JPS62187721A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPS62187721A JPS62187721A JP2888186A JP2888186A JPS62187721A JP S62187721 A JPS62187721 A JP S62187721A JP 2888186 A JP2888186 A JP 2888186A JP 2888186 A JP2888186 A JP 2888186A JP S62187721 A JPS62187721 A JP S62187721A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- organopolysiloxane
- resin composition
- curing agent
- gel
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 85
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- -1 polysiloxane Polymers 0.000 claims description 12
- 229920003986 novolac Polymers 0.000 claims description 11
- 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 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002026 crystalline silica Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 31
- 238000005452 bending Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 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
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000001246 bromo group Chemical group Br* 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
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 150000004756 silanes Chemical class 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は、特に半導体装置封止用等として好適に用いら
れるエポキシ樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition particularly suitable for use in encapsulating semiconductor devices.
従 の’４１Ｕ び、■が解ンしようとする問題寺エ
ポキシ樹脂、硬化剤及びこれに無機充填剤を配合したエ
ポキシ樹脂組成物は、一般に他の熱硬化性樹脂に比べて
成形性、接着性、電気特性、機械的特性、耐湿性等に優
れているため、各種成形材料、粉体塗料用材料、電気絶
縁材料等として広く利用され、特に最近においては半導
体装置封止用材料として多量に使用されている。Epoxy resins, curing agents, and epoxy resin compositions containing inorganic fillers generally have better moldability and adhesive properties than other thermosetting resins. Due to its excellent electrical properties, mechanical properties, moisture resistance, etc., it is widely used as various molding materials, powder coating materials, electrical insulation materials, etc., and recently it has been especially used in large quantities as a material for encapsulating semiconductor devices. has been done.
しかしながら、従来のエポキシ樹脂組成物は、高弾性率
で可撓性に乏しいため、素子への成形、加工を行なう時
やヒートサイクル試験時においてクランクが発生し易く
、また、過大なストレスがかかって素子が変形するなど
により素子の機能低下や破損が生じ易いなどといった欠
陥を有するものであった。However, conventional epoxy resin compositions have a high modulus of elasticity and poor flexibility, so they tend to crack when molded and processed into devices or during heat cycle tests, and are susceptible to excessive stress. The device had defects such as deterioration of the device's function and easy breakage due to deformation of the device.
これらの問題に対し、本発明者らは先に硬化性エポキシ
樹脂にオルガノポリシロキサンを配合したエポキシ樹脂
組成物（特開昭５６−１２９２４６号）、更には芳香族
重合体とオルガノポリシロキサンとからなるブロック共
重合体を添加したエポキシ樹脂組成物（特開昭５８−２
１４１７号）を提案し、エポキシ樹脂組成物の耐クラン
ク性を改善した。In order to solve these problems, the present inventors have developed an epoxy resin composition in which organopolysiloxane is blended with a curable epoxy resin (Japanese Unexamined Patent Publication No. 56-129246), and furthermore an aromatic polymer and an organopolysiloxane. An epoxy resin composition to which a block copolymer is added (JP-A-58-2
No. 1417) was proposed to improve the crank resistance of epoxy resin compositions.
上述した耐クラツク性の改善にもかかわらず、近年、益
々半導体装置封止用材料等への要求特性が厳しくなり、
現在では更に耐クランク性に優れ、かつガラス転移点が
高く、低膨張係数を有し、しかも曲げ強度を損なうこと
のないなどの特性を存する材料の開発が望まれている。Despite the improvements in crack resistance mentioned above, in recent years, the characteristics required for semiconductor device encapsulation materials have become increasingly strict.
Currently, there is a desire to develop materials that have properties such as superior crank resistance, a high glass transition point, a low coefficient of expansion, and no loss of bending strength.
また、前記提案のエポキシ樹脂組成物に使用したシリコ
ーン変性化合物は、いずれも高価であり、このためエポ
キシ樹脂組成物、従ってこれを応用した各種成形、加工
物の価格に少なからぬ影響を与え、これらの価格の低価
格化への障害となる場合もあった。Furthermore, the silicone-modified compounds used in the epoxy resin composition proposed above are all expensive, which has a considerable impact on the price of the epoxy resin composition and, therefore, the various molded and processed products to which it is applied. In some cases, this became an obstacle to lowering prices.
本発明は上記事情に鑑みなされたもので、流動性及び曲
げ強度や曲げ弾性率等の機械的強度が優れている上、膨
張係数が低（てガラス転移温度が高く、かつ、耐クラツ
ク性に優れ、経済的にも有利なエポキシ樹脂組成物を提
供することを目的とする。The present invention was developed in view of the above circumstances, and has excellent fluidity and mechanical strength such as bending strength and bending modulus, as well as a low coefficient of expansion (and high glass transition temperature), and excellent crack resistance. The purpose of the present invention is to provide an excellent and economically advantageous epoxy resin composition.
５ 占を ゛するための び
、 本発明者らは、上記目的を達成するため鋭意検討を
重ねた結果、硬化性エポキシ樹脂と、硬化剤と、無機充
填剤とを含有するエポキシ樹脂組成物に特定のオルガノ
ポリシロキサンゲルを含有、複合化するという簡単な方
法が有効であることを見出したものである。5. In order to achieve the above object, the present inventors have made extensive studies and have developed an epoxy resin composition containing a curable epoxy resin, a curing agent, and an inorganic filler. It has been discovered that a simple method of containing and compositing a specific organopolysiloxane gel is effective.
即ち、上述したエポキシ樹脂組成物に反応性の官能基を
１分子中に２個以上有するオルガノポリシロキサンを配
合分散すると、ガラス転移点を低下させることなく内部
応力が低下して耐クラツク性が向上する上に、この種の
オルガノポリシロキサンは比較的安価であって経済的に
有利なエポキシ樹脂組成物が得られるものであるが、こ
の方法は配合したオルガノポリシロキサンがエポキシ樹
脂組成物の表面や、エポキシ樹脂組成物を用いて半導体
装置の封止を行なった場合にリードフレームとの界面に
移行してマーキング不良や密着不良を引き起すなどの弊
害が生じる。更に、エポキシ樹脂組成物が未硬化状態で
長期に亘って保存される場合にも同様のオルガノポリシ
ロキサンの移行やシリコーン分散粒子の凝集を起して著
しく分散度が変化するため、硬化後本来の機能が得られ
にくいといった問題も生じる。That is, when an organopolysiloxane having two or more reactive functional groups in one molecule is blended and dispersed in the above-mentioned epoxy resin composition, the internal stress is lowered without lowering the glass transition point and the crack resistance is improved. In addition, this type of organopolysiloxane is relatively inexpensive and provides an economically advantageous epoxy resin composition. When a semiconductor device is sealed using an epoxy resin composition, it migrates to the interface with the lead frame, causing problems such as poor marking and poor adhesion. Furthermore, when an epoxy resin composition is stored in an uncured state for a long period of time, similar migration of organopolysiloxane and agglomeration of silicone dispersed particles occur, resulting in a significant change in dispersion. The problem also arises that it is difficult to obtain certain functions.
