JP2615550B2 - Resin-sealed electronic components - Google Patents
Resin-sealed electronic componentsInfo
- Publication number
- JP2615550B2 JP2615550B2 JP60203294A JP20329485A JP2615550B2 JP 2615550 B2 JP2615550 B2 JP 2615550B2 JP 60203294 A JP60203294 A JP 60203294A JP 20329485 A JP20329485 A JP 20329485A JP 2615550 B2 JP2615550 B2 JP 2615550B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyphenylene sulfide
- styrene
- copolymer
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 42
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 23
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 229920001955 polyphenylene ether Polymers 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 15
- 150000001993 dienes Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011256 inorganic filler Chemical class 0.000 claims description 4
- 229910003475 inorganic filler Chemical class 0.000 claims description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 12
- 239000005060 rubber Substances 0.000 description 11
- 239000011342 resin composition Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- -1 transducers Substances 0.000 description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- UMTNVLRKTUVQTC-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile;prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1.N#CC=CC=CC1=CC=CC=C1 UMTNVLRKTUVQTC-UHFFFAOYSA-N 0.000 description 1
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001368 Crepe rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 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 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- H01L23/295—Organic, e.g. plastic containing a filler
-
- 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
-
- 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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Graft Or Block Polymers (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Organic Insulating Materials (AREA)
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は機械的性質が改善され、かつ電子部品の信頼
性を高めうるポリフェニレンサルファイド樹脂組成物で
封止された樹脂封止電子部品に関するものであり、IC、
トランジスター、キャパシター、レジスター、ダイオー
ド、トリオード、サイリスター、コイル、バリスター、
コネクター、コンデンサー、トランスデューサー、水晶
発振器、ヒューズ、整流器、電源、マイクロスイッチ、
およびこれらの複合部品等の電子部品に利用される。Description: TECHNICAL FIELD The present invention relates to a resin-sealed electronic component sealed with a polyphenylene sulfide resin composition which has improved mechanical properties and can enhance the reliability of the electronic component. And IC,
Transistors, capacitors, resistors, diodes, triodes, thyristors, coils, varistors,
Connectors, capacitors, transducers, crystal oscillators, fuses, rectifiers, power supplies, micro switches,
And electronic components such as composite components.
(従来の技術および発明が解決しようとする問題点) IC、トランジスター、キャパシター、レジスター等、
上記に挙げた電子部品は電気絶縁性の保持、機械的保
護、外部雰囲気による特性変化の防止等の目的で合成樹
脂で封止することが広く行われている。合成樹脂として
は従来エポキシ樹脂やシリコン樹脂等の熱硬化性樹脂が
主に使用されているが、これらの熱硬化性樹脂を用いて
電子部品を封止する際、成形サイクルが長い、バリが出
やすい、樹脂自体の保存性が充分でない、スプルーラン
ナーの再利用ができない、等の欠点がある。(Problems solved by conventional technology and invention) ICs, transistors, capacitors, resistors, etc.
The above-mentioned electronic components are widely sealed with a synthetic resin for the purpose of maintaining electrical insulation, mechanical protection, preventing a change in characteristics due to an external atmosphere, and the like. Conventionally, thermosetting resins such as epoxy resins and silicone resins have been mainly used as synthetic resins.However, when using these thermosetting resins to seal electronic components, the molding cycle is long and burrs appear. There are drawbacks such as that the resin is not easily preserved, the preservability of the resin itself is not sufficient, and the sprue runner cannot be reused.
一方、ポリフェニレンサルファイド樹脂は耐熱性、難
燃性、耐薬品性に優れ、かつ熱可塑性樹脂であるため
に、上記の熱硬化性樹脂にみられる欠点がなく、生産性
が高いと言う利点を有していることから、近年電子部品
封止用樹脂として注目されている。On the other hand, polyphenylene sulfide resin has excellent heat resistance, flame retardancy, chemical resistance, and is a thermoplastic resin, and therefore has the advantages of high productivity without the above-mentioned drawbacks of thermosetting resins. In recent years, it has attracted attention as a resin for electronic component sealing.
