JP5543738B2 - Sheet-like epoxy resin composition for sealing electronic components and electronic component device using the same - Google Patents
Sheet-like epoxy resin composition for sealing electronic components and electronic component device using the same Download PDFInfo
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- JP5543738B2 JP5543738B2 JP2009182614A JP2009182614A JP5543738B2 JP 5543738 B2 JP5543738 B2 JP 5543738B2 JP 2009182614 A JP2009182614 A JP 2009182614A JP 2009182614 A JP2009182614 A JP 2009182614A JP 5543738 B2 JP5543738 B2 JP 5543738B2
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- epoxy resin
- sheet
- resin composition
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- electronic component
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- 239000003822 epoxy resin Substances 0.000 title claims description 100
- 229920000647 polyepoxide Polymers 0.000 title claims description 100
- 239000000203 mixture Substances 0.000 title claims description 67
- 238000007789 sealing Methods 0.000 title claims description 22
- -1 Phosphazene compound Chemical class 0.000 claims description 22
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 20
- 150000004692 metal hydroxides Chemical class 0.000 claims description 20
- 239000005011 phenolic resin Substances 0.000 claims description 13
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000000806 elastomer Substances 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- LFMQNMXVVXHZCC-UHFFFAOYSA-N 1,3-benzothiazol-2-yl n,n-diethylcarbamodithioate Chemical compound C1=CC=C2SC(SC(=S)N(CC)CC)=NC2=C1 LFMQNMXVVXHZCC-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000000843 powder Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000005350 fused silica glass Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- 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 6
- 229920006243 acrylic copolymer Polymers 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- 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 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 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 3
- 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 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 125000004036 acetal group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- MUCRYNWJQNHDJH-OADIDDRXSA-N Ursonic acid Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C MUCRYNWJQNHDJH-OADIDDRXSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 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 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
- H01L2924/191—Disposition
- H01L2924/19101—Disposition of discrete passive components
- H01L2924/19105—Disposition of discrete passive components in a side-by-side arrangement on a common die mounting substrate
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
本発明は、半導体素子、コンデンサおよび抵抗素子等の電子部品封止用のシート状エポキシ樹脂組成物およびそれを用いた電子部品装置に関するものである。 The present invention relates to a sheet-like epoxy resin composition for sealing electronic components such as a semiconductor element, a capacitor, and a resistance element, and an electronic component device using the same.
従来、実装基板上の半導体素子、コンデンサおよび抵抗素子等の電子部品の封止は、粉末状エポキシ樹脂組成物によるトランスファー封止や、液状エポキシ樹脂組成物、シリコーン樹脂等によるポッティング、ディスペンス、印刷等によって行われているが、近年、より安価で簡便な封止方法としてシート状エポキシ樹脂組成物を用いたシート封止が提案されている。（特許文献１〜３）
また、最近では安全性の観点から、電子部品装置および実装基板に難燃性が求められる場合が多くなっている。（特許文献４〜６）
Conventionally, sealing of electronic components such as semiconductor elements, capacitors and resistor elements on a mounting substrate is performed by transfer sealing with a powdered epoxy resin composition, potting with a liquid epoxy resin composition, silicone resin, etc., dispensing, printing, etc. In recent years, sheet sealing using a sheet-like epoxy resin composition has been proposed as a cheaper and simpler sealing method. (Patent Documents 1 to 3)
In recent years, from the viewpoint of safety, electronic component devices and mounting boards are often required to have flame retardancy. (
しかし、上記シート状エポキシ樹脂組成物は、シート封止に必要な可撓性を得るために、エラストマー等の非難燃性の可撓性付与剤を多量に添加する必要があり、難燃性を高めることは困難であった。 However, the sheet-like epoxy resin composition needs to add a large amount of a non-flammable flexibility imparting agent such as an elastomer in order to obtain the flexibility necessary for sheet sealing, It was difficult to increase.
本発明はこのような事情に鑑みなされたもので、難燃性のみならず、接着性、ボイド生成抑制にも優れた電子部品封止用のシート状エポキシ樹脂組成物およびそれを用いた電子部品装置を提供することをその目的とする。 The present invention has been made in view of such circumstances, and is a sheet-like epoxy resin composition for sealing electronic components that is excellent not only in flame retardancy but also in adhesion and void generation suppression, and an electronic component using the same The object is to provide a device.
上記の目的を達成するため、本発明の電子部品封止用のシート状エポキシ樹脂組成物は、下記Ａ〜Ｆ成分を含有し、Ｅ成分およびＦ成分の合計含有量が、シート状エポキシ樹脂組成物全体の７０〜９０重量％であり、Ｃ成分の含有量が、シート状エポキシ樹脂組成物全体の１０〜２５重量％であることを特徴とする。
Ａ：エポキシ樹脂
Ｂ：フェノール樹脂
Ｃ：エラストマー
Ｄ：硬化促進剤
Ｅ：金属水酸化物
Ｆ：式（１）で表されるホスファゼン化合物
In order to achieve the above object, the sheet-like epoxy resin composition for electronic component sealing of the present invention contains the following components A to F, and the total content of the component E and component F is a sheet-like epoxy resin composition. Ri 70-90 wt% der of the total object, the content of C component, characterized in that 10 to 25% by weight of the entire sheet-like epoxy resin composition.
A: Epoxy resin B: Phenol resin C: Elastomer D: Curing accelerator E: Metal hydroxide F: Phosphazene compound represented by formula (1 )
また、本発明の電子部品装置は、上記シート状エポキシ樹脂組成物を用いることを特徴とする。 Moreover, the electronic component device of the present invention is characterized by using the sheet-like epoxy resin composition.
本発明の電子部品封止用のシート状エポキシ樹脂組成物は、シート封止用の樹脂組成物として求められる可撓性を有しつつ、接着性、ボイド生成抑制および難燃性にも優れた効果を発揮する。また、本発明の電子部品封止用のシート状エポキシ樹脂組成物を用いると、高い難燃性を有する電子部品装置を容易に得ることができる。 The sheet-like epoxy resin composition for encapsulating electronic components of the present invention has excellent flexibility required as a resin composition for encapsulating a sheet, and is excellent in adhesion, void formation suppression, and flame retardancy. Demonstrate the effect. Moreover, if the sheet-like epoxy resin composition for electronic component sealing of this invention is used, the electronic component apparatus which has high flame retardance can be obtained easily.
