JPH0959385A - New modified organopolysiloxane compound and epoxy resin composition for semiconductor sealing using the same - Google Patents
New modified organopolysiloxane compound and epoxy resin composition for semiconductor sealing using the sameInfo
- Publication number
- JPH0959385A JPH0959385A JP23068495A JP23068495A JPH0959385A JP H0959385 A JPH0959385 A JP H0959385A JP 23068495 A JP23068495 A JP 23068495A JP 23068495 A JP23068495 A JP 23068495A JP H0959385 A JPH0959385 A JP H0959385A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- compound
- epoxy resin
- same
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 71
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 36
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000004065 semiconductor Substances 0.000 title claims description 25
- 238000007789 sealing Methods 0.000 title 1
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 13
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000002252 acyl group Chemical group 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000005538 encapsulation Methods 0.000 claims description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 9
- -1 organosiloxane compound Chemical class 0.000 abstract description 6
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 4
- 229930195733 hydrocarbon Natural products 0.000 abstract 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001721 transfer moulding Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- 229930003836 cresol Natural products 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000000217 alkyl 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
- 239000012298 atmosphere Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 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
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な変性オルガ
ノポリシロキサン化合物の製造方法、その方法により製
造された新規な変性オルガノポリシロキサン化合物およ
びそれを配合した半導体封止用エポキシ樹脂組成物に関
する。更に詳しくは、成形時に優れた離型性を示し、成
形後には耐水性、ＩＣ基盤との密着性および耐熱性が良
く、信頼性の優れた半導体封止用エポキシ樹脂組成物を
与える変性オルガノポリシロキサン化合物およびそれを
配合した半導体封止用エポキシ樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a method for producing a novel modified organopolysiloxane compound, a novel modified organopolysiloxane compound produced by the method, and an epoxy resin composition for semiconductor encapsulation containing the same. More specifically, a modified organopolysiloxane that exhibits excellent releasability during molding, and is excellent in water resistance, adhesion to an IC substrate, and heat resistance after molding, and which is highly reliable and provides an epoxy resin composition for semiconductor encapsulation. The present invention relates to a siloxane compound and a semiconductor encapsulating epoxy resin composition containing the same.
【０００２】[0002]
【従来の技術とその問題点】従来より、半導体封止用に
エポキシ樹脂組成物が用いられ、応力緩和や離型性の向
上の目的で各種シリコーンオイル類が配合されてきた。
特公平２−３６１４８号では、エポキシ基とポリオキシ
アルキレン基を有する変性オルガノポリシロキサンを配
合することによりトランスファーモールディング時の離
型性、捺印性および密着性が優れた成形用エポキシ樹脂
組成物が得られることが開示されている。しかし、この
成形用エポキシ樹脂組成物は、耐水性、ＩＣ基盤との密
着性、耐熱性が不十分であり、これを封止剤として用い
て製造した半導体は信頼性が不十分であった。2. Description of the Related Art Conventionally, epoxy resin compositions have been used for semiconductor encapsulation, and various silicone oils have been blended for the purpose of stress relaxation and improvement of releasability.
In Japanese Patent Publication No. 2-36148, a molding epoxy resin composition having excellent releasability, imprintability and adhesiveness during transfer molding is obtained by blending a modified organopolysiloxane having an epoxy group and a polyoxyalkylene group. Is disclosed. However, this epoxy resin composition for molding has insufficient water resistance, adhesion to an IC substrate, and heat resistance, and the semiconductor manufactured using this as a sealant has insufficient reliability.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、半導体封止
用に有用な耐水性、ＩＣ基盤との密着性、耐熱性、トラ
ンスファーモールディング時の離型性、捺印性が良く、
信頼性の優れた半導体封止用エポキシ樹脂組成物を提供
することを課題とする。SUMMARY OF THE INVENTION The present invention has good water resistance useful for semiconductor encapsulation, adhesion to an IC substrate, heat resistance, releasability during transfer molding, and imprintability.
An object of the present invention is to provide a highly reliable epoxy resin composition for semiconductor encapsulation.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題に
ついて鋭意検討した結果、前記特公平２−３６１４８号
記載の変性オルガノポリシロキサンは、遊離した未反応
原料のポリオキシアルキレン化合物を多く含むために、
半導体封止用エポキシ樹脂組成物の耐水性、ＩＣ基盤と
の密着性、耐熱性に悪影響を与え信頼性を悪くしている
ことを見出だした。そこで各種シリコーンオイル類とそ
の製造方法について検討したところ、特定の方法により
製造した新規な変性オルガノポリシロキサン化合物は、
エポキシ基との反応性基とポリオキシアルキレン基を有
しているが、未反応のポリオキシアルキレン化合物の殆
どはエポキシ樹脂組成物の硬化時に反応するので、耐水
性、ＩＣ基盤との密着性、耐熱性、トランスファーモー
ルディング時の離型性、捺印性等に悪影響を与えず、信
頼性に優れた半導体を製造できることを見出だし、更に
検討した結果本発明を完成させた。DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors on the above problems, the modified organopolysiloxane described in JP-B-2-36148 contains a large amount of unreacted starting polyoxyalkylene compound. for,
It has been found that the epoxy resin composition for semiconductor encapsulation adversely affects the water resistance, the adhesion to the IC substrate, and the heat resistance, resulting in poor reliability. Therefore, when various silicone oils and the production method thereof were examined, the new modified organopolysiloxane compound produced by the specific method was
Although it has a group reactive with an epoxy group and a polyoxyalkylene group, most of the unreacted polyoxyalkylene compound reacts when the epoxy resin composition is cured, so that water resistance, adhesion to an IC substrate, It has been found that a semiconductor having excellent reliability can be manufactured without adversely affecting heat resistance, releasability during transfer molding, imprintability, etc., and further studies have completed the present invention.