ところが、電子部品にストレスを与えずに樹脂封止を
行うためには、該ポリフェニレンサルファイド樹脂組成
物は低い溶融粘度であることが必要であり、そのために
は該ポリフェニレンサルファイド樹脂自体を低分子量と
し、低い溶融粘度としているが、本来、ポリフェニレン
サルファイド樹脂自体、伸びが少ないこともあり、当該
樹脂組成物から得られる電子部品封止成形物が極めて脆
弱となり、その一部が欠けたりクラックをおこすような
問題があった。更に、樹脂自体の柔軟性、親水性が少な
いために電子部品のリード金属との密着性にも欠け、電
子部品の信頼性が高くないと言う問題もあった。However, in order to perform resin sealing without applying stress to electronic components, the polyphenylene sulfide resin composition needs to have a low melt viscosity, and for that purpose, the polyphenylene sulfide resin itself has a low molecular weight, Although it has a low melt viscosity, originally, the polyphenylene sulfide resin itself, there is also a small elongation, the electronic component encapsulation molded product obtained from the resin composition becomes extremely brittle, such that part of it may be chipped or cracked There was a problem. Furthermore, since the resin itself has low flexibility and low hydrophilicity, there is also a problem that the adhesion of the electronic component to a lead metal is lacking and the reliability of the electronic component is not high.
(問題点を解決するための手段) 本発明者らは、上記の如き状況に鑑み、機械的性質お
よびリード金属との密着性が改善されたポリフェニレン
サルファイド樹脂組成物で封止され、機械的保護性およ
び電気的性質が改善された樹脂封止電子部品を得るべく
鋭意検討した結果、無機充填材を含む特定のメルトフロ
ーレートのポリフェニレンサルファイド樹脂にポリフェ
ニレンエーテル樹脂と水素化ジエンとスチレンのゴム状
共重合体とを添加することで上記の問題点が解決される
ことを見出し、本発明に至ったものである。(Means for Solving the Problems) In view of the above situation, the inventors of the present invention sealed with a polyphenylene sulfide resin composition having improved mechanical properties and adhesion to a lead metal to provide mechanical protection. As a result of intensive studies to obtain resin-encapsulated electronic components with improved properties and electrical properties, a polyphenylene sulfide resin with a specific melt flow rate containing an inorganic filler and a rubber-like copolymer of polyphenylene ether resin, hydrogenated diene and styrene The inventors have found that the above problems can be solved by adding a polymer, and have reached the present invention.
本発明のポリフェニレンサルファイド樹脂は一般式 の繰り返し単位を有し、本発明の目的を逸脱しない範囲
で共重合体樹脂も用いることができる。又、該ポリフェ
ニレンサルファイド樹脂はASTM D 1238−74(316
℃、5kg荷重)で測定されたメルトフローレイトが500〜
10000g/10分の範囲であり、電子部品の種類によって、
適切なメルトフローレイトを選択できる。例えば半導体
電子部品に適したポリフェニレンサルファイド樹脂のメ
ルトフローレイトは、3000〜10000g/10分である。該リ
フェニレンサルファイド樹脂は架橋していない重合体、
酸素、イオウ、3官能モノマーで架橋した重合体および
これらの混合物が含まれる。The polyphenylene sulfide resin of the present invention has a general formula And a copolymer resin may be used without departing from the purpose of the present invention. The polyphenylene sulfide resin is ASTM D 1238-74 (316
Melt flow rate measured at 500 ° C, 5kg load) is 500 ~
10000g / 10min range, depending on the type of electronic components
An appropriate melt flow rate can be selected. For example, the melt flow rate of polyphenylene sulfide resin suitable for semiconductor electronic components is 3000 to 10,000 g / 10 minutes. The phenylene sulfide resin is a non-crosslinked polymer,
Oxygen, sulfur and polymers crosslinked with trifunctional monomers and mixtures thereof are included.
