WO2016145650A1 - Epoxy molding compound with high adhesion for nickel surface, method for preparing the same and uses thereof - Google Patents
Epoxy molding compound with high adhesion for nickel surface, method for preparing the same and uses thereof Download PDFInfo
- Publication number
- WO2016145650A1 WO2016145650A1 PCT/CN2015/074571 CN2015074571W WO2016145650A1 WO 2016145650 A1 WO2016145650 A1 WO 2016145650A1 CN 2015074571 W CN2015074571 W CN 2015074571W WO 2016145650 A1 WO2016145650 A1 WO 2016145650A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- molding compound
- epoxy
- group
- compound according
- epoxy molding
- Prior art date
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- 229920006336 epoxy molding compound Polymers 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 18
- 229910052759 nickel Inorganic materials 0.000 title description 3
- 239000003822 epoxy resin Substances 0.000 claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 49
- 229920003986 novolac Polymers 0.000 claims abstract description 29
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims abstract description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003063 flame retardant Substances 0.000 claims abstract description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 18
- -1 imidazole compound Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 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 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229930003836 cresol Natural products 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 2
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 2
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005350 fused silica glass Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- KPXVKOYWKPPTAU-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethenyl]silane Chemical compound C1C(C=C[Si](OC)(OC)OC)CCC2OC21 KPXVKOYWKPPTAU-UHFFFAOYSA-N 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003852 triazoles Chemical group 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 230000032798 delamination Effects 0.000 abstract description 3
- 238000005538 encapsulation Methods 0.000 abstract 1
- 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 21
- 238000012360 testing method Methods 0.000 description 15
- 239000004843 novolac epoxy resin Substances 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 101150091203 Acot1 gene Proteins 0.000 description 4
- 102100025854 Acyl-coenzyme A thioesterase 1 Human genes 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- 125000002723 alicyclic group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 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 1
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
Definitions
- This invention relates to an epoxy molding compound (EMC) ; in particularly, to an epoxy molding compound with high adhesion for Ni surface, a preparation and use thereof.
- EMC epoxy molding compound
- Molded epoxy resin products are widely used as component parts in electrical and electronic devices, such as transistors and integrated circuit boards, because epoxy resin has well balanced properties including molding property, electrical property, moisture resistance, heat resistance, mechanical property and adhesion to component inserted therein, etc.
- Epoxy Molding Compound has the advantages of high reliability, low cost, simple production and etc., and it is widely used in the fields of semiconductor device, integrated circuit, automobile, consumer electronics, military, and a large number of other fields of package application; and occupies more than 95% market share of encapsulating materials.
- IT information technology
- High performance Epoxy Molding Compound used for semiconductor package requires high adhesion to various substrates.
- metal materials used for electrical package are Cu and Ag-plated Cu, and so far conventional EMC would approximately meet their requirements.
- Ni is usually plated on Cu leadframe to form a Ni surface. Because of their attractive appearance, low corrosivity, and resistance to particle release, Ni surface is widely used for high reliability requirement application.
- traditional EMC barely has adhesion on Ni surface, and delamination between EMC and Ni metal will be usually incurred.
- high temperature and high humidity conditions will speed up delamination phenomenon, and moisture will penetrate into the package material to corrode the semiconductor chip and thus deteriorate insulation property thereof, then the semiconductor package electrical performance will deteriorate as well.
- US 5532024A provides a “method for improving the adhesion of polymeric adhesives to nickel surfaces” .
- the method involve a pre-treatment of the Ni-surface with hydrogen peroxide solution having a temperature of at least about 40 °C for a time sufficient to form a wettable oxide surface having a water contact angle of less than about 10°, so that further adhesive adhesion can be enhanced.
- hydrogen peroxide solution having a temperature of at least about 40 °C for a time sufficient to form a wettable oxide surface having a water contact angle of less than about 10°
- the present inventors find that the combination use of specific types of adhesion promoters is an effective approach to increase the adhesion between EMC and Ni metal or surface.
- the object of the present invention is to provide an epoxy molding compound, which has high adhesion on Ni surface after post mold cure (PMC) , and the adhesion strength value is more than 100N (10.2Kgf) .
- PMC post mold cure
- this invention is able to provide an EMC with high adhesion for various forms of packages, such as those packaging forms of TO220, TO3P, TO92, TO94, TO252, and so on, which are known in the art.
- the present invention provides an epoxy molding compound, comprising:
- adhesion promoter comprises silane and azole.
- the present invention provides a method for manufacturing the epoxy molding compound of the present invention, comprising steps of:
- the present invention provides the use of the epoxy molding compound according to the present invention in electrical encapsulating material, for example, as a reflector material in a LED device.
- the present invention provides an epoxy molding compound, comprising: a) an epoxy resin; b) a novolac resin curing agent; c) a filler; d) a catalyst; e) an adhesion promoter, and optionally f) additives; wherein said adhesion promoter comprises silane and azole.
- epoxy resin means a polymer containing generally two or more epoxide groups per molecule.
- any epoxy resins commonly used are suitable.