これに対し、このようなオルガノポリシロキサンを反応
させ、わずかに架橋せしめて特定範囲の稠度と弾性率、
即ちＪＩＳ−に２８０８に準じて測定した稠度が３０〜
１３０、弾性率が１０３〜１０５ダイン／ ｅｌｍ ”
の低架橋状態のオルガノポリシロキサンゲルをエポキシ
樹脂組成物に配合し分散すると、この種のオルガノポリ
シロキサンゲルはエポキシ樹脂組成物中で移行せず、し
かも耐クラツク性の向上が図られる上、通常のシリコー
ンゴム系化合物を配合した場合に観察されるエポキシ樹
脂組成物の流動性や分散状態の劣化が起こらず、このた
めエポキシ樹脂組成物を応用した各種成形、加工が比較
的容易に行ない得ることを知見し、本発明を完成するに
至ったものである。In contrast, such organopolysiloxanes are reacted and slightly crosslinked to achieve consistency and elastic modulus within a specific range.
That is, the consistency measured according to JIS-2808 is 30~
130, elastic modulus is 103-105 dynes/elm”
When an organopolysiloxane gel with a low crosslinking state of The fluidity and dispersion state of the epoxy resin composition do not deteriorate, which is observed when the silicone rubber compound of This discovery led to the completion of the present invention.
従って、本発明は、硬化性エポキシ樹脂と、硬化剤と、
無機充填剤とを含有するエポキシ樹脂組成物に対し、Ｊ
ＩＳ−に２８０８に準じて測定した稠度が３０〜１３０
、弾性率が１０３〜１０５ダイン／ｃｔｎ２のオルガノ
ポリシロキサンゲルを配合したエポキシ樹脂組成物又は
該オルガノポリシロキサンゲルを形成可能なオルガノポ
リシロキサン組成物を含有するエポキシ樹脂組成物を提
供するものである。Therefore, the present invention provides a curable epoxy resin, a curing agent,
For epoxy resin compositions containing inorganic fillers, J
Consistency measured according to IS-2808 is 30-130
, an epoxy resin composition containing an organopolysiloxane gel having an elastic modulus of 103 to 105 dynes/ctn2, or an organopolysiloxane composition capable of forming the organopolysiloxane gel. .
以下、本発明を更に詳しく説明する。The present invention will be explained in more detail below.
まず、本発明のエポキシ樹脂組成物を構成する硬化性エ
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
エポキシ樹脂であって、このエポキシ樹脂は後述する各
種硬化剤により硬化し得るものであれば分子構造、分子
量等に制限はなく、従来から知られている種々のものを
使用することができ、具体的には例えばエピクロルヒド
リンとビスフェノールＡをはじめとする各種ノボラック
樹脂から合成されるノボラック型エポキシ樹脂、ビスフ
ェノールＡ型エポキシ樹脂、脂環式エポキシ樹脂あるい
は塩素や臭素原子等のハロゲン原子を導入した置換エポ
キシ樹脂などが挙げられ、中でも置換又は非置換のノボ
ラック型エポキシ樹脂及びビスフェノールＡ型エポキシ
樹脂が好適である。First, the curable epoxy resin constituting the epoxy resin composition of the present invention is an epoxy resin having two or more epoxy groups in one molecule, and this epoxy resin can be cured with various curing agents described below. There are no restrictions on molecular structure, molecular weight, etc., and various conventionally known ones can be used. Specifically, for example, novolac type synthesized from various novolac resins including epichlorohydrin and bisphenol A. Examples include epoxy resins, bisphenol A type epoxy resins, alicyclic epoxy resins, and substituted epoxy resins into which halogen atoms such as chlorine and bromine atoms are introduced, among which substituted or unsubstituted novolak type epoxy resins and bisphenol A type epoxy resins. is suitable.
なお、上記エポキシ樹脂の使用に際して、モノエポキシ
化合物を適宜併用することは差支えなく、このモノエポ
キシ化合物としてはスチレンオキシド、シクロヘキセン
オキシド、プロピレンオキシド、メチルグリシジルエー
テル、エチルグリシジルエーテル、フェニルグリシジル
エーテル、アリルグリシジルエーテル、オクチレンオキ
シド、ドデセンオキシドなどが例示される。上記エポキ
シ樹脂は、その使用にあたっては必ずしも１種類のみの
使用に限定されるものではなく、２種もしくはそれ以上
を混合して使用してもよい。In addition, when using the above-mentioned epoxy resin, there is no problem in using a monoepoxy compound as appropriate, and examples of this monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl. Examples include ether, octylene oxide, and dodecene oxide. The above-mentioned epoxy resins are not necessarily limited to the use of only one type, but may be used in combination of two or more types.
また、硬化剤としてはジアミノジフェニルメタン、ジア
ミノジフェニルスルホン、メタフェニレンジアミン等に
代表されるアミン系硬化剤、無水フタル酸、無水ピロメ
リット酸、無水ベンゾフェノンテトラカルボン酸等の酸
無水物系硬化剤、あるいはフェノールノボラック、クレ
ゾールノボラック等の１分子中に２個以上の水酸基を有
するフェノールノボラック硬化剤等が例示される。In addition, as a curing agent, an amine curing agent represented by diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylene diamine, etc., an acid anhydride curing agent such as phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, or Examples include phenol novolak curing agents having two or more hydroxyl groups in one molecule, such as phenol novolak and cresol novolak.
更に、本発明においては上記した硬化剤とエポキシ樹脂
との反応を促進させる目的で各種硬化促進剤、例えばイ
ミダゾールあるいはその誘導体、三級アミン系誘導体、
ホスフィン系誘導体、シクロアミジン誘導体等を併用す
ることは何ら差支えない。Furthermore, in the present invention, various curing accelerators such as imidazole or its derivatives, tertiary amine derivatives,
There is no problem in using phosphine derivatives, cycloamidine derivatives, etc. in combination.
なお、前記硬化剤の使用量は通常使用される量であり、
硬化促進剤の配合量も通常の範囲とすることができる。In addition, the amount of the curing agent used is the amount normally used,
The amount of the curing accelerator can also be within a normal range.