【０００５】[0005]
【発明の実施の形態】従って、本発明は次式（１）：Accordingly, the present invention is based on the following formula (1):
【化６】 ［式中、Ｒは同一または相異なり、水素原子または１価
の炭化水素基を表し、Ｒ1 はエポキシ基含有基を表し、
Ｒ2 は次式：[Chemical 6] [In the formula, R are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group, and R 1 represents an epoxy group-containing group,
R 2 is the following formula:
【化７】 （式中、Ｒ5 は炭素原子数２以上の２価の炭化水素基を
表し、Ｒ6 は水素原子基、１価の炭化水素基またはアシ
ル基を表し、ａおよびｂは０または正数で、かつａ＋ｂ
≧１である）で表される有機置換基を表し、Ｒ3 は次
式：[Chemical 7] (In the formula, R 5 represents a divalent hydrocarbon group having 2 or more carbon atoms, R 6 represents a hydrogen atom group, a monovalent hydrocarbon group or an acyl group, and a and b are 0 or a positive number. , And a + b
≧ 1) and R 3 is represented by the following formula:
【化８】 （式中、Ｒ7 は炭素原子数２以上の２価の炭化水素基を
表し、Ｒ8 はエポキシ基含有基を表し、ｃおよびｄは０
または正数で、かつａ＋ｂ≧１である）で表される有機
置換基を表し、Ｒ4 はＲ、Ｒ1 またはＲ2 のいずれかに
定義された意味を表し、ｌ、ｍ、ｎおよびｏはそれぞれ
平均数でｌ、ｍおよびｎは０〜１０００でありｏは１〜
１０００であり、それらは１≦ｌ＋ｍ＋ｎ＋ｏ≦１００
０を満足する値であり、更にＲ4 がＲ2 の場合は１≧ｏ
／（ｎ＋ｏ＋２）≧０．０２を、それ以外の場合は１≧
ｏ／（ｎ＋ｏ）≧０．０２を満足する値であるが、ただ
し、ｍが０の場合はＲ4 はＲ1 に定義された意味を表
し、ｎが０の場合はＲ4 はＲ2 に定義された意味を表
す］で表される変性オルガノポリシロキサン化合物の製
造方法、その方法により製造された前記式（１）で表さ
れる変性オルガノポリシロキサン化合物およびそれを用
いた半導体封止用エポキシ樹脂組成物に関する。Embedded image (In the formula, R 7 represents a divalent hydrocarbon group having 2 or more carbon atoms, R 8 represents an epoxy group-containing group, and c and d are 0.
Or a positive number and a + b ≧ 1), R 4 represents the meaning defined for R, R 1 or R 2 , and l, m, n and o Is an average number of 1, m and n are 0 to 1000, and o is 1 to
1000 and they are 1 ≦ l + m + n + o ≦ 100
Is a value satisfying 0, and when R 4 is R 2 , 1 ≧ o
/(N+o+2)≧0.02, otherwise 1 ≧
A value satisfying o / (n + o) ≧ 0.02, provided that when m is 0, R 4 has the meaning defined in R 1 , and when n is 0, R 4 is R 2 . A modified organopolysiloxane compound represented by the above formula, modified organopolysiloxane compound represented by the above formula (1) produced by the method, and epoxy for semiconductor encapsulation using the same It relates to a resin composition.
【０００６】本発明の変性オルガノポリシロキサン化合
物は上記式（１）で表される。式（１）中、Ｒは同一ま
たは相異なり、水素原子または１価の炭化水素基（例え
ばアルキル基、フェニル基、アルキルフェニル基、ナフ
チル基等）を表すが、好ましくはメチル基、エチル基、
プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプ
チル基、オクチル基、ノニル基、デシル基、ウンデシル
基、ドデシル基、トリデシル基、テトラデシル基、ペン
タデシル基、ヘキサデシル基、ヘプタデシル基、オクタ
デシル基、ノナデシル基等の直鎖または分岐した炭素数
１〜１８のアルキル基またはフェニル基であり特に好ま
しくはメチル基である。上記Ｒ1 基はエポキシ基含有基
であり、具体的な例としては、The modified organopolysiloxane compound of the present invention is represented by the above formula (1). In the formula (1), R is the same or different and represents a hydrogen atom or a monovalent hydrocarbon group (for example, an alkyl group, a phenyl group, an alkylphenyl group, a naphthyl group, etc.), preferably a methyl group, an ethyl group,
Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group And a linear or branched alkyl group having 1 to 18 carbon atoms or a phenyl group, and particularly preferably a methyl group. The R 1 group is an epoxy group-containing group, and specific examples thereof include
【化９】 Embedded image
【化１０】 を挙げることができる。上記Ｒ2 基中のＲ5 基とＲ3 基
中のＲ7 基はそれぞれ炭素原子数２以上の２価の炭化水
素基を表し、例えば直鎖または分岐したアルキレン基が
挙げられ、具体的な例としては、Embedded image Can be mentioned. The R 5 group in the R 2 group and the R 7 group in the R 3 group each represent a divalent hydrocarbon group having 2 or more carbon atoms, and examples thereof include a linear or branched alkylene group. For example,
【化１１】 Embedded image
【化１２】 [Chemical 12]
【化１３】 等を挙げることができる。上記Ｒ2 基中のＲ6 基は上記
Ｒで例示したのと同じ基またはアシル基から選択される
が好ましくは水素原子、メチル基、エチル基、ブチル基
である。上記Ｒ3 基中のＲ8 基は上記Ｒ1 基で例示した
のと同様の基から選択される。Embedded image And the like. The R 6 group in the R 2 group is selected from the same groups as those exemplified for R or the acyl group, but is preferably a hydrogen atom, a methyl group, an ethyl group or a butyl group. The R 8 group in the R 3 group is selected from the same groups as exemplified for the R 1 group.
【０００７】上記の（１）式中のｎとｏの比は、Ｒ4 が
Ｒ2 の場合は１≧ｏ／（ｎ＋ｏ＋２）≧０．０２を、そ
れ以外の場合は１≧ｏ／（ｎ＋ｏ）≧０．０２を満足す
る値であることが必須で、好ましくはＲ4 がＲ2 の場合
は０．５≧ｏ／（ｎ＋ｏ＋２）≧０．０５でそれ以外の
場合は０．５≧ｏ／（ｎ＋ｏ）≧０．０５である。この
比が大き過ぎるとエポキシ樹脂組成物の流動性が悪くな
り、この比が小さ過ぎるとエポキシ樹脂組成物の硬化後
の遊離ポリオキシアルキレン成分が多くなり、いずれも
半導体封止剤として不適となる。また、これと１≦ｌ＋
ｍ＋ｎ＋ｏ≦１０００およびａ＋ｂ≧１である以外に
ｌ、ｍ、ｎ、ｏ、ａおよびｂの値は限定されないが、そ
れらの好ましい値は、５≦ｌ≦３００、１≦ｍ≦５０、
１≦ｎ≦３０、１≦ｏ≦２０、０≦ａ≦３０、１≦ｂ≦
３０である。The ratio of n to o in the above equation (1) is 1 ≧ o / (n + o + 2) ≧ 0.02 when R 4 is R 2 , and 1 ≧ o / (n + o) otherwise. ) ≧ 0.02 is essential, preferably 0.5 ≧ o / (n + o + 2) ≧ 0.05 when R 4 is R 2 and 0.5 ≧ o otherwise. /(N+o)≧0.05. If this ratio is too large, the fluidity of the epoxy resin composition will deteriorate, and if this ratio is too small, the amount of free polyoxyalkylene component after curing of the epoxy resin composition will increase, and both will be unsuitable as semiconductor encapsulants. . Also, this and 1 ≦ l +
The values of l, m, n, o, a and b are not limited except that m + n + o ≦ 1000 and a + b ≧ 1, but preferred values thereof are 5 ≦ l ≦ 300, 1 ≦ m ≦ 50,
1 ≦ n ≦ 30, 1 ≦ o ≦ 20, 0 ≦ a ≦ 30, 1 ≦ b ≦
30.