- bisphenol epoxy resins such as bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, and the like; biphenyl epoxy resins such as biphenyl epoxy reins, tetramethylbiphenyl epoxy resins, and the like; novolac epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, epoxy compounds of condensates of phenols and phenolic hydroxyl group-containing aromatic aldehyde, biphenyl novolac epoxy resins, and the like; triphenylmethane epoxy resins; tetraphenylethane epoxy resins; dicyclopentadiene phenol addition reaction-type epoxy resins; phenolaralkyl epoxy resins; epoxy resins each having a naphthalene skeleton in
- epoxy resins bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, tetramethylbiphenyl epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, naphthol novolac epoxy resins, naphtholaralkyl epoxy resins, brominated bisphenol epoxy resins, alicyclic epoxy resins, glycidyl ether epoxy resins are preferred.
- Epoxy o-cresol novolac resin EOCN
- DCPD dicyclopentadiene epoxy resin
- MAR multi-aromatic epoxy resin
- MN multi-functional epoxy resin
- biphenyl epoxy resin EOCN
- EOCN Epoxy o-cresol novolac resin
- DCPD dicyclopentadiene epoxy resin
- MAR multi-aromatic epoxy resin
- MN multi-functional epoxy resin
- biphenyl epoxy resin the structures thereof are shown as follows, respectively:
- the amount of the epoxy resin a) in the epoxy molding compound is preferably 4-20 wt. %, more preferably 5-15 wt. % based on the total weight of the epoxy molding compound.
- Novolac resin of the present invention is mainly used as a curing agent and has a linear chain structure, and said novolac resin curing agent contains two or more than two hydroxyl group per molecule.
- the novolac resin b) used in the epoxy molding compound of the present invention any novolac resins commonly used in the art are suitable. There are no particular limitations thereon.
- the novolac resin used in the present application can preferably be one or more selected from the group consisting of phenolic novolac resin (PN novolac) , cresol novolac resin, phenol aralkyl novolac resin (Xylok resin) , multi-aromatic novolac resin, and multi-functional novolac resin (MFN novolac) .
- PN novolac phenolic novolac resin
- cresol novolac resin cresol novolac resin
- Xylok resin phenol aralkyl novolac resin
- MFN novolac multi-aromatic novolac resin
- the amount of the novolac resin b) in the epoxy molding compound is preferably 2-12 wt. %, more preferably 3.7-8 wt. % based on the total weight of the epoxy molding compound.
- the ratio of the number of phenolic hydroxyls in said novolac resin to the number of the epoxy groups in the epoxy resin is preferably 0.5-1.4, more preferably 0.9-1.2.
- a wide range of fillers may be used in the epoxy molding compound of the present invention to impart certain properties thereto, such as abrasion resistance, moisture resistance, thermal conductivity or electrical properties.
- said filler can be one or more selected from the group consisting of crystalline silica, fused silica, spherical silica, titanium oxide, aluminium hydroxide, magnesium hydroxide, zirconium dioxide, calcium carbonate, calcium silicate, talc, clay, carbon fiber and glass fiber,
- the amount of the filler c) in the epoxy molding compound is preferably 60-95 wt. %, more preferably 74-89.8 wt. % based on the total weight of the epoxy molding compound.
- the epoxy molding compound further contains catalyst which is also referred to as curing accelerator, the catalyst may catalyze or accelerate the curing reaction between the epoxy resin and the curing agents.
- catalyst which is also referred to as curing accelerator, the catalyst may catalyze or accelerate the curing reaction between the epoxy resin and the curing agents.
- said catalyst can be one or more selected from the group consisting of amide compound, phosphine, tetraphenyl-phosphonium adduct and azole compound.
- Said catalyst preferably is selected from triphenyl phosphine (TPP) , 1,8-dizzabicyclo (5, 4, 0) undecene-7 (DBU) , 2, 4-diamino-6 [2′-methylimidazolyl-(1′) ] ethyl-s-triazine and N, N-Dimethyl benzyl amine. Any of the above listed catalyst can be used alone or in a combination of two or more.
- the amount of the catalyst d) in the epoxy molding compound is preferably 0.1-1 wt. %, more preferably 0.2-0.4 wt. % based on the total weight of the epoxy molding compound.
- the epoxy molding compound further comprises adhesion promoter which is essential to the present application.
- the adhesion promoter comprises silane and azole, wherein the silane can be one or more selected from the group consisting of epoxy-containing silane, vinyl-containing silane, methypropenyl-containing silane, amino-containing silane, and mercapto-containing silane.
- the silanes can be selected from the group consisting of epoxy silane, vinyl silane, methypropenyl silane, amino silane, mercapto silane and mixtures thereof.
- Most preferred silane adhesion promoter can be selected from the group consisting of 3- (glycidoxypropyl) trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethenyl-trimethoxy silane, 2-propenyl-trimethoxy silane, 2-propenyl-trimethoxy silane, 3-mercapto propyl trimethoxy silane, 3-amino propyl trimethoxy silane, and mixtures thereof.
- the azole compound can preferably be a triazole compound represented by following formula I:
- R 1 , R 2 , R 3 each independently denote a hydrogen, a methyl group, a carboxyl group, an amino group, a mercapto group, or an acyl group.
- the triazole compound can be one or more selected from the group consisting of 3-mercapto-1, 2, 4-triazole, 1-amino-1, 3, 4-triazole and mixtures thereof.