本発明に用いられるポリフェニレンエーテル樹脂は一
般式 (式中一つの単位の酸素原子は次に隣接する単位のベン
ゼン核に接続し、Qは水素、ハロゲン、三級α−炭素原
子を含有しない炭化水素基、ハロゲン原子とフェニル核
の間に少なくとも2個の炭素原子を有するハロゲン炭化
水素基、炭化水素オキシ基およびハロゲン原子とフェニ
ル核の間に少なくとも2個の炭素原子を有するハロ炭化
水素オキシ基からなる群から選択した一価置換基を表
す) の繰り返し単位を有し、例えばポリ(2,6−ジメチル−
1,4−フェニレン)エーテル;ポリ(2,6−ジエチル−1,
4−フェニレン)エーテル;ポリ(2−メチル−6−エ
チル−1,4−フェニレン)エーテル;ポリ(2−メチル
−6−プロピル−1,4−フェニレン)エーテル;ポリ
(2,6−ジプロピル−1,4−フェニレン)エーテルおよび
ポリ(2−エチル−6−プロピル−1,4−フェニレン)
エーテルを含む。好ましいのはポリ(2,6−ジメチル−
1,4−フェニレン)エーテルである。The polyphenylene ether resin used in the present invention has a general formula (Where the oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, and Q is hydrogen, halogen, a hydrocarbon group containing no tertiary α-carbon atom, at least between the halogen atom and the phenyl nucleus. Represents a monovalent substituent selected from the group consisting of a halogenated hydrocarbon group having two carbon atoms, a hydrocarbonoxy group, and a halohydrocarbonoxy group having at least two carbon atoms between the halogen atom and the phenyl nucleus ), For example, poly (2,6-dimethyl-
1,4-phenylene) ether; poly (2,6-diethyl-1,
4- (phenylene) ether; poly (2-methyl-6-ethyl-1,4-phenylene) ether; poly (2-methyl-6-propyl-1,4-phenylene) ether; poly (2,6-dipropyl- 1,4-phenylene) ether and poly (2-ethyl-6-propyl-1,4-phenylene)
Contains ether. Preferred is poly (2,6-dimethyl-
1,4-phenylene) ether.
該ポリフェニレンエーテル樹脂は、上記単独重合体だ
けでなく本発明の目的を損なわぬ限り共重合体であって
もよく、特に好ましいのはスチレングラフトポリフェニ
レンエーテル樹脂である。該スチレングラフトポリフェ
ニレンエーテル樹脂に用いるスチレンは例えばポリスチ
レン、ポリクロロスチレン、ポリ−α−メチルスチレン
等のホモポリマー;スチレン含有共重合体例えばスチレ
ン−アクリロニトリル共重合体、エチルビニルベンゼン
とジビニルベンゼンの共重合体、スチレン−アクリロニ
トリル−メチルスチレン三元共重合体等を含む。この群
の好ましいポリスチレン樹脂はホモポリスチレン、ポリ
−α−メチルスチレン、スチレン−アクリロニトリル共
重合体、スチレン−α−メチルスチレン共重合体、スチ
レン−メチルメタクリレート共重合体、およびポリ−α
−クロロスチレンから選択される重合体が含まれる。こ
れらの共重合体を製造する方法は特開昭50−51197号公
報などで開示されている。更に本発明で好ましいポリフ
ェニレンエーテル共重合体の例として、ポリフェニレン
エーテル樹脂とポリフェニレンサルファイド樹脂とのブ
ロック又はグラフト共重合体が含まれる。該共重合体は
例えばポリフェニレンエーテル重合体の末端基をアルコ
ラートとし、ポリフェニレンサルファイドの重合中に加
える方法、あるいはポリフェニレンエーテル重合体とポ
リフェニレンサルファイド重合体を均一に混合後、約20
0℃〜400℃の温度で加熱する方法をとることにより得る
ことができる。The polyphenylene ether resin may be not only the above-mentioned homopolymer but also a copolymer as long as the object of the present invention is not impaired. Particularly preferred is a styrene-grafted polyphenylene ether resin. Styrene used for the styrene-grafted polyphenylene ether resin is, for example, a homopolymer such as polystyrene, polychlorostyrene, or poly-α-methylstyrene; a styrene-containing copolymer such as styrene-acrylonitrile copolymer, or a copolymer of ethylvinylbenzene and divinylbenzene. And a styrene-acrylonitrile-methylstyrene terpolymer. Preferred polystyrene resins of this group are homopolystyrene, poly-α-methylstyrene, styrene-acrylonitrile copolymer, styrene-α-methylstyrene copolymer, styrene-methyl methacrylate copolymer, and poly-α.