【０００８】上記の変性オルガノポリシロキサン化合物
は、ＳｉＨ基含有オルガノポリシロキサン化合物に触媒
の存在下に（ａ）１分子中にエポキシ基とアルケニル基
を同時に持つ化合物、（ｂ）次式（２）：The above modified organopolysiloxane compound is (a) a compound having both an epoxy group and an alkenyl group in one molecule in the presence of a catalyst in a SiH group-containing organopolysiloxane compound, and (b) the following formula (2): :
【化１４】 （式中、Ｒ6 、ａおよびｂは前記式（１）で定義したの
と同じ意味を表し、Ｒ10はアルケニル基を表す）で表さ
れる化合物および（ｃ）次式（３）：Embedded image (Wherein R 6 , a and b represent the same meaning as defined in the above formula (1), and R 10 represents an alkenyl group), and (c) the following formula (3):
【化１５】 （式中、Ｒ8 、ａおよびｂは前記式（１）で定義したの
と同じ意味を表し、Ｒ11はアルケニル基を表す）で表さ
れる化合物を付加させる工程により製造される。Embedded image (Wherein R 8 , a and b have the same meanings as defined in the above formula (1) and R 11 represents an alkenyl group).
【０００９】前記のＳｉＨ基含有オルガノポリシロキサ
ン化合物は、ＳｉＨ基を３つ以上持ち、重合度が１００
０以下であること以外は特に限定されず、例えば次式：The above-mentioned SiH group-containing organopolysiloxane compound has three or more SiH groups and has a polymerization degree of 100.
It is not particularly limited except that it is 0 or less. For example, the following formula:
【化１６】 （式中、Ｒ、ｌ、ｍ、ｎおよびｏは前記式（１）で定義
したのと同じ意味を表し、Ｒ9 は水素原子基またはＲと
同じ意味を表す）で示される。また、エポキシ基とアル
ケニル基を同時に持つ化合物として、例えば次式：Embedded image (In the formula, R, 1, m, n and o have the same meanings as defined in the above formula (1), and R 9 has the same meaning as a hydrogen atom group or R). Further, as a compound having an epoxy group and an alkenyl group at the same time, for example, the following formula:
【化１７】 Embedded image
【化１８】 等の化合物が挙げられる。Embedded image And the like.
【００１０】本発明においては、前記の式（１）で表さ
れる変性オルガノポリシロキサン化合物の製造時にＳｉ
Ｈ基含有オルガノポリシロキサン化合物に（ｂ）を付加
させた後に（ｃ）を付加させることが必須である。逆の
順番で製造した変性オルガノポリシロキサン化合物で
は、それとエポキシ樹脂組成物中の遊離ポリオキシアル
キレン化合物量が多くなり、半導体封止用としては不適
となるからである。尚、（ａ）の付加時期は特に限定さ
れない。例えば（ｂ）および（ｃ）の付加前後に付加さ
せたり、（ｂ）または（ｃ）と同時に付加させたりすれ
ば良い。In the present invention, Si is used during the production of the modified organopolysiloxane compound represented by the above formula (1).
It is essential to add (c) after adding (b) to the H group-containing organopolysiloxane compound. This is because the modified organopolysiloxane compound produced in the reverse order increases the amount of the free polyoxyalkylene compound in the epoxy resin composition and the modified organopolysiloxane compound, and is not suitable for semiconductor encapsulation. The time of adding (a) is not particularly limited. For example, it may be added before or after adding (b) and (c), or may be added at the same time as (b) or (c).
【００１１】本発明の半導体封止用エポキシ樹脂組成物
はエポキシ樹脂と前記方法で製造された前記式（１）で
示される変性オルガノポリシロキサン化合物を主成分と
する。エポキシ樹脂は１分子中に２個以上のエポキシ基
を有するものであれば特に限定されない。具体的にはビ
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、フェノールノボラック型エポキシ樹脂、ク
レゾールノボラック型エポキシ樹脂、脂環式エポキシ樹
脂、トリアジン核含有エポキシ樹脂およびこれらの変性
樹脂等の１種または２種以上を用いることができる。The semiconductor encapsulating epoxy resin composition of the present invention contains an epoxy resin and a modified organopolysiloxane compound of the above formula (1) produced by the above method as main components. The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, one or two of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, triazine nucleus-containing epoxy resin and modified resins thereof. More than one species can be used.
【００１２】前記方法で製造された前記式（１）で示さ
れる変性オルガノポリシロキサン化合物は、必要に応じ
て１種または２種以上を用いることができる。その配合
割合は限定されないが、エポキシ樹脂組成物１００重量
部に対して０．１重量部〜２０重量部、特には０．５〜
１５重量部の範囲が好ましい。その理由は、配合割合が
上記範囲以下であると、変性オルガノポリシロキサン化
合物を配合しない場合と比較してトランスファーモール
ディング時の離型性、ＩＣ基盤との密着性、耐熱性、耐
水性、捺印性等の向上が見られないし、上記範囲以上で
あると機械強度、電気特性、耐水性等がかえって低下す
ることがあるからである。The modified organopolysiloxane compound represented by the formula (1) produced by the above method may be used alone or in combination of two or more, if necessary. The mixing ratio is not limited, but is 0.1 to 20 parts by weight, particularly 0.5 to 100 parts by weight with respect to the epoxy resin composition.
