WO2015046921A1 - Thermosetting resin composition for semiconductor package, prepreg using same and metal foil laminate - Google Patents
Thermosetting resin composition for semiconductor package, prepreg using same and metal foil laminate Download PDFInfo
- Publication number
- WO2015046921A1 WO2015046921A1 PCT/KR2014/008974 KR2014008974W WO2015046921A1 WO 2015046921 A1 WO2015046921 A1 WO 2015046921A1 KR 2014008974 W KR2014008974 W KR 2014008974W WO 2015046921 A1 WO2015046921 A1 WO 2015046921A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- resin composition
- type
- weight
- epoxy resin
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 66
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 239000004065 semiconductor Substances 0.000 title claims abstract description 17
- 239000011888 foil Substances 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 108
- 239000011347 resin Substances 0.000 claims abstract description 108
- 239000003822 epoxy resin Substances 0.000 claims abstract description 51
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 51
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 9
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 30
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 29
- 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 21
- 239000011521 glass Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000004643 cyanate ester Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 15
- 229930185605 Bisphenol Natural products 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- -1 curing accelerators Substances 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920003986 novolac Polymers 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 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 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 claims description 3
- KNWKZOKQUOIVBL-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)-3-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC(N2C(C=CC2=O)=O)=CC=C1N1C(=O)C=CC1=O KNWKZOKQUOIVBL-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims 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 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims 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 claims description 3
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 3
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 1
- 229940071182 stannate Drugs 0.000 claims 1
- 125000005402 stannate group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 13
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 239000011889 copper foil Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002966 varnish Substances 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- 238000005698 Diels-Alder reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 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 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 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 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 2
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- SHEYGOVZCIDOEH-UHFFFAOYSA-N bis(2-prop-1-enylphenyl) sulfate Chemical class CC=CC1=CC=CC=C1OS(=O)(=O)OC1=CC=CC=C1C=CC SHEYGOVZCIDOEH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PJGPQOXWPYYELJ-UHFFFAOYSA-N 2,4-dichloro-5-ethyl-1h-imidazole Chemical compound CCC=1NC(Cl)=NC=1Cl PJGPQOXWPYYELJ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 1
- LCXFHGRFFYYUSF-UHFFFAOYSA-N 2-ethyl-5-methyl-1H-imidazole Chemical compound C(C)C=1NC=C(N1)C.C(C)C=1NC=C(N1)C LCXFHGRFFYYUSF-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 206010042674 Swelling Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- HVPIEVBJUZUBKB-UHFFFAOYSA-N phenyl-[2-(2-prop-1-enylphenoxy)phenyl]methanone Chemical class CC=CC1=CC=CC=C1OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HVPIEVBJUZUBKB-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester 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
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
- C08G73/0655—Preparatory processes from polycyanurates
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/10—Epoxy resins modified by unsaturated compounds
Definitions
- the present invention relates to a curable resin composition capable of improving the desmear characteristics of a printed circuit board (PCB) for a semiconductor package and a paper, and a prepreg and a metal foil laminate using the same.
- PCB printed circuit board
- Copper clad laminate used in the conventional printed circuit board is impregnated with the varnish of the glass fiber (glass fabric) and then semi-cured to become a prepreg, it is heated and pressurized together with the copper foil The prepreg is used again for the purpose of constructing a circuit pattern on the copper foil laminate and building up thereon.
- thermosetting resin composition exhibiting low thermal expansion properties and facilitating a desmear process to improve workability of a printed circuit board manufacturing process.
- the present invention is a weak desmear characteristic in the manufacturing process of the printed circuit board It is to provide a thermosetting resin composition for a semiconductor package having excellent drill and workability by improving the problem.
- Another object of the present invention is to provide a prepreg having a high heat resistance and reliability using the thermosetting resin composition and a metal red plate including the same.
- the present invention provides a binder comprising an epoxy resin and a bismaleimide-based resin, and a resin composition comprising benzoxazine water; And a slurry-type layer jinje; includes the benzoxazine provides a thermosetting resin composition for a semiconductor package comprising more than 10% by weight, based on the total weight of the whole, the resin composition.
- the filler of the slurry type may be included in 160 to 350 parts by weight based on 100 parts by weight of the resin composition.
- the benzoxazine is preferably included in 2 to 10% by weight based on the total weight of the total resin composition.
- the binder may include 80 wt% of the inner molecular weight of the epoxy resin and 20 to 80 wt% of the bismaleimide-based resin.
- the binder may further include a cyanate ester resin.
- the binder is 20 to 60% by weight epoxy resin, cyanate ester It may include 30 to 70% by weight of the resin and 20 to 70% by weight of the basmaleimide-based resin.
- the slurry type layering agent is silica, aluminum trihydrate, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, caroline, It is preferable to use a slurry containing at least one inorganic filler selected from the group consisting of talc, calcined chlorine, calcined talc, mica, short glass fiber, glass fine powder and hollow glass.
- the epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dovolac type epoxy resin, phenol novolac epoxy resin, cresol novolac type epoxy resin, tetraphenyl ethane type epoxy resin, naphthalene type It may be at least one selected from the group consisting of an epoxy resin, a biphenyl type epoxy resin and a dicyclopentadiene type epoxy resin.
- the bismaleimide-based resin BT (Bismaleimide-Triazine) resin, 4, 4'- bismaleimido- diphenylmethane, 1, 4-bismaleimido-2-methylbenzene and mixtures thereof; Modified mismaleimide resins containing Diels-Alder comonomers; And 4,4'-bismaleimido—diphenylmethane and allylphenyl compound; Or partially upgraded bismaleimide based on aromatic amines.
- BT Bismaleimide-Triazine
- the Diels-Alder comonomer is styrene And styrene derivatives, bis (propenylphenoxy) compounds, 4 4'-bis (propenylphenoxy) sulfones, 4 4'-bis (propenylphenoxy) benzophenones and 4 4'-1- (1-methyl) Ethylidene) bis (2- (2-propenyl) phenol).
- the cyanate ester resin is at least one selected from the group consisting of bisphenol A type, bisphenol F type, bisphenol E type, bisphenol H type, bisphenol N type, phenol novolac type, dicyclopentadiene bisphenol type cyanate ester resin. Can be.
- the thermosetting resin composition may further include at least one additive selected from the group consisting of a solvent, a curing accelerator, a dispersant, and a silane coupling agent.
- the present invention also provides a prepreg prepared by impregnating the thermosetting resin composition on a fiber substrate.
- the present invention also the prepreg; And a metal foil comprising integrally with the prepreg by heating and pressurizing.
- thermosetting resin composition of the present invention exhibits high physical properties using not only epoxy resins but also cyanate resins, and provides the effect of curing bismaleimide-based resins by using benzoxazine instead of conventional phenol curing agents. . Therefore, the present invention by suppressing the smear generated by high heat during the conventional drill operation Provides excellent desmear characteristics.
- thermosetting resin composition of the present invention unlike the conventional, using a slurry-type layering agent, while exhibiting the same physical properties as those of the conventional ' high heat resistance and reliability, and can improve the chemical resistance. Accordingly, the present invention can provide a prepreg and a metal laminate having excellent chemical resistance.
- thermosetting resin composition according to a specific embodiment of the present invention will be described in detail.
- a binder comprising an epoxy resin and a bismaleimide-based resin, and a resin composition comprising a benzoxazine resin; And a slurry-type layering agent; wherein the benzoxazine is provided in the thermosetting resin composition for a semiconductor package containing 10% by weight or less based on the total weight of the total resin composition.
- the slurry-based layering agent may be included in an amount of 160 to 350 parts by weight based on 100 parts by weight of the resin composition.
- the benzoxazine is preferably included in 2 to 10% by weight based on the total weight of the total resin composition.
- thermosetting resin composition of the present invention instead of the conventional phenol curing agent Benzoxazine may be used to induce the curing of bismaleimide-based resins, and the slurry type may be used as a filler to increase interfacial adhesion between the resin and the filler, thereby improving chemical resistance.
- the composition of the present invention can implement higher physical properties by using a cyanate ester resin.
- the present invention by using less than 10% by weight of the benzoxazine used as a curing agent in the thermosetting resin composition, it is possible to implement a chemical resistance and high Tg value, it is possible to increase the content of the filler.
- thermosetting resin composition may improve desmear characteristics by improving chemical resistance.
- thermosetting resin composition of the present invention having such properties, a prepreg and a metal plate laminated board using the same can be applied to both the production as well as the double-sided printed circuit board ', the multi-layer printed circuit board.
- thermosetting resin composition of this invention is demonstrated more concretely.
- thermosetting resin composition of this invention contains the binder component containing an epoxy resin and a special resin, contains a layering agent, and may also contain a hardening
- the present invention is characterized by using a benzoxazine of a specific content as a curing agent, using a slurry-type filler based on the content of the benzoxazine.
- the content of the benzoxazine according to the present invention is used at 10% by weight or less based on the total weight of the total resin composition, More preferably in 2 to 10 increments 3 ⁇ 4>.
- the content of the benzoxazine is more than 10% by weight, the physical properties are worse, it may not exhibit excellent chemical resistance and high Tg. That is, when the benzoxazine resin is included in an excessive amount, the curing reaction rate may be too high during the preparation of the prepreg, and thus the process efficiency may be reduced. In addition, if the content of benzoxazine is too low, less than 2% by weight, chemical resistance and Tg cannot be improved because the effect as a desired curing agent cannot be exhibited.
- the benzoxazine resin used in the present invention is capable of controlling the reaction rate, thereby improving the flowability of the resin, thereby securing the flowability of the prepreg.
- benz oxazine enables the curing of the bismaleimide resin described above.
- the benzoxazine resin may be used as a curing agent for the bismaleimide-based resin.
- the present invention uses the benzoxazine resin as a curing agent of the bismaleimide-based resin, thereby providing an effect of improving resin flowability and allowing full curing even under low temperature conditions. Therefore, when prepreg is manufactured using the said resin composition, it is high under low temperature pressurization. It is possible to provide a prepreg indicating the glass transition temperature.
- the benzoxazine resin as a hardening
- the effect which slows the rate of hardening reaction of an epoxy resin relatively can be acquired.
- a time during which the resin composition is sufficiently impregnated into the fibrous substrate during the production of the prepreg can be ensured, and the appearance defect can be minimized.
- the benzoxazine resin may have a weight average molecular weight of 200 to 400 in terms of securing a curing effect and mechanical properties.
- the present invention by using a slurry-type layering agent, unlike the conventional, it is possible to improve the chemical resistance of the prepreg by increasing the interfacial adhesion between the resin and the filler compared to the case of using a conventional powder-type layering agent. That is, the slurry type filler of the present invention is advantageous in improving the resin dispersibility compared to the powder type layering agent.
- the "slurry type filler" described in the specification of the present invention may mean a suspension dispersed in a state in which the inorganic filler is dissolved in a solvent.
- the present invention uses the correlation that the lower the content of the benzoxazine, the higher the content of the layering agent.
- the benzoxazine includes 2 to 10% by weight or less based on the total weight of the entire resin composition.
- the resin flows during pressing and The separation of the filler (separat i on) may occur a lot, and if it exceeds 350 parts by weight, the filler is not filled in the glass fiber (Gl ass Fabr ic), so that the dry shape of the glass fiber (Glass Fabr ic) surface after pressing There is a problem.
- the slurry-type inorganic filler may be prepared by a method well known in the art, and the method is not particularly limited, and preferably, the inorganic filler may be prepared by dispersing the inorganic filler in a solvent.
- the slurry-type filler is silica, aluminum tr hydrate, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc st annate, alumina, clay And a slurry containing at least one inorganic layering agent selected from the group consisting of kaolin, talc, calcined kaline, calcined talc, mica, glass short fiber glass fine powder and hollow glass.
- average particle diameter (D50) of the jinje layer is not particularly limited, for example, is an average particle diameter (D50) of the inorganic layer damping material is preferably 0.2 to 5 micrometers in view of dispersion.
- these fillers may be surface treated with epoxy silanes.