つぎに、本発明の実施の形態について詳しく説明する。 Next, embodiments of the present invention will be described in detail.
本発明の電子部品封止用のシート状エポキシ樹脂組成物は、下記Ａ〜Ｆ成分を含有し、かつＥ成分およびＦ成分の合計含有量がシート状エポキシ樹脂組成物全体の７０〜９０重量％である。
Ａ：エポキシ樹脂
Ｂ：フェノール樹脂
Ｃ：エラストマー
Ｄ：硬化促進剤
Ｅ：金属水酸化物
Ｆ：式（１）で表されるホスファゼン化合物
The sheet-like epoxy resin composition for electronic component sealing of the present invention contains the following components A to F, and the total content of the component E and the component F is 70 to 90% by weight of the whole sheet-like epoxy resin composition. It is.
A: Epoxy resin B: Phenol resin C: Elastomer D: Curing accelerator E: Metal hydroxide F: Phosphazene compound represented by formula (1 )
エポキシ樹脂（Ａ成分）としては、特に限定されるものではない。例えば、トリフェニルメタン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、変性ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、変性ビスフェノールＦ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、フェノキシ樹脂等の各種のエポキシ樹脂を用いることができる。これらエポキシ樹脂は単独で用いてもよいし２種以上併用してもよい。エポキシ樹脂の硬化後の靭性及びエポキシ樹脂の反応性を確保する観点からは、エポキシ当量１５０〜２５０、軟化点もしくは融点が５０〜１３０℃の常温で固形のものが好ましく、中でも、信頼性の観点から、トリフェニルメタン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂が好ましい。また、低応力性の観点から、アセタール基やポリオキシアルキレン基等の柔軟性骨格を有する変性ビスフェノールＡ型エポキシ樹脂が好ましく、アセタール基を有する変性ビスフェノールＡ型エポキシ樹脂は、液体状で取り扱いが良いであることから、特に好適に用いることができる。 The epoxy resin (component A) is not particularly limited. For example, triphenylmethane type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, modified bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, modified bisphenol F type epoxy resin, dicyclopentadiene type Various epoxy resins such as an epoxy resin, a phenol novolac type epoxy resin, and a phenoxy resin can be used. These epoxy resins may be used alone or in combination of two or more. From the viewpoint of ensuring the toughness after curing of the epoxy resin and the reactivity of the epoxy resin, those having an epoxy equivalent of 150 to 250 and a softening point or melting point of 50 to 130 ° C. are preferably solid, and in particular, from the viewpoint of reliability. Therefore, triphenylmethane type epoxy resin, cresol novolac type epoxy resin, and biphenyl type epoxy resin are preferable. Also, from the viewpoint of low stress, a modified bisphenol A type epoxy resin having a flexible skeleton such as an acetal group or a polyoxyalkylene group is preferable, and a modified bisphenol A type epoxy resin having an acetal group is liquid and easy to handle. Therefore, it can be particularly preferably used.
エポキシ樹脂（Ａ成分）の含有量は、シート状エポキシ樹脂組成物全体に対して１〜１０重量％の範囲に設定することが好ましい。 The content of the epoxy resin (component A) is preferably set in the range of 1 to 10% by weight with respect to the whole sheet-like epoxy resin composition.
フェノール樹脂（Ｂ成分）は、エポキシ樹脂（Ａ成分）との間で硬化反応を生起するものであれば特に限定されるものではない。例えば、フェノールノボラック樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、ジシクロペンタジエン型フェノール樹脂、クレゾールノボラック樹脂、レゾール樹脂、等が用いられる。これらフェノール樹脂は単独で用いてもよいし、２種以上併用してもよい。そして、フェノール樹脂としては、エポキシ樹脂（Ａ成分）との反応性の観点から、水酸基当量が７０〜２５０、軟化点が５０〜１１０℃のものを用いることが好ましく、中でも硬化反応性が高いという観点から、フェノールノボラック樹脂を好適に用いることができる。また、信頼性の観点から、フェノールアラルキル樹脂やビフェニルアラルキル樹脂のような低吸湿性のものも好適に用いることができる。 The phenol resin (component B) is not particularly limited as long as it causes a curing reaction with the epoxy resin (component A). For example, a phenol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a dicyclopentadiene type phenol resin, a cresol novolak resin, a resole resin, or the like is used. These phenolic resins may be used alone or in combination of two or more. And as a phenol resin, it is preferable to use a hydroxyl equivalent of 70-250 and a softening point of 50-110 degreeC from a reactive viewpoint with an epoxy resin (A component). From the viewpoint, a phenol novolac resin can be preferably used. From the viewpoint of reliability, low hygroscopic materials such as phenol aralkyl resins and biphenyl aralkyl resins can also be suitably used.
そして、エポキシ樹脂（Ａ成分）とフェノール樹脂（Ｂ成分）の配合割合は、硬化反応性という観点から、エポキシ樹脂（Ａ成分）中のエポキシ基１当量に対して、フェノール樹脂（Ｂ成分）中の水酸基の合計が０．７〜１．５当量となるように配合することが好ましく、より好ましくは０．９〜１．２当量である。 And the compounding ratio of an epoxy resin (A component) and a phenol resin (B component) is a phenol resin (B component) with respect to 1 equivalent of epoxy groups in an epoxy resin (A component) from a viewpoint of hardening reactivity. It is preferable to mix | blend so that the sum total of a hydroxyl group may be 0.7-1.5 equivalent, More preferably, it is 0.9-1.2 equivalent.