- the azole compound can also be an imidazole compound; and the imidazole compound can be one or more selected from the group consisting of 2-Methylimidazole, 4, 5-dicarboxyimidazole, 2-mecaptoimidazole and mixtures thereof.
- the amount of adhesion promoter e) in the epoxy molding compound is preferably 0.1-2 wt. %, more preferably 0.2-1.0 wt. % based on the total weight of the epoxy molding compound.
- additive means any compounding additives conventionally used in molding compound, especially epoxy molding compound.
- the epoxy resin composition of the present invention may further comprise one or more additives selected from a mold releasing agent, a pigment, a mold stress modifier, and an ion trapping agent.
- Said flame retardant preferably includes brominated epoxy resin, antimony trioxide, melamine cyanurate, aluminium hydroxide, magnesium hydroxide, zinc borate, titanium oxide and calcium silicate, one or more.
- the amount of the flame retardant therein may be preferably 0-20 wt. %, more preferably 0-16.8 wt. % based on the total weight of the epoxy molding compound.
- Said pigment can be, for example, carbon black.
- the amount of the pigment in the compound may be preferably 0-3 wt. %, more preferably 0.2-0.3 wt. % based on the total weight of the epoxy molding compound.
- Said stress modifier can be, for example, organic siloxane compound or silicon rubber, preferably, for example, epoxidized silicone glycidyl resin.
- the amount of the stress modifier in the compound may be preferably 0-4 wt. %, more preferably 0-1.2 wt. % based on the total weight of the epoxy molding compound.
- Said release agent can be nature wax or synthetic wax, preferably, for example, Carnauba Wax.
- the amount of the release agent can be preferably 0.1-1.5 wt. %, more preferably 0.4-1.2 wt. % based on the total weight of the epoxy molding compound.
- the flow property of the epoxy molding compound was determined by measuring the length and weight of the resin flowing along the path of a spiral cavity.
- Sample for the spiral flow test was the powder sample of the epoxy molding compound. No additional preparation was required.
- the spiral flow test was done according to the method EMI-1-66. Test conditions were set as follows: temperature 175 °C, pressure 70km/cm 2 and cure time 90s.
- the gelation point of the epoxy molding compound was tested.
- a hot plate was heated to the temperature of 175°C.
- the powder sample of the epoxy molding compound was placed on the hot plate and let it stand as long as the sample was gelled, with stopwatch gelation time was measured (stopwatch was started immediately when the sample is placed on the hot plate and stopped when gelation was complete) .
- Glass transition temperature of the epoxy molding compound can be determined by various method, such as Dynamic Mechanical Analyzer (DMA) , and Thermo-mechanical Analyzer (TMA) and so on.
- DMA Dynamic Mechanical Analyzer
- TMA Thermo-mechanical Analyzer
- the sample from the extruder was made to be a sheet by a molding machine at a molding temperature of 180°C for 150s. After molding, put the sheet into an oven at a temperature of 180°C for 6 hours. The sheet size is 5cm*1cm*0.4cm.
- Tg of the sheet was measured using DMA, where the sample was placed in the DMA machine, the heating rate was 3°C/min, the heating was carried out until 300°C, the frequency was 5Hz and the Tg was the peak of tan ⁇ figure.
- the CTE1 and CTE2 values were determined using a thermomechanical analyzer (TMA) Q-400 from TA Instruments, and test conditions were as follows: heating the sample piece from room temperature to 280 °C at a rate of 10 °C/min, and the load being 0.1 N.
- TMA thermomechanical analyzer
- CTE1 represents the coefficient of thermal expansion below the temperature of Tg
- CTE2 represents the coefficient of thermal expansion above the temperature of Tg
- standard calculation temperatures range for CTE1 is from 80°C to 100°C
- calculation temperatures range for CTE2 is from 220° -240°C.
- the value of Tg can be calculated as well by determining the crossing point of the two figures.
- Moisture absorption rate test method was carried out in accordance with the method of “PCT24 “; in which sample piece size was set as ⁇ 50*3mm; and test condition is 121°C/100RH%/2atm/24hrs; moisture absorption rate can be calculated as: Weight increment of sample piece after PCT24hrs /Weight of sample piece*100%.
- Adhesion Strength test was carried out in accordance with SEMI test standard SEMI G69-0996, which is the measurement of adhesion strength between Ni-plated leadframes and epoxy molding compounds.
- Sample Preparation Condition was set as follows: molding pressure was set as 6.8-7.8MPa (70-80 kgf/cm2) ; cure temperature was set as 170-180°C, cure time was set as 120 seconds, PMC temperature was set as 175 ⁇ 5 °C, and PMC time was set as 4-8 hours.
- the test was carried out in a Tensile Tester, for example, an universal tensile machine, the measurement range was set as 980N max. (100kgf) ; the accuracy was set as ⁇ 1%, and the crosshead speed was set as 2-10mm/min at a constant speed.
- examples 1 to 10 provided an epoxy molding compound having an adhesion strength by tab pull test of more than 100N, and examples 1 to 10 all use silane adhesion promotor and azole adhesion promotor together; whereas comparative examples 1-2 hardly provide adhesion on Ni plated surface, in which only one type of adhesion promotor was used therein.
- the other performances in examples 1 to 10 remain the same lavel as those in comparative examples, or even better.