- the layering agent is surface-treated by a wet / dry method using 0.3 to 1 parts by weight of epoxy silane based on 100 parts by weight of the inorganic layering agent.
- the epoxy silane may have a weight average molecular weight of 200 to 400.
- the binder contains an epox resin and a bismaleimide-based resin. In this case, the binder may include 20 to 80% by weight of epoxy resin and 20 to 80% by weight of bismaleimide-based resin.
- the binder may further include a cyanate ester resin.
- the binder may include 20 to 60% by weight of epoxy resin, 30 to 70% by weight of cyanate ester resin, and 20 to 70% by weight of bismaleimide-based resin.
- thermosetting resin composition for prepregs for the said epoxy resin can be used, The kind is not limited.
- the epoxy resin is bisphenol A epoxy resin, bisphenol
- F type epoxy resin bisphenol S type epoxy resin, novolac type epoxy resin, phenol novolac epoxy resin, cresol novolac type epoxy resin, tetraphenyl ethane type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and dicyclo
- pentadiene type epoxy resins One or more types selected from the group consisting of pentadiene type epoxy resins can be used.
- the special resin is characterized by using a cyanate ester resin and a bismaleimide resin.
- the present invention can improve the resin physical properties by using the cyanate ester resin in the epoxy resin.
- the cyanate ester resin exhibits a high glass transition temperature due to an increase in the crosslinking density, thereby providing excellent thermal and Electrical characteristics.
- the cyanate ester resin is at least one selected from the group consisting of bisphenol A type, bisphenol F type, bisphenol E type, bisphenol H type, bisphenol N type, phenol novolak type and dicyclopentadiene bisphenol type cyanate ester resin. Can be. In addition, in consideration of flowability of the resin, it is preferable to use a cyanate ester resin having a weight average molecular weight of 200 to 400.
- the bismaleimide-based resin is BT (Bismaleimide-Triazine) resin, 4,4'-bismaleimido-diphenylmethane, 1,4-bismaleimido-2-methylbenzene, and mixtures thereof; Modified mismaleimide resins containing Diels-Alder comonomers; And 4, 4'-bismaleimido-diphenylmethane and allylphenyl compound; Or partially upgraded bismaleimide based on aromatic amines.
- the bismaleimide-based resin can be used that has an increased average molecular weight of 2,000 to 5,000.
- the Diels-Alder comonomers include styrene and styrene derivatives, bis (propenylphenoxy) compounds, 4,4'-bis (propenylphenoxy) sulfones, 4,4'-bis (pros) Phenylphenoxy) benzophenone and 4,4'-1- (1-methylethylidene) bis (2- (2-propenyl) phenol).
- the bismaleimide-based resin is bismaleimide triazine (BT), or 4,4'-bismaleimido- It may be a combination of diphenylmethane and allylphenyl compound.
- the BT resin is a thermosetting resin that can be used as an insulating layer of an electromagnetic plate that requires high performance and high integration, and may have a weight average molecular weight of 2,000 to 5,000.
- the binder component is a mixture of an epoxy resin and a bismaleimide resin, or a mixture of an epoxy resin, a cyanate ester resin, and a bismaleimide resin, as described above, in consideration of physical properties required as a binder. It can be used by adjusting appropriately so that the total resin mixture may be 100% by weight.
- the thermosetting resin composition according to the embodiment of the present invention may further include at least one additive selected from the group consisting of a solvent, a curing accelerator, a dispersant, and a silane coupling agent. .
- the present invention can be used as a solution by adding a solvent to the resin composition as needed.
- the solvent is not particularly limited as long as it exhibits good solubility in the resin component, and alcohol, ether, ketone, amide, aromatic hydrocarbon, ester, nitrile, and the like may be used. Or you may use the combined solvent which used 2 or more types together.
- the content of the solvent is not particularly limited as long as the resin composition may be impregnated into the glass fiber during prepreg manufacture.
- the curing accelerator may be used for the purpose of promoting the curing of the binder described above. have.
- the kind and compounding quantity of a hardening accelerator are not specifically limited, For example, an imidazole compound, a tertiary amine, a quaternary ammonium salt, etc. are used, 2 or more types can also be used together.
- the present invention uses an imidazole compound as a curing accelerator.
- the content of the curing agent may be used in an amount of about 0.1 to 1 parts by weight based on 100 parts by weight of the binder.
- imidazole-based curing accelerator 1-methyl imidazole, 2-methyl imidazole, 2-ethyl 4-methyl imidazole (2-ethyl 4-methyl imidazole), 2-phenyl imidazole, 2-cyclonuxyl 4-methyl imidazole, 2-butyl imidazole, 4-butyl 5-ethyl imidazole 5-ethyl-imidazole), 2-methyl 5-ethyl imidazole, 2-octyl 4-nuxyl imidazole, 2,5-dichloro-4 Imidazoles such as -ethyl imidazole, 2,5-dichloro-4-ethyl imidazole, 2-butoxy 4-allyl imidazole, and the imidazole derivatives, and the like. 2-methyl imidazole or 2-phenyl imidazole is preferred because of its good reaction stability and low cost.
- thermosetting resin composition of the present invention may further include at least one additive selected from the group consisting of a dispersing agent and a silane coupling agent which are usually added as needed.
- resin composition of the present invention other thermosetting resins, thermoplastic resins and It may further include various high polymer compounds, other flame resistant compounds or additives such as oligomers and elastomers thereof. These are not particularly limited as long as they are selected from those commonly used.
- Thermosetting resin composition according to an embodiment of the present invention including these components exhibits a viscosity of 20 cps to 50 cps at a temperature of 20 t to 35 ° C, providing excellent flowability compared to the existing. '
- thermosetting resin composition prepared by impregnating the thermosetting resin composition on a fiber substrate.
- the prepreg means that the thermosetting resin composition is impregnated into the fiber substrate in a semi-cured state.
- polyamide-based resin fibers such as glass fiber base material, polyamide resin fiber, aromatic polyamide resin fiber, polyester resin fiber, aromatic polyester resin fiber ⁇ all aromatic polyester Synthetic fiber base composed of woven or nonwoven fabric mainly composed of polyester resin fibers such as resin fibers, polyimide resin fibers, fluorine resin fibers, kraft paper, cotton linter paper, stray paper of linter and kraft pulp, etc.
- a paper substrate may be used, and preferably a glass fiber substrate is used.
- the glass fiber substrate can improve the strength of the prepreg, lower the water absorption rate, and reduce the coefficient of thermal expansion.
- the glass substrates used may be selected from glass substrates used for various printed circuit board materials.
- glass fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, and NE glass.
- the glass-based material may be selected according to the intended use or performance. Glass-based forms are typically woven, nonwoven, roving, chopped strand mats or surfacing mats. Although the thickness of the glass substrate is not particularly limited, about 0.01 to 0.3 mm or the like can be used. Of these materials, glass fiber materials are more preferred in terms of strength and water absorption properties.
- the method for preparing the prepreg in the present invention is not particularly limited, and may be prepared by a method well known in the art.
- the method of manufacturing the prepreg may be used by an impregnation method, a coating method using various coaters, a spray injection method, or the like.
- the prepreg after preparing the varnish, may be prepared by impregnating the fiber substrate with the varnish.
- the conditions for producing the prepreg are not particularly limited, but are preferably used in a varnish state in which a solvent is added to the thermosetting resin composition.
- the resin varnish solvent is compatible with the resin component and is good. It will not specifically limit, if it has solubility. Examples include acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone and cyclonuxanone, aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide and dimethylacetamide, methyl cellosolve, Aliphatic alcohols such as butyl cellosolve.
- the solvent used is volatilized by 80% by weight or more. Accordingly, also the manufacturing method and drying conditions are limited, the temperature during drying is about 80 ° C to 180 ° C, the time is not particularly limited to the balance with the varnish gelling time.
- the impregnation amount of the varnish is preferably such that the resin solid content of the varnish is about 30 to 80% by weight relative to the total amount of the resin solid content of the varnish and the base material.
- the prepreg On the other hand, according to another embodiment of the present invention, the prepreg; And a metal foil comprising integrally with the prepreg by heating and pressurizing.
- the metal foil may be copper foil.
- the copper foil included in the copper foil laminate of the present invention may be made of copper or a copper alloy.
- the copper foil since the copper foil may be conventional in the art to which the present invention belongs, its physical properties are not particularly limited.
- the copper foil may have a roughness Rz of Matt surface of 0.01 to 2.5 m , preferably 0.2 to 2.0, more preferably 0.2 to 1.0, and the thickness thereof is 1 or more. , Preferably 2 to 18 Can be applied.
- the maximum temperature of the lamination (press) may be about 200 ° C or more, usually 220 ° C. have.
- the pressure condition at the time of pressurizing the metal red plate is not particularly limited, preferably about 35 to 50 kgf / cuf.
- the metal laminate including the prepreg thus prepared can be used for the manufacture of double-sided or multilayer printed circuit boards after laminating in one or more sheets.
- the present invention can manufacture a double-sided or multi-layer printed circuit board by circuit processing the metal foil laminate, the circuit processing can be applied to a method performed in a general double-sided or multi-layer printed circuit board manufacturing process.
- thermosetting resin composition As described above, according to the present invention, by using the above-mentioned resin thermosetting resin composition, it can be applied to all printed circuit boards of various fields, and can be preferably used for the manufacture of printed circuit boards for semiconductor packages.
- thermosetting resin compositions of Examples and Comparative Examples were mixed in the following compositions and contents to prepare thermosetting resin compositions of Examples and Comparative Examples, respectively.
- thermosetting resin composition and the filler were mixed and then mixed in a high speed stirrer to prepare a resin varnish.
- the resin varnish was impregnated into 45 m thick glass fibers (1078, manufactured by Nittobo, T-glass), followed by hot air drying at a temperature of 140 ° C. to prepare a prepreg.
- each component used in the preparation of the resin varnish is as follows:
- Bismaleimide-based resins BMI-2300, DAIWA Corporation
- BT resin Nazine 600
- Nanokor Co. Novolac type yanate resin (PT-30S, from Lonza); Naphthalene epoxy resins (HP4710, DIC Corporation); Phenolphthalein benzoxazan resin (XU8282, Huns t man); Epoxysilane treated slurry type silica (SC2050FNC from Admatechs); Powder-type filler (SFP-30NHE, Denka); However, the content of the resin component in Tables 1 and 2 is 100% by weight (total 100 weight, and the silica content is based on 100 parts by weight of the resin).
- the two prepregs prepared above were laminated, and copper foil (thickness 12, manufactured by Mitsui) was placed on both sides of the prepreg, and laminated at a pressure of 50 kg / cii at 2201 temperature using a press for 75 minutes. Copper foil by heating and pressurizing during A laminated plate (thickness: 100) was produced. After etching the copper foil laminate thus produced, basic physical properties and chemical resistance tests were performed.
- Epoxy resin Naphthalene epoxy resin (HP4710, DIC Corporation)
- BT resin (Nanozine 600, Nanokor)
- Cyanate ester resin Novolac cyanate resin (PT-30S, Lonza)
- BMT resin Bismaleimide resin (BMI-2300, DAIWA)
- benzoxazine resin phenolphthalein-based benzoxazine resin (XU8282, Hunstman)
- Phenolic Curing Agent Cresol-Novolac Curing Agent (GPX-41, Gi fu Shel lac)
- Inorganic layering agent B powder type filler (SFP-30MHE, Denka)
- thermosetting resin composition obtained by the Example and the comparative example the physical property was evaluated by the following method.
- the glass transition temperature was measured at a temperature rising rate of 10 ° C / min using TMA (Thermo Mechanical Analysis).
- DMA Dynamic Mechanical
Abstract
The present invention relates to a thermosetting resin composition for a semiconductor package, a prepreg using the same, and a metal foil laminate. More specifically, the present invention provides a thermosetting resin composition for a semiconductor package, a prepreg using the same, and a metal foil laminate, the composition exhibiting a high heat resistance and reliability by using cyanate resin and benzoxizine for an epoxy-resin based thermosetting resin composition, thereby improving desmear properties, and in particular using a slurry-type filler, thereby improving chemical resistance properties.
