Ｂ）10〜80重量部のベンゾオキサジン樹脂と、
（Ｃ）10〜50重量部のジシクロペンタジエン・フェノール樹脂と、
（Ｄ）0.5〜5重量部のアミン系硬化剤と
を含み、
ジアリルビスフェノールA（DABPA）を含まない、
樹脂組成物。 (A) 100 parts by weight of epoxy resin;
(B) 10 to 80 parts by weight of a benzoxazine resin;
(C) 10 to 50 parts by weight of dicyclopentadiene / phenol resin;
(D) 0.5 to 5 parts by weight of an amine curing agent,
Does not contain diallyl bisphenol A (DABPA),
Resin composition.
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