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Abstract
An epoxy molding compound (EMC) with high adhesion on Ni material or surface for semiconductor encapsulation is provided. The EMC contains epoxy resin, novolac resin, filler, catalyst, adhesion promoter, and optional additives, such as flame retardant, pigment, stress modifier and release agent. By adding adhesion promoter, the cured EMC adhesion on Ni is at least 100N (10.2Kgf), and it is suitable for high delamination and high electrical requirement package application.
Description
This invention relates to an epoxy molding compound (EMC) ； in particularly， to an epoxy molding compound with high adhesion for Ni surface， a preparation and use thereof.
Background Art
Molded epoxy resin products are widely used as component parts in electrical and electronic devices， such as transistors and integrated circuit boards， because epoxy resin has well balanced properties including molding property， electrical property， moisture resistance， heat resistance， mechanical property and adhesion to component inserted therein， etc.
Epoxy Molding Compound (EMC) has the advantages of high reliability， low cost， simple production and etc.， and it is widely used in the fields of semiconductor device， integrated circuit， automobile， consumer electronics， military， and a large number of other fields of package application； and occupies more than 95％ market share of encapsulating materials. Nowadays， rapid development of information technology (IT) industry requires， for example， the semiconductor device to be more and more the reliable， so than high performance packaging materials are much desired all around the world.
High performance Epoxy Molding Compound used for semiconductor package requires high adhesion to various substrates. Usually， metal materials used for electrical package are Cu and Ag-plated Cu， and so far conventional EMC would approximately meet their requirements. However， in order to further improve the performances of electrical package materials， Ni is usually plated on Cu leadframe to form a Ni surface. Because of their attractive appearance， low corrosivity， and resistance to particle release， Ni surface is widely used for high reliability requirement application. However， traditional EMC barely has adhesion on Ni surface， and delamination between EMC and Ni metal will be usually incurred. Furthermore， high temperature and high humidity conditions will speed up delamination phenomenon， and moisture will penetrate into the package material to corrode the semiconductor chip and thus deteriorate insulation property thereof， then the semiconductor package electrical performance will deteriorate as well.
In order to improve the adhesion to Ni material or surface， for example， US 5532024A provides a “method for improving the adhesion of polymeric adhesives to nickel surfaces” . The method involve a pre-treatment of the
Ni-surface with hydrogen peroxide solution having a temperature of at least about 40 ℃ for a time sufficient to form a wettable oxide surface having a water contact angle of less than about 10°， so that further adhesive adhesion can be enhanced. However， such a method is relatively complicated and costly and environmental unfriendly.
So far， it is desired to have an adhesive or epoxy molding compound having high adhesion for Ni surface， which can be applied to Ni-surface directly， so that the semiconductor electrical performance can be enhanced accordingly.
Particularly， it is much desired to have a high Ni adhesion EMC to improve semiconductor electrical performance.
Surprisingly， the present inventors find that the combination use of specific types of adhesion promoters is an effective approach to increase the adhesion between EMC and Ni metal or surface.
Summary of the Invention
Accordingly， the object of the present invention is to provide an epoxy molding compound， which has high adhesion on Ni surface after post mold cure (PMC) ， and the adhesion strength value is more than 100N (10.2Kgf) . By way of this epoxy molding compound， this invention is able to provide an EMC with high adhesion for various forms of packages， such as those packaging forms of TO220， TO3P， TO92， TO94， TO252， and so on， which are known in the art.
In one aspect， the present invention provides an epoxy molding compound， comprising：
a) an epoxy resin；
b) a novolac resin curing agent；
c) a filler；
d) a catalyst；
e) an adhesion promoter； and optionally
f) additives；
wherein said adhesion promoter comprises silane and azole.
In another aspect， the present invention provides a method for manufacturing the epoxy molding compound of the present invention， comprising steps of：
(1) grinding all components of an EMC to small size， preferably in a ball mill， and then mixing the small sized components homogeneously， preferably in a high speed mixer， to obtain a pre-mixed resultant；
(2) feeding the premixed resultant into an extruder to further mix the pre-mixed resultant， and then crushing or pulverize the extrudate into powder form； and optionally
(3) storing the powder form extrudate in a cooling place， preferably below the temperature of 5 ℃.
Yet in another aspect， the present invention provides the use of the epoxy molding compound according to the present invention in electrical encapsulating material， for example， as a reflector material in a LED device.
In the following passages the present invention is described in more detail. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular， any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In the context of the present invention， the terms used are to be construed in accordance with the following definitions， unless a context dictates otherwise. As used herein， the singular forms “a” ， “an” and “the” include both singular and plural referents unless the context clearly dictates otherwise.
The terms “comprising” ， “comprises” and “comprised of” as used herein are synonymous with “including” ， “includes” or “containing” ， “contains” ， and are inclusive or open-ended and do not exclude additional， non-recited members， elements or method steps. Whereas the term “consisting of “should be interpreted as exclusive or close-ended.
The recitation of numerical end points includes all numbers and fractions subsumed within the respective ranges， as well as the recited end points. When an amount， a concentration or other values or parameters is/are expressed in form of a range， a preferable range， or a preferable upper limit value and a preferable lower limit value， it should be understood as that any ranges obtained by combining any upper limit or preferable value with any lower limit or preferable value are specifically disclosed， without considering whether the obtained ranges are clearly mentioned in the context.