Description
【명세서】 【Specification】
【발명의 명칭】 [Name of invention]
반도체 패키지용 열경화성 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판 Thermosetting resin composition for semiconductor package and prepreg and metal foil laminate using same
【기술분야】 Technical Field
본 발명은 반도체 패키.지용 인쇄 회로 기판 (Printed Circuit Board, PCB)의 디스미어 (desmear)특성을 개선할 수 있는 ί경화성 수지 조성물과 이를 이용한 프리프레그 및 금속박 적층판에 관한 것이다. The present invention relates to a curable resin composition capable of improving the desmear characteristics of a printed circuit board (PCB) for a semiconductor package and a paper, and a prepreg and a metal foil laminate using the same.
【발명의 배경이 되는 기술】 [Technique to become background of invention]
종래의 인쇄회로기판에 사용되는 동박적층판 (copper clad laminate)은 유리 섬유 (Glass Fabric)의 기재를 상기 열경화성 수지의 바니시에 함침한 후 반경화시켜 프리프레그가 되게 되고， 이를 다시 동박과 함께 가열 가압하여 제조한다ᅳ 이러한 동박 적층판에 회로 패턴을 구성하고 이 위에 빌드업 (buildup)을 하는 용도로 프리프레그가 다시 사용되게 된다. Copper clad laminate used in the conventional printed circuit board is impregnated with the varnish of the glass fiber (glass fabric) and then semi-cured to become a prepreg, it is heated and pressurized together with the copper foil The prepreg is used again for the purpose of constructing a circuit pattern on the copper foil laminate and building up thereon.
그런데， 인쇄회로기판 제조 공정 중 전기적 신호를 위해 드릴 작업을 하게 되는데, 이 드릴 작업 중 고열에 의하여 수지들이 녹아 내려 내부 층 (inner layer)과 홀 (hole)을 덮는 찌꺼기인 스미어 (smear)가 발생하게 된다. By the way, during the manufacturing process of the printed circuit board, a drill is performed for electrical signals. During this drill work, resins are melted by high heat, and smear, which is a residue covering the inner layer and the hole, is generated. Done.
이러한 스미어의 경우 수분 흡습 전기 접속의 불량 둥의 문제를 발생시키는 문제가 있다. 따라서 바닥에 녹아 내린 수지를 강알칼리성
수용액이나 플라즈마 등으로 제거하게 되는데， 이러한 공정흘 디스미어 공정 (desmear process)이라고 한다. 하지만, 기존의 수지 조성물은 내화학성이 약한 에폭시 수지 등으로 이루어져 있기 때문에, 디스미어 공정에 취약한 단점이 있다. ' In the case of such a smear, there is a problem of causing a problem of poor moisture absorption and electrical connection. Therefore, the resin melted on the floor is strongly alkaline It is removed by an aqueous solution or plasma, such a process is called a desmear process (desmear process). However, since the existing resin composition is made of an epoxy resin, such as weak chemical resistance, there is a disadvantage in the desmear process. '
또한， 전자기기가 얇아지고 경량화가 되면서 반도체 패키지 역시 박형화， 고밀도화가 이루어지고 있다. 하지만， 반도체 패키지의 박형화 및 고밀도화에 따라 패키지가 휘어지는 현상 (warpage)이 발생하게 된다. 이러한 휨 현상 (warpage)을 최소화하기 위해서는 패키지에 사용되는 동박적층판이 저열팽창화 (Low CTE)를 나타내야 한다. 이를 위해서 열팽창율이 낮은 무기충전재를 다량으로 사용하여 저열팽창화를 만드는 방법이 있다. 하지만 무기 충전재를 많이 사용할수록 드릴 가공성이 나빠져 디스미어 공정이 증요하게 되었다. In addition, as electronic devices become thinner and lighter, semiconductor packages are becoming thinner and denser. However, the warpage of the package may occur due to the thinning and densification of the semiconductor package. To minimize this warpage, the copper clad laminates used in the package should exhibit low thermal expansion (Low CTE). To this end, there is a method of making low thermal expansion by using a large amount of inorganic filler having a low thermal expansion rate. However, the more inorganic fillers are used, the worse the drill processability and the desmear process is required.
따라서， 저열팽창율의 특성을 나타내며 디스미어 공정을 용이하게 하여 인쇄회로기판 제조 공정의 작업성을 향상시킬 수 있는 열경화성 수지 조성물의 개발이 요구된다. Accordingly, there is a need for development of a thermosetting resin composition exhibiting low thermal expansion properties and facilitating a desmear process to improve workability of a printed circuit board manufacturing process.
【발명의 내용】 [Content of invention]
【해결하고자 하는 과제】 Problem to be solved
본 발명은 인쇄회로기판의 제조공정에서 디스미어 특성이 취약한
문제점을 개선하여 드릴， 가공성이 우수한 반도체 패키지용 열경화성 수지 조성물을 제공하는 것이다. The present invention is a weak desmear characteristic in the manufacturing process of the printed circuit board It is to provide a thermosetting resin composition for a semiconductor package having excellent drill and workability by improving the problem.
본 발명의 다른 목적은 상기 열경화성 수지 조성물을 이용하여 고내열성과 신뢰성을 갖는 프리프레그와 이를 포함한 금속 적측판을 제공하기 위한 것이다. Another object of the present invention is to provide a prepreg having a high heat resistance and reliability using the thermosetting resin composition and a metal red plate including the same.
【과제의 해결 수단】 [Measures of problem]
본 발명은 에폭시 수지와 비스말레이미드계 수지를 포함하는 바인더 , 및 벤즈옥사진 수자를 포함하는 수지 조성물; 및 슬러리 타입의 층진제；를 포함하며， 상기 벤즈옥사진은 상기 전체' 수지 조성물의 총 중량을 기준으로 10 중량 % 이하로 포함하는， 반도체 패키지용 열경화성 수지 조성물을 제공한다. The present invention provides a binder comprising an epoxy resin and a bismaleimide-based resin, and a resin composition comprising benzoxazine water; And a slurry-type layer jinje; includes the benzoxazine provides a thermosetting resin composition for a semiconductor package comprising more than 10% by weight, based on the total weight of the whole, the resin composition.
또한， 상기 슬러리 타입의 충진제는 상기 수지 조성물 100 중량부에 대하여 160 내지 350 중량부로 포함될 수 있다. 또한 상기 벤즈옥사진은 상기 전체 수지 조성물의 총 중량을 기준으로 2 내지 10 중량 %로 포함하는 것이 바람직하다. In addition, the filler of the slurry type may be included in 160 to 350 parts by weight based on 100 parts by weight of the resin composition. In addition, the benzoxazine is preferably included in 2 to 10% by weight based on the total weight of the total resin composition.
상기 바인더는 에폭시 수지 20 내자 80 중량 % 및 비스말레이미드계 수지 20 내지 80 중량 %를 포함할 수 있다. The binder may include 80 wt% of the inner molecular weight of the epoxy resin and 20 to 80 wt% of the bismaleimide-based resin.
또한， 상기 바인더는 시아네이트계 에스터 수지를 더 포함할 수 있다. 이러한 경우， 상기 바인더는 에폭시 수지 20 내지 60 중량 %， 시아네이트 에스터
수지 30 내지 70 중량 % 및 바스말레이미드계 수지 20 내지 70 중량 %를 포함할 수 있다. In addition, the binder may further include a cyanate ester resin. In this case, the binder is 20 to 60% by weight epoxy resin, cyanate ester It may include 30 to 70% by weight of the resin and 20 to 70% by weight of the basmaleimide-based resin.
상기 슬러리 타입의 층진제는 실리카， 알루미늄 트리하이드레이트 (aluminium trihydrate), 마그네슘 하이드록사이드， 몰리브데늄 옥사이드， 징크 몰리브데이트， 징크 보레이트， 징크 스탄네이트 (zinc stannate), 알루미나， 클레이， 카을린， 탈크， 소성 카을린， 소성 탈크， 마이카， 유리 단섬유， 글래스 미세 파우더 및 중공 글래스로 이루어지는 군에서 선택된 1 종 이상의 무기 충진제를 포함한 슬러리를 사용하는 것이 바람직하다. The slurry type layering agent is silica, aluminum trihydrate, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, caroline, It is preferable to use a slurry containing at least one inorganic filler selected from the group consisting of talc, calcined chlorine, calcined talc, mica, short glass fiber, glass fine powder and hollow glass.
상기 에폭시 수지는 비스페놀 A 형 에폭시 수지， 비스페놀 F 형 에폭시 수지， 비스페놀 S 형 에폭시 수지, 도볼락형 에폭시 수지， 페놀 노볼락 에폭시 수지， 크레졸 노볼락형 에폭시 수지， 테트라페닐 에탄형 에폭시 수지， 나프탈렌형 에폭시 수지， 바이페닐형 에폭시 수지 및 디시클로펜타디엔형 에폭시 수지로 이투어진 군에서 선택된 1종 이상일 수 있다. The epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dovolac type epoxy resin, phenol novolac epoxy resin, cresol novolac type epoxy resin, tetraphenyl ethane type epoxy resin, naphthalene type It may be at least one selected from the group consisting of an epoxy resin, a biphenyl type epoxy resin and a dicyclopentadiene type epoxy resin.
상기 비스말레이미드계 수지는， BT(Bismaleimide-Triazine) 수지， 4，4'- 비스말레이미도-디페닐메탄， 1， 4-비스말레이미도 -2-메틸벤젠 및 이들의 혼합물; 딜스 -알더 (Diels-Alder) 공단량체를 함유하는 개질된 미스말레이미드 수지 ; 및 4，4'-비스말레이미도—디페닐메탄 및 알릴페닐 화합물; 또는 방향족 아민을 기재로 하는 부분적으로 고급화된 비스말레이미드;로 이루어진 군에서 선택되는 1 종 이상일 수 있다. 그리고, 상기 딜스ᅳ알더 (Diels-Alder) 공단량체는 스티렌
및 스티렌 유도체， 비스 (프로페닐페녹시) 화합물， 4 4 ' - 비스 (프로페닐페녹시)술폰， 4 4 ' -비스 (프로페닐페녹시)벤조페논 및 4 4 ' -1-( 1- 메틸에틸리덴)비스 (2-(2-프로페닐)페놀)로 이루어진 군에서 선택될 수 있다. 상기 시아네이트 에스터 수지는 비스페놀 A 형， 비스페놀 F 형， 비스페놀 E 형， 비스페놀 H 형， 비스페놀 N 형， 페놀 노볼락형， 디시클로펜타디엔비스페놀형의 시아네이트 에스터 수지로 이루어진 군에서 선택된 1종 이상일 수 있다. 또한 상기 열경화성 수지 조성물은 용제， 경화촉진제， 분산제 및 실란커플링제로 이루어지는 군에서 선택된 1 종 이상의 첨가제를 더 포함할 수 있다. The bismaleimide-based resin, BT (Bismaleimide-Triazine) resin, 4, 4'- bismaleimido- diphenylmethane, 1, 4-bismaleimido-2-methylbenzene and mixtures thereof; Modified mismaleimide resins containing Diels-Alder comonomers; And 4,4'-bismaleimido—diphenylmethane and allylphenyl compound; Or partially upgraded bismaleimide based on aromatic amines. And, the Diels-Alder comonomer is styrene And styrene derivatives, bis (propenylphenoxy) compounds, 4 4'-bis (propenylphenoxy) sulfones, 4 4'-bis (propenylphenoxy) benzophenones and 4 4'-1- (1-methyl) Ethylidene) bis (2- (2-propenyl) phenol). The cyanate ester resin is at least one selected from the group consisting of bisphenol A type, bisphenol F type, bisphenol E type, bisphenol H type, bisphenol N type, phenol novolac type, dicyclopentadiene bisphenol type cyanate ester resin. Can be. In addition, the thermosetting resin composition may further include at least one additive selected from the group consisting of a solvent, a curing accelerator, a dispersant, and a silane coupling agent.