-A polymer selected from chlorostyrene. The method for producing these copolymers is disclosed in JP-A-50-51197. Further, examples of the preferred polyphenylene ether copolymer in the present invention include a block or graft copolymer of a polyphenylene ether resin and a polyphenylene sulfide resin. The copolymer is, for example, a method in which the end group of the polyphenylene ether polymer is used as an alcoholate and added during the polymerization of the polyphenylene sulfide, or after the polyphenylene ether polymer and the polyphenylene sulfide polymer are uniformly mixed, about 20
It can be obtained by taking a method of heating at a temperature of 0 ° C to 400 ° C.
上記ポリフェニレンエーテル樹脂の配合量はポリフェ
ニレンエーテル重合体単独成分換算としてポリフェニレ
ンサルファイド樹脂100重量部に対し、0.1〜30重量部が
本発明電子部品の樹脂成形物の機械的性質および樹脂電
子部品の信頼性の改善効果が大きく、しかも耐熱性、溶
融時の流動性に優れるので好ましい。The blending amount of the polyphenylene ether resin is 0.1 to 30 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin in terms of the polyphenylene ether polymer alone, and the mechanical properties of the resin molded product of the electronic component of the present invention and the reliability of the resin electronic component. This is preferable because the effect of improving the heat resistance is large, and the heat resistance and the fluidity during melting are excellent.
本発明に用いるポリフェニレンサルファイド樹脂組成
物中にポリフェニレンエーテル樹脂のほか水素化ジエン
とスチレンのゴム状共重合体(以下、ゴムという。)が
添加できる。該ゴムの添加量はポリフェニレンエーテル
樹脂の単独又は共重合体100重量部に対し1〜100重量部
の範囲が好ましい。該ゴムの添加により、本発明の効果
即ち、外部からの衝撃、力などに対して改善された機械
的性質を有し且つ高められた信頼性を有する効果はより
高められる。当該ゴムに併用できるその他のゴムとして
は、天然又は合成ゴムがあり、例えばポリブタジエン、
ポリイソプレンおよび同等物、およびかかるジエンとビ
ニル単量体例えばスチレンの如きビニル芳香族単量体と
の共重合体がある。併用に好適なゴムまたはゴム状重合
体の例には天然クレープゴム、熱間または冷間乳化重合
によって製造されるブタジエン40〜98重量%とスチレン
60〜2重量%を含有する合成SBR型ゴム、ブタジエン65
〜82重量%とアクリロニトリル35〜18重量%を含有する
合成GR−N型ゴム、およびトリアルキルアルミニウムお
よびハロゲン化チタンの如き不均質触媒系を用いる方法
によって例えばブタジエン、ブタジエン−スチレンまた
はイソプレンから作られた合成ゴムがある。本発明組成
物を製造するに当たって併用しうる合成ゴムの中には、
弾性体状変性ジエンホモポリマー、例えばヒドロキシ−
およびカルボキシ−末端停止ポリブタジエン、ポリクロ
ロブタジエン例えばネオプレン;ポリイソブチレン、お
よびイソブチレンとブタジエンまたはイソプレンとの共
重合体;ポリイソプレン;エチレンとプロピレンの共重
合体およびこれらとブタジエンの共重合体;サイオコー
ルゴム;多硫化ゴム;アクリルゴム;ポリウレタンゴ
ム;ジエン例えばブタジエンおよびイソプレンと各種の
単量体例えばアルキル不飽和エステル、(例えばメチル
メタクリレート)、不飽和ケトン(例えばメチルイソプ
ロペニルケトン)、ビニル複素環例えばビニルピリジン
との共重合体;ポリエーテルゴム;エピクロロヒドリン
ゴム等がある。本発明で必須ゴムは上記の通り水素化ジ
エンとスチレンのゴム状共重合体である。In addition to the polyphenylene ether resin, a rubbery copolymer of hydrogenated diene and styrene (hereinafter referred to as rubber) can be added to the polyphenylene sulfide resin composition used in the present invention. The amount of the rubber is preferably in the range of 1 to 100 parts by weight based on 100 parts by weight of the polyphenylene ether resin alone or copolymer. By the addition of the rubber, the effect of the present invention, that is, the effect of having improved mechanical properties against external impact, force, and the like and having increased reliability is further enhanced. Other rubbers that can be used in combination with the rubber include natural or synthetic rubbers, such as polybutadiene,
There are polyisoprenes and equivalents, and copolymers of such dienes with vinyl monomers such as vinyl aromatic monomers such as styrene. Examples of suitable rubbers or rubbery polymers for use in combination are natural crepe rubber, 40-98% by weight of butadiene produced by hot or cold emulsion polymerization and styrene.