エポキシ樹脂（Ａ成分）およびフェノール樹脂（Ｂ成分）とともに用いられるエラストマー（Ｃ成分）は、シート封止に必要な可撓性をエポキシ樹脂組成物に付与するものであり、このような作用を奏するものであれば特にその構造を限定するものではない。例えば、ポリアクリル酸エステル等の各種アクリル系共重合体、スチレンアクリレート系共重合体、ブタジエンゴム、スチレン−ブタジエンゴム（ＳＢＲ）、エチレン−酢酸ビニルコポリマー（ＥＶＡ）、イソプレンゴム、アクリロニトリルゴム等のゴム質重合体を用いることができる。中でも、エポキシ樹脂（Ａ成分）へ分散させやすく、またエポキシ樹脂（Ａ成分）との反応性も高いために、得られるエポキシ樹脂組成物の耐熱性や強度を向上させることができるという観点から、アクリル系共重合体を用いることが好ましい。これらは単独で用いてもよいし、２種以上併せて用いてもよい。なお、アクリル系共重合体は、例えば、所定の混合比にしたアクリルモノマー混合物を、定法によってラジカル重合することにより合成することができる。ラジカル重合の方法としては、有機溶剤を溶媒に行う溶液重合法や、水中に原料モノマーを分散させながら重合を行う懸濁重合法が用いられる。 The elastomer (C component) used together with the epoxy resin (A component) and the phenol resin (B component) imparts flexibility necessary for sheet sealing to the epoxy resin composition, and exhibits such an action. If it is a thing, the structure in particular will not be limited. For example, various acrylic copolymers such as polyacrylates, styrene acrylate copolymers, butadiene rubber, styrene-butadiene rubber (SBR), ethylene-vinyl acetate copolymer (EVA), isoprene rubber, acrylonitrile rubber, etc. Polymers can be used. Among them, from the viewpoint that it is easy to disperse in the epoxy resin (component A) and the reactivity with the epoxy resin (component A) is high, so that the heat resistance and strength of the resulting epoxy resin composition can be improved. It is preferable to use an acrylic copolymer. These may be used alone or in combination of two or more. The acrylic copolymer can be synthesized, for example, by radical polymerization of an acrylic monomer mixture having a predetermined mixing ratio by a conventional method. As a method for radical polymerization, a solution polymerization method in which an organic solvent is used as a solvent or a suspension polymerization method in which polymerization is performed while dispersing raw material monomers in water are used.
エラストマー（Ｃ成分）の含有量は、シート状エポキシ樹脂組成物全体の１０〜２５重量％の範囲に設定することが好ましい。すなわち、エラストマー（Ｃ成分）の含有量が１０重量％未満では、シート封止に十分な可撓性を得ることが困難となる。また、含有量が２５重量％を越えると、シート状エポキシ樹脂組成物の難燃性を得ることが困難となるとともに、シート状エポキシ樹脂組成物の硬化物の強度も低下する傾向がみられ、電子部品装置の信頼性を損なうおそれがある。 The content of the elastomer (component C) is preferably set in the range of 10 to 25% by weight of the entire sheet-like epoxy resin composition. That is, when the content of the elastomer (C component) is less than 10% by weight, it is difficult to obtain sufficient flexibility for sheet sealing. Moreover, when the content exceeds 25% by weight, it becomes difficult to obtain the flame retardancy of the sheet-shaped epoxy resin composition, and the strength of the cured product of the sheet-shaped epoxy resin composition tends to decrease, There is a risk of impairing the reliability of the electronic component device.
硬化促進剤（Ｄ成分）は、エポキシ樹脂とフェノール樹脂の硬化を進行させるものであれば特に限定されるものではないが、硬化性と保存性の観点から、トリフェニルホスフィンやテトラフェニルホスホニウムテトラフェニルボレート等の有機リン系化合物や、イミダゾール系化合物が好適に用いられる。これら硬化促進剤は、単独で用いても良いし、他の硬化促進剤と併用しても構わない。 The curing accelerator (component D) is not particularly limited as long as it allows curing of the epoxy resin and the phenol resin, but from the viewpoint of curability and storage stability, triphenylphosphine and tetraphenylphosphonium tetraphenyl. Organic phosphorus compounds such as borates and imidazole compounds are preferably used. These curing accelerators may be used alone or in combination with other curing accelerators.
金属水酸化物（Ｅ成分）は難燃剤として使用する。金属水酸化物（Ｅ成分）としては、水酸化アルミニウム、水酸化マグネシウム、水酸化鉄、水酸化カルシウム、水酸化スズ、複合化金属水酸化物等の各種金属水酸化物を用いることができる。比較的少ない添加量で難燃性を発揮できる点や、コスト的な観点から水酸化アルミニウムまたは水酸化マグネシウムを用いることが好ましく、水酸化アルミニウムを用いることが特に好ましい。金属水酸化物（Ｅ成分）の平均粒径としては、シート状エポキシ樹脂組成物を加熱した際に適当な流動性を確保するという観点から、平均粒径が１〜１０μｍであることが好ましく、さらに好ましくは２〜５μｍである。金属水酸化物（Ｅ成分）の平均粒径が１μｍ未満では、シート状エポキシ樹脂組成物中に均一に分散させることが困難となるとともに、シート状エポキシ樹脂組成物の加熱時における流動性が十分に得られない傾向がある。また、平均粒径が１０μｍを超えると、金属水酸化物（Ｅ成分）の添加量あたりの表面積が小さくなるため、難燃効果が低下する傾向がみられる。 Metal hydroxide (E component) is used as a flame retardant. As the metal hydroxide (E component), various metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide, calcium hydroxide, tin hydroxide, and composite metal hydroxide can be used. Aluminum hydroxide or magnesium hydroxide is preferably used, and aluminum hydroxide is particularly preferably used from the viewpoint that flame retardancy can be exhibited with a relatively small addition amount and from the viewpoint of cost. The average particle diameter of the metal hydroxide (E component) is preferably 1 to 10 μm from the viewpoint of ensuring appropriate fluidity when the sheet-like epoxy resin composition is heated. More preferably, it is 2-5 micrometers. When the average particle diameter of the metal hydroxide (E component) is less than 1 μm, it becomes difficult to uniformly disperse the sheet-like epoxy resin composition, and the fluidity during heating of the sheet-like epoxy resin composition is sufficient. There is a tendency not to be obtained. Moreover, since the surface area per addition amount of a metal hydroxide (E component) will become small when an average particle diameter exceeds 10 micrometers, the tendency for a flame-retardant effect to fall is seen.