A range of 15 parts by weight is preferred. The reason for this is that when the compounding ratio is less than the above range, the releasability during transfer molding, the adhesion to the IC substrate, the heat resistance, the water resistance, and the imprinting property are higher than those when the modified organopolysiloxane compound is not compounded. And the like, and mechanical strength, electrical characteristics, water resistance and the like may be rather deteriorated if the content is more than the above range.
【００１３】本発明の半導体封止用エポキシ樹脂組成物
には、通常用いられる硬化剤を用いることができる。例
えば無水フタル酸、無水ヘキサヒドロフタル酸、テトラ
ヒドロ無水フタル酸、無水ピロメリット酸等の酸無水
物、エチレンジアミン、ジエチレントリアミン、トリエ
チレンテトラミン、ジエチルアミノプロピルアミン、Ｎ
−アミノエチルピペラジン、ビス（４−アミノ−３−メ
チルシクロヘキシル）メタン、メタンジアミン等のアミ
ン化合物、あるいはフェノール、ビスフェノールＡ、ビ
スフェノールＦ、テトラブロモビスフェノールＡ、クレ
ゾール等のフェノール化合物、キシレン樹脂等を挙げる
ことができる。これらの硬化剤以外に通常使用される硬
化促進剤、例えばＢＤＭＡ等の第３アミン類、イミダゾ
ール類、有機リン化合物類等を使用することができる。
更に本組成物には通常用いられる無機充填剤やシランカ
ップリング剤、難燃剤、着色剤、離型剤、シリコーンオ
イル類（ジメチルポリシロキサン及びメチル基の一部を
エポキシ基、カルボキシル基、アミノ基等で変性したジ
メチルポリシロキサン等）、ゴム等の低応力剤等の添加
剤を配合することができる。In the epoxy resin composition for semiconductor encapsulation of the present invention, a curing agent which is usually used can be used. For example, acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic dianhydride, ethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, N
-Amine compounds such as aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane and methanediamine, or phenol compounds such as phenol, bisphenol A, bisphenol F, tetrabromobisphenol A and cresol, xylene resin, etc. be able to. In addition to these curing agents, commonly used curing accelerators, for example, tertiary amines such as BDMA, imidazoles, organic phosphorus compounds and the like can be used.
Further, in the present composition, there are generally used inorganic fillers, silane coupling agents, flame retardants, colorants, mold release agents, silicone oils (dimethylpolysiloxane and a part of methyl groups are epoxy groups, carboxyl groups, amino groups). Additives such as dimethylpolysiloxane modified with the like), a low stress agent such as rubber, and the like can be blended.
【００１４】[0014]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれに限定されるものではなく、本発明の技術思
想を利用する実施態様は全て本発明の範囲に含まれるも
のである。実施例に先立ち半導体封止用エポキシ樹脂組
成物の評価方法を示す。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto, and all embodiments utilizing the technical idea of the present invention are included in the scope of the present invention. . Prior to Examples, a method for evaluating an epoxy resin composition for semiconductor encapsulation will be shown.
【００１５】耐水性 Ｔｏ−２０２トランジスター２０個取り金型を利用し、
１７５℃で２分間の成形条件でトランスファー成形して
半導体を封止した。この成形物をレッドチェック液に各
１００個浸漬し、２４時間煮沸させた後取りだし、成形
物とリードフレームとの境界面へのレッドチェック液の
浸透具合を顕微鏡で観察し、僅かでも浸透が認められた
ものの個数を判定した。耐熱性 １７５℃で８時間の成形条件でトランスファー成形した
６×６×２．０５ｍｍの成形品を温度サイクルテスト
（１５０℃〜−１９６℃）にかけ、５００サイクルのテ
ストをおこない、クラックの発生した成形品の個数を判
定した。金型離型性 断面積１ｃｍ2 の円筒形キャビティを有する金型で、
１．５ｇの各組成物を１７５℃で２分間圧縮成形し、成
形直後の金型からの離型押し出し力（ｋｇ）をプッシュ
プルゲージで測定した。これを１０回繰り返し、その最
低と最高の値をとった。捺印性 Ｔｏ−２０２トランジスタ２０個取り金型を使用し、１
７５℃で２分間トランスファー成形した成形表面に、マ
ーケム社７２６１インクを捺印し、１５０℃で１時間イ
ンクを硬化させた後、インク表面にセロファンテープを
密着させ、それを急激にはがしたときのテープ側へのイ
ンクの転写性を肉眼で判定した。これを１０回繰り返
し、１０共テープ側に全く転写しないものを○印、テー
プ側に一部でも転写したものが１回以上あるものを×印
とした。Using a water-resistant To-202 transistor 20-piece mold,
The semiconductor was sealed by transfer molding under molding conditions of 175 ° C. for 2 minutes. Each 100 of this molded product was immersed in the red check liquid, boiled for 24 hours, and then taken out. The penetration condition of the red check liquid into the boundary surface between the molded product and the lead frame was observed with a microscope, and even slight penetration was observed. The number of samples that were given was determined. Heat resistance 175 ° C. Transfer molding of a molded product of 6 × 6 × 2.05 mm under a molding condition of 8 hours was subjected to a temperature cycle test (150 ° C. to −196 ° C.) and 500 cycles of the test were carried out, and cracking occurred. The number of items was determined. Mold releasability A mold having a cylindrical cavity with a cross-sectional area of 1 cm 2 ,
1.5 g of each composition was compression-molded at 175 ° C. for 2 minutes, and the mold release force (kg) from the mold immediately after molding was measured with a push-pull gauge. This was repeated 10 times and the lowest and highest values were taken. Using the stamping To-202 transistor 20-piece die, 1
Markem 7261 ink is imprinted on the molding surface transferred at 75 ° C. for 2 minutes, the ink is cured at 150 ° C. for 1 hour, and then cellophane tape is adhered to the ink surface, which is rapidly peeled off. The transferability of the ink to the tape side was visually evaluated. This was repeated 10 times, and 10 was marked with ◯ when it was not transferred at all on the tape side, and was marked with x when there was a partial transfer to the tape side at least once.
【００１６】変性オルガノポリシロキサン化合物の製造
例 実施例１ 機械的撹拌機、凝縮器、温度計および窒素挿入口を備え
た３つ口フラスコに次式（４）：Preparation of Modified Organopolysiloxane Compound
Examples Example 1 A three neck flask equipped with a mechanical stirrer, condenser, thermometer and nitrogen inlet was of the formula (4):
【化１９】 で示されるジメチルハイドロジェンポリシロキサン１．
００モル、次式（５）：Embedded image Dimethyl hydrogen polysiloxane represented by 1.