本発明において使用される無機充填剤は、エポキシ樹脂
と硬化剤の総ｆｉ１００重量部に対し１００重量部未満
では得られるエポキシ樹脂組成物の膨張係数が大きく耐
クラツク性などの物性面でも満足する結果が得られない
場合が生じ、一方１０００重量部を越えると流動性が悪
くなり、無機充填剤の分散が困難となる場合があるので
、１００〜１０００重量部とすることが好ましく、より
好ましくは２５０〜７５０重量部である。なお、無機充
填剤の種類、単独使用あるいは複数種の併用等に制限は
なく、エポキシ樹脂組成物の目的、用途等に応じて適宜
選択され、例えば結晶性シリカ、非結晶性シリカ等の天
然シリカ、合成高純度シリカ、合成球状シリカ、タルク
、マイカ、窒化珪素、炭化珪素、窒化アルミニウム、ポ
ロンナイトライド、アルミナなどから選ばれる１種又は
２種以上を使用することができる。If the inorganic filler used in the present invention is less than 100 parts by weight with respect to the total fi of 100 parts by weight of the epoxy resin and curing agent, the expansion coefficient of the obtained epoxy resin composition is large and the result is satisfactory in terms of physical properties such as crack resistance. On the other hand, if it exceeds 1,000 parts by weight, fluidity may deteriorate and it may be difficult to disperse the inorganic filler, so it is preferably 100 to 1,000 parts by weight, more preferably 250 ~750 parts by weight. Note that there are no restrictions on the type of inorganic filler, whether it is used alone or in combination, and it may be selected appropriately depending on the purpose and use of the epoxy resin composition. , synthetic high-purity silica, synthetic spherical silica, talc, mica, silicon nitride, silicon carbide, aluminum nitride, poron nitride, alumina, and the like can be used.
本発明のエポキシ樹脂組成物に配合されるオルガノポリ
シロキサンゲルは、上述したように１分子中に少なくと
も２個以上の反応性の官能基を有するオルガノポリシロ
キサンを反応させ、わずかに架橋−１士しめて得られる
低架橋状態のオルガノポリシロキサンであって、そのＪ
ＩＳ−に２８０８に準じて測定した稠度が３０〜１３０
かっ弾性率が１０３〜１０５ダイン／ｃｆｆｌｚである
ものである。オルガノポリシロキサンゲルの稠度が３０
未満の場合、あるいは弾性率が１０３ダイン／ ｃｍ
２未満の場合には、このオルガノポリシロキサンゲルを
配合したエポキシ樹脂組成物の流動性には好ましい結果
を与えるものの、硬化後のエポキシ樹脂組成物のシール
特性、印刷特性に不具合が生じ易く、また機械的強度の
劣化が起るなどするために実用的でない。（ｔｔｒ方、
オルガノポリシロキサンゲルの稠度が１３０を越える場
合、あるいは弾性率が１０’ダイン／ ｃｍ ”を越え
る場合には、いずれもこのオルガノポリシロキサンゲル
を配合したエポキシ樹脂組成物の流動性、分散性の低下
を招き、また、硬化後のエポキシ樹脂組成物の応力低下
に十分な硬化を与えることができず、このため耐クラツ
ク性も改博し得ないなどの点で本発明の目的に対し不適
である。The organopolysiloxane gel blended into the epoxy resin composition of the present invention is produced by reacting organopolysiloxanes having at least two or more reactive functional groups in one molecule, as described above, to create a slightly cross-linked organopolysiloxane gel. An organopolysiloxane in a low crosslinked state obtained by
Consistency measured according to IS-2808 is 30-130
The elastic modulus is 103 to 105 dynes/cfflz. Organopolysiloxane gel consistency is 30
or if the modulus is less than 103 dynes/cm
If it is less than 2, although favorable results are obtained for the fluidity of the epoxy resin composition containing this organopolysiloxane gel, problems tend to occur in the sealing properties and printing properties of the epoxy resin composition after curing, and This is not practical because it causes deterioration in mechanical strength. (ttr way,
If the consistency of the organopolysiloxane gel exceeds 130, or if the modulus of elasticity exceeds 10'dynes/cm'', the fluidity and dispersibility of the epoxy resin composition containing the organopolysiloxane gel will decrease. Furthermore, it is not suitable for the purpose of the present invention in that it cannot provide sufficient curing to reduce the stress of the epoxy resin composition after curing, and therefore cannot improve crack resistance. .
ここで、本発明のエポキシ樹脂組成物に配合されるオル
ガノポリシロキサンゲルは、１分子中に少なくとも２個
以上の反応性の官能基を有するオルガノポリシロキサン
に、架橋剤と、必要に応じて白金、硫酸、塩酸、苛性カ
リ、テトラメチルアンモニウムハイドロオキサイド、テ
トラブチルホスホニウムハイドロオキサイド、ホスホニ
トリルクロライド等の公知の触媒の１種又は２種以上を
適量含有するオルガノポリシロキサン組成物を反応硬化
させることにより得ることができる。Here, the organopolysiloxane gel blended into the epoxy resin composition of the present invention is an organopolysiloxane having at least two or more reactive functional groups in one molecule, a crosslinking agent, and, if necessary, platinum. , sulfuric acid, hydrochloric acid, caustic potash, tetramethylammonium hydroxide, tetrabutylphosphonium hydroxide, phosphonitrile chloride, etc., by reaction-curing an organopolysiloxane composition containing an appropriate amount of one or more of known catalysts such as phosphonitrile chloride. be able to.