ホスファゼン化合物（Ｆ成分）は、式（１）で表されるホスファゼン化合物である。 The phosphazene compound (component F) is a phosphazene compound represented by the formula (1 ) .
上記式（１）で表されるホスファゼン化合物（Ｆ成分）は、上記金属水酸化物（Ｅ成分）とともに難燃剤として使用する。このホスファゼン化合物（Ｆ成分）は、ＳＰＲ−１００、ＳＡ−１００、ＳＰ−１００（以上、大塚化学株式会社）、ＦＰ−１００、ＦＰ−１１０（以上、株式会社伏見製薬所）等が市販品として入手可能である。少量でも難燃効果を発揮するという観点から、式（１）で表されるホスファゼン化合物に含まれるリン元素の含有率は、１２重量％以上であることが好ましい。また、安定性およびボイドの生成抑制という観点から、式（３）で表される環状ホスファゼンオリゴマーを用いることが好ましい。式（３）で表される環状ホスファゼンオリゴマーは、ＦＰ−１００、ＦＰ−１１０（以上、株式会社伏見製薬所）等が市販品として入手可能である。 The phosphazene compound (F component) represented by the above formula (1 ) is used as a flame retardant together with the metal hydroxide (E component). This phosphazene compound (component F) is commercially available as SPR-100, SA-100, SP-100 (above, Otsuka Chemical Co., Ltd.), FP-100, FP-110 (above, Fushimi Pharmaceutical Co., Ltd.), etc. It is available. From the viewpoint of exhibiting a flame retardant effect even in a small amount, the content of the phosphorus element contained in the phosphazene compound represented by the formula (1 ) is preferably 12% by weight or more. Moreover, it is preferable to use the cyclic phosphazene oligomer represented by Formula (3) from a viewpoint of stability and suppression of void formation. As for the cyclic phosphazene oligomer represented by the formula (3), FP-100, FP-110 (above, Fushimi Pharmaceutical Co., Ltd.) and the like are commercially available.
なお、上記金属水酸化物（Ｅ成分）およびホスファゼン化合物（Ｆ成分）を併用することにより、シート封止に必要な可撓性を確保しつつ、難燃性に優れたシート状エポキシ樹脂組成物を得ることが可能となる。すなわち、難燃剤として金属水酸化物（Ｅ成分）のみを用いた場合は、十分な可撓性を得ることが困難となり、ホスファゼン化合物（Ｆ成分）のみを用いた場合は、十分な難燃性を得ることが困難となる。 In addition, by using together the said metal hydroxide (E component) and a phosphazene compound (F component), the sheet-like epoxy resin composition excellent in the flame retardance was ensured, ensuring the flexibility required for sheet sealing. Can be obtained. That is, when only a metal hydroxide (E component) is used as a flame retardant, it becomes difficult to obtain sufficient flexibility, and when only a phosphazene compound (F component) is used, sufficient flame retardancy is obtained. It becomes difficult to obtain.
金属水酸化物（Ｅ成分）およびホスファゼン化合物（Ｆ成分）の含有量は、両成分の合計量が、シート状エポキシ樹脂組成物全体の７０〜９０重量％であり、好ましくは７５〜８５重量％である。すなわち、合計量が７０重量％未満では、シート状エポキシ樹脂組成物の十分な難燃性が得ることが困難となり、９０重量％を超えると、シート状エポキシ樹脂組成物の被着体への接着性が低下し、ボイドが発生する傾向がみられる。 The content of the metal hydroxide (component E) and the phosphazene compound (component F) is such that the total amount of both components is 70 to 90% by weight, preferably 75 to 85% by weight, based on the total amount of the sheet-like epoxy resin composition. It is. That is, when the total amount is less than 70% by weight, it becomes difficult to obtain sufficient flame retardancy of the sheet-like epoxy resin composition, and when it exceeds 90% by weight, adhesion of the sheet-like epoxy resin composition to the adherend is difficult. Tend to be reduced and voids tend to occur.
また、ホスファゼン化合物（Ｆ成分）の含有量が、シート状エポキシ樹脂組成物中に含まれる、エポキシ樹脂（Ａ成分）、フェノール樹脂（Ｂ成分）、エラストマー（Ｃ成分）、硬化促進剤（Ｄ成分）およびホスファゼン化合物（Ｆ成分）を含む有機成分全体の１０〜３０重量％であることが好ましい。すなわち、ホスファゼン化合物（Ｆ成分）の含有量が、有機成分全体の１０重量％未満では、シート状エポキシ樹脂組成物の難燃性が低下するとともに、被着体に対する凹凸追従性が低下し、ボイドが発生する傾向がみられる。含有量が有機成分全体の３０重量％を超えると、シート状エポキシ樹脂組成物の表面にタックが生じやすくなり、シート状エポキシ樹脂組成物を被着体に位置合わせしにくくなる等作業性が低下する傾向がみられる。 In addition, the content of the phosphazene compound (component F) is contained in the sheet-shaped epoxy resin composition, epoxy resin (component A), phenol resin (component B), elastomer (component C), curing accelerator (component D) ) And the phosphazene compound (F component), the total content is preferably 10 to 30% by weight. That is, when the content of the phosphazene compound (component F) is less than 10% by weight of the whole organic component, the flame retardancy of the sheet-like epoxy resin composition is lowered, and the unevenness followability to the adherend is lowered, resulting in voids. There is a tendency to occur. When the content exceeds 30% by weight of the total organic components, tackiness is likely to occur on the surface of the sheet-like epoxy resin composition, and workability such as difficulty in aligning the sheet-like epoxy resin composition with the adherend is reduced. There is a tendency to
なお、本発明のシート状エポキシ樹脂組成物では、上記の各成分以外に必要に応じて、シリカ粉末をはじめとする金属水酸化物（Ｅ成分）以外の無機充填剤、カーボンブラックをはじめとする顔料等、他の添加剤を適宜配合することができる。 In addition, in the sheet-like epoxy resin composition of the present invention, an inorganic filler other than the metal hydroxide (E component) including silica powder and carbon black are included as necessary in addition to the above components. Other additives such as pigments can be appropriately blended.