Butadiene 65, a synthetic SBR type rubber containing 60-2% by weight
For example made from butadiene, butadiene-styrene or isoprene by methods using synthetic GR-N type rubbers containing .about.82% by weight and 35-18% by weight of acrylonitrile and heterogeneous catalyst systems such as trialkylaluminum and titanium halide. There is synthetic rubber. Among the synthetic rubbers that can be used together in producing the composition of the present invention,
Elastomeric modified diene homopolymers such as hydroxy-
And carboxy-terminated polybutadienes, polychlorobutadienes such as neoprene; polyisobutylene and copolymers of isobutylene and butadiene or isoprene; polyisoprene; copolymers of ethylene and propylene and copolymers of these with butadiene; Polysulfide rubbers; acrylic rubbers; polyurethane rubbers; dienes such as butadiene and isoprene and various monomers such as alkyl unsaturated esters (eg, methyl methacrylate), unsaturated ketones (eg, methyl isopropenyl ketone), vinyl heterocycles such as vinyl Copolymers with pyridine; polyether rubber; epichlorohydrin rubber and the like. The essential rubber in the present invention is a rubbery copolymer of a hydrogenated diene and styrene as described above.
更にまた、本発明に用いるポリフェニレンサルファイ
ド樹脂組成物中にポリスチレン類などの他の重合体を添
加することは本発明の目的を損なわぬ限り何ら差し支え
ない。Furthermore, addition of another polymer such as polystyrene to the polyphenylene sulfide resin composition used in the present invention does not hinder at all unless the object of the present invention is impaired.
本発明では、無機充填材をポリフェニレンサルファイ
ド樹脂組成物中30〜80重量%配合することができるが、
特に好ましいのは55〜75重量%である。無機充填材の例
として、シリカ、ケイソウ土、アルミナ、酸化チタン、
酸化亜鉛、酸化アンチモン、軽石、炭酸カルシウム、炭
酸マグネシウム、チタン酸カリウム、硫酸カルシウム、
硫酸バリウム、タルク、クレー、マイカ、アスベスト、
ガラス、ケイ酸カルシウム、モンモリロナイト、ベント
ナイト、ウォラストナイト、炭化ケイ素などの粒状ある
いは繊維状の定形又は不定形のもの及びこれらの混合物
が挙げられる。In the present invention, the inorganic filler may be blended in the polyphenylene sulfide resin composition at 30 to 80% by weight,
Particularly preferred is 55-75% by weight. Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide,
Zinc oxide, antimony oxide, pumice, calcium carbonate, magnesium carbonate, potassium titanate, calcium sulfate,
Barium sulfate, talc, clay, mica, asbestos,
Specific examples include glass, calcium silicate, montmorillonite, bentonite, wollastonite, silicon carbide and other granular or fibrous shaped or amorphous shaped materials, and mixtures thereof.
本発明で用いるポリフェニレンサルファイド樹脂組成
物は、公知の添加剤、例えばカップリング剤、酸化防止
剤、熱安定剤、腐食防止剤、滑剤、着色剤等を添加する
ことができる。The polyphenylene sulfide resin composition used in the present invention may contain known additives such as a coupling agent, an antioxidant, a heat stabilizer, a corrosion inhibitor, a lubricant, and a coloring agent.
本発明の樹脂電子部品は例えばフロレス、トランスフ
ァー、射出成形機などの樹脂封止用成形機を用いて樹脂
温度260℃〜400℃、金型温度20℃〜220℃、成形圧力100
0kg/cm2以下、特に好ましくは500kg/cm2以下の成形条件
で得ることができる。The resin electronic component of the present invention is, for example, a resin temperature of 260 ° C to 400 ° C, a mold temperature of 20 ° C to 220 ° C, and a molding pressure of 100 ° C using a resin molding machine such as a flowless, transfer, or injection molding machine.