こうしたオルガノポリシロキサンゲルを得るためのオル
ガノポリシロキサンとしては、１分子中に少なくとも２
個以上の反応性の官能基を有するものであれば特に制限
はないが、例えば、下記一般式（１）
％式％（１）
（但し、式中Ｒは水素又は置換もしくは非置換の１価炭
化水素基を表わし、ａは１．５〜２．０５である。）
で示され、反応性の官能基としてビニル基、アミノプロ
ピル基、グリシドキシプロビル基、メルカプトプロピル
基などの１種又は２種以上を１分子中に少なくとも２個
以上有するオルガノポリシロキサンが挙げられ、具体的
には以下の式■〜■ＭｅｚＳｉＯ＋ｚｚ
００．”、■（以下、Ｍと略称する。）
Ｍｅ２ＳｉＯ・・・・・・■
（以下、Ｄと略称する。）
１１Ｍｔ４ｓｉＯ＋ｚｚ ０
．’ ４０．■（以下、Ｍｌ＋と略称する。）
（ＣＨｚ ＝ＣＨ）ＭｅＳｉＯ＝−■
（以下、ＤＶと略称する。）
φ２ＳｉＯ・・・・・・■
（以下、Ｄφと略称する。）
（ＣＨｚ−Ｃ８）ＭｅｚＳｉＯ＋７＝
”’ ・・’■（以下、ＭＶと略称する。）
ＭｅＳｉＯｓｚ□ ・・・・・
・■（以下、Ｔと略称する。）
ＮＨ２ＣＨｚＣｔｌｚ ・Ｍｅ２ＳｉＯ＋ｚｚ
”’−■（以下、ＭＮと略称する。）
（以下、Ｄ′と略称する。）
で表わされるオルガノシロキサンの２種以上を結合単位
として、各オルガノシロキサン結合単位が以下の比率（
モル％）で結合したオルガノポリシロキサン（１１〜（
７〕
オルガノポリシロキサン（１）
Ｍ ： Ｄｖ： Ｄ＝０．８ ： １．６ ： ９７．
６オルガノポリシロキサン（２）
ＭＵＭｖ：Ｔ：Ｄ ＝４．０３： ０．７５： ５．６
２： ８９．６０オルガノポリシロキサン（３）
Ｍ： Ｄ’： Ｄ４：Ｄ＝０．８： １．６： １
．６： ９６．０オルガノポリシロキサン（４）
Ｍ’：Ｄ＝１０：９０
オルガノポリシロキサン（５）
ＭＡＤ’ ：Ｄ＝２０：３０：５０
オルガノポリシロキサン（６）
ＭＮ：Ｄ＝１０：９０
オルガノポリシロキサン（７）
Ｍ ：Ｄｆ： Ｄ＝０．８ ： １．６ ： ９７．６
などの１種又は２種以上が使用し得る。The organopolysiloxane used to obtain such an organopolysiloxane gel should contain at least 2
There is no particular restriction as long as it has at least 2 reactive functional groups, but for example, the following general formula (1) % formula % (1) (wherein R is hydrogen or a substituted or unsubstituted monovalent represents a hydrocarbon group, a is 1.5 to 2.05), and one type of reactive functional group such as a vinyl group, an aminopropyl group, a glycidoxypropyl group, a mercaptopropyl group, etc. Or organopolysiloxane having at least two or more types in one molecule, specifically, the following formulas - MezSiO+zz
00. ”, ■ (hereinafter abbreviated as M) Me2SiO...■ (hereinafter abbreviated as D) 11Mt4siO+zz 0
．． '40. ■ (Hereinafter, abbreviated as Ml+.) (CHz = CH)MeSiO=-■ (Hereinafter, abbreviated as DV.) φ2SiO...■ (Hereinafter, abbreviated as Dφ.) (CHz-C8) MezSiO+7=
”'・・・'■ (hereinafter abbreviated as MV) MeSiOsz□ ・・・・・・
・■ (hereinafter abbreviated as T) NH2CHzCtlz ・Me2SiO+zz
``'-■ (hereinafter abbreviated as MN) (hereinafter abbreviated as D') Each organosiloxane bond unit has the following ratio (
Organopolysiloxanes (11 to (mol%)) bonded with
7] Organopolysiloxane (1) M: Dv: D=0.8: 1.6: 97.
6 organopolysiloxane (2) MUMv:T:D =4.03: 0.75: 5.6
2: 89.60 organopolysiloxane (3) M: D': D4:D=0.8: 1.6: 1
．． 6: 96.0 Organopolysiloxane (4) M':D=10:90 Organopolysiloxane (5) MAD' :D=20:30:50 Organopolysiloxane (6) MN:D=10:90 Organopoly Siloxane (7) M:Df: D=0.8: 1.6: 97.6
One or more of these may be used.
また、本発明に係るオルガノポリシロキサンゲルを得る
ための架橋剤としては、上述したオルガノポリシロキサ
ンの有する反応性の官能基と反応して架橋し得る化合物
であれば特に制限はないが、例えば、活性水素を２個以
上有するオルガノポリシロキサンが挙げられる。Further, the crosslinking agent for obtaining the organopolysiloxane gel according to the present invention is not particularly limited as long as it is a compound capable of crosslinking by reacting with the reactive functional group of the organopolysiloxane described above, but for example, Examples include organopolysiloxanes having two or more active hydrogen atoms.
とりわけ本発明に係るオルガノポリシロキサンゲルを得
るためのオルガノポリシロキサンと架橋剤との組合せと
しては、オルガノポリシロキサンとして上述したオルガ
ノポリシロキサン（１１〜（３）の様なメチルビニルポ
リシロキサンを用い、これに架橋剤としてメチルハイド
ロジエンオルガノポリシロキサンを用いたものが好適で
あり、更にこれらメチルビニルポリシロキサンとメチル
ハイドロジエンポリシロキサンとを白金触媒存在下で反
応して得られたオルガノポリシロキサンゲルが、本発明
に係るオルガノポリシロキサンゲルとして好適に使用し
得るものである。In particular, as the combination of organopolysiloxane and crosslinking agent for obtaining the organopolysiloxane gel according to the present invention, the above-mentioned organopolysiloxanes (methyl vinyl polysiloxanes such as 11 to (3)) are used as the organopolysiloxane, It is preferable to use a methylhydrodiene organopolysiloxane as a crosslinking agent, and an organopolysiloxane gel obtained by reacting these methylvinyl polysiloxane and methylhydrodiene polysiloxane in the presence of a platinum catalyst. , which can be suitably used as the organopolysiloxane gel according to the present invention.
中でも、メチルビニルポリシロキサンとして両末端トリ
メチルシリルメチルビニルポリシロキサン及び／又は両
末端トリメチルシリルメチルビニルフェニルポリシロキ
サンを用い、メチルハイドロジエンポリシロキサンとし
て両末端ハイドロジエンジメチルポリシロキサン及び／
又は両末端ハイドロジエンメチルフェニルポリシロキサ
ンを用いたものが本発明の目的に対しより好適である。Among them, trimethylsilylmethylvinylpolysiloxane at both ends and/or trimethylsilylmethylvinylphenylpolysiloxane at both ends is used as the methylvinylpolysiloxane, and hydrodiene dimethylpolysiloxane and/or at both ends as the methylhydrogen polysiloxane.
Alternatively, those using hydrogen-terminated hydrodiene methylphenyl polysiloxane are more suitable for the purpose of the present invention.
なお、本発明に係るオルガノポリシロキサンゲルを得る
ためのオルガノポリシロキサンと架橋剤との配合量は、
架橋剤として上述したメチルハイドロジエンポリシロキ
サンを用いた場合においては両者を任意の割合で配合し
得、特に制限はないが、両者の反応性の官能基数がほぼ
等しい割合となるように調製することが好ましい。The blending amounts of organopolysiloxane and crosslinking agent to obtain the organopolysiloxane gel according to the present invention are as follows:
When using the above-mentioned methylhydrodiene polysiloxane as a crosslinking agent, both can be blended in any ratio, and there is no particular restriction, but the number of reactive functional groups of both should be adjusted to be approximately the same ratio. is preferred.