上記金属水酸化物（Ｅ成分）以外の無機充填剤としては、特に限定されるものではなく従来公知の各種充填剤を用いることができる。例えば、石英ガラス粉末、タルク、シリカ粉末（溶融シリカ粉末や結晶性シリカ粉末等）、アルミナ粉末、窒化アルミニウム粉末、窒化ケイ素粉末等が挙げられる。これらは単独で用いても良いし、２種以上併用してもよい。中でも、コストの観点および得られる硬化体の熱線膨張係数を低下させて内部応力を低減できるという観点から、シリカ粉末を用いることが好ましく、上記シリカ粉末の中でも溶融シリカ粉末を用いることが、高充填性および高流動性という点から特に好ましい。上記溶融シリカ粉末としては、球状溶融シリカ粉末、破砕溶融シリカ粉末が挙げられるが、流動性という観点から、球状溶融シリカ粉末を用いることが特に好ましい。中でも、平均粒径が０．１〜３０μｍの範囲のものを用いることが好ましく、０．３〜１５μｍの範囲のものを用いることが特に好ましい。なお、上記平均粒径は、例えば、母集団から任意に抽出される試料を用い、レーザー回折散乱式粒度分布測定装置を用いて測定することにより導き出すことができる。 The inorganic filler other than the metal hydroxide (component E) is not particularly limited, and various conventionally known fillers can be used. Examples thereof include quartz glass powder, talc, silica powder (such as fused silica powder and crystalline silica powder), alumina powder, aluminum nitride powder, and silicon nitride powder. These may be used alone or in combination of two or more. Among them, silica powder is preferably used from the viewpoint of cost and the thermal stress of the resulting cured body can be reduced to reduce internal stress, and among the above silica powder, it is preferable to use fused silica powder. Is particularly preferable from the viewpoint of the property and the high fluidity. Examples of the fused silica powder include spherical fused silica powder and crushed fused silica powder. From the viewpoint of fluidity, it is particularly preferable to use a spherical fused silica powder. Among them, those having an average particle size in the range of 0.1 to 30 μm are preferably used, and those having a range of 0.3 to 15 μm are particularly preferable. In addition, the said average particle diameter can be derived | led-out by measuring using the laser diffraction scattering type particle size distribution measuring apparatus, for example using the sample extracted arbitrarily from a population.
また、本発明のシート状エポキシ樹脂組成物は、例えば以下のようにして製造することができる。 Moreover, the sheet-like epoxy resin composition of this invention can be manufactured as follows, for example.
まず、各配合成分を混合することによりエポキシ樹脂組成物を調製するが、各配合成分が均一に分散混合される方法であれば特に限定するものではない。例えば、各配合成分を有機溶剤等に溶解または分散したワニスを塗工してシート状に形成する。あるいは、各配合成分を直接ニーダー等で混練することにより固形樹脂組成物を調製し、このようにして得られた固形樹脂組成物を押し出してシート状に形成してもよい。中でも、簡便に均一な厚みのシートを得ることができるという点から、上記ワニス塗工を好適に用いることができる。 First, an epoxy resin composition is prepared by mixing each compounding component, but there is no particular limitation as long as each compounding component is uniformly dispersed and mixed. For example, a varnish in which each compounding component is dissolved or dispersed in an organic solvent or the like is applied to form a sheet. Alternatively, a solid resin composition may be prepared by directly kneading each compounding component with a kneader or the like, and the solid resin composition thus obtained may be extruded to form a sheet. Especially, the said varnish coating can be used suitably from the point that the sheet | seat of uniform thickness can be obtained simply.
より具体的には、上記Ａ〜Ｆ成分および必要に応じて他の添加剤を常法に準じて適宜混合し、有機溶剤に均一に溶解あるいは分散させ、ワニスを調製する。ついで、上記ワニスをポリエステル等の基材上に塗布し乾燥させることによりシート状エポキシ樹脂組成物を得ることができる。そして必要により、シート状エポキシ樹脂組成物の表面を保護するためにポリエステルフィルム等の剥離シートを貼り合わせてもよい。剥離シートは封止時に剥離する。 More specifically, the above A to F components and, if necessary, other additives are appropriately mixed according to a conventional method, and uniformly dissolved or dispersed in an organic solvent to prepare a varnish. Subsequently, the sheet-like epoxy resin composition can be obtained by applying the varnish on a substrate such as polyester and drying it. And if necessary, in order to protect the surface of a sheet-like epoxy resin composition, you may bond together peeling sheets, such as a polyester film. The release sheet peels at the time of sealing.
上記有機溶剤としては、特に限定するものではなく従来公知の各種有機溶剤、例えばメチルエチルケトン、アセトン、シクロヘキサノン、ジオキサン、ジエチルケトン、トルエン、酢酸エチル等を用いることができる。これらは単独で用いてもよいし、２種以上併せて用いてもよい。また通常、ワニスの固形分濃度が３０〜６０重量％の範囲となるように有機溶剤を用いることが好ましい。 The organic solvent is not particularly limited, and various conventionally known organic solvents such as methyl ethyl ketone, acetone, cyclohexanone, dioxane, diethyl ketone, toluene, and ethyl acetate can be used. These may be used alone or in combination of two or more. Usually, it is preferable to use an organic solvent so that the solid content concentration of the varnish is in the range of 30 to 60% by weight.
有機溶剤乾燥後のシートの厚みは、特に制限されるものではないが、厚みの均一性と残存溶剤量の観点から、通常、５〜１００μｍに設定することが好ましく、より好ましくは２０〜７０μｍである。このようにして得られたシート状エポキシ樹脂組成物は、必要により所望の厚みとなるように積層して使用してもよい。すなわち、シート状エポキシ樹脂組成物は、単層構造にて使用してもよいし、２層以上の多層構造に積層してなる積層体として使用してもよい。 Although the thickness of the sheet after drying the organic solvent is not particularly limited, it is usually preferably set to 5 to 100 μm, more preferably 20 to 70 μm, from the viewpoint of uniformity of thickness and the amount of residual solvent. is there. The sheet-like epoxy resin composition thus obtained may be used by being laminated so as to have a desired thickness if necessary. That is, the sheet-like epoxy resin composition may be used in a single layer structure, or may be used as a laminate formed by laminating two or more multilayer structures.