또한 본 발명은 상기 열경화성 수지 조성물을 섬유 기재에 함침시켜 제조된 프리프레그를 제공한다. 또한 본 발명은 상기 프리프레그; 및 가열 및 가압에 의해 상기 프리프레그와 일체화된 포함하는 금속박；을 포함하는 금속박 적층판을 제공한다. The present invention also provides a prepreg prepared by impregnating the thermosetting resin composition on a fiber substrate. The present invention also the prepreg; And a metal foil comprising integrally with the prepreg by heating and pressurizing.
【발명의 효과】 본 발명의 열경화성 수지 조성물은 에폭시 수지뿐만 아니라 시아네이트 수지를 사용하여 높은 물성을 나타내며 또한 기존 페놀 경화제 대신 벤즈옥사진을 사용하여 비스말레이미드계 수지의 경화가 가능한 효과를 제공한다. 따라서， 본 발명은 기존 대비 드릴 작업시 고열에 의한 스미어 발생을 억제하여
우수한 디스미어 특성을 제공한다 . 또한， 본 발명의 열경화성 수지 조성물은 기존과 달리 슬러리 타입의 층진제를 사용하여， 기존과 동등 이상의 물성을 나타내면서도 '고내열성과 신뢰성을 나타내고, 내화학성을 향상시킬 수 있다. 따라서， 본 발명은 내화학성이 우수한 프리프레그 및 금속 적층판을 제공할 수 있다. [Effects of the Invention] The thermosetting resin composition of the present invention exhibits high physical properties using not only epoxy resins but also cyanate resins, and provides the effect of curing bismaleimide-based resins by using benzoxazine instead of conventional phenol curing agents. . Therefore, the present invention by suppressing the smear generated by high heat during the conventional drill operation Provides excellent desmear characteristics. In addition, the thermosetting resin composition of the present invention, unlike the conventional, using a slurry-type layering agent, while exhibiting the same physical properties as those of the conventional ' high heat resistance and reliability, and can improve the chemical resistance. Accordingly, the present invention can provide a prepreg and a metal laminate having excellent chemical resistance.
【발명을 실시하기 위한 구체적인 내용】 [Specific contents to carry out invention]
이하， 발명의 구체적인 구현예에 따른 열경화성 수지 조성물에 대해 구체적으로 설명하기로 한다 . Hereinafter, a thermosetting resin composition according to a specific embodiment of the present invention will be described in detail.
본 발명의 일 구현예에 따라， 에폭시 수지와 비스말레이미드계 수지를 포함하는 바인더， 및 벤즈옥사진 수지를 포함하는 수지 조성물; 및 슬러리 타입의 층진제；를 포함하며， 상기 벤즈옥사진은 상기 전체 수지 조성물의 총 중량을 기준으로 10 중량 % 이하로 포함하는， 반도체 패키지용 열경화성 수지 조성물이 제공된다.. According to one embodiment of the present invention, a binder comprising an epoxy resin and a bismaleimide-based resin, and a resin composition comprising a benzoxazine resin; And a slurry-type layering agent; wherein the benzoxazine is provided in the thermosetting resin composition for a semiconductor package containing 10% by weight or less based on the total weight of the total resin composition.
또한， 상기 슬러리 타입의 층진제는 상기 수지 조성물 100 중량부에 대하여 160 내지 350 중량부로 포함될 수 있다. 또한 상기 벤즈옥사진은 상기 전체 수지 조성물의 총 중량을 기준으로 2 내지 10 중량 %로 포함하는 것이 바람직하다. In addition, the slurry-based layering agent may be included in an amount of 160 to 350 parts by weight based on 100 parts by weight of the resin composition. In addition, the benzoxazine is preferably included in 2 to 10% by weight based on the total weight of the total resin composition.
본 발명의 열경화성 수지 조성물은 기존의 페놀 경화제 대신
벤즈옥사진을 사용하여 비스말레이미드계 수지의 경화를 유도하며， 충진제로써 슬러리 타입을 사용하여 수지와 충진제 간의 계면 접착력을 높여 내화학성을 향상시킬 수 있다. 또한， 본 발명의 조성물은 시아네이트 에스터 수지를 사용하여 더욱 높은 물성을 구현할 수 있다. The thermosetting resin composition of the present invention instead of the conventional phenol curing agent Benzoxazine may be used to induce the curing of bismaleimide-based resins, and the slurry type may be used as a filler to increase interfacial adhesion between the resin and the filler, thereby improving chemical resistance. In addition, the composition of the present invention can implement higher physical properties by using a cyanate ester resin.
또한， 기존에는 주로 난연 특성 부여를 위해 벤즈옥사진을 사용하였지만， 이러한 경우 필연적으로 그 함량이 높아 물성이 떨어지는 결과를 초래하며， 벤즈옥사진 수지의 경화제 특성으로 인해 함량을 높일 경우 필러의 함량을 높일 수가 없다. In addition, although benzoxazine was mainly used for imparting flame retardant properties, in this case, its content is inevitably high, resulting in a drop in physical properties. Can't increase
하지만， 본 발명은 열경화성 수지 조성물 중에 경화제로 사용하는 벤즈옥사진의 함량을 10 중량 % 어하로 적게 사용함으로써， 내화학성과 높은 Tg값을 구현할 수 있고, 필러의 함량을 높일 수 있다. However, the present invention by using less than 10% by weight of the benzoxazine used as a curing agent in the thermosetting resin composition, it is possible to implement a chemical resistance and high Tg value, it is possible to increase the content of the filler.
이에 따라， 본 발명의 . 열경화성 수지 조성물은 내화학성 향상으로 디스미어 특성을 개선할 수 있다. 이러한 특성을 갖는 본 발명의 열경화성 수지 조성물과， 이를 이용한 프리프레그 및 금속판 적층판은 양면 인쇄회로기판 뿐 ' 아니라， 다층 인쇄회로 기판의 제조에 모두 적용될 수 있다. Accordingly, the present invention . The thermosetting resin composition may improve desmear characteristics by improving chemical resistance. And thermosetting resin composition of the present invention having such properties, a prepreg and a metal plate laminated board using the same can be applied to both the production as well as the double-sided printed circuit board ', the multi-layer printed circuit board.
그러면， 본 발명의 열경화성 수지 조성물의 성분에 대하여 보다 구체적으로 설명한다. Then, the component of the thermosetting resin composition of this invention is demonstrated more concretely.
본 발명의 열경화성 수지 조성물은 에폭시 수지 및 특수 수지를 포함하는 바인더 성분과， 층진제를 포함하고， 경화제도 포함할 수 있다.
이때， 본 발명은 경화제로 특정 함량의 벤즈옥사진을 사용하며， 상기 벤즈옥사진의 함량에 기초하여 슬러리 타입의 충진제를 사용함을 특징으로 한다. 상기 바인더에 포함되는 비스말레이미드계 수지의 충분한 경화가 유도될 수 있도록 하기 위하여， 본 발명에 따른 상기 벤즈옥사진의 함량은 상기 전체 수지 조성물의 총 중량을 기준으로 10 중량 % 이하로 사용하고， 2 내지 10 증량 ¾>로 사용하는 것이 더 바람직하다. 상기 벤즈옥사진의 함량이 10 중량 %를 초과하는 경우 물성이 더 나빠지므로 우수한 내화학성 및 높은 Tg 를 나타낼 수 없다. 즉， 상기 벤즈옥사진 수지가 과량으로 포함될 경우 프리프레그의 제조시 경화 반응 속도가 지나치게 빨라져서 공정 효율이 저하될 수 있다. 또한 벤즈옥사진의 함량이 2 중량 % 미만으로 너무 낮으면 원하는 경화제로서의 효과를 나타낼 수 없기 때문에 내화학성 및 Tg를 향상시킬 수 없다. The thermosetting resin composition of this invention contains the binder component containing an epoxy resin and a special resin, contains a layering agent, and may also contain a hardening | curing agent. At this time, the present invention is characterized by using a benzoxazine of a specific content as a curing agent, using a slurry-type filler based on the content of the benzoxazine. In order to induce sufficient curing of the bismaleimide-based resin included in the binder, the content of the benzoxazine according to the present invention is used at 10% by weight or less based on the total weight of the total resin composition, More preferably in 2 to 10 increments ¾>. If the content of the benzoxazine is more than 10% by weight, the physical properties are worse, it may not exhibit excellent chemical resistance and high Tg. That is, when the benzoxazine resin is included in an excessive amount, the curing reaction rate may be too high during the preparation of the prepreg, and thus the process efficiency may be reduced. In addition, if the content of benzoxazine is too low, less than 2% by weight, chemical resistance and Tg cannot be improved because the effect as a desired curing agent cannot be exhibited.
본 발명에서 사용하는 벤즈옥사진 수지 (benzoxazine)은 반웅속도 조절이 가능하여 수지의 흐름성을 향상시켜 프리프레그의 흐름성을 확보할 수 있게 한다. 또한， 벤즈 옥사진은 상술한 비스말레이미드 수지의 경화를 가능하게 한다. The benzoxazine resin used in the present invention is capable of controlling the reaction rate, thereby improving the flowability of the resin, thereby securing the flowability of the prepreg. In addition, benz oxazine enables the curing of the bismaleimide resin described above.
즉， 상기 벤즈옥사진 수지는 상기 비스말레이미드계 수지에 대한 경화제의 용도로 사용될 수 있다. 본 발명은 상기 벤즈옥사진 수지를 상기 비스말레이미드계 수지의 경화제로 사용함에 따라， 수지 흐름성을 향상시키고 저온 조건 하에서도 완전 경화가 가능한 효과를 제공한다. 그에 따라, 상기 수지 조성물을 사용하여 프리프레그를 제조할 경우, 저온 가압 하에서 높은
유리전이온도를 나타내는 프리프레그의 제공이 가능하다. That is, the benzoxazine resin may be used as a curing agent for the bismaleimide-based resin. The present invention uses the benzoxazine resin as a curing agent of the bismaleimide-based resin, thereby providing an effect of improving resin flowability and allowing full curing even under low temperature conditions. Therefore, when prepreg is manufactured using the said resin composition, it is high under low temperature pressurization. It is possible to provide a prepreg indicating the glass transition temperature.
나아가， 상기 비스말레이미드계 수지의 경화제로 벤즈옥사진 수지를 사용함으로써, 에폭시 수지의 경화 반웅의 속도를 상대적으로 늦추는 효과를 얻을 수 있다. 그에 따라， 프리프레그의 제조시 섬유 기재에 수지 조성물이 충분히 함침될 수 있는 시간이 확보될 수 있으며， 외관 불량도 최소화될 수 있다. 부가하여， 상기 벤즈옥사진 수지는 200 내지 400 의 중량평균분자량을 갖는 것이 경화 효과 및 기계적 물성의 확보 측면에서 바람직할 수 있다. Furthermore, by using benzoxazine resin as a hardening | curing agent of the said bismaleimide-type resin, the effect which slows the rate of hardening reaction of an epoxy resin relatively can be acquired. As a result, a time during which the resin composition is sufficiently impregnated into the fibrous substrate during the production of the prepreg can be ensured, and the appearance defect can be minimized. In addition, the benzoxazine resin may have a weight average molecular weight of 200 to 400 in terms of securing a curing effect and mechanical properties.
한편， 본 발명에서는 기존과 달리 슬러리 타입의 층진제를 사용함으로써， 기존 일반적인 파우더 타입의 층진제를 사용한 경우 대비 수지와 충진제 간의 계면 접착력을 높여 프리프레그의 내화학성을 향상시킬 수 있다. 즉， 본 발명의 슬러리 타입의 충진제는 파우더 타입의 층진제 대비 수지 분산성을 향상시키는데- 유리하다. On the other hand, in the present invention, by using a slurry-type layering agent, unlike the conventional, it is possible to improve the chemical resistance of the prepreg by increasing the interfacial adhesion between the resin and the filler compared to the case of using a conventional powder-type layering agent. That is, the slurry type filler of the present invention is advantageous in improving the resin dispersibility compared to the powder type layering agent.