また、本発明に係るオルガノポリシロキサンゲルの配合
量は、本発明の目的を効果的に発揮するために硬化性エ
ポキシ樹脂と硬化剤との総量１００重量部当り１〜５０
重量部、特に５〜３０重量部とすることが好ましく、上
記配合量が１重量部未満の場合には目的とする耐クラツ
ク性の向上に寄与するに十分な応力低下を付与すること
が難しく、また、５０重量部を越える場合には、硬化後
のエポキシ樹脂組成物の機械的強度が低下する傾向を示
し、いずれの場合にも本発明の目的に対して好ましくな
い。In addition, in order to effectively achieve the purpose of the present invention, the amount of the organopolysiloxane gel according to the present invention is 1 to 50 parts by weight per 100 parts by weight of the total amount of the curable epoxy resin and the curing agent.
Parts by weight, particularly 5 to 30 parts by weight, are preferred; if the above-mentioned amount is less than 1 part by weight, it is difficult to provide a stress reduction sufficient to contribute to the desired improvement in crack resistance. Moreover, if it exceeds 50 parts by weight, the mechanical strength of the epoxy resin composition after curing tends to decrease, which is not preferable for the purpose of the present invention in either case.
本発明のエポキシ樹脂組成物には、更に必要によりその
目的、用途などに応じ、各種の添加剤を配合することが
できる。例えば接着性向上のための炭素官能性シラン、
ワックス類、ステアリン酸などの脂肪酸及びその金属塩
等の離型剤、カーボンブラック等の顔料、染料、酸化防
止剤、離燃化剤、Ｔ−グリシドキシプロビルトリメトキ
シシラン等の表面処理剤、その他の添加剤を配合するこ
とは差支えない。The epoxy resin composition of the present invention may further contain various additives depending on its purpose, use, etc., if necessary. e.g. carbon-functional silanes for improved adhesion;
Waxes, mold release agents such as fatty acids such as stearic acid and their metal salts, pigments such as carbon black, dyes, antioxidants, flame retardants, surface treatment agents such as T-glycidoxypropyl trimethoxysilane, etc. , and other additives may be blended.
本発明のエポキシ樹脂組成物の製造方法について特に制
限はないが、以下の（ｉ）〜（ｉｖ）の製造方法が好適
に採用し得る。Although there are no particular limitations on the method for producing the epoxy resin composition of the present invention, the following production methods (i) to (iv) can be suitably employed.
（ｉ）硬化性エポキシ樹脂、硬化剤、無機充填剤等のエ
ポキシ樹脂組成物に直接、オルガノポリシロキサン、架
橋剤及びこれらの反応触媒を混練して、エポキシ樹脂組
成物の硬化と同時にオルガノポリシロキサンゲルをも反
応形成するようにする方法。(i) Organopolysiloxane, a crosslinking agent, and a reaction catalyst thereof are kneaded directly into an epoxy resin composition such as a curable epoxy resin, a curing agent, and an inorganic filler to simultaneously cure the epoxy resin composition. A method that also allows reaction formation of gels.
（ｉｉ）溶液中でオルガノポリシロキサンと架橋剤とか
ら必要により触媒の存在下でオルガノポリシロキサンゲ
ルを反応形成した後、溶剤を留去したものをエポキシ樹
脂組成物に配合し、混練する方法。(ii) A method in which an organopolysiloxane gel is reacted and formed from an organopolysiloxane and a crosslinking agent in a solution in the presence of a catalyst if necessary, and then the solvent is distilled off and the gel is blended into an epoxy resin composition and kneaded.
（ｉｉｉ ）オルガノポリシロキサンと架橋剤とにシリ
カ等の無機充填剤を加え、必要により触媒の存在下にお
いて、溶液中で攪拌混合することなどしてオルガノポリ
シロキサンゲルを反応形成させる共に、これを無機充填
剤に吸着させ、得られたオルガノポリシロキサンゲルを
吸着した無機充填剤を硬化性エポキシ樹脂、硬化剤等の
エポキシ樹脂組成物に配合し混練する方法。(iii) Add an inorganic filler such as silica to the organopolysiloxane and the crosslinking agent, stir and mix in a solution, if necessary in the presence of a catalyst, to react and form an organopolysiloxane gel. A method in which the inorganic filler adsorbs the obtained organopolysiloxane gel to an epoxy resin composition such as a curable epoxy resin and a curing agent and kneads the inorganic filler.
（ｉｖ）上記（ｉ ） 〜（ｉｉｉ）の併用、例えば（
ｉｉｉ ）の製造方法に従った製造過程で得られたオル
ガノポリシロキサンゲル吸着の無機充填剤を用い、更に
（ｉ）及び／又は（ｉｉ）の方法に従ってエポキシ樹脂
組成物を得る方法。(iv) Combination of (i) to (iii) above, for example (
A method of obtaining an epoxy resin composition using an organopolysiloxane gel-adsorbed inorganic filler obtained in the manufacturing process according to the manufacturing method of iii), and further following the method of (i) and/or (ii).
なお、本発明のエポキシ樹脂組成物は、その製造に際し
、上述した成分の所定量を均一に攪拌、混合し、予め７
０〜９５℃に加熱しであるニーダ−、ロール、エクスト
ルーダーなどで混練、冷却し、粉砕するなどの方法で得
ることができる。なお、成分の配合順序に特に制限はな
い。In addition, when producing the epoxy resin composition of the present invention, predetermined amounts of the above-mentioned components are uniformly stirred and mixed, and the epoxy resin composition is prepared in advance for 7 days.
It can be obtained by heating to 0 to 95°C, kneading with a kneader, roll, extruder, etc., cooling, and pulverizing. Note that there is no particular restriction on the order of blending the components.
本発明のエポキシ樹脂組成物は、成形材料、粉体塗装用
材料として好適に使用し得るほか、ＩＣ１ＬＳＩ 、ｌ
−ランリスク、サイリスク、ダイオード等の半導体装置
の封止用、プリント回路板の製造などにも有効に使用で
きる。The epoxy resin composition of the present invention can be suitably used as a molding material and a powder coating material, as well as for IC1LSI, l
- It can be effectively used for sealing semiconductor devices such as run-risks, silicon-risks, and diodes, and for manufacturing printed circuit boards.