00 mol, the following formula (5):
【化２０】 で表される化合物２．１０モル、上記ジメチルハイドロ
ジェンポリシロキサンと同重量のトルエンおよび白金濃
度が上記ジメチルハイドロジェンポリシロキサンに対し
て２０ｐｐｍとなる量の塩化白金酸の１０％メタノール
溶液を入れ窒素雰囲気下で撹拌した。さらに窒素雰囲気
下、８０〜１００℃で反応させた。前記化合物が２．０
０モル付加したことを確認してから５０℃／１ｍｍＨｇ
で溶媒と未反応原料を除去した。更に温度を４０℃以下
にして、次式（６）：Embedded image 2.10 mol of the compound represented by the formula, toluene in the same weight as the dimethylhydrogenpolysiloxane, and a 10% methanol solution of chloroplatinic acid in an amount such that the platinum concentration is 20 ppm with respect to the dimethylhydrogenpolysiloxane are charged with nitrogen. Stirred under atmosphere. Further, the reaction was carried out at 80 to 100 ° C. in a nitrogen atmosphere. The compound is 2.0
After confirming that 0 mol was added, 50 ° C / 1 mmHg
The solvent and unreacted raw materials were removed by. Further, by setting the temperature to 40 ° C. or lower, the following formula (6):
【化２１】 で表される化合物４．５１モルと前回と同量のトルエン
を加えた後、窒素雰囲気下、８０〜１００℃で反応さ
せ、前記化合物が４．３モル付加したことを確認した。
更に温度を４０℃以下にして次式（７）：[Chemical 21] After adding 4.51 mol of the compound represented by and the same amount of toluene as the previous time, they were reacted at 80 to 100 ° C. in a nitrogen atmosphere, and it was confirmed that 4.3 mol of the compound was added.
Further, by setting the temperature to 40 ° C. or lower, the following formula (7):
【化２２】 で表される化合物１．１９モルを加えた後、窒素雰囲気
下、ＳｉＨ基が確認されなくなるまで８０〜１００℃で
反応させた。その後ＮａＨＣＯ3 で中和し、濾過後に５
０℃／１ｍｍＨｇで溶媒と未反応原料を除去し、次式
（８）：Embedded image After adding 1.19 mol of the compound represented by the following, it was made to react at 80-100 degreeC under nitrogen atmosphere until SiH group was not confirmed. Then neutralize with NaHCO 3 and after filtration 5
The solvent and unreacted raw materials were removed at 0 ° C./1 mmHg, and the following formula (8):
【化２３】 で表される本発明の変性オルガノポリシロキサン化合物
を得た。以下、これを化合物１とする。尚、上記の製造
において、付加反応の進行は、残存ＳｉＨ基量をＫＯＨ
のアルコール溶液との水素ガス発生量により測定するこ
とにより確認した。Embedded image A modified organopolysiloxane compound of the present invention represented by Hereinafter, this is referred to as Compound 1. In the above production, the progress of the addition reaction depends on the amount of residual SiH groups in KOH.
It was confirmed by measuring the amount of hydrogen gas generated with the alcohol solution.
【００１７】実施例２ 実施例１と同様の反応装置に前記式（４）で示されるジ
メチルハイドロジェンポリシロキサン１．００モル、前
記式（６）で表される化合物４．５１モルおよび実施例
１と同量のトルエンと塩化白金酸の１０％メタノール溶
液を入れ窒素雰囲気下で撹拌した。さらに窒素雰囲気
下、８０〜１００℃で反応させた。前記化合物が４．３
モル付加したことを確認してから温度を４０℃以下にし
て、前記式（７）で表される化合物１．１９モルを加え
た後、窒素雰囲気下、８０〜１００℃で反応させ、前記
化合物が０．７モル付加したことを確認した。更に温度
を４０℃以下にして前記式（５）で表される化合物２．
１０モルを加えた後、窒素雰囲気下、ＳｉＨ基が確認さ
れなくなるまで８０〜１００℃で反応させた。その後Ｎ
ａＨＣＯ3 で中和し、濾過後に回転式蒸発装置により５
０℃／１ｍｍＨｇで溶媒と未反応原料を除去し、実施例
１と同様に前記式（８）で表される本発明の変性オルガ
ノポリシロキサン化合物を得た。以下、これを化合物２
とする。 Example 2 In the same reactor as in Example 1, 1.00 mol of dimethylhydrogenpolysiloxane represented by the above formula (4), 4.51 mol of the compound represented by the above formula (6) and the example were used. Toluene and 10% methanol solution of chloroplatinic acid in the same amount as 1 were added and stirred under a nitrogen atmosphere. Further, the reaction was carried out at 80 to 100 ° C. in a nitrogen atmosphere. The compound is 4.3
After confirming that the compound had been added in a mole, the temperature was lowered to 40 ° C. or lower, 1.19 mol of the compound represented by the formula (7) was added, and the mixture was reacted at 80 to 100 ° C. in a nitrogen atmosphere to give the compound. It was confirmed that 0.7 mol was added. Further, the temperature is set to 40 ° C. or lower and the compound represented by the formula (5) 2.