All references cited in the present specification are hereby incorporated by reference in their entirety.
Unless otherwise defined， all terms used in the disclosure of the invention，
including technical and scientific terms， have the meaning as commonly understood by one of the ordinary skill in the art to which this invention belongs to. By means of further guidance， term definitions are included to better appreciate the teaching of the present invention.
The present invention provides an epoxy molding compound， comprising： a) an epoxy resin； b) a novolac resin curing agent； c) a filler； d) a catalyst； e) an adhesion promoter， and optionally f) additives； wherein said adhesion promoter comprises silane and azole.
a) Epoxy resin
As used herein， the term “epoxy resin” means a polymer containing generally two or more epoxide groups per molecule.
As to the epoxy resin (a) used in the epoxy molding compound of the present invention， any epoxy resins commonly used are suitable. There are no particular limitations. Examples thereof Include but not limited to bisphenol epoxy resins such as bisphenol A epoxy resins， bisphenol F epoxy resins， bisphenol S epoxy resins， and the like； biphenyl epoxy resins such as biphenyl epoxy reins， tetramethylbiphenyl epoxy resins， and the like； novolac epoxy resins such as phenol novolac epoxy resins， cresol novolac epoxy resins， bisphenol A novolac epoxy resins， epoxy compounds of condensates of phenols and phenolic hydroxyl group-containing aromatic aldehyde， biphenyl novolac epoxy resins， and the like； triphenylmethane epoxy resins； tetraphenylethane epoxy resins； dicyclopentadiene phenol addition reaction-type epoxy resins； phenolaralkyl epoxy resins； epoxy resins each having a naphthalene skeleton in its molecular structure， such as naphthol novolac epoxy resins， naphtholaralkyl epoxy resins， and the like； brominated bisphenol epoxy resins， alicyclic epoxy resins， and glycidyl ether epoxy resins. These epoxy resins may be used alone or as a mixture of two or more.
Among the above-described epoxy resins， bisphenol A epoxy resins， bisphenol F epoxy resins， bisphenol S epoxy resins， biphenyl epoxy resins， tetramethylbiphenyl epoxy resins， phenol novolac epoxy resins， cresol novolac epoxy resins， naphthol novolac epoxy resins， naphtholaralkyl epoxy resins， brominated bisphenol epoxy resins， alicyclic epoxy resins， glycidyl ether epoxy resins are preferred.
Particularly preferred is Epoxy o-cresol novolac resin (EOCN) ，
dicyclopentadiene epoxy resin (DCPD) ， multi-aromatic epoxy resin (MAR) ， multi-functional epoxy resin (MFN) and biphenyl epoxy resin； the structures thereof are shown as follows， respectively：
The amount of the epoxy resin a) in the epoxy molding compound is preferably 4-20 wt. ％， more preferably 5-15 wt. ％ based on the total weight of the epoxy molding compound.
b) Novolac resin curing agent
Novolac resin of the present invention is mainly used as a curing agent and has a linear chain structure， and said novolac resin curing agent contains two or more than two hydroxyl group per molecule.
As to the novolac resin b) used in the epoxy molding compound of the present invention， any novolac resins commonly used in the art are suitable. There are no particular limitations thereon. Among these， the novolac resin used in the present application can preferably be one or more selected from the group consisting of phenolic novolac resin (PN novolac) ， cresol novolac resin， phenol aralkyl novolac resin (Xylok resin) ， multi-aromatic novolac resin， and multi-functional novolac resin (MFN novolac) . The structures thereof are shown as follows， respectively：
The amount of the novolac resin b) in the epoxy molding compound is preferably 2-12 wt. ％， more preferably 3.7-8 wt. ％ based on the total weight of the epoxy molding compound.
In another aspect of the present invention， as to above components a) and b) ， the ratio of the number of phenolic hydroxyls in said novolac resin to the number of the epoxy groups in the epoxy resin is preferably 0.5-1.4， more preferably 0.9-1.2.
c) Filler
A wide range of fillers may be used in the epoxy molding compound of the present invention to impart certain properties thereto， such as abrasion resistance， moisture resistance， thermal conductivity or electrical properties.
Preferably， said filler can be one or more selected from the group consisting of crystalline silica， fused silica， spherical silica， titanium oxide， aluminium hydroxide， magnesium hydroxide， zirconium dioxide， calcium carbonate， calcium silicate， talc， clay， carbon fiber and glass fiber，
The amount of the filler c) in the epoxy molding compound is preferably 60-95 wt. ％， more preferably 74-89.8 wt. ％ based on the total weight of the epoxy molding compound.
d) Catalyst
The epoxy molding compound further contains catalyst which is also referred to as curing accelerator， the catalyst may catalyze or accelerate the curing reaction between the epoxy resin and the curing agents.
As the catalyst d) used in the epoxy molding compound of the present invention， various compounds commonly used in the art can be used， for example， said catalyst can be one or more selected from the group consisting of amide compound， phosphine， tetraphenyl-phosphonium adduct and azole compound. Said catalyst preferably is selected from triphenyl phosphine (TPP) ， 1，8-dizzabicyclo (5， 4， 0) undecene-7 (DBU) ， 2， 4-diamino-6 [2′-methylimidazolyl-(1′) ] ethyl-s-triazine and N， N-Dimethyl benzyl amine. Any of the above listed catalyst can be used alone or in a combination of two or more.