なお、半導体装置の封止を行なう場合は、従来より採用
されている成形法、例えばトランスファ成形、インジェ
クション成形、注型法などを採用して行なうことができ
る。この場合、エポキシ樹脂組成物の成形温度は１５０
〜１８０℃、ポストキュアーは１５０〜１８０℃で２〜
１６時間行うことが好ましい。Note that when sealing the semiconductor device, conventionally employed molding methods such as transfer molding, injection molding, and casting methods can be employed. In this case, the molding temperature of the epoxy resin composition is 150
~180℃, post cure at 150~180℃ for 2~
It is preferable to carry out the treatment for 16 hours.
光皿皇効米
以上説明したように本発明のエポキシ樹脂組成物は、硬
化性エポキシ樹脂と、硬化剤と、無機充填剤と、ＪＩＳ
−に２８０８に準じて測定した稠度が３０〜１３０、弾
性率が１０″〜１０Ｓダイン／ｃ＋ｎ”のオルガノポリ
シロキサンゲル又は該オルガノポリシロキサンゲルを形
成可能なオルガノポリシロキサン組成物を含有させたこ
とにより、流動性及び曲げ強度や曲げ弾性率等の機械的
強度を損なうことなく、膨張係数が低くてガラス転移温
度が高く、しかも耐クラツク性に優れまた半導体装ヱの
封止に用いた場合アルミニウム電極の変形量が小さい上
、経済的にも有利であり、このため半導体装置封止用等
として好適に用いられるエポキシ樹脂組成物が得られる
ものである。As explained above, the epoxy resin composition of the present invention comprises a curable epoxy resin, a curing agent, an inorganic filler, and a JIS
- contains an organopolysiloxane gel having a consistency of 30 to 130 and a modulus of elasticity of 10'' to 10S dyne/c+n'' as measured in accordance with 2808, or an organopolysiloxane composition capable of forming the organopolysiloxane gel. As a result, it has a low expansion coefficient and a high glass transition temperature without impairing fluidity, mechanical strength such as bending strength and bending modulus, and has excellent crack resistance. The amount of deformation of the electrode is small, and it is also economically advantageous, so that an epoxy resin composition can be obtained that is suitably used for encapsulating semiconductor devices.
以下、実施例と比較例を示し、本発明を具体的に説明す
るが、本発明は下記の実施例に制限されるものではない
。EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.
なお、実施例と比較例を示すのに先立ち、実施例及び比
較例中にて採用した以下の（イ）〜（ホ）の測定項目及
びその測定方法及びオルガノポリシロキサンゲルの製造
例を示す。In addition, prior to showing Examples and Comparative Examples, the following measurement items (A) to (E) adopted in Examples and Comparative Examples and their measurement methods, and manufacturing examples of organopolysiloxane gels will be shown.
（イ）スパイラルレフロー直 ＥＭＭＩ規格に準じた金型を使用して、１７５℃。(a) Spiral reflow direct 175℃ using a mold that complies with EMMI standards.
７０ｋｇ／ａｍ”の条件で測定した。The measurement was carried out under the condition of "70 kg/am".
（ロ）貝Ｕえ的ｆｉ直−（曲げ強度 び曲げ弾性力）Ｊ
ＩＳ−Ｋ６９１１に準じて１７５℃、 ７ Ｑ ｋｇ
／ｃｍ” 。(b) shellfish straightness (bending strength and bending elastic force) J
175℃, 7 Q kg according to IS-K6911
/cm”.
成形時間２分の条件で１１０Ｘ４Ｘ１００１の抗折棒を
成形し、１８０℃で４時間ポストキュアーしたものにつ
いて測定した。Measurements were made on a 110 x 4 x 1001 bending rod that was molded under conditions of a molding time of 2 minutes and post-cured at 180° C. for 4 hours.
（ハ）′−、ガラス″：庁
４龍φＸ１５ｍの試験片を用いて、ディラドメーターに
より毎分５℃の速さで昇温した時の値を測定した。(c)'-, Glass'': Using a test piece of 15 m in diameter, the value was measured using a diradometer when the temperature was raised at a rate of 5°C per minute.
（ニ）旦９５ヱ又性
９、 ＯＸ ４．５ Ｘ ０．５ ｍの大きさのシリコ
ンチップを１４ＰｒＮ−ＩＣフレーム（４２７０イ）に
接着し、これにエポキシ樹脂組成物を成形条件１８０℃
×２分で成形し、１８０℃で４時間ポストキュアーした
後、−１９６℃×１分〜２６０℃×３０秒の熱サイクル
を繰返して加え、５０サイクル後の樹脂クラック発生率
を測定した。（ｎ＝５０）（ホ）アルミニウム電極の・
３゜
３、４ ｘ １０．２ ｘ ０．３龍の大きさのシリコ
ンチップ上にアルミニウム電極を蒸着した変形量測定素
子を１４ＰｒＮ−ＩＣフレーム（４２７０イ）にボンデ
ィングし、これにエポキシ樹脂組成物を成形条件１８０
℃×２分で成形し、１８０℃で４時間ポストキュアーし
た後、−１９６℃×１分〜１５０℃×１分の熱サイクル
を繰返して加え、２００サイクル後のアルミニウム電極
の変形量を調べた。(d) A silicon chip measuring 4.5 x 0.5 m was glued to a 14PrN-IC frame (4270), and an epoxy resin composition was applied to it under molding conditions of 180°C.
After molding for 2 minutes and post-curing at 180°C for 4 hours, thermal cycles of -196°C x 1 minute to 260°C x 30 seconds were repeated, and the resin crack occurrence rate after 50 cycles was measured. (n=50) (e) Aluminum electrode
A deformation measurement element made of a 3°3,4 x 10.2 x 0.3 dragon-sized silicon chip with an aluminum electrode deposited on it was bonded to a 14PrN-IC frame (4270I), and an epoxy resin composition was applied to this. Molding conditions 180
After molding at ℃ x 2 minutes and post-curing at 180℃ for 4 hours, heat cycles from -196℃ x 1 minute to 150℃ x 1 minute were repeated, and the amount of deformation of the aluminum electrode after 200 cycles was investigated. .
（ｎ＝３）
〔製造例１〜７〕
オルガノポリシロキサンとして下記式（Ａ）〜（Ｅ）＜
ＩＥ （Ｊ
ロ （３）で表わされる化合
物を第１表に示す割合で配合し、これに白金濃度１０ｐ
ｐｍの白金触媒２−エチルヘキサノール変性塩化白金酸
を加えてから１５０ ’Ｃで３０分間加熱してオルガノ
ポリシロキサンを製造した。(n=3) [Production Examples 1 to 7] The following formulas (A) to (E) <
IE (J
B. Blend the compound represented by (3) in the proportion shown in Table 1, and add it to a platinum concentration of 10p.