After adding 10 mol, the reaction was carried out at 80 to 100 ° C. in a nitrogen atmosphere until SiH groups were not confirmed. Then N
neutralize with aHCO 3 and after filtration 5 by rotary evaporator
The solvent and unreacted raw materials were removed at 0 ° C./1 mmHg to obtain a modified organopolysiloxane compound of the present invention represented by the above formula (8) as in Example 1. Hereinafter, this is compound 2
And
【００１８】比較例１ 実施例１と同様の反応装置に前記式（４）で示されるジ
メチルハイドロジェンポリシロキサン１．００モル、前
記式（５）で表される化合物２．１０モルおよび実施例
１と同量のトルエンと塩化白金酸の１０％メタノール溶
液を入れ窒素雰囲気下で撹拌した。さらに窒素雰囲気
下、８０〜１００℃で反応させた。前記化合物が２．０
０モル付加したことを確認してから温度を４０℃以下に
して前記式（７）で表される化合物０．７４モルを加
え、窒素雰囲気下、８０〜１００℃で反応させ、前記化
合物が０．７モル付加したことを確認した。更に温度を
４０℃以下にして前記式（６）で表される化合物４．９
６モルを加えた後、窒素雰囲気下、ＳｉＨ基が確認され
なくなるまで８０〜１００℃で反応させた。その後Ｎａ
ＨＣＯ3 で中和し、濾過後に回転式蒸発装置により５０
℃／１ｍｍＨｇで溶媒と未反応原料を除去し、実施例１
と同様に前記式（８）で表されるが本発明とは異なる変
性オルガノポリシロキサン化合物を得た。以下、これを
化合物３とする。[0018] Comparative Example 1 Example 1 Formula dimethylhydrogenpolysiloxane 1.00 mol represented by (4), compounds 2.10 mol represented by the formula (5) and Example To the same reactor Toluene and 10% methanol solution of chloroplatinic acid in the same amount as 1 were added and stirred under a nitrogen atmosphere. Further, the reaction was carried out at 80 to 100 ° C. in a nitrogen atmosphere. The compound is 2.0
After confirming that 0 mol was added, the temperature was lowered to 40 ° C. or lower, 0.74 mol of the compound represented by the formula (7) was added, and the mixture was reacted at 80 to 100 ° C. under a nitrogen atmosphere to give 0 It was confirmed that 0.7 mol was added. Further, the temperature is set to 40 ° C. or lower and the compound 4.9 represented by the formula (6).
After adding 6 mol, the reaction was carried out at 80 to 100 ° C. under a nitrogen atmosphere until SiH groups were not confirmed. Then Na
Neutralize with HCO 3 and filter to 50 after rotary evaporation.
The solvent and unreacted raw materials were removed at 1 ° C./1 mmHg, and Example 1 was used.
In the same manner as above, a modified organopolysiloxane compound represented by the above formula (8) but different from the present invention was obtained. Hereinafter, this is referred to as Compound 3.
【００１９】比較例２ 実施例１と同様の反応装置に前記式（４）で示されるジ
メチルハイドロジェンポリシロキサン１．００モル、前
記式（７）で表される化合物０．７４モルおよび実施例
１と同量のトルエンと塩化白金酸の１０％メタノール溶
液を入れ窒素雰囲気下で撹拌した。さらに窒素雰囲気
下、８０〜１００℃で反応させた。前記化合物が０．７
モル付加したことを確認してから温度を４０℃以下にし
て前記式（６）で表される化合物４．９６モルを加え、
窒素雰囲気下、８０〜１００℃で反応させ、前記化合物
が４．３モル付加したことを確認した。更に温度を４０
℃以下にして前記式（５）で表される化合物２．２０モ
ルを加えた後、窒素雰囲気下、ＳｉＨ基が確認されなく
なるまで８０〜１００℃で反応させた。その後ＮａＨＣ
Ｏ3 で中和し、濾過後に回転式蒸発装置により５０℃／
１ｍｍＨｇで溶媒と未反応原料を除去し、実施例１と同
様に前記式（８）で表されるが本発明とは異なる変性オ
ルガノポリシロキサン化合物を得た。以下、これを化合
物４とする。 Comparative Example 2 1.00 mol of dimethylhydrogenpolysiloxane represented by the above formula (4), 0.74 mol of the compound represented by the above formula (7) were added to the same reaction apparatus as in Example 1 and Example. Toluene and 10% methanol solution of chloroplatinic acid in the same amount as 1 were added and stirred under a nitrogen atmosphere. Further, the reaction was carried out at 80 to 100 ° C. in a nitrogen atmosphere. The compound is 0.7
After confirming that the mole addition has been performed, the temperature is lowered to 40 ° C. or lower and 4.96 mole of the compound represented by the formula (6) is added,
It was made to react at 80-100 degreeC in nitrogen atmosphere, and it confirmed that the said compound added 4.3 mol. Further increase the temperature to 40
2.20 mol of the compound represented by the above formula (5) was added at a temperature of not more than 0 ° C., and then the mixture was reacted at 80 to 100 ° C. in a nitrogen atmosphere until SiH groups were not confirmed. Then NaHC
Neutralize with O 3 and after filtration 50 ° C /
The solvent and unreacted raw materials were removed at 1 mmHg to obtain a modified organopolysiloxane compound represented by the above formula (8) but different from the present invention as in Example 1. Hereinafter, this is referred to as Compound 4.
【００２０】比較例３ 前記式（６）で表される化合物の使用量を４．７０モル
とした以外は比較例１と同様の方法で合成試験をおこな
ったが、式（６）で表される化合物の反応工程を１０時
間続けてもＳｉＨ基が検出され、その後は、更に１０時
間反応を続けてもＳｉＨ基の検出量に変化がなかったの
で、合成試験を中断した。 Comparative Example 3 A synthetic test was conducted in the same manner as in Comparative Example 1 except that the amount of the compound represented by the formula (6) used was 4.70 mol. The SiH group was detected even after continuing the reaction step of the compound for 10 hours, and thereafter, even if the reaction was continued for 10 hours, the detected amount of SiH group did not change, so the synthetic test was interrupted.
【００２１】実施例３ 実施例１と同様の反応装置に次式： Example 3 A reactor similar to that of Example 1 has the following formula:
【化２４】 で示されるジメチルハイドロジェンポリシロキサン１．
００モル、次式：Embedded image Dimethyl hydrogen polysiloxane represented by 1.
00 mol, the following formula:
【化２５】 で表される化合物１．６０モルおよび上記ジメチルハイ
ドロジェンポリシロキサンと同重量のトルエンおよび白
金濃度が上記ジメチルハイドロジェンポリシロキサンに
対して２０ｐｐｍとなる量の塩化白金酸の１０％メタノ
ール溶液を入れ窒素雰囲気下で撹拌した。さらに窒素雰
囲気下、８０〜１００℃で反応させた。前記化合物が
１．５モル付加したことを確認してから５０℃／１ｍｍ
Ｈｇで溶媒と未反応原料を除去した。更に温度を４０℃
以下にして、次式：Embedded image 1.60 mol of the compound represented by the formula (1) and toluene in the same weight as the dimethylhydrogenpolysiloxane, and a 10% methanol solution of chloroplatinic acid in an amount such that the platinum concentration is 20 ppm with respect to the dimethylhydrogenpolysiloxane are charged with nitrogen Stirred under atmosphere. Further, the reaction was carried out at 80 to 100 ° C. in a nitrogen atmosphere. 50 ° C / 1mm after confirming that 1.5 moles of the compound has been added
The solvent and unreacted raw materials were removed with Hg. Furthermore, the temperature is 40 ° C.