The amount of the catalyst d) in the epoxy molding compound is preferably 0.1-1 wt. ％， more preferably 0.2-0.4 wt. ％ based on the total weight of the epoxy molding compound.
e) Adhesion Promoter
The epoxy molding compound further comprises adhesion promoter which is essential to the present application.
The adhesion promoter comprises silane and azole， wherein the silane can be one or more selected from the group consisting of epoxy-containing silane， vinyl-containing silane， methypropenyl-containing silane， amino-containing silane， and mercapto-containing silane. Preferred examples of the silanes can be selected from the group consisting of epoxy silane， vinyl silane， methypropenyl silane， amino silane， mercapto silane and mixtures thereof.
Most preferred silane adhesion promoter can be selected from the group consisting of 3- (glycidoxypropyl) trimethoxy silane， 2- (3， 4-epoxycyclohexyl) ethenyl-trimethoxy silane， 2-propenyl-trimethoxy silane， 2-propenyl-trimethoxy silane， 3-mercapto propyl trimethoxy silane， 3-amino propyl trimethoxy silane， and mixtures thereof.
The azole compound can preferably be a triazole compound represented by following formula I：
wherein R1， R2， R3 each independently denote a hydrogen， a methyl group， a carboxyl group， an amino group， a mercapto group， or an acyl group.
More preferably， the triazole compound can be one or more selected from the group consisting of 3-mercapto-1， 2， 4-triazole， 1-amino-1， 3， 4-triazole and mixtures thereof.
The azole compound can also be an imidazole compound； and the imidazole compound can be one or more selected from the group consisting of 2-Methylimidazole， 4， 5-dicarboxyimidazole， 2-mecaptoimidazole and mixtures thereof.
The amount of adhesion promoter e) in the epoxy molding compound is preferably 0.1-2 wt. ％， more preferably 0.2-1.0 wt. ％ based on the total weight of the epoxy molding compound.
f) Additives
The term “additive” as used herein means any compounding additives conventionally used in molding compound， especially epoxy molding compound.
According to the actual requirments， the epoxy resin composition of the present invention may further comprise one or more additives selected from a mold releasing agent， a pigment， a mold stress modifier， and an ion trapping agent.
Said flame retardant preferably includes brominated epoxy resin， antimony trioxide， melamine cyanurate， aluminium hydroxide， magnesium hydroxide， zinc borate， titanium oxide and calcium silicate， one or more. When used in the compound， the amount of the flame retardant therein may be preferably 0-20 wt. ％， more preferably 0-16.8 wt. ％ based on the total weight of the epoxy molding compound.
Said pigment can be， for example， carbon black. The amount of the pigment in the compound may be preferably 0-3 wt. ％， more preferably 0.2-0.3 wt. ％ based on the total weight of the epoxy molding compound.
Said stress modifier can be， for example， organic siloxane compound or silicon rubber， preferably， for example， epoxidized silicone glycidyl resin. The amount of the stress modifier in the compound may be preferably 0-4 wt. ％， more preferably 0-1.2 wt. ％ based on the total weight of the epoxy molding compound.
Said release agent can be nature wax or synthetic wax， preferably， for example， Carnauba Wax. The amount of the release agent can be preferably 0.1-1.5 wt. ％， more preferably 0.4-1.2 wt. ％ based on the total weight of the
epoxy molding compound.
Examples
The present invention will be illustrated in details by means of examples below. However， It is to be understood by one of ordinary skill in the art that this part is a description of exemplary embodiments only， and is not intended to limit the scope of the present invention.
Raw materials
All the raw materials listed in the present description could be any commercially available industrial products.
Test methods
SPIRAL FLOW
In the spiral flow test the flow property of the epoxy molding compound was determined by measuring the length and weight of the resin flowing along the path of a spiral cavity. Sample for the spiral flow test was the powder sample of the epoxy molding compound. No additional preparation was required. The spiral flow test was done according to the method EMI-1-66. Test conditions were set as follows： temperature 175 ℃， pressure 70km/cm2 and cure time 90s.
GELATION TIME
In the GELATION TIME test the gelation point of the epoxy molding compound was tested. In the test， a hot plate was heated to the temperature of 175℃. The powder sample of the epoxy molding compound was placed on the hot plate and let it stand as long as the sample was gelled， with stopwatch gelation time was measured (stopwatch was started immediately when the sample is placed on the hot plate and stopped when gelation was complete) .
GLASS TRANSITION TEMPERATURE Tg
Glass transition temperature of the epoxy molding compound can be determined by various method， such as Dynamic Mechanical Analyzer (DMA) ， and Thermo-mechanical Analyzer (TMA) and so on. Specifically， in the present application， the sample from the extruder was made to be a sheet by a molding machine at a molding temperature of 180℃ for 150s. After molding， put the sheet into an oven at a temperature of 180℃ for 6 hours. The sheet size is 5cm＊1cm＊0.4cm. Tg of the sheet was measured using DMA， where the sample was placed in the DMA machine， the heating rate was 3℃/min， the heating
was carried out until 300℃， the frequency was 5Hz and the Tg was the peak of tan δ figure.