이때， 본 발명의 명세서에서 기재하는 "슬러리 타입의 충진제 "는 무기충진제가 용매에 용해되어 있는 상태로 분산된 현탁액을 의미할 수 있다. 또한 본 발명은 벤즈옥사진의 함량이 낮아질수록 층진제 함량이 높아지는 상관관계를 이용한다. 상기 슬러리 타입의 층진제가 수지 조성물 100 중량부에 대하여 160 내지 350 중량부로 포함할 경우， 상기 벤즈옥사진은 상기 전체 수지 조성물의 총 중량을 기준으로 2 내지 10 중량 % 이하로 포함한다. 이때, 슬러리 타입의 층진제 함량이 160 중량부 미만이면 프레스 시 수지가 흐르면서 수지와
필러가 나뉘는 분리 (separat i on)이 많이 발생할 수 있으며， 350 중량부를 초과하면 유리 섬유 (Gl ass Fabr ic)에 필러가 충진아 되지 않아 프레스 후 유리 섬유 (Glass Fabr i c) 표면이 드러나는 dry 형상이 생기는 문제가 있다. At this time, the "slurry type filler" described in the specification of the present invention may mean a suspension dispersed in a state in which the inorganic filler is dissolved in a solvent. In addition, the present invention uses the correlation that the lower the content of the benzoxazine, the higher the content of the layering agent. When the slurry type layering agent is included in an amount of 160 to 350 parts by weight based on 100 parts by weight of the resin composition, the benzoxazine includes 2 to 10% by weight or less based on the total weight of the entire resin composition. At this time, when the content of the slurry-type layering agent is less than 160 parts by weight, the resin flows during pressing and The separation of the filler (separat i on) may occur a lot, and if it exceeds 350 parts by weight, the filler is not filled in the glass fiber (Gl ass Fabr ic), so that the dry shape of the glass fiber (Glass Fabr ic) surface after pressing There is a problem.
' 또한 본 발명의 층진제는 슬러리 타입의 무기 층진제를 사용하는 것이 바람직하다. 상기 슬러리 타입의 무기 충진제는 이 분야에 잘 알려진 방법으로 제조될 수 있으며， 그 방법이 특별히 제한되지 않지만， 바람직하게 무기 충진제를 용매에 분산시키는 방법으로 제조할 수 있다. In addition, it is preferable to use the slurry type inorganic layer thickener of the present invention. The slurry-type inorganic filler may be prepared by a method well known in the art, and the method is not particularly limited, and preferably, the inorganic filler may be prepared by dispersing the inorganic filler in a solvent.
바람직하게， 상기 슬러리 타입의 충진제는 실리카， 알루미늄 트리하이드레이트 (aluminium tr ihydrate) , 마그네슘 하이드록사이드, 몰리브데늄 옥사이드， 징크 몰리브데이트， 징크 보레이트， 징크 스탄네이트 (zinc st annate) , 알루미나， 클레이， 카올린， 탈크, 소성 카을린， 소성 탈크， 마이카， 유리 단섬유 글래스 미세 파우더 및 중공 글래스로 이루어지는 군에서 선택된 1 종 이상의 무기 층진제를 포함한 슬러리를 사용한다. 또한 상기 층진제의 '평균 입자 직경 (D50)은 특별히 한정하지 않으며, 예를 들면 상기 무기 층진재의 평균 입자 직경 (D50)은 분산성의 관점에서 0.2 내지 5 마이크로미터가 바람직하다. 또한， 이러한 충진제는 에폭시 실란으로 표면처리될 수 있다. 층진제를 표면처리하는 경우， 무기 층전제 100 중량부를 기준으로 0.3 내지 1 중량부의 에폭시실란을 사용하여 습 /건식방법으로 층진제를 표면처리하여 사용한다. 또한 상기 에폭시 실란은 200 내지 400의 중량평균분자량을 가질 수 있다.
한편， 상기 바인더는 에폭사 수지와 비스말레이미드계 수지를 포함한다. 이러한 경우 바인더는 에폭시 수지 20 내지 80 중량 % 및 비스말레이미드계 수지 20 내지 80 중량 %를 포함할 수 있다. Preferably, the slurry-type filler is silica, aluminum tr hydrate, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc st annate, alumina, clay And a slurry containing at least one inorganic layering agent selected from the group consisting of kaolin, talc, calcined kaline, calcined talc, mica, glass short fiber glass fine powder and hollow glass. In addition, "average particle diameter (D50) of the jinje layer is not particularly limited, for example, is an average particle diameter (D50) of the inorganic layer damping material is preferably 0.2 to 5 micrometers in view of dispersion. In addition, these fillers may be surface treated with epoxy silanes. In the case of surface treatment of the layering agent, the layering agent is surface-treated by a wet / dry method using 0.3 to 1 parts by weight of epoxy silane based on 100 parts by weight of the inorganic layering agent. In addition, the epoxy silane may have a weight average molecular weight of 200 to 400. On the other hand, the binder contains an epox resin and a bismaleimide-based resin. In this case, the binder may include 20 to 80% by weight of epoxy resin and 20 to 80% by weight of bismaleimide-based resin.
또한， 상기 바인더는 시아네이트계 에스터 수지를 더 포함할 수 있다. 이러한 경우， 상기 바인더는 에폭시 수지 20 내지 60 중량 %， 시아네이트 에스터 수지 30 내지 70 중량 % 및 비스말레이미드계 수지 20 내지 70 중량 %를 포함할 수 있다. In addition, the binder may further include a cyanate ester resin. In this case, the binder may include 20 to 60% by weight of epoxy resin, 30 to 70% by weight of cyanate ester resin, and 20 to 70% by weight of bismaleimide-based resin.
상기 에폭시 수지는 통상 프리프레그용 열경화성 수지 조성물에 사용되는 것을 사용 가능하고, 그 종류가 한정되지는 않는다. What is normally used for the thermosetting resin composition for prepregs for the said epoxy resin can be used, The kind is not limited.
예를 들면， 상기 에폭시 수지는 비스페놀 A 형 에폭시 수지， 비스페놀 For example, the epoxy resin is bisphenol A epoxy resin, bisphenol
F 형 에폭시 수지， 비스페놀 S 형 에폭시 수지， 노볼락형 에폭시 수지， 페놀 노볼락 에폭시 수지， 크레졸 노볼락형 에폭시 수지， 테트라페닐 에탄형 에폭시 수지， 나프탈렌형 에폭시 수지, 바이페닐형 에폭시 수지 및 디시클로펜타디엔형 에폭시 수지로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다. F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, phenol novolac epoxy resin, cresol novolac type epoxy resin, tetraphenyl ethane type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and dicyclo One or more types selected from the group consisting of pentadiene type epoxy resins can be used.
또한, 상기 특수 수지는 시아네이트 에스터 수지 및 비스말레이미드계 수지를 사용하는 특징이 있다. In addition, the special resin is characterized by using a cyanate ester resin and a bismaleimide resin.
이때， 본 발명은 상기 에폭시 수지에 시아네이트 에스터 수지를 사용함으로써 , 수지 물성을 향상시킬 수 있다. 또한， 상기 시아네이트 에스터 수지는 가교 밀도 증가에 의한 높은 유리전이 온도를 나타내어 우수한 열적 및
전기적 특성을 나타낸다. In this case, the present invention can improve the resin physical properties by using the cyanate ester resin in the epoxy resin. In addition, the cyanate ester resin exhibits a high glass transition temperature due to an increase in the crosslinking density, thereby providing excellent thermal and Electrical characteristics.
상기 시아네이트 에스터 수지는 비스페놀 A 형， 비스페놀 F 형， 비스페놀 E 형， 비스페놀 H 형， 비스페놀 N 형， 페놀 노볼락형 및 디시클로펜타디엔비스페놀형의 시아네이트 에스터 수지로 이루어진 군에서 선택된 1종 이상일 수 있다. 또한 수지의 흐름성을 고려하여 시아네이트 에스터 수지는 중량평균분자량이 200 내지 400인 것을 사용함이 바람직하다. The cyanate ester resin is at least one selected from the group consisting of bisphenol A type, bisphenol F type, bisphenol E type, bisphenol H type, bisphenol N type, phenol novolak type and dicyclopentadiene bisphenol type cyanate ester resin. Can be. In addition, in consideration of flowability of the resin, it is preferable to use a cyanate ester resin having a weight average molecular weight of 200 to 400.
또한， 상기 비스말레이미드계 수지는 BT(Bismaleimide-Triazine) 수지， 4，4'-비스말레이미도-디페닐메탄， 1,4-비스말레이미도 -2-메틸벤젠 및 이들의 흔합물; 딜스—알더 (Diels-Alder) 공단량체를 함유하는 개질된 미스말레이미드 수지; 및 4， 4'-비스말레이미도 -디페닐메탄 및 알릴페닐 화합물; 또는 방향족 아민을 기재로 하는 부분적으로 고급화된 비스말레이미드;로 이루어진 군에서 선택된 1 종 이상일 수 있다. 또한 비스말레이미드계 수지는 증량평균분자량이 2,000 내지 5,000인 것을 사용할 수 있다. In addition, the bismaleimide-based resin is BT (Bismaleimide-Triazine) resin, 4,4'-bismaleimido-diphenylmethane, 1,4-bismaleimido-2-methylbenzene, and mixtures thereof; Modified mismaleimide resins containing Diels-Alder comonomers; And 4, 4'-bismaleimido-diphenylmethane and allylphenyl compound; Or partially upgraded bismaleimide based on aromatic amines. In addition, the bismaleimide-based resin can be used that has an increased average molecular weight of 2,000 to 5,000.
그리고， 상기 딜스 -알더 (Diels-Alder) 공단량체는 스티렌 및 스티렌 유도체， 비스 (프로페닐페녹시) 화합물, 4，4'-비스 (프로페닐페녹시)술폰， 4，4'- 비스 (프로페닐페녹시)벤조페논 및 4,4'-1-(1-메틸에틸리덴)비스 (2-(2- 프로페닐)페놀)로 이루어진 군에서 선택될 수 있다. In addition, the Diels-Alder comonomers include styrene and styrene derivatives, bis (propenylphenoxy) compounds, 4,4'-bis (propenylphenoxy) sulfones, 4,4'-bis (pros) Phenylphenoxy) benzophenone and 4,4'-1- (1-methylethylidene) bis (2- (2-propenyl) phenol).
보다 바람직하게， 상기 비스말레이미드계 수지는 비스말레이미드- 트리아진 수지 (bismaleimide triazine, 이하 BT)； 또는 4，4'-비스말레이미도-
디페닐메탄 및 알릴페닐 화합물의 흔합물일 수 있다. More preferably, the bismaleimide-based resin is bismaleimide triazine (BT), or 4,4'-bismaleimido- It may be a combination of diphenylmethane and allylphenyl compound.
또한, 상기 BT 수지는 고성능 및 고집적화를 필요로 하는 전자기판의 절연층으로 사용할 수 있는 열경화성 수지로서， 중량평균분자량이 2 , 000 내지 5 , 000인 것을 사용할 수 있다 . In addition, the BT resin is a thermosetting resin that can be used as an insulating layer of an electromagnetic plate that requires high performance and high integration, and may have a weight average molecular weight of 2,000 to 5,000.
또한， 상기 바인더 성분은 상술한 바대로 에폭시 수지 및 비스말레이미드계 수지의 흔합물, 또는 에폭시 수지， 시아네이트계 에스터 수지 및 비스말레이미드계 수지의 흔합물로서， 바인더로써 요구되는 물성을 고려하여 전체 수지 흔합물이 100 중량 %가 될 수 있도록 적절히 조절하여 사용할 수 있다. 한편， 본 발명의 일 구현예에 따른 열경화성 수지 조성물은 용제， 경화촉진제， 분산제 및 실란커플링제로 이루어지는 군에서 선택된 1 종 이상의 첨가제를 더 포함할 수 있다. . In addition, the binder component is a mixture of an epoxy resin and a bismaleimide resin, or a mixture of an epoxy resin, a cyanate ester resin, and a bismaleimide resin, as described above, in consideration of physical properties required as a binder. It can be used by adjusting appropriately so that the total resin mixture may be 100% by weight. Meanwhile, the thermosetting resin composition according to the embodiment of the present invention may further include at least one additive selected from the group consisting of a solvent, a curing accelerator, a dispersant, and a silane coupling agent. .