上記のようにして得られる本発明のシート状エポキシ樹脂組成物を用いると、高い難燃性を有する電子部品装置を容易に得ることができる。この電子部品装置（図１）は、例えば以下のようにして製造することができる。 When the sheet-like epoxy resin composition of the present invention obtained as described above is used, an electronic component device having high flame retardancy can be easily obtained. This electronic component device (FIG. 1) can be manufactured as follows, for example.
まず、実装基板上に電子部品を、実装基板の接続用電極部と電子部品の接続用電極部が接続するように設置する。 First, the electronic component is installed on the mounting substrate so that the connection electrode portion of the mounting substrate and the connection electrode portion of the electronic component are connected.
シート状エポキシ樹脂組成物を、電子部品を覆うように実装基板上に載置する。 The sheet-like epoxy resin composition is placed on the mounting substrate so as to cover the electronic component.
ついで、シート状エポキシ樹脂組成物を、温度６０〜１２０℃、圧力１００〜２０００ｋＰａでプレスすることにより、電子部品および実装基板と接着する。その際、プレス時間は０．５〜５分が好ましい。また、電子部品と実装基板による凹凸部に対するシート状エポキシ樹脂組成物の追従性および密着性を向上させるため、真空条件下で加圧することが好ましい。 Next, the sheet-like epoxy resin composition is pressed at a temperature of 60 to 120 ° C. and a pressure of 100 to 2000 kPa to adhere to the electronic component and the mounting substrate. At that time, the pressing time is preferably 0.5 to 5 minutes. Moreover, in order to improve the followability | trackability and adhesiveness of the sheet-like epoxy resin composition with respect to the uneven | corrugated | grooved part by an electronic component and a mounting substrate, it is preferable to pressurize on vacuum conditions.
その後、シート状エポキシ樹脂組成物を、大気圧下で、温度１００〜２００℃で硬化することにより、その硬化体からなる封止樹脂層によって電子部品が封止された電子部品装置集合体を得る。その際、速やかに、かつ完全に熱硬化を進行させるため、加熱時間は３０〜１２０分であることが好ましい。 Thereafter, the sheet-like epoxy resin composition is cured at a temperature of 100 to 200 ° C. under atmospheric pressure, thereby obtaining an electronic component device assembly in which the electronic components are sealed with a sealing resin layer made of the cured product. . In that case, in order to advance thermosetting rapidly and completely, it is preferable that heating time is 30 to 120 minutes.
最後に、樹脂封止面にダイシングテープを貼り、電子部品装置集合体をダイシングすることにより、電子部品装置（図１）を得る。 Finally, a dicing tape is applied to the resin sealing surface, and the electronic component device assembly is diced to obtain an electronic component device (FIG. 1).
また、電子部品装置の別の形態として、電子部品側面を樹脂封止した電子部品装置（図２）については、例えば以下のようにして製造することができる。 As another form of the electronic component device, an electronic component device (FIG. 2) in which the side surface of the electronic component is sealed with resin can be manufactured, for example, as follows.
実装基板上に載置された電子部品の位置に合わせて予めパンチ等で貫通孔を設けておいたシート状エポキシ樹脂組成物を、電子部品が貫通孔の中に含まれるようにして前記実装基板上に設置する。ついで、上型が柔軟なゴム製シートからなるプレス装置を用い、それ以外は上記電子部品装置の製法と同様にして、電子部品装置（図２）を得る。 A sheet-like epoxy resin composition in which a through hole is provided in advance by a punch or the like in accordance with the position of the electronic component placed on the mounting substrate, and the electronic component is included in the through hole. Install on top. Next, an electronic component device (FIG. 2) is obtained in the same manner as the above-described electronic component device manufacturing method, except that a press device in which the upper mold is made of a flexible rubber sheet is used.
つぎに、実施例について比較例と併せて説明する。ただし、本発明は、これら実施例に限定されるものではない。 Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.
まず、下記に示す各成分を準備した。
〔エポキシ樹脂ａ〕
変性ビスフェノールＡ型エポキシ樹脂（ＤＩＣ株式会社、ＥＰＩＣＬＯＮ ＥＸＡ−４８５０−１５０）
〔エポキシ樹脂ｂ〕
トリフェニルメタン型エポキシ樹脂（日本化薬株式会社、ＥＰＰＮ−５０１ＨＹ）
〔フェノール樹脂〕
ノボラック型フェノール樹脂（荒川化学工業株式会社、Ｐ−２００）
〔エラストマーａ〕
アクリル系共重合体（ブチルアクリレート：アクリロニトリル：グリシジルメタクリレート＝８５：８：７重量％からなる共重合体。重量平均分子量８０万）
上記アクリル系共重合体は、以下のように合成した。ブチルアクリレート、アクリロニトリル、グリシジルメタクリレートを８５：８：７の仕込み重量比率にて、２，２’−アゾビスイソブチロニトリルを重合開始剤に用い、メチルエチルケトン中で窒素気流下、７０℃で５時間と８０℃で1時間のラジカル重合を行うことにより、目的とするアクリル系共重合体を得た。
〔エラストマーｂ〕
スチレンアクリレート系共重合体（東亜合成株式会社、ＵＧ−４０４０）
〔硬化促進剤〕
２−フェニル−４，５−ジヒドロキシメチルイミダゾール（四国化成工業株式会社、２ＰＨＺ−ＰＷ）
〔金属水酸化物ａ〕
平均粒径２．７μｍの水酸化アルミニウム粉末（昭和電工株式会社、ＨＰ−３６０）
〔金属水酸化物ｂ〕
平均粒径１．２μｍの水酸化マグネシウム（タテホ化学工業株式会社、ＰＺ−１）
〔ホスファゼン化合物〕
下記の式（４）で表されるホスファゼン化合物（株式会社伏見製薬所、ＦＰ−１００）
First, each component shown below was prepared.