Coefficient of Thermal Expansion (CTE)
The CTE1 and CTE2 values were determined using a thermomechanical analyzer (TMA) Q-400 from TA Instruments， and test conditions were as follows： heating the sample piece from room temperature to 280 ℃ at a rate of 10 ℃/min， and the load being 0.1 N. To be specific， CTE1 represents the coefficient of thermal expansion below the temperature of Tg， and CTE2 represents the coefficient of thermal expansion above the temperature of Tg， and standard calculation temperatures range for CTE1 is from 80℃ to 100℃， and calculation temperatures range for CTE2 is from 220° -240℃.
From the testing figures determing the CTE1 and CTE2 value， the value of Tg can be calculated as well by determining the crossing point of the two figures.
Moisture Absorption
Moisture absorption rate test method was carried out in accordance with the method of “PCT24 “； in which sample piece size was set asφ50＊3mm； and test condition is 121℃/100RH％/2atm/24hrs； moisture absorption rate can be calculated as： Weight increment of sample piece after PCT24hrs /Weight of sample piece＊100％.
Adhesion Strength
Adhesion Strength test was carried out in accordance with SEMI test standard SEMI G69-0996， which is the measurement of adhesion strength between Ni-plated leadframes and epoxy molding compounds.
Sample Preparation Condition was set as follows： molding pressure was set as 6.8-7.8MPa (70-80 kgf/cm2) ； cure temperature was set as 170-180℃， cure time was set as 120 seconds， PMC temperature was set as 175±5 ℃， and PMC time was set as 4-8 hours.
The test was carried out in a Tensile Tester， for example， an universal tensile machine， the measurement range was set as 980N max. (100kgf) ； the accuracy was set as ±1％， and the crosshead speed was set as 2-10mm/min at a constant speed.
Examples 1-10 and Comparative Examples 1-2
Preparation of Epoxy Molding Compounds
The raw materials used for the epoxy molding compounds of Examples 1-10 (inventive) and Comparative Examples 1-2 (not inventive) were weighed out
as shown in Table 1. All the raw material components were ground into small size by a ball mill and then fed into a high speed mixer， and therein they were mixed for 15 minutes at 300r/min under room temperature to obtain a premixed powder. The premixed powder was then fed into a twin-screw extruder， and therein was extruded at a temperature of about 100-110℃ with the rotation speed of the screw being about 120rpm. The extrudate thus obtained was crushed into powder thereafter.
Table 1：
Tests as described above were conducted to the thus obtained epoxy molding compounds from examples 1 to 10 and comparative examples 1-2， and testing results were shown in the following table 2：
Table 2：
As can be seen from the results in above table 2， examples 1 to 10 provided an epoxy molding compound having an adhesion strength by tab pull test of more than 100N， and examples 1 to 10 all use silane adhesion promotor and azole adhesion promotor together； whereas comparative examples 1-2 hardly provide adhesion on Ni plated surface， in which only one type of adhesion promotor was used therein. In the meantime， the other performances in examples 1 to 10 remain the same lavel as those in comparative examples， or even better.
Claims (20)
- An epoxy molding compound comprisinga) an epoxy resin；b) a novolac resin curing agent；c) a filler；d) a catalyst； ande) an adhesion promoter； and optionallyf) an additive；wherein said adhesion promoter comprises silane and azole.
- The epoxy molding compound according to claim 1, wherein the epoxy resin constitutes 4-20％by weight of the total weight of the molding compound, preferably 5-15％； the novolac resin curing agent constitutes 2-12％by weight of the total weight of the molding compound, preferably 3.7-8％； the filler constitutes 60-95％by weight of the total weight of the molding compound, preferably 74-89.8％； the catalyst constitutes 0.1-1％by weight of the total weight of the molding compound, preferably 0.2-0.4％； and the adhesion promoter constitutes 0.1-2％by weight of the total weight of the molding compound, preferably 0.2-1.0％.
- The epoxy molding compound according to claim 1 or 2, wherein said silane adhesion promoter is selected from the group consisting of epoxy silane, vinyl silane, methypropenyl silane, amino silane, mercapto silane and mixtures thereof.
- The epoxy molding compound according to claim 1 or 2, wherein said silane adhesion promoter is selected from the group consisting of 3-(glycidoxypropyl) trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethenyl-trimethoxy silane, 2-propenyl-trimethoxy silane, 2-propenyl-trimethoxy silane, 3-mercapto propyl trimethoxy silane, 3-amino propyl trimethoxy silane, and mixtures thereof.
- The epoxy molding compound according to any of claims 1 to 4, wherein said azole adhesion promoter is a triazole represented by the following formula I:
wherein R1, R2, R3 each independently denotes a hydrogen, a methyl group, a carboxyl group, an amino group, a mercapto group, or an acyl group. - The epoxy molding compound according to claim 5, wherein said azole adhesion promoter is one or more selected from the group consisting of 3-mercapto-1, 2, 4-triazole, 1-amino-1, 3, 4-triazole and mixtures thereof.
- The epoxy molding compound according to any of claims 1 to 4, wherein said azole is an imidazole compound.
- The epoxy molding compound according claim 7, wherein said imidazole compound is one or more selected from the group consisting of 2-methylimidazole, 4, 5-dicarboxyimidazole, 2-mecaptoimidazole and mixtures thereof.