After adding pm of platinum catalyst 2-ethylhexanol modified chloroplatinic acid, the mixture was heated at 150'C for 30 minutes to prepare an organopolysiloxane.
得られたオルガノポリシロキサンゲルにつき、ＪＩＳ−
に２８０８に準じて１７４インチミクロ稠度計で稠度を
測定し、また、粘弾性スペクトロメータで弾性率を測定
した。Regarding the obtained organopolysiloxane gel, JIS-
The consistency was measured using a 174-inch micro-consistency meter according to 2808, and the elastic modulus was measured using a viscoelasticity spectrometer.
測定結果を第１表に伴記する。The measurement results are included in Table 1.
〔実施例１〜８．比較例１〜５〕
エポキシ当量２００のエポキシ化クレゾールノボラック
樹脂（表中硬化性エポキシ樹脂ＣＩ）で示す。）、下記
方法で得られたアリル基含有エポキシ化ノボラック樹脂
とオルガノポリシロキサンとの共重合体（表中共重合体
（ｎ）で示す、）、フェノール当ｆｆ１ｌｌＯのフェノ
ールノボラック樹脂、製造例１〜７で得られたオルガノ
ポリシロキサンゲル（表中オルガノポリシロキサンゲル
（１）〜〔■〕で示す、）、トリフェニルホスフィン（
表中ＴＰＰで示す。’） 、１．８−ジアザビシクロウ
ンデセン−７（表中ＯＢＵで示す、）をそれぞれ第２表
に示す配合量で使用し、これに臭素化エポキシノボラッ
ク樹脂７部、溶融シリカ粉２６０部、３−グリシドキシ
プロビルトリメトキシシラン１．５部、ワックス８１．
５部、カーボンブラック１．０部を加えて得られた配合
物を熱二本ロールで均一に溶融混合して１１種のエポキ
シ樹脂組成物（実施例１〜８、比較例１〜３）を製造し
た。[Examples 1 to 8. Comparative Examples 1 to 5] An epoxidized cresol novolac resin having an epoxy equivalent weight of 200 (curable epoxy resin CI in the table) was used. ), copolymer of allyl group-containing epoxidized novolac resin and organopolysiloxane obtained by the following method (indicated by copolymer (n) in the table), phenol novolac resin with ff1llO of phenol, Production Examples 1 to 7 The organopolysiloxane gels obtained in (indicated by organopolysiloxane gels (1) to [■] in the table), triphenylphosphine (
It is indicated by TPP in the table. ') and 1.8-diazabicycloundecene-7 (indicated by OBU in the table) were used in the amounts shown in Table 2, and 7 parts of brominated epoxy novolac resin and 260 parts of fused silica powder were added to this. , 1.5 parts of 3-glycidoxypropyltrimethoxysilane, 81.0 parts of wax.
5 parts of carbon black and 1.0 parts of carbon black were uniformly melted and mixed using two heated rolls to obtain 11 types of epoxy resin compositions (Examples 1 to 8, Comparative Examples 1 to 3). Manufactured.
なお、アリル恭含有エポキシ化ノボランク樹脂とオルガ
ノポリシロキサンとの共重合体は、リフランクスコンデ
ンサー、温度計、攪拌機および滴下ロートを具備した１
１の４つロフラスコにアリル基含有エポキシ樹脂１２０
ｇ、メチルイソブチルケトン１００ｇ、トルエン２００
ｇ、白金濃度２％の２−エチルヘキサノール変性塩化
白金酸溶液 ０．０４ｇを入れてから攪拌、加熱し、還
流温度に達した時点から、オルガノポリシロキサンとし
て下記式（Ｆ）
で表わされる化合物８０ｇを滴下時間３０分間にて滴下
し、滴下終了後、更に同一温度で４時間反応させた後、
得られた内容物を水洗し、減圧乾燥を行なうことにより
、製造され、得られたものは１５０℃での溶融粘度が７
６０ｃｐの白黄色不透明固体であった。In addition, the copolymer of allyl-containing epoxidized novolank resin and organopolysiloxane was prepared in a container equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel.
1. Allyl group-containing epoxy resin 120 in a 4-bottle flask
g, methyl isobutyl ketone 100g, toluene 200g
g, 0.04 g of 2-ethylhexanol-modified chloroplatinic acid solution with a platinum concentration of 2% was added, stirred and heated, and from the time the reflux temperature was reached, 80 g of a compound represented by the following formula (F) as an organopolysiloxane was added. was added dropwise for 30 minutes, and after the addition was completed, the reaction was continued at the same temperature for 4 hours.
It is manufactured by washing the obtained contents with water and drying under reduced pressure, and the obtained product has a melt viscosity of 7 at 150°C.
It was a 60 cp white yellow opaque solid.
上記方法により得られたエポキシ樹脂組成物につき、上
述した（イ）〜（ホ）の諸試験を行なった。The various tests (a) to (e) described above were conducted on the epoxy resin composition obtained by the above method.
結果を第２表に伴記する。The results are included in Table 2.
第２表の結果から、オルガノポリシロキサンゲルを含ま
ない比較例３のエポキシ樹脂組成物及び稠度又は弾性率
が本発明の範囲から外れたオルガノポリシロキサンゲル
を配合した比較例１．２のエポキシ樹脂組成物はいずれ
も耐クラツク性に劣りアルミニウム電極の変形が観察さ
れるのに対し、本発明のエポキシ樹脂組成物は採用した
測定条件下でクランクの発生及びアルミニウム電極の変
形が観察されず、かつ流動性、曲げ強度や曲げ弾性率に
見られる機械的強度、膨張係数、ガラス転移温度も実用
の水準をクリアーしていることから本発明の効果が確認
された。なお、比較例１のエポキシ樹脂組成物において
は、成形物表面にシリコーンかにじみ出すことにより外
観不良及びマーキング不良が生じた。From the results in Table 2, the epoxy resin composition of Comparative Example 3 which does not contain organopolysiloxane gel and the epoxy resin of Comparative Example 1.2 which contains organopolysiloxane gel whose consistency or elastic modulus is outside the range of the present invention. All of the compositions had poor crack resistance and deformation of the aluminum electrode was observed, whereas the epoxy resin composition of the present invention did not exhibit cracking or deformation of the aluminum electrode under the measurement conditions adopted. The effectiveness of the present invention was confirmed because the mechanical strength, expansion coefficient, and glass transition temperature as seen in fluidity, bending strength and bending modulus also cleared practical levels. In addition, in the epoxy resin composition of Comparative Example 1, poor appearance and poor marking occurred due to silicone seeping onto the surface of the molded product.