구체적으로， 본 발명은 필요에 따라 수지 조성물에 용제를 첨가하여 용액으로 사용할 수 있다. 상기 용제로는 수지 성분에 대해 양호한 용해성을 나타내는 것이면 그 종류가 특별히 한정되지 않으며， 알코을계， 에테르계， 케톤계， 아미드계, 방향족 탄화수소계， 에스테르계， 니트릴계 등을 사용할 수 있고， 이들은 단독 또는 2 종 이상 병용한 흔합 용제를 이용할 수도 있다. 또한 상기 용매의 함량은 프리프레그 제조시 유리섬유에 수지 조성물을 함침할 수 있는 정도면 특별히 한정되지 않는다. Specifically, the present invention can be used as a solution by adding a solvent to the resin composition as needed. The solvent is not particularly limited as long as it exhibits good solubility in the resin component, and alcohol, ether, ketone, amide, aromatic hydrocarbon, ester, nitrile, and the like may be used. Or you may use the combined solvent which used 2 or more types together. In addition, the content of the solvent is not particularly limited as long as the resin composition may be impregnated into the glass fiber during prepreg manufacture.
상기 경화촉진제는 상술한 바인더의 경화를 촉진시킬 목적으로 사용할 수
있다. 경화 촉진제의 종류나 배합량은 특별히 한정하는 것은 아니며， 예를 들면 이미다졸계 화합물， 3급 아민， 4급 암모늄염 등이 이용되고， 2종 이상을 병용할 수도 있다. 바람직하게는, 본 발명은 이미다졸계 화합물을 경화촉진제로 사용한다. 상기 이미다졸계 경화촉진제가 사용될 경우 상기 경화제의 함량은 상기 바인더 100 중량부에 대하여 약 0.1 내지 1 중량부로 사용할 수 있다. 또한 상기 이미다졸계 경화 촉진제의 예로는， 1-메틸 이미다졸 (1-methyl imidazole), 2-메틸 이미다졸 (2-methyl imidazole), 2-에틸 4-메틸 이미다졸 (2- ethyl 4-methyl imidazole) , 2-페닐 이미다졸 (2-phenyl imidazole) , 2- 시클로핵실 4-메틸 이미다졸(2ᅳ0 01^^71 4-methyl imidazole), 4-부틸 5-에틸 이미다졸 (4-butyl 5-ethyl - imidazole), 2-메틸 5-에틸 이미다졸 (2-methyl 5- ethyl imidazole), 2ᅳ옥틸 4-핵실 이미다졸 (2—octhyl 4-hexyl imidazole), 2,5- 디클로로— 4-에틸 이미다졸 (2,5-dichloro-4-ethyl imidazole), 2-부특시 4—알릴 이미다졸 (2-butoxy 4-allyl imidazole) 등과 같은 이미다졸， 및 상기 이미다졸 유도체 등이 있으며， 특히 우수한 반웅 안정성 및 저가로 인해 2-메틸 이미다졸 또는 2—페닐 이미다졸이 바람직하다. The curing accelerator may be used for the purpose of promoting the curing of the binder described above. have. The kind and compounding quantity of a hardening accelerator are not specifically limited, For example, an imidazole compound, a tertiary amine, a quaternary ammonium salt, etc. are used, 2 or more types can also be used together. Preferably, the present invention uses an imidazole compound as a curing accelerator. When the imidazole-based curing accelerator is used, the content of the curing agent may be used in an amount of about 0.1 to 1 parts by weight based on 100 parts by weight of the binder. In addition, examples of the imidazole-based curing accelerator, 1-methyl imidazole, 2-methyl imidazole, 2-ethyl 4-methyl imidazole (2-ethyl 4-methyl imidazole), 2-phenyl imidazole, 2-cyclonuxyl 4-methyl imidazole, 2-butyl imidazole, 4-butyl 5-ethyl imidazole 5-ethyl-imidazole), 2-methyl 5-ethyl imidazole, 2-octyl 4-nuxyl imidazole, 2,5-dichloro-4 Imidazoles such as -ethyl imidazole, 2,5-dichloro-4-ethyl imidazole, 2-butoxy 4-allyl imidazole, and the imidazole derivatives, and the like. 2-methyl imidazole or 2-phenyl imidazole is preferred because of its good reaction stability and low cost.
또한 본 발명의 열경화성 수지 조성물은 필요에 따라 통상적으로 첨가되는 분산제 및 실란커플링제로 이루어지는 군에서 1 종 이상 선택된 첨가제를 추가로 포함할 수 있다. 또한 본 발명의 수지 조성물은， 수지 조성물 고유의 특성을 손상시키지 않는 한, 기타 열경화성 수지, 열가소성 수지 및
이들의 올리고머 및 엘라스토머와 같은 다양한 고폴리머 화합물， 기타 내염 화합물 또는 첨가제를 더 포함할 수도 있다 . 이들은 통상적으로 사용되는 것으로부터 선택되는 것이라면 특별히 한정하지 않는다. In addition, the thermosetting resin composition of the present invention may further include at least one additive selected from the group consisting of a dispersing agent and a silane coupling agent which are usually added as needed. In addition, the resin composition of the present invention, other thermosetting resins, thermoplastic resins and It may further include various high polymer compounds, other flame resistant compounds or additives such as oligomers and elastomers thereof. These are not particularly limited as long as they are selected from those commonly used.
이러한 성분들을 포함하는 본 발명의 일 구현예에 따른 열경화성 수지 조성물은 20t 내지 35°C의 온도에서 20cps 내지 50cps의 점도를 나타내어， 기존 대비 흐름성이 우수한 효과를 제공한다. ' Thermosetting resin composition according to an embodiment of the present invention including these components exhibits a viscosity of 20 cps to 50 cps at a temperature of 20 t to 35 ° C, providing excellent flowability compared to the existing. '
한편 본 발명의 다른 구현예에 따르면， 상기 열경화성 수지 조성물을 섬유 기재에 함침시켜 제조된 프리프레그가 제공된다. . Meanwhile, according to another embodiment of the present invention, a prepreg prepared by impregnating the thermosetting resin composition on a fiber substrate is provided. .
상기 프리프레그는 상기 열경화성 수지 조성물이 반경화 상태로 섬유 기재에 함침되어 있는 것을 의미한다. The prepreg means that the thermosetting resin composition is impregnated into the fiber substrate in a semi-cured state.
상기 섬유 기재는 그 종류가 특별히 한정되지는 않으나, 유리 섬유 기재， 폴리아미드 수지 섬유， 방향족 폴리아미드 수지 섬유 등의 폴리아미드계 수지 섬유， 폴리에스테르 수지 섬유, 방향족 폴리에스테르 수지 섬유ᅳ 전 방향족 폴리에스테르 수지 섬유 등의 폴리에스테르계 수지 섬유， 폴리이미드 수지 섬유， 불소 수지 섬유 등을 주성분으로 하는 직포 또는 부직포로 구성되는 합성 섬유 기재， 크래프트지， 코튼 린터지， 린터와 크래프트 펄프의 흔초지 등을 주성분으로 하는 종이 기재 등이 사용될 수 있으며， 바람직하게 유리 섬유 기재를 사용한다. 상기 유리 섬유 기재는 프리프레그의 강도가 향상되고 흡수율을 내릴 수 있으며， 또 열팽창 계수를 작게 할 수 있다. 본 발명에서
사용되는 유리기재는 다양한 인쇄회로기판 물질용으로 사용되는 유리기재로부터 선택될 수 있다. 이들의 예로서는， E 글래스， D 글래스, S 글래스， T 글래스, Q 글래스， L 글래스 및 NE 글래스와 같은 유리 섬유를 포함하나 이에 한정되는 것은 아니다. 필요에 따라서 의도된 용도 또는 성능에 따라, 상기 유리기재 물질을 선택할 수 있다. 유리기재 형태는 전형적으로 직포， 부직포, 로빙 (roving) , 잘개 다진 스트랜드 매트 (chopped strand mat ) 또는 서페이싱 매트 (surfacing mat )이다. 상기 유리기재 기재의 두께는 특별히 한정되지 않지만, 약 0.01 내지 0.3mm 등을 사용할 수 있다. 상기 물질 중， 글래스 파이버 물질이 강도 및 수 흡수 특성 면에서 더욱 바람직하다. Although the kind of the fiber base material is not particularly limited, polyamide-based resin fibers such as glass fiber base material, polyamide resin fiber, aromatic polyamide resin fiber, polyester resin fiber, aromatic polyester resin fiber ᅳ all aromatic polyester Synthetic fiber base composed of woven or nonwoven fabric mainly composed of polyester resin fibers such as resin fibers, polyimide resin fibers, fluorine resin fibers, kraft paper, cotton linter paper, stray paper of linter and kraft pulp, etc. A paper substrate may be used, and preferably a glass fiber substrate is used. The glass fiber substrate can improve the strength of the prepreg, lower the water absorption rate, and reduce the coefficient of thermal expansion. In the present invention The glass substrates used may be selected from glass substrates used for various printed circuit board materials. Examples thereof include, but are not limited to, glass fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, and NE glass. If necessary, the glass-based material may be selected according to the intended use or performance. Glass-based forms are typically woven, nonwoven, roving, chopped strand mats or surfacing mats. Although the thickness of the glass substrate is not particularly limited, about 0.01 to 0.3 mm or the like can be used. Of these materials, glass fiber materials are more preferred in terms of strength and water absorption properties.
또한 본 발명에서 상기 프리프레그를 제조하는 방법은 특별히 한정되지 않으며， 이 분야에 잘 알려진 방법에 의해 제조될 수 있다. 예를 들면， 상기 프리프레그의 제조방법은 함침법， 각종 코터를 이용하는 코팅법， 스프레이 분사법 등을 이용할 수 있다. In addition, the method for preparing the prepreg in the present invention is not particularly limited, and may be prepared by a method well known in the art. For example, the method of manufacturing the prepreg may be used by an impregnation method, a coating method using various coaters, a spray injection method, or the like.
상기 함침법의 경우 바니시를 제조한 후， 상기 섬유 기재를 바니시에 함침하는 방법으로 프리프레그를 제조할 수 있다. In the case of the impregnation method, after preparing the varnish, the prepreg may be prepared by impregnating the fiber substrate with the varnish.
즉， 상기 프리프레그의 제조 조건 등;은" 특별히 제한하는 것은 아니지만， 상기 열경화성 수지 조성물에 용제를 첨가한 바니시 상태로 사용하는 것이 바람직하다. 상기 수지 바니시용 용제는 상기 수지 성분과 흔합 가능하고 양호한 용해성을 갖는 것이라면 특별히 한정하지 않는다. 이들의 구체적인
예로는， 아세톤， 메틸 에틸 케톤， 메틸이소부틸 케톤 및 시클로핵사논과 같은 케톤， 벤젠, 를루엔 및 자일렌과 같은 방향족 하이드로카본， 및 디메틸포름아미드 및 디메틸아세트아미드와 같은 아미드， 메틸셀로솔브， 부틸셀로솔브 같은 알리파틱 알코을 등이 있다. In other words, the conditions for producing the prepreg are not particularly limited, but are preferably used in a varnish state in which a solvent is added to the thermosetting resin composition. The resin varnish solvent is compatible with the resin component and is good. It will not specifically limit, if it has solubility. Examples include acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone and cyclonuxanone, aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide and dimethylacetamide, methyl cellosolve, Aliphatic alcohols such as butyl cellosolve.