It can be obtained under molding conditions of 0 kg / cm 2 or less, particularly preferably 500 kg / cm 2 or less.
(発明の効果) 本発明のポリフェニレンサルファイド樹脂組成物で封
止された樹脂電子部品は外部からの力、衝撃に対し改善
された機械的性質を有し、かつ高められた信頼性を有す
る。(Effect of the Invention) The resin electronic component sealed with the polyphenylene sulfide resin composition of the present invention has improved mechanical properties against external force and impact, and has enhanced reliability.
(実施例) 以下、本発明を実施例および比較例により説明する。Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.
参考例1〜5、参考比較例1 メルトフローレイトが8500のポリフェニレンサルファ
イド樹脂とポリフェニレンエーテル樹脂(クロロホルム
1%溶液、30℃で測定された固有粘度0.41)の合計量10
0重量部に対し、溶融シリカ150重量部、ウォラストナイ
ト50重量部の組成のものを65mm押出機を用いて300℃で
溶融混練したのち、3オンス射出成形機を用いて、310
℃、射出圧力150kg/cm2で14pinのICを封止し(センター
ゲート)成形時のクラック発生割合、およびボンディン
グワイヤー断線個数の割合を調べたのが第1表の結果で
ある。Reference Examples 1 to 5 and Reference Comparative Example 1 The total amount of polyphenylene sulfide resin having a melt flow rate of 8500 and polyphenylene ether resin (chloroform 1% solution, intrinsic viscosity 0.41 measured at 30 ° C.) 10
With respect to 0 parts by weight, a composition having a composition of 150 parts by weight of fused silica and 50 parts by weight of wollastonite was melt-kneaded at 300 ° C. using a 65 mm extruder, and then 310 knitted using a 3 oz.
Table 1 shows the results of Table 1 in which a 14-pin IC was sealed at a temperature of 150 ° C. and an injection pressure of 150 kg / cm 2 , and the rate of occurrence of cracks and the number of broken bonding wires during molding (center gate) were examined.
参考例1〜6 参考例1〜5で用いたポリフェニレンサルファイド樹
脂およびポリフェニレンエーテル樹脂に、更に水素添加
タイプスチレン−ブタジエン共重合体(シェル化学製、
クレイトンG−1650)あるいはポリスチレン樹脂(大日
本インキ化学製、ディックスチレンGH−8000)を配合
し、同様に実験を行った結果を第2表に示した。 Reference Examples 1 to 6 In addition to the polyphenylene sulfide resin and the polyphenylene ether resin used in Reference Examples 1 to 5, a hydrogenated styrene-butadiene copolymer (manufactured by Shell Chemical Co., Ltd.)
Clayton G-1650) or a polystyrene resin (manufactured by Dainippon Ink and Chemicals, Dick Styrene GH-8000) was blended, and the same experiment was conducted. The results are shown in Table 2.
参考例6〜13、参考比較例2 メルトフローレイトが4600のポリフェニレンサルファ
イド樹脂と第3表に示したポリフェニレンエーテル樹脂
を合計100重量部および溶融シリカ200重量部を参考例1
〜4と同様の方法でICを封止し、得られたIC封止成形品
を121℃、2気圧下で赤インク中に浸漬し、10時間保持
し、金属表面の赤インク浸透度合(第1図参照)を観察
した。ICのリードは42アロイを用いた。又樹脂組成物の
アイゾット衝撃強度もテストピースを作成し測定した。 Reference Examples 6 to 13 and Reference Comparative Example 2 A total of 100 parts by weight of a polyphenylene sulfide resin having a melt flow rate of 4600 and a polyphenylene ether resin shown in Table 3 and 200 parts by weight of fused silica were used in Reference Example 1.
IC was sealed in the same manner as in Examples 1 to 4, and the obtained IC-sealed molded product was immersed in red ink at 121 ° C. and 2 atm. (See FIG. 1). The lead of IC used 42 alloy. Also, the Izod impact strength of the resin composition was measured by preparing a test piece.