- The epoxy molding compound according to any of claims 1 to 7, wherein said epoxy resin contains at least two epoxy groups.
- The epoxy molding compound according to claim 9, wherein said epoxy resin is selected from the group consisting of epoxy o-cresol novolac resin, dicyclopentadiene epoxy resin, multi-aromatic epoxy resin, multi-functional epoxy resin, biphenyl epoxy resin and mixtures thereof.
- The epoxy molding compound according to any of claims 1 to 10, wherein said epoxy resin contains hydroxyl group, and the molar ratio of epoxy group and hydroxyl group is 0.5-1.4, preferably 0.9-1.2.
- The epoxy molding compound according to any of claims 1 to 11, wherein said novolac resin curing agent contains at least two hydroxyl groups.
- The epoxy molding compound according to any of claims 1 to 12, wherein said novolac resin curing agent is selected from the group consisting of phenolic novolac resin, cresol novolac resin, phenol aralkyl novolac resin, multi-aromatic novolac resin, and multi-functional novolac resin and mixtures thereof.
- The epoxy molding compound according to any of claims 1 to 13, wherein said filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, titanium oxide, aluminium hydroxide, magnesium hydroxide, zirconium dioxide, calcium carbonate, calcium silicate, talc, clay, carbon fiber, glass fiber and mixtures thereof.
- The epoxy molding compound according to any of claims 1 to 14, wherein said catalyst is selected from the group consisting of amide compound, phosphine compound, tetraphenylphosphonium adduct, azole compound and mixtures thereof.
- The epoxy molding compound according to claim 15, wherein said catalyst is selected from the group consisting of triphenyl phosphine, 1,8-dizzabicyclo (5, 4, 0) undecene-7, 2, 4-diamino-6 [ 2'-methylimidazolyl- (1') ] -ethyl-s-triazine, N, N-dimethyl benzyl amine and mixtures thereof.
- The epoxy molding compound according to any of claims 1 to 16, wherein said additive is selected from the group consisting of flame retardant, pigment, stress modifier, ion capturer and release agent.
- Method for preparing the epoxy molding compound according to any of claims 1 to 17, comprising the steps of:(1) grinding all components of the EMC to small size and then mixing all components of the EMC homogeneously, to obtain a pre-mixed resultant；(2) feeding the pre-mixed resultant into an extruder to further mix the pre-mixed resultant, and then crushing or pulverize the extrudate into a powder form； andoptionally(3) storing the powder form extrudate in a cooling place, preferably below a temperature of 5 ℃.
- Use of an epoxy molding compound according to any of the preceding claims 1-16 in electrical encapsulating materials.
- Use of an epoxy molding compound according to any of the preceding claims 1-16 as a reflector material in a LED device.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2015/074571 WO2016145650A1 (en) | 2015-03-19 | 2015-03-19 | Epoxy molding compound with high adhesion for nickel surface, method for preparing the same and uses thereof |
| CN201580077913.6A CN107636071B (en) | 2015-03-19 | 2015-03-19 | Epoxy molding compounds having high adhesion to nickel surfaces, method for the production thereof and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2015/074571 WO2016145650A1 (en) | 2015-03-19 | 2015-03-19 | Epoxy molding compound with high adhesion for nickel surface, method for preparing the same and uses thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016145650A1 true WO2016145650A1 (en) | 2016-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2015/074571 WO2016145650A1 (en) | 2015-03-19 | 2015-03-19 | Epoxy molding compound with high adhesion for nickel surface, method for preparing the same and uses thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN107636071B (en) |
| WO (1) | WO2016145650A1 (en) |
Cited By (2)
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|---|---|---|---|---|
| WO2020027219A1 (en) | 2018-07-31 | 2020-02-06 | 日本製鉄株式会社 | Grain-oriented electromagnetic steel sheet |
| DE102019101631A1 (en) * | 2019-01-23 | 2020-07-23 | Infineon Technologies Ag | Corrosion-protected molding compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110128781A (en) * | 2018-02-09 | 2019-08-16 | 衡所华威电子有限公司 | Epoxy molding plastic, preparation method and use |
| CN112980137B (en) * | 2019-12-17 | 2024-02-02 | 衡所华威电子有限公司 | Epoxy molding compound and preparation method and application thereof |
| CN113278249A (en) * | 2020-02-19 | 2021-08-20 | 衡所华威电子有限公司 | Epoxy resin composition and preparation method thereof |
| CN114644810B (en) * | 2020-12-18 | 2024-03-01 | 衡所华威电子有限公司 | High-temperature fast-curing low-stress epoxy resin composition and preparation method thereof |
| CN114672134B (en) * | 2020-12-24 | 2024-02-02 | 衡所华威电子有限公司 | Low-friction epoxy resin composition and preparation method thereof |
| CN113201204B (en) * | 2021-04-23 | 2023-06-02 | 衡所华威电子有限公司 | High Tg and low warp MUF epoxy resin composition and preparation method thereof |
| CN114369338B (en) * | 2021-12-31 | 2024-03-15 | 江苏中科科化新材料股份有限公司 | Epoxy resin composition and application thereof, epoxy resin and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN107636071A (en) | 2018-01-26 |
| CN107636071B (en) | 2020-08-18 |
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