또한， 상기 프리프레그로 제조시, 사용된 용제가 80 중량 % 이상 휘발하는 것이 바람직하다. 이 때문에， 제조 방법이나 건조 조건 등도 제한은 없고， 건조시의 온도는 약 80°C 내지 180°C , 시간은 바니시의 겔화 시간과의 균형으로 특별히 제한은 없다. 또한， 바니시의 함침량은 바니시의 수지 고형분과 기재의 총량에 대하여 바니시의 수지 고형분이 약 30 내지 80 중량 %가 되도록 하는 것이 바람직하다. In addition, when preparing the prepreg, it is preferable that the solvent used is volatilized by 80% by weight or more. Accordingly, also the manufacturing method and drying conditions are limited, the temperature during drying is about 80 ° C to 180 ° C, the time is not particularly limited to the balance with the varnish gelling time. In addition, the impregnation amount of the varnish is preferably such that the resin solid content of the varnish is about 30 to 80% by weight relative to the total amount of the resin solid content of the varnish and the base material.
한편， 본 발명의 또 다른 구현예에 따르면, 상기 프리프레그; 및 가열 및 가압에 의해 상기 프리프레그와 일체화된 포함하는 금속박；을 포함하는 금속박 적층판이 제공된다. On the other hand, according to another embodiment of the present invention, the prepreg; And a metal foil comprising integrally with the prepreg by heating and pressurizing.
바람직하게， 상기 금속박은 동박일 수 있다. 본 발명의 동박 적층판에 포함되는 상기 동박은 구리 또는 구리 합금으로 이루어질 수 있다. 이때， 상기 동박은 본 발명이 속하는 기술분야에서 통상적인 것일 수 있으므로， 그 물성은 특별히 제한되지 않는다. 다만， 본 .발명에 따르면， 상기 동박은 Matt면의 조도 (Rz)가 0. 1 내지 2.5 m , 바람직하게는 0.2 내지 2.0 , 보다 바람직하게는 0.2 내지 1.0 인 것일 수 있고， 그 두께는 1 이상， 바람직하게는 2 내지 18
인 것이 적용될 수 있다. Preferably, the metal foil may be copper foil. The copper foil included in the copper foil laminate of the present invention may be made of copper or a copper alloy. At this time, since the copper foil may be conventional in the art to which the present invention belongs, its physical properties are not particularly limited. However, according to the present invention, the copper foil may have a roughness Rz of Matt surface of 0.01 to 2.5 m , preferably 0.2 to 2.0, more preferably 0.2 to 1.0, and the thickness thereof is 1 or more. , Preferably 2 to 18 Can be applied.
또한 상기 프리프레그를 포함하는 금속박을 가열시， 모든 수지는 전체적으로 약 200 °C 이상에서 경화되므로， 적층 (프레스) 최고온도는 약 200 °C 이상이 될 수 있고, 통상 220 °C정도가 될 수 있다. 또한 상기 금속 적충판 가압시 압력 조건은 특별히 한정되지 않으나, 약 35 내지 50 kgf /cuf가 바람직하다. In addition, when heating the metal foil containing the prepreg, all the resin is cured at about 200 ° C or more as a whole, the maximum temperature of the lamination (press) may be about 200 ° C or more, usually 220 ° C. have. In addition, the pressure condition at the time of pressurizing the metal red plate is not particularly limited, preferably about 35 to 50 kgf / cuf.
이렇게 제조된 프리프레그를 포함하는 금속 적층판은 1 매 이상으로 적층한 후， 양면 또는 다층 인쇄 회로 기판의 제조에 사용할 수 있다. 본 발명은 상기 금속박 적층판을 회로 가공하여 양면 또는 다층 인쇄회로기판을 제조할 수 있으며 , 상기 회로 가공은 일반적인 양면 또는 다층 인쇄 회로 기판 제조 공정에서 행해지는 방법을 적용할 수 있다. The metal laminate including the prepreg thus prepared can be used for the manufacture of double-sided or multilayer printed circuit boards after laminating in one or more sheets. The present invention can manufacture a double-sided or multi-layer printed circuit board by circuit processing the metal foil laminate, the circuit processing can be applied to a method performed in a general double-sided or multi-layer printed circuit board manufacturing process.
이와 같이， 본 발명에 따르면 상술한 수지 열경화성 수지 조성물을 이용함으로써， 다양한 분야의 인쇄회로기판에 모두 적용 가능하며， 바람직하게 반도체 패키지용 인쇄회로기판의 제조에 사용될 수 있다. As described above, according to the present invention, by using the above-mentioned resin thermosetting resin composition, it can be applied to all printed circuit boards of various fields, and can be preferably used for the manufacture of printed circuit boards for semiconductor packages.
이하， 발명의 구체적인 실시예를 통해， 발명의 작용 및 효과를 보다 상술하기로 한다. 다만， 이러한 실시예는 발명의 예시로 제시된 것에 불과하며， 이에 의해 발명의 권리범위가 정해지는 것은 아니다.
실시예 1내지 2및 비교예 1내지 3 Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific embodiments of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined. Examples 1 to 2 and Comparative Examples 1 to 3
다음 표 1 과 같은 조성과 함량으로 각 성분을 흔합하여， 각각 실시예 및 비교예의 열경화성 수지 조성물을 제조하였다. Each component was mixed in the following compositions and contents to prepare thermosetting resin compositions of Examples and Comparative Examples, respectively.
각각의 열경화성 수지 조성물과 충진재를 흔합한 뒤， 고속 교반기에서 흔합하여 수지 바니시를 제조하였다. Each thermosetting resin composition and the filler were mixed and then mixed in a high speed stirrer to prepare a resin varnish.
이어서， 상기 수지 바니시를 두께 45 m 유리섬유 (Nittobo 사 제조 1078， T-glass)에 함침시킨 후， 140°C의 온도에서 열풍 건조하여 프리프레그를 제조하였다. Subsequently, the resin varnish was impregnated into 45 m thick glass fibers (1078, manufactured by Nittobo, T-glass), followed by hot air drying at a temperature of 140 ° C. to prepare a prepreg.
이때, 상기 수지 바니시의 제조에 사용된 각 성분은 다음과 같다: At this time, each component used in the preparation of the resin varnish is as follows:
비스말레이미드계 수지 (BMI-2300, DAIWA 사); BT 수지 (Nanozine 600, Bismaleimide-based resins (BMI-2300, DAIWA Corporation); BT resin (Nanozine 600,
Nanokor 사); 노볼락형 사아네이트 수지 (PT-30S, Lonza 사); 나프탈렌계 에폭시 수지 (HP4710, DIC 사) ; 페놀프탈레인계 벤즈옥사잔 수지 (XU8282, Huns t man 사) ; 에폭시실란 처리된 슬러리 타입의 실리카 (SC2050FNC, Admatechs 사); 파우더 타입의 필러 (SFP— 30NHE, Denka )； 단, 하기 표 1 및 2에서 수지 성분의 함량은 중량 % (합 100 중량 이고， 실리카의 함량은 상기 수지 100 중량부를 기준으로 한 것이다. Nanokor Co.); Novolac type yanate resin (PT-30S, from Lonza); Naphthalene epoxy resins (HP4710, DIC Corporation); Phenolphthalein benzoxazan resin (XU8282, Huns t man); Epoxysilane treated slurry type silica (SC2050FNC from Admatechs); Powder-type filler (SFP-30NHE, Denka); However, the content of the resin component in Tables 1 and 2 is 100% by weight (total 100 weight, and the silica content is based on 100 parts by weight of the resin).
그런 다음, 상기에서 제조된 프리프레그 2 매를 적층한 후， 그 양면에 동박 (두께 12 , Mitsui 사 제조)을 위치시켜 적층하고， 프레스를 이용하여 2201 온도에서 50 kg/cii의 압력으로 75 분 동안 가열 및 가압하여 동박
적층판 (두께 : 100 )을 제조하였다. 이렇게 제조된 동박 적층판을 에칭한 후, 기본적인 물성과 내화학성 테스트를 실시하였다. Then, the two prepregs prepared above were laminated, and copper foil (thickness 12, manufactured by Mitsui) was placed on both sides of the prepreg, and laminated at a pressure of 50 kg / cii at 2201 temperature using a press for 75 minutes. Copper foil by heating and pressurizing during A laminated plate (thickness: 100) was produced. After etching the copper foil laminate thus produced, basic physical properties and chemical resistance tests were performed.
【표 1] [Table 1]
【표 2】 Table 2
비교예 1 비교예 2 비교예 3 비교예 4 비교예 5 에폭시수지 20 30 50 30 12 시아네이트 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Epoxy Resin 20 30 50 30 12 Cyanate
35 40 - 40 16 에스터 수지 35 40-40 16 Ester Resin
BT수지 - - ᅳ 0 ᅳ BT Resin--ᅳ 0 ᅳ
BMT 수지 30 25 45 25 28 벤즈옥사진 BMT Resin 30 25 45 25 28 Mercedes Benz Photo
15 0 5 5 44 수지
경화촉진제 0.3 0.1 페놀 경화제 15 0 5 5 44 Resin Curing Accelerator 0.3 0.1 Phenolic Curing Agent
무기충진제 A 180 180 180 80 무기층진제 B 180 Inorganic filler A 180 180 180 80 Inorganic filler B 180
주) week)
1) 에폭시수지 : 나프탈렌계 에폭시 수지 (HP4710 , DIC사) 1) Epoxy resin: Naphthalene epoxy resin (HP4710, DIC Corporation)
2) BT수지 : BT 수지 (Nanozine 600 , Nanokor사) 2) BT resin: BT resin (Nanozine 600, Nanokor)
3) 시아네이트 에스터 수지 : 노볼락형 시아네이트 수지 (PT-30S, Lonza사) 3) Cyanate ester resin: Novolac cyanate resin (PT-30S, Lonza)
4) BMT 수지 : 비스말레이미드계 수지 (BMI-2300 , DAIWA사) 4) BMT resin: Bismaleimide resin (BMI-2300, DAIWA)
5) 벤즈옥사진 수지: 페놀프탈레인계 벤즈옥사진 수지 (XU8282 , Hunstman사) 5) benzoxazine resin: phenolphthalein-based benzoxazine resin (XU8282, Hunstman)
6) 경화촉진제: 페닐이미다졸 (2PZ , Shikoku사) 6) Curing accelerator: Phenylimidazole (2PZ, Shikoku)
7) 페놀 경화제 : 크레졸-노볼락 경화제 (GPX-41 , Gi fu Shel lac사) 7) Phenolic Curing Agent: Cresol-Novolac Curing Agent (GPX-41, Gi fu Shel lac)
8) 무기 충진제 A: 에폭신실란 처리된 슬러리 타입의 실리카 (SC2050FNC, Admatechs사) 8) Inorganic Filler A: Epoxysilane-Treated Slurry Type Silica (SC2050FNC, Admatechs)
9) 무기 층진제 B: 파우더 타입의 필러 (SFP-30MHE, Denka사) 9) Inorganic layering agent B: powder type filler (SFP-30MHE, Denka)
실험예 ： 물성 평가 실시예 및 비교예에서 얻어진 열경화성 수지 조성물에 대하여， 다음 방법으로 물성을 평가하였다. Experimental example: Physical property evaluation About the thermosetting resin composition obtained by the Example and the comparative example, the physical property was evaluated by the following method.
1. 점도 평가 수지 흐름성을 평가하기 위해， 25°C의 온도에서 브룩필드 점도계를 이용하여， 실시예 및 비교예의 열경화성 수지 조성물의 점도를 측정하였다. 2. 동박적층판에 대한 물성 평가 상기 실시예 및 비교예에서 제조된 동박 적층판에 대하여， 하기의 방법으로 물성을 평가하였고 그 결과를 표 3 및 4에 나타내었다. 1. Viscosity Evaluation In order to evaluate resin flowability, the viscosity of the thermosetting resin compositions of Examples and Comparative Examples was measured using a Brookfield viscometer at a temperature of 25 ° C. 2. Evaluation of Physical Properties for Copper Clad Laminates The copper foil laminates prepared in Examples and Comparative Examples were evaluated for physical properties by the following methods, and the results are shown in Tables 3 and 4.