Then, the following formula:
【化２６】 で表される化合物１０．００モルと前回と同量のトルエ
ンを加えた後、窒素雰囲気下、８０〜１００℃で反応さ
せ、前記化合物が９．３モル付加したことを確認した。
更に温度を４０℃以下にして次式：[Chemical formula 26] After adding 10.00 mol of the compound represented by and the same amount of toluene as the previous time, they were reacted at 80 to 100 ° C. under a nitrogen atmosphere, and it was confirmed that 9.3 mol of the compound was added.
Further, by setting the temperature to 40 ° C. or lower, the following formula:
【化２７】 で表される化合物１．００モルを加えた後、窒素雰囲気
下、ＳｉＨ基が確認されなくなるまで８０〜１００℃で
反応させた。その後ＮａＨＣＯ3 で中和し、濾過後に５
０℃／１ｍｍＨｇで溶媒と未反応原料を除去し、次式：Embedded image After adding 1.00 mol of the compound represented by the above, the reaction was carried out at 80 to 100 ° C. in a nitrogen atmosphere until SiH groups were not confirmed. Then neutralize with NaHCO 3 and after filtration 5
The solvent and unreacted raw materials were removed at 0 ° C./1 mmHg, and the following formula:
【化２８】 で表される本発明の変性オルガノポリシロキサン化合物
を得た。以下、これを化合物６とする。尚、上記製造に
おいて、付加反応の進行は、残存ＳｉＨ基量をＫＯＨの
アルコール溶液との水素ガス発生量により測定すること
により確認した。Embedded image A modified organopolysiloxane compound of the present invention represented by Hereinafter, this is referred to as Compound 6. In the above production, the progress of the addition reaction was confirmed by measuring the amount of residual SiH groups by the amount of hydrogen gas generated with the alcohol solution of KOH.
【００２２】半導体封止用エポキシ樹脂組成物の調製 エポキシ当量２２０、軟化点８０℃のクレゾールノボラ
ックエポキシ樹脂７５重量部、エポキシ当量４００、軟
化点７０℃、臭素含有量４５重量％の臭素化ビスフェノ
ールＡ型エポキシ樹脂２５部、硬化剤として軟化点９０
℃のフェノールノボラック樹脂５０部、無機質充填剤と
して溶融シリカ粉末４２０部、硬化促進剤として２−メ
チル−４−イミダゾール１部、顔料としてカーボンブラ
ック２部、三酸化アンチモン２０部および表１に示す種
類のオルガノポリシロキサン化合物２部を加え、８０〜
９０℃の熱ロールで混練し、冷却後粉砕して実施例１〜
３および比較例１〜５の半導体封止用エポキシ樹脂組成
物を得た。 Preparation of epoxy resin composition for semiconductor encapsulation Brominated bisphenol A having an epoxy equivalent of 220, a cresol novolac epoxy resin having a softening point of 80 ° C. 75 parts by weight, an epoxy equivalent of 400, a softening point of 70 ° C. and a bromine content of 45% by weight. Type epoxy resin 25 parts, softening point 90 as a curing agent
50 parts of phenol novolac resin at 40 ° C., 420 parts of fused silica powder as an inorganic filler, 1 part of 2-methyl-4-imidazole as a curing accelerator, 2 parts of carbon black as a pigment, 20 parts of antimony trioxide and the types shown in Table 1. 2 parts of the organopolysiloxane compound of
Kneading with a hot roll of 90 ° C., cooling and pulverization, and then Examples 1 to 1
3 and the epoxy resin compositions for semiconductor encapsulation of Comparative Examples 1 to 5 were obtained.
【００２３】半導体封止用エポキシ樹脂組成物の評価 上記実施例１〜３および比較例１の半導体封止用エポキ
シ樹脂組成物を用いて耐水性、耐熱性および金型離型性
を試験し、結果を表１に示した。表１より本発明の半導
体封止用エポキシ樹脂組成物は比較例よりも、優れた耐
水性と耐熱性を持ち、更に従来の物と同程度の離型性を
持つことが示され、半導体封止用に有用であることがわ
かった。 Evaluation of epoxy resin composition for semiconductor encapsulation Using the epoxy resin compositions for semiconductor encapsulation of Examples 1 to 3 and Comparative Example 1 above, water resistance, heat resistance and mold releasability were tested. The results are shown in Table 1. It is shown from Table 1 that the epoxy resin composition for semiconductor encapsulation of the present invention has superior water resistance and heat resistance as compared with Comparative Examples, and further has releasability comparable to that of conventional products. It was found to be useful for stopping.
【００２４】[0024]
【表１】 表１において、化合物５は次式を有する化合物である。[Table 1] In Table 1, compound 5 is a compound having the following formula.
【化２９】 [Chemical 29]
【００２５】[0025]
【発明の効果】以上詳細に説明したように、本発明の方
法により製造された新規な変性オルガノポリシロキサン
化合物は、それを配合することにより耐水性、ＩＣ基盤
との密着性、耐熱性、離型性、捺印性および信頼性の優
れた半導体封止用エポキシ樹脂組成物を提供することが
できるので産業上非常に有用である。また、本発明の半
導体封止用エポキシ樹脂組成物は耐水性、ＩＣ基盤との
密着性、耐熱性、トランスファーモールディング時の離
型性、捺印性が良く、信頼性が優れているので産業上非
常に有用である。As described in detail above, the novel modified organopolysiloxane compound produced by the method of the present invention can be blended with water resistance, adhesion to an IC substrate, heat resistance and release. Since it is possible to provide an epoxy resin composition for semiconductor encapsulation which is excellent in moldability, imprintability and reliability, it is very useful industrially. In addition, the epoxy resin composition for semiconductor encapsulation of the present invention is excellent in water resistance, adhesion to an IC substrate, heat resistance, releasability during transfer molding, and imprintability, and is excellent in reliability. Useful for.