第3表より明らかなようにポリフェニレンエーテル樹
脂の添加により、赤インクの浸透度合は減少し、ICの耐
湿性が向上することを示している。As is clear from Table 3, the addition of the polyphenylene ether resin indicates that the penetration of the red ink is reduced, and the moisture resistance of the IC is improved.
第1図は6.2mm×19.0mmのIC封止成形品の右上部分のみ
を具体的に示した図であり、図中、〜の数字はリー
ド線金属表面の赤インク浸透度合を示す。FIG. 1 is a view specifically showing only the upper right portion of a 6.2 mm × 19.0 mm IC-encapsulated molded product. In the figure, the numeral “〜” indicates the degree of penetration of the red ink on the lead wire metal surface.
Claims (1)
ニレンエーテル樹脂、ASTM D1238−73(316℃、5kg荷
重)で測定されたメルトフローレートが500〜10000g/10
分のポリフェニレンサルファイド樹脂、水素化ジエンと
スチレンのゴム状共重合体および無機充填材を含む組成
物で封止したことを特徴とする樹脂封止電子部品。An electronic component having a lead metal has a melt flow rate of 500 to 10,000 g / 10 measured with a polyphenylene ether resin, ASTM D1238-73 (316 ° C., 5 kg load).
A resin-sealed electronic component characterized by being sealed with a composition containing a polyphenylene sulfide resin, a rubber-like copolymer of hydrogenated diene and styrene, and an inorganic filler.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60203294A JP2615550B2 (en) | 1985-09-17 | 1985-09-17 | Resin-sealed electronic components |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60203294A JP2615550B2 (en) | 1985-09-17 | 1985-09-17 | Resin-sealed electronic components |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6265351A JPS6265351A (en) | 1987-03-24 |
JP2615550B2 true JP2615550B2 (en) | 1997-05-28 |
Family
ID=16471654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60203294A Expired - Fee Related JP2615550B2 (en) | 1985-09-17 | 1985-09-17 | Resin-sealed electronic components |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2615550B2 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0249023A (en) * | 1988-05-25 | 1990-02-19 | Mitsubishi Gas Chem Co Inc | Resin composition |
JPH02229858A (en) * | 1988-11-12 | 1990-09-12 | Kureha Chem Ind Co Ltd | Resin composition for sealing electronic parts and sealed electronic parts |
KR940003263B1 (en) * | 1989-12-27 | 1994-04-16 | 폴리 플라스틱스 가부시끼가이샤 | Resin material for inserting lead frame |
JP3237757B2 (en) * | 1989-12-28 | 2001-12-10 | 呉羽化学工業株式会社 | Resin composition for sealing electronic parts and sealed electronic parts |
US6303708B1 (en) | 1995-03-17 | 2001-10-16 | General Electric Company | Functional poly(phenylene ether)/poly(arylene sulfide)/epoxy function alpha olefin elastomer/elastomeric block copolymer/metal salt compositions and process for making thereof |
US5504165A (en) * | 1995-03-17 | 1996-04-02 | General Electric Company | Poly(phenylene ether)-poly(arylene sulfide)resin compositions. |
SG74539A1 (en) * | 1995-03-17 | 2000-08-22 | Gen Electric | Compositions of poly (phenylene ether) poly (arylene sulfide) polyester resins and a comptibilizer compound |
JPH09124931A (en) * | 1995-06-07 | 1997-05-13 | General Electric Co <Ge> | Composition consisting of poly(phenylene ether), poly(arylene sulfide) and orthoester compound |
US7037986B2 (en) * | 2003-12-19 | 2006-05-02 | General Electric Company | Lead free solder friendly thermoplastic blends and methods of manufacture thereof |
CN100410308C (en) * | 2003-12-19 | 2008-08-13 | 通用电气公司 | Lead free solder friendly thermoplastic blends and methods of manufacture thereof |
Family Cites Families (3)
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JPS5921472B2 (en) * | 1979-08-28 | 1984-05-19 | 松下電器産業株式会社 | air conditioner |
JPS6011063B2 (en) * | 1983-03-10 | 1985-03-22 | 大日本インキ化学工業株式会社 | resin composition |
JPS59213758A (en) * | 1983-05-20 | 1984-12-03 | Dainippon Ink & Chem Inc | Resin composition |
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