(a) 내화학성 평가 디스미어 평가에서， 전체적인 공정 조건의 분위기는 알칼리성이며 공정은 swel l ing, permanganat , neutral izing 의 공정 순으로 진행 ¾다. 용액은
시판되고 있는 Atotech사의 용액을사용했다. (a) Chemical resistance evaluation In the desmear evaluation, the overall process conditions are alkaline and the process proceeds in the order of swel ling, permanganat, and neutralizing. The solution is Atotech's commercially available solution was used.
평가는 동박 적층판의 동박층을 에칭하여 제거한 후, 디스미어 공정 전후의 셈플의 무게 차이 (etch rate)를 측정하였다. Evaluation evaluated the weight difference (etch rate) of the sample before and after a desmear process, after etching and removing the copper foil layer of the copper foil laminated board.
(b) 유리 전이온도 (b) glass transition temperature
동박 적층판의 동박층을 에칭하여 제거한 후， DM Dymamic Mechanical After etching and removing the copper foil layer of the copper foil laminated sheet, DM Dymamic Mechanical
Analysis)를 이용하여 승온속도 5°C/min으로 유리 전이온도를 측정하였다. Analysis) was used to measure the glass transition temperature at a temperature increase rate of 5 ° C / min.
동박 적층판의 동박층을 에칭하여 제거한 후， TMA(Thermo Mechanical Analysis)를 이용하여 승온속도 10°C/min으로 유리 전이온도를 측정하였다. After the copper foil layer of the copper foil laminate was etched and removed, the glass transition temperature was measured at a temperature rising rate of 10 ° C / min using TMA (Thermo Mechanical Analysis).
(c) 탄성율 (c) modulus of elasticity
동박 적층판의 동박층을 에칭하여 제거한 후， DMA(Dymamic Mechanical After etching and removing the copper foil layer of a copper foil laminated board, DMA (Dymamic Mechanical)
Analysis)를 이용하여 승온속도 5°C/min 으로 30°C , 260°C에서의 탄성율을 측정하였다. Analysis) was used to measure the elastic modulus at 30 ° C, 260 ° C at a temperature increase rate of 5 ° C / min.
(d) 열팽창계수 (CTE) (d) coefficient of thermal expansion (CTE)
동박 적층판의 동박층을 에칭하여 제거한 후， TMA Thermo Mechanical Analysis)를 이용하여 승온속도 10°C/min으로 열팽창계수를 측정하였다. After the copper foil layer of the copper foil laminate was etched and removed, the coefficient of thermal expansion was measured at a temperature rising rate of 10 ° C / min using TMA Thermo Mechanical Analysis.
(e) 톱수율 (water absorption) (e) water absorption
동박 적층판의 동박층을 에칭하여 제거한 후， 85°C/85% 조건 하에서 항온항습기를 이용하여 측정하였다. After etching by removing the copper foil layer of the copper foil laminate, it was measured using a thermo-hygrostat under 85 ° C. / 85% conditions.
(f ) 접착성 평가 (peel strength)
Texture ananlyer 를 이용하여 동박 적층판의 폭 1cm 의 구간의 접착력을 평가하였다. (f) Peel strength The texture ananlyer was used to evaluate the adhesion of the section of 1cm width of the copper foil laminate.
【표 3] [Table 3]
【표 4】 Table 4
Claims
【청구항 1】 【Claim 1】
에폭시 수지와 비스말레이미드계 수지를 포함하는 바인더， 및 벤즈옥사진 수지를 포함하는 수지 조성물; 및 슬러리 타입의 충진제；를 포함하며， A binder containing an epoxy resin and a bismaleimide resin, and a resin composition containing a benzoxazine resin; And a slurry type filler;
상기 벤즈옥사진은 상기 전체 수지 조성물의 총 중량을 기준으로 10 중량 % 이하로 포함하는， 반도체 패키지용 열경화성 수지 조성물. A thermosetting resin composition for a semiconductor package, wherein the benzoxazine is contained in an amount of 10% by weight or less based on the total weight of the entire resin composition.
【청구항 2】 【Claim 2】
제 1항에 있어서， In clause 1,
상기 슬러리 타입의 층진제는 상기 수지 조성물 100 중량부에 대하여 160 내지 350 증량부로 포함하는， 반도체 패키지용 열경화성 수지 조성물. A thermosetting resin composition for a semiconductor package, wherein the slurry type layering agent is included in an amount of 160 to 350 parts by weight based on 100 parts by weight of the resin composition.
【청구항 3】 【Claim 3】
제 1항에 있어서， In clause 1,
상기 벤즈옥사진은 상기 전체 수지 조성물의 총 중량을 기준으로 2 내지 10 중량 %로 포함하는， 반도체 패키지용 열경화성 수지 조성물. A thermosetting resin composition for a semiconductor package, wherein the benzoxazine is contained in an amount of 2 to 10% by weight based on the total weight of the entire resin composition.
【청구항 4】 【Claim 4】
제 1항에 있어서
상기 바인더는 에폭시 수지 20 내지 80 중량 ¾> 및 비스말레이미드계 수지 20 내지 80 중량 %를 포함하는 반도체 패키지용 열경화성 수지 조성물. In paragraph 1 The binder is a thermosetting resin composition for a semiconductor package comprising 20 to 80% by weight of an epoxy resin and 20 to 80% by weight of a bismaleimide resin.
【청구항 53 【Claim 53
제 1항에 있어서， In clause 1,
상기 바인더는 시아네이트계 에스터 수지를 더 포함하는 반도체 패키지용 열경화성 수지 조성물. The binder is a thermosetting resin composition for a semiconductor package further comprising a cyanate-based ester resin.
【청구항 6】 【Claim 6】
제 5항에 있어서， In clause 5,
상기 바인더는 에폭시 수지 20 내지 60 중량 ¾， 시아네이트 에스터 수지 30 내지 70 증량 % 및 비스말레이미드계 수지 20 내지 70 중량 %를 포함하는 반도체 패키지용 열경화성 수지 조성물. The binder is a thermosetting resin composition for a semiconductor package containing 20 to 60% by weight of an epoxy resin, 30 to 70% by weight of a cyanate ester resin, and 20 to 70% by weight of a bismaleimide-based resin.
【청구항 7】 【Claim 7】
제 1항에 있어서， In clause 1,
상기 슬러리 타입의 충진제는 실리카， 알루미늄 트리하이드레이트， 마그네슘 하이드록사이드, 몰리브데늄 옥사이드， 징크 몰리브데이트， 징크 보레이트， 징크 스탄네이트 (z inc stannate) , 알루미나, 클레이, 카올린, 탈크，
소성 카올린, 소성 탈크， 마이카， 유리 단섬유， 글래스 미세 파우더 및 중¾ 글래스로 이루어지는 군에서 선택된 1 종 이상의 무기 충진제를 포함한 슬러리를 사용하는， 열경화성 수지 조성물. The slurry type filler includes silica, aluminum trihydrate, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate (z inc stannate), alumina, clay, kaolin, talc, A thermosetting resin composition using a slurry containing at least one inorganic filler selected from the group consisting of calcined kaolin, calcined talc, mica, short glass fibers, glass fine powder, and medium ¾ glass.
【청구항 8】 【Claim 8】
제 1 항에 있어서， According to claim 1,
상기 에폭시 수지는 비스페놀 A 형 에폭시 수지， 비스페놀 F 형 에폭시 수지， 비스페놀 S 형 에폭시 수지， 노블락형 에폭시 수지， 페놀 노볼락 에폭시 수지， 크레졸 노볼락형 에폭시 수지， 테트라페닐 에탄형 에폭시 수지， 나프탈렌형 에폭시 수지， 바이페닐형 에폭시 수지 및 디시클로펜타디엔형 에폭사 수지로 이루어진 군에서 선택된 1종 이상인 열경화성 수지 조성물. The epoxy resin is bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolac-type epoxy resin, phenol novolak-type epoxy resin, cresol novolac-type epoxy resin, tetraphenyl ethane-type epoxy resin, naphthalene-type epoxy. A thermosetting resin composition that is at least one selected from the group consisting of resin, biphenyl-type epoxy resin, and dicyclopentadiene-type epoxy resin.
【청구항 9】 【Claim 9】
제 1 항에 있어서， According to claim 1,
상기 비스말레이미드계 수지는 BT(Bi smaleimide-Tr i azine) 수지， 4，4 ' - 비스말레이미도-디페닐메탄， 1， 4-비스말레이미도 -2-메틸벤젠 및 이들의 흔합물; 딜스 -알더 (Di el s-Alder ) 공단량체를 함유하는 개질된 미스말레이미드 수지 ; 및 4，4 ' -비스말레이미도—디페닐메탄 및 알릴페닐 화합물; 또는 방향족 아민을 기재로 하는 부분적으로 고급화된 비스말레이미드;로 이루어진 군에서 선택되는
1종 이상인 열경화성 The bismaleimide-based resin includes BT (Bi smaleimide-Tr i azine) resin, 4,4 '-bismaleimido-diphenylmethane, 1, 4-bismaleimido-2-methylbenzene, and mixtures thereof; Modified mismaleimide resin containing Di el s-Alder comonomer; and 4,4'-bismaleimido—diphenylmethane and allylphenyl compounds; or a partially advanced bismaleimide based on an aromatic amine; One or more types of thermosetting
【청구항 10】 【Claim 10】
' 제 1 항에 있어서， ' In paragraph 1,
상기 시아네이트 에스터 수지는 비스페놀 A 형， 비스페놀 F 형， 비스페놀 E 형， 비스페놀 H 형， 비스페놀 N 형， 페놀 노볼락형， 디시클로펜타디엔비스페놀형의 시아네이트 에스터 수지로 이루어진 군에서 선택된 1종 이상인 열경화성 수지 조성물. The cyanate ester resin is at least one selected from the group consisting of bisphenol A type, bisphenol F type, bisphenol E type, bisphenol H type, bisphenol N type, phenol novolak type, and dicyclopentadiene bisphenol type cyanate ester resin. Thermosetting resin composition.
【청구항 11】 【Claim 11】
제 1 항에 있어서, According to claim 1,
용제， 경화촉진제， 분산제 및 실란커플링제로 이루어지는 군에서 선택된 1종 이상의 첨가제를 더 포함하는， 열경화성 수지 조성물. A thermosetting resin composition further comprising one or more additives selected from the group consisting of solvents, curing accelerators, dispersants, and silane coupling agents.
【청구항 12】 【Claim 12】
게 1항 내지 제 11항 중 어느 한 항에 따른 열경화성 수지 조성물을 섬유 기재에 함침시켜 제조된 프리프레그. A prepreg prepared by impregnating a fiber substrate with the thermosetting resin composition according to any one of claims 1 to 11.
【청구항 13】
제 12항에 따른 프리프레그; 및 가열 및 가압에 의해 상기 프리프레그와 일체화된 포함하는 금속박；을 포함하는 금속박 적층판.
【Claim 13】 A prepreg according to claim 12; And a metal foil that is integrated with the prepreg by heating and pressing. A metal foil laminate comprising a.
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| CN201480042067.XA CN105408418B (en) | 2013-09-30 | 2014-09-25 | Thermosetting resin composition for semiconductor package, prepreg using same and metal foil laminate |
| US14/901,895 US11535750B2 (en) | 2013-09-30 | 2014-09-25 | Thermosetting resin composition for semiconductor package and prepreg and metal clad laminate using the same |
| JP2016538868A JP6301473B2 (en) | 2013-09-30 | 2014-09-25 | Thermosetting resin composition for semiconductor package, prepreg and metal foil laminate using the same |
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| KR10-2014-0128140 | 2014-09-25 | ||
| KR1020140128140A KR101677736B1 (en) | 2013-09-30 | 2014-09-25 | Thermosetting resin composition for semiconductor package and Prepreg and Metal Clad laminate using the same |
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