Claims (1)
ＪＩＳ−Ｋ２８０８に準じて測定した稠度が３０〜１３
０、弾性率が１０＾３〜１０＾５ダイン／ｃｍ＾２のオ
ルガノポリシロキサンゲル又は該オルガノポリシロキサ
ンゲルを形成可能なオルガノポリシロキサン組成物を含
有してなることを特徴とするエポキシ樹脂組成物。 ２、硬化性エポキシ樹脂が置換及び非置換のノボラック
型エポキシ樹脂並びにビスフェノールＡ型エポキシ樹脂
から選ばれる１種又は２種以上である特許請求の範囲第
１項記載のエポキシ樹脂組成物。 ３、オルガノポリシロキサンゲルがメチルビニルポリシ
ロキサンとメチルハイドロジエンポリシロキサンとを反
応して得られたものである特許請求の範囲第１項又は第
２項記載のエポキシ樹脂組成物。 ４、メチルビニルポリシロキサンが両末端トリメチルシ
リルメチルビニルポリシロキサン及び／又は両末端トリ
メチルシリルメチルビニルフェニルポリシロキサンであ
り、メチルハイドロジエンポリシロキサンが両末端ハイ
ドロジエンジメチルポリシロキサン及び／又は両末端ハ
イドロジエンメチルフェニルポリシロキサンである特許
請求の範囲第３項記載のエポキシ樹脂組成物。 ５、オルガノポリシロキサンゲルの配合量が硬化性エポ
キシ樹脂と硬化剤との総量１００重量部当り１〜５０重
量部である特許請求の範囲第１項乃至第４項のいずれか
１項に記載のエポキシ樹脂組成物。 ６、無機充填剤の配合量が硬化性エポキシ樹脂と硬化剤
との総量１００重量部当り１００〜１０００重量部であ
る特許請求の範囲第１項乃至第５項のいずれか１項に記
載のエポキシ樹脂組成物。[Claims] 1. A curable epoxy resin, a curing agent, an inorganic filler,
Consistency measured according to JIS-K2808 is 30-13
0, an epoxy resin composition comprising an organopolysiloxane gel having an elastic modulus of 10^3 to 10^5 dynes/cm^2 or an organopolysiloxane composition capable of forming the organopolysiloxane gel. thing. 2. The epoxy resin composition according to claim 1, wherein the curable epoxy resin is one or more selected from substituted and unsubstituted novolak epoxy resins and bisphenol A epoxy resins. 3. The epoxy resin composition according to claim 1 or 2, wherein the organopolysiloxane gel is obtained by reacting methylvinylpolysiloxane and methylhydrodienepolysiloxane. 4. Methylvinylpolysiloxane is trimethylsilylmethylvinylpolysiloxane at both ends and/or trimethylsilylmethylvinylphenylpolysiloxane at both ends, and methylhydrodienepolysiloxane is hydrogenate dimethylpolysiloxane at both ends and/or hydrogenmethylphenyl at both ends. The epoxy resin composition according to claim 3, which is a polysiloxane. 5. The organopolysiloxane gel is blended in an amount of 1 to 50 parts by weight per 100 parts by weight of the total amount of the curable epoxy resin and curing agent, according to any one of claims 1 to 4. Epoxy resin composition. 6. The epoxy according to any one of claims 1 to 5, wherein the inorganic filler is blended in an amount of 100 to 1000 parts by weight per 100 parts by weight of the curable epoxy resin and curing agent. Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2888186A JPS62187721A (en) | 1986-02-14 | 1986-02-14 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2888186A JPS62187721A (en) | 1986-02-14 | 1986-02-14 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62187721A true JPS62187721A (en) | 1987-08-17 |
| JPH0346486B2 JPH0346486B2 (en) | 1991-07-16 |
Family
ID=12260739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2888186A Granted JPS62187721A (en) | 1986-02-14 | 1986-02-14 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62187721A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01182357A (en) * | 1988-01-14 | 1989-07-20 | Matsushita Electric Works Ltd | Epoxy resin molding material |
| JPH01185320A (en) * | 1988-01-18 | 1989-07-24 | Matsushita Electric Works Ltd | Epoxy resin molding material |
| JPH01299816A (en) * | 1988-05-26 | 1989-12-04 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JPH02170819A (en) * | 1988-12-23 | 1990-07-02 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JPH02170821A (en) * | 1988-12-23 | 1990-07-02 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JP2006273953A (en) * | 2005-03-28 | 2006-10-12 | Fuji Xerox Co Ltd | Hardened material, coating liquid for forming hardened material, photo conductor for electrophotography, coating liquid for forming top layer, process cartridge and image forming device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136816A (en) * | 1980-03-31 | 1981-10-26 | Shin Etsu Chem Co Ltd | Epoxy resin composition |
| JPS6031523A (en) * | 1983-07-29 | 1985-02-18 | Toshiba Chem Corp | Sealing resin composition |
| JPS6069129A (en) * | 1983-09-27 | 1985-04-19 | Toshiba Corp | Epoxy resin composition |
| JPS62184017A (en) * | 1986-02-08 | 1987-08-12 | Matsushita Electric Works Ltd | Epoxy resin molding material |
-
1986
- 1986-02-14 JP JP2888186A patent/JPS62187721A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136816A (en) * | 1980-03-31 | 1981-10-26 | Shin Etsu Chem Co Ltd | Epoxy resin composition |
| JPS6031523A (en) * | 1983-07-29 | 1985-02-18 | Toshiba Chem Corp | Sealing resin composition |
| JPS6069129A (en) * | 1983-09-27 | 1985-04-19 | Toshiba Corp | Epoxy resin composition |
| JPS62184017A (en) * | 1986-02-08 | 1987-08-12 | Matsushita Electric Works Ltd | Epoxy resin molding material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01182357A (en) * | 1988-01-14 | 1989-07-20 | Matsushita Electric Works Ltd | Epoxy resin molding material |
| JPH01185320A (en) * | 1988-01-18 | 1989-07-24 | Matsushita Electric Works Ltd | Epoxy resin molding material |
| JPH01299816A (en) * | 1988-05-26 | 1989-12-04 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JPH02170819A (en) * | 1988-12-23 | 1990-07-02 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JPH02170821A (en) * | 1988-12-23 | 1990-07-02 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JP2006273953A (en) * | 2005-03-28 | 2006-10-12 | Fuji Xerox Co Ltd | Hardened material, coating liquid for forming hardened material, photo conductor for electrophotography, coating liquid for forming top layer, process cartridge and image forming device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0346486B2 (en) | 1991-07-16 |
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