[Epoxy resin a]
Modified bisphenol A type epoxy resin (DIC Corporation, EPICLON EXA-4850-150)
[Epoxy resin b]
Triphenylmethane type epoxy resin (Nippon Kayaku Co., Ltd., EPPN-501HY)
[Phenolic resin]
Novolac type phenolic resin (Arakawa Chemical Industries, Ltd., P-200)
[Elastomer a]
Acrylic copolymer (copolymer composed of butyl acrylate: acrylonitrile: glycidyl methacrylate = 85: 8: 7 wt%. Weight average molecular weight 800,000)
The acrylic copolymer was synthesized as follows. Butyl acrylate, acrylonitrile, glycidyl methacrylate in a weight ratio of 85: 8: 7, using 2,2′-azobisisobutyronitrile as a polymerization initiator in methyl ethyl ketone at 70 ° C. for 5 hours under a nitrogen stream And the intended acrylic copolymer was obtained by performing radical polymerization at 80 ° C. for 1 hour.
[Elastomer b]
Styrene acrylate copolymer (Toa Gosei Co., Ltd., UG-4040)
[Curing accelerator]
2-Phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemicals Co., Ltd., 2PHZ-PW)
[Metal hydroxide a]
Aluminum hydroxide powder having an average particle size of 2.7 μm (Showa Denko KK, HP-360)
[Metal hydroxide b]
Magnesium hydroxide having an average particle size of 1.2 μm (Tateho Chemical Industries, PZ-1)
[Phosphazene compounds]
Phosphazene compound represented by the following formula (4) (Fushimi Pharmaceutical Co., Ltd., FP-100)
〔ホスファゼン化合物以外の有機リン化合物ａ〕
下記の式（５）で表されるビフェニルリン酸エステル化合物（三光株式会社、ＨＣＡ）
[Organic phosphorus compounds a other than phosphazene compounds]
Biphenyl phosphate compound represented by the following formula (5) (Sanko Co., Ltd., HCA)
〔ホスファゼン化合物以外の有機リン化合物ｂ〕
下記の式（６）で表されるトリフェニルホスフェート（大八化学工業株式会社、ＴＰＰ）
[Organic phosphorus compounds b other than phosphazene compounds]
Triphenyl phosphate represented by the following formula (6) (Daihachi Chemical Industry Co., Ltd., TPP)
〔無機充填材〕
平均粒径７μｍの球状溶融シリカ粉末（電気化学工業株式会社、ＦＢ−７ＳＤＣ）
〔実施例１、２、５、６、参考例１〜４、比較例１〜４〕
〔シート状エポキシ樹脂組成物の作製〕
表１〜表３に示す割合で各成分を分散混合し、これに各成分の合計量と同量のメチルエチルケトンを加えて、塗工用ワニスを調製した。
[Inorganic filler]
Spherical fused silica powder with an average particle size of 7 μm (Electrochemical Co., Ltd., FB-7SDC)
[Examples 1 , 2, 5, 6, Reference Examples 1-4, Comparative Examples 1-4]
[Preparation of sheet-like epoxy resin composition]
Each component was dispersed and mixed in the proportions shown in Tables 1 to 3, and methyl ethyl ketone in the same amount as the total amount of each component was added thereto to prepare a coating varnish.
つぎに、上記ワニスを、厚さ３８μｍのポリエステルフィルム（三菱樹脂株式会社、ＭＲＦ−３８）の剥離処理面上にコンマコーターにて塗工し、乾燥することにより厚みが５０μｍのシート状エポキシ樹脂組成物を得た。 Next, the varnish is coated on a release treatment surface of a 38 μm thick polyester film (Mitsubishi Resin Co., Ltd., MRF-38) with a comma coater, and dried to form a sheet-like epoxy resin composition having a thickness of 50 μm. I got a thing.
ついで、別途用意したポリエステルフィルムの剥離処理面を、シート状エポキシ樹脂組成物に貼り合わせて巻き取った。その後、ポリエステルフィルムを適宜剥離しながら、ロールラミネーターにより上記シート状エポキシ樹脂組成物を３枚積層することにより、厚さ１５０μｍのシート状エポキシ樹脂組成物を得た。
〔電子部品装置集合体の作製〕
電子部品として積層セラミックコンデンサ（コンデンサ厚み５００μｍ）を碁盤目状に１万個配列載置した縦１５０ｍｍ、横１５０ｍｍ、厚み３００μｍのガラス−エポキシ（ＦＲ−４）基板を準備し、得られたシート状エポキシ樹脂組成物を基板上の全ての電子部品を覆うように配置した。配置したシート状エポキシ樹脂組成物を、真空下（０．１ｋＰａ）、温度８０℃、圧力３００ｋＰａでプレスすることにより、電子部品および実装基板と接着した。ついで、大気圧下でシート状エポキシ樹脂組成物を熱硬化（１５０℃、１時間）させて電子部品を封止し、常温まで自然冷却させることにより電子部品装置集合体を得た。最後に、樹脂封止面にダイシングテープを貼り、前記電子部品装置集合体をダイシングすることにより、電子部品装置を得た。
〔難燃性〕
得られたシート状エポキシ樹脂組成物の難燃性を以下のように評価した。
Subsequently, the release treatment surface of the separately prepared polyester film was bonded to the sheet-like epoxy resin composition and wound up. Then, the sheet-like epoxy resin composition having a thickness of 150 μm was obtained by laminating three sheets of the sheet-like epoxy resin composition with a roll laminator while appropriately peeling the polyester film.
[Production of electronic device assembly]
As an electronic component, a glass-epoxy (FR-4) substrate having a length of 150 mm, a width of 150 mm, and a thickness of 300 μm in which 10,000 multilayer ceramic capacitors (capacitor thickness of 500 μm) are arranged in a grid pattern is prepared, and the obtained sheet shape The epoxy resin composition was disposed so as to cover all the electronic components on the substrate. The placed sheet-like epoxy resin composition was bonded to an electronic component and a mounting substrate by pressing under vacuum (0.1 kPa) at a temperature of 80 ° C. and a pressure of 300 kPa. Next, the sheet-shaped epoxy resin composition was thermally cured (150 ° C., 1 hour) under atmospheric pressure to seal the electronic component, and naturally cooled to room temperature to obtain an electronic component device assembly. Finally, a dicing tape was applied to the resin sealing surface, and the electronic component device assembly was diced to obtain an electronic component device.