Claims (3)
合物に触媒の存在下に下記（ａ）、（ｂ）および（ｃ）
の三種の化合物を付加させることにより次式（１）： 【化１】 ［式中、Ｒは同一または相異なり、水素原子または１価
の炭化水素基を表し、 Ｒ1 はエポキシ基含有基を表し、 Ｒ2 は次式： 【化２】 （式中、Ｒ5 は炭素原子数２以上の２価の炭化水素基を
表し、Ｒ6 は水素原子基、１価の炭化水素基またはアシ
ル基を表し、ａおよびｂは０または正数で、かつａ＋ｂ
≧１である）で表される有機置換基を表し、 Ｒ3 は次式： 【化３】 （式中、Ｒ7 は炭素原子数２以上の２価の炭化水素基を
表し、Ｒ8 はエポキシ基含有基を表し、ｃおよびｄは０
または正数で、かつａ＋ｂ≧１である）で表される有機
置換基を表し、 Ｒ4 はＲ、Ｒ1 またはＲ2 のいずれかに定義された意味
を表し、 ｌ、ｍ、ｎおよびｏはそれぞれ平均数でｌ、ｍおよびｎ
は０〜１０００でありｏは１〜１０００であり、それら
は１≦ｌ＋ｍ＋ｎ＋ｏ≦１０００を満足する値であり、
更にＲ4 がＲ2 の場合は１≧ｏ／（ｎ＋ｏ＋２）≧０．
０２を、それ以外の場合は１≧ｏ／（ｎ＋ｏ）≧０．０
２を満足する値であるが、ただし、ｍが０の場合はＲ4
はＲ1 に定義された意味を表し、ｎが０の場合はＲ4 は
Ｒ2 に定義された意味を表す］で表される変性オルガノ
ポリシロキサン化合物を製造するにあたり、（ｂ）の化
合物の付加工程の後に（ｃ）の化合物の付加工程を行う
ことを特徴とする式（１）の変性オルガノポリシロキサ
ン化合物の製造方法： （ａ）エポキシ基とアルケニル基を同時に持つ化合物、
（ｂ）次式（２）： 【化４】 （式中、Ｒ6 、ａおよびｂは前記式（１）で定義したの
と同じ意味を表し、Ｒ10はアルケニル基を含有する一価
の炭化水素基を表す）で表される化合物、（ｃ）次式
（３）： 【化５】 （式中、Ｒ8 、ａおよびｂは前記式（１）で定義したの
と同じ意味を表し、Ｒ11はアルケニル基を含有する一価
の炭化水素基を表す）で表される化合物。1. The following (a), (b) and (c) in the presence of a catalyst in the SiH group-containing organopolysiloxane compound:
The following formula (1): [Wherein, R is the same or different and represents a hydrogen atom or a monovalent hydrocarbon group, R 1 represents an epoxy group-containing group, and R 2 represents the following formula: (In the formula, R 5 represents a divalent hydrocarbon group having 2 or more carbon atoms, R 6 represents a hydrogen atom group, a monovalent hydrocarbon group or an acyl group, and a and b are 0 or a positive number. , And a + b
≧ 1) and R 3 is represented by the following formula: (In the formula, R 7 represents a divalent hydrocarbon group having 2 or more carbon atoms, R 8 represents an epoxy group-containing group, and c and d are 0.
Or a positive number and a + b ≧ 1), R 4 represents an organic substituent represented by R, R 1 or R 2 , and l, m, n and o Are the average numbers of l, m and n, respectively.
Is 0 to 1000 and o is 1 to 1000, which are values satisfying 1 ≦ l + m + n + o ≦ 1000,
Further, when R 4 is R 2 , 1 ≧ o / (n + o + 2) ≧ 0.
02, otherwise 1 ≧ o / (n + o) ≧ 0.0
It is a value satisfying 2, but when m is 0, R 4
Represents the meaning defined in R 1 and, when n is 0, R 4 represents the meaning defined in R 2. ] to produce a modified organopolysiloxane compound represented by the formula (b) A method for producing a modified organopolysiloxane compound of the formula (1), characterized in that an addition step of the compound (c) is carried out after the addition step: (a) a compound having an epoxy group and an alkenyl group at the same time,
(B) The following equation (2): (Wherein R 6 , a and b represent the same meaning as defined in the above formula (1), and R 10 represents a monovalent hydrocarbon group containing an alkenyl group), ( c) The following formula (3): (Wherein R 8 , a and b represent the same meaning as defined in the above formula (1), and R 11 represents a monovalent hydrocarbon group containing an alkenyl group).
求項１における式（１）で表される変性オルガノポリシ
ロキサン化合物。2. A modified organopolysiloxane compound represented by the formula (1) according to claim 1, which is produced by the method according to claim 1.
オルガノポリシロキサン化合物を主剤とする半導体封止
用エポキシ樹脂組成物。3. An epoxy resin composition for semiconductor encapsulation, which comprises an epoxy resin and the modified organopolysiloxane compound according to claim 2 as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23068495A JP3602619B2 (en) | 1995-08-17 | 1995-08-17 | Novel modified organopolysiloxane compound and epoxy resin composition for semiconductor encapsulation using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23068495A JP3602619B2 (en) | 1995-08-17 | 1995-08-17 | Novel modified organopolysiloxane compound and epoxy resin composition for semiconductor encapsulation using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0959385A true JPH0959385A (en) | 1997-03-04 |
| JP3602619B2 JP3602619B2 (en) | 2004-12-15 |
Family
ID=16911697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23068495A Expired - Fee Related JP3602619B2 (en) | 1995-08-17 | 1995-08-17 | Novel modified organopolysiloxane compound and epoxy resin composition for semiconductor encapsulation using the same |
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| Country | Link |
|---|---|
| JP (1) | JP3602619B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003085023A1 (en) * | 2002-04-10 | 2003-10-16 | Sanyo Chemical Industries, Ltd. | Polyurethane resin based slush molding material |
| JP2008063583A (en) * | 2007-10-22 | 2008-03-21 | Asahi Kasei Chemicals Corp | Modified polysiloxane |
-
1995
- 1995-08-17 JP JP23068495A patent/JP3602619B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003085023A1 (en) * | 2002-04-10 | 2003-10-16 | Sanyo Chemical Industries, Ltd. | Polyurethane resin based slush molding material |
| US7405257B2 (en) | 2002-04-10 | 2008-07-29 | Sanyo Chemical Industries, Ltd. | Polyurethane resin-based material for slush molding |
| JP2008063583A (en) * | 2007-10-22 | 2008-03-21 | Asahi Kasei Chemicals Corp | Modified polysiloxane |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3602619B2 (en) | 2004-12-15 |
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