〔Flame retardance〕
The flame retardancy of the obtained sheet-like epoxy resin composition was evaluated as follows.
シート状エポキシ樹脂組成物を、熱硬化（条件：１５０℃、１時間加熱）させて硬化物を作製し、得られた硬化物についてＵＬ９４Ｖ−０規格に従って評価し、ＵＬ９４Ｖ−０規格に合格したものを○、不合格のものを×とした。
〔表面タック〕
得られたシート状エポキシ樹脂組成物の表面タックの有無を、指触テストにて判定した。
〔内部ボイドの有無〕
得られた電子部品装置中の内部ボイド有無について、高速フーリエ変換型超音波顕微鏡（Ｃ−ＳＡＭ Ｄ６０００、日本バーンズ株式会社）を用いて確認を行った。５０μｍ以下の微小な内部ボイドが０だったものを○、１〜５０個だったものを△、５１個以上だったものを×とした。
〔接続信頼性〕
得られた電子部品装置を、半田リフロー時の条件下（２６０℃で１０秒間の加熱を３回反復）にさらした。ついで、封止樹脂層と実装基板や電子部品との剥離の有無を、前記高速フーリエ変換型超音波顕微鏡にて観察し、剥離がなかったものを○、あったものを×とした。
A sheet-like epoxy resin composition is heat-cured (conditions: 150 ° C., heated for 1 hour) to produce a cured product. Was marked with ◯, and rejected with x.
[Surface tack]
The presence or absence of surface tack of the obtained sheet-like epoxy resin composition was determined by a finger touch test.
[Existence of internal voids]
The presence or absence of internal voids in the obtained electronic component device was confirmed using a fast Fourier transform type ultrasonic microscope (C-SAM D6000, Nihon Burns Co., Ltd.). A case where the number of minute internal voids of 50 μm or less was 0 was evaluated as “◯”, a case where it was 1-50, “Δ”, and a case where it was 51 or more, ×.
[Connection reliability]
The obtained electronic component device was exposed to the conditions during solder reflow (heating at 260 ° C. for 10 seconds three times). Subsequently, the presence or absence of peeling between the sealing resin layer and the mounting substrate or the electronic component was observed with the fast Fourier transform ultrasonic microscope.
その結果、実施例品は、難燃性および接続信頼性に優れていることがわかる。特に、ホスファゼン化合物（Ｆ成分）の含有量が、有機成分全体の１０〜３０重量％である実施例１、２、５は、ボイド生成抑制および表面タック生成抑制にも優れていることがわかる。 As a result, it can be seen that the example products are excellent in flame retardancy and connection reliability. In particular, it can be seen that Examples 1 , 2, and 5 in which the content of the phosphazene compound (F component) is 10 to 30% by weight of the entire organic component are excellent in suppressing void generation and surface tack generation.
これに対して、金属水酸化物（Ｅ成分）およびホスファゼン化合物（Ｆ成分）の合計含有量が、シート状エポキシ樹脂組成物全体の７０〜９０重量％の範囲から外れる比較例１および２は、難燃性または接続信頼性に劣るものであった。また、ホスファゼン化合物Ｆ成分以外の有機リン系の難燃剤を用いた比較例３および４では、十分な難燃性が得られないことがわかる。金属水酸化物ではなく球状溶融シリカ粉末を用いた比較例５についても、十分な難燃性が得られないことがわかる。 On the other hand, Comparative Examples 1 and 2 in which the total content of the metal hydroxide (E component) and the phosphazene compound (F component) is out of the range of 70 to 90% by weight of the entire sheet-like epoxy resin composition are as follows: It was inferior in flame retardancy or connection reliability. Moreover, it turns out that sufficient flame retardance is not obtained in Comparative Examples 3 and 4 using an organophosphorus flame retardant other than the phosphazene compound F component. It can be seen that sufficient flame retardancy cannot be obtained for Comparative Example 5 using spherical fused silica powder instead of metal hydroxide.
１ 電子部品
２ 実装基板
３ 電子部品の接続用電極部
４ 封止樹脂層
５ 貫通孔
DESCRIPTION OF SYMBOLS 1
Claims (4)
Ａ：エポキシ樹脂
Ｂ：フェノール樹脂
Ｃ：エラストマー
Ｄ：硬化促進剤
Ｅ：金属水酸化物
Ｆ：式（１）で表されるホスファゼン化合物
A: Epoxy resin B: Phenol resin C: Elastomer D: Curing accelerator E: Metal hydroxide F: Phosphazene compound represented by formula (1)
The electronic component apparatus formed by sealing an electronic component using the sheet-like epoxy resin composition in any one of Claims 1-3.
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| JP2013007028A (en) * | 2011-05-20 | 2013-01-10 | Nitto Denko Corp | Sealing sheet and electronic component device |
| WO2013073846A1 (en) * | 2011-11-14 | 2013-05-23 | 주식회사 엘지화학 | Adhesive film and method for encapsulating organic electronic device using same |
| JP2016166279A (en) * | 2015-03-09 | 2016-09-15 | 三菱化学株式会社 | Thermosetting resin composition and molded article thereof |
| JP2017139413A (en) * | 2016-02-05 | 2017-08-10 | 日立化成株式会社 | Method of manufacturing semiconductor device |
| JP6805518B2 (en) * | 2016-03-28 | 2020-12-23 | 味の素株式会社 | Resin composition, resin sheet, printed wiring board and semiconductor device |
| JP7258906B2 (en) * | 2018-03-15 | 2023-04-17 | アプライド マテリアルズ インコーポレイテッド | Planarization for semiconductor device package manufacturing process |
| JP2022075360A (en) * | 2020-11-06 | 2022-05-18 | 東洋インキＳｃホールディングス株式会社 | Electronic device package and manufacturing method of the same |
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