JPH02305848A - Liquid epoxy resin composition and its cured product - Google Patents
Liquid epoxy resin composition and its cured productInfo
- Publication number
- JPH02305848A JPH02305848A JP12707489A JP12707489A JPH02305848A JP H02305848 A JPH02305848 A JP H02305848A JP 12707489 A JP12707489 A JP 12707489A JP 12707489 A JP12707489 A JP 12707489A JP H02305848 A JPH02305848 A JP H02305848A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- molecule
- viscosity
- liquid epoxy
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 title claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 40
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- 230000009974 thixotropic effect Effects 0.000 abstract description 26
- 150000001875 compounds Chemical class 0.000 abstract description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 3
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 abstract description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011342 resin composition Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 239000013008 thixotropic agent Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- -1 aminopropyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- 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 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
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000013466 adhesive and sealant Substances 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
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 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
- 239000012530 fluid 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
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material 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
- 239000006082 mold release agent Substances 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
- 239000003960 organic solvent 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 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
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、低粘度で、しかもチクソトロビック性を有す
る液状エポキシ樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a liquid epoxy resin composition having low viscosity and thixotropic properties.
〔従来の技術及び発明が解決しようとする課題〕周知の
ように、エポキシ樹脂組成物は、接着性、硬化性、機械
的強度、電気特性等に優れているため、建築、電気、電
子分野において巾広く使用されており、特に液状のエポ
キシ樹脂組成物は、常温で注型等により硬化させること
ができ、各種産業分野での接着剤やシール材に用いられ
、とりわけチップオンボード等の半導体の封止用として
好適に使用されている。[Prior art and problems to be solved by the invention] As is well known, epoxy resin compositions have excellent adhesive properties, hardenability, mechanical strength, electrical properties, etc., and are therefore used in the fields of architecture, electricity, and electronics. It is widely used, and liquid epoxy resin compositions in particular can be cured at room temperature by casting, etc., and are used as adhesives and sealants in various industrial fields, especially for semiconductors such as chip-on-board. It is suitably used for sealing purposes.
しかし、従来のエポキシ樹脂組成物は注型性等の点から
その粘度をあまり高くできないため、使用時にたれ落ち
たり、流れ出したりする等１作業性に問題があった。However, since the viscosity of conventional epoxy resin compositions cannot be increased too high from the viewpoint of castability, there have been problems with workability such as dripping or flowing out during use.
これを防止するためには、液状のエポキシ樹脂組成物に
チク、ソトロピック性を付与することが望まれるが、従
来、低粘度でかつ優れたチクソトロピック性を有する液
状エポキシ樹脂組成物に関する提案は殆んどなく、この
ため、低粘度で良好なチクソトロピック性を有し、しか
も保存中に経時変化を生じず、そのチクソトロビック性
を長期間維持できる液状エポキシ樹脂組成物が求められ
る。In order to prevent this, it is desirable to impart thixotropic properties to liquid epoxy resin compositions, but there have been few proposals regarding liquid epoxy resin compositions that have low viscosity and excellent thixotropic properties. Therefore, there is a need for a liquid epoxy resin composition that has low viscosity and good thixotropic properties, does not change over time during storage, and can maintain its thixotropic properties for a long period of time.
本発明は、上記事情に鑑みなされたもので、低粘度であ
り、しかも良好なチクソトロピック性を有し、かつ保存
安定性の良い液状エポキシ樹脂組成物及びその硬化物を
提供することを目的とする。The present invention was made in view of the above circumstances, and aims to provide a liquid epoxy resin composition that has low viscosity, good thixotropic properties, and good storage stability, and a cured product thereof. do.
〔課厘を解決するための手段及び作用〕本発明者は上記
目的を達成するため鋭意研究を重ねた結果、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と硬化剤を
含有するエポキシ樹脂組成物に、１分子中にポリオキシ
アルキレンブロックを２０重量％以上有する有機化合物
とヒユームドシリカを併用して配合した場合、このエポ
キシ樹脂組成物は２５℃におけるＢＨ型回転粘度での２
Ｑｒｐｍの粘度が２０００ポイズ以下という低粘度であ
りながら良好なチクソトロピック性を有し、しかもその
チクソトロピック性は経時変化がほとんどなく、優れた
チクソトロピック性を維持できることを見い出した。[Means and effects for solving the problem] As a result of intensive research to achieve the above object, the present inventor has developed an epoxy resin containing an epoxy resin having two or more epoxy groups in one molecule and a curing agent. When an organic compound having 20% by weight or more of polyoxyalkylene blocks in one molecule and fumed silica are combined in a resin composition, the epoxy resin composition has a BH rotational viscosity of 2 at 25°C.
It has been found that although the viscosity of Qrpm is as low as 2000 poise or less, it has good thixotropic properties, and that the thixotropic properties hardly change over time, and that the excellent thixotropic properties can be maintained.
即ち、液状エポキシ樹脂に単にヒユームドシリカを配合
しただけでは、液状エポキシ樹脂にチクソトロピック性
をある程度付与し得るものの、そのチクソトロピック性
は不十分であり、しかも粘度が増加してしまう上、経時
変化が著しく、保存中にチクソトロピック性が劣化して
しまうものである。一方、１分子中にポリオキシアルキ
レンブロックを２０重量％以上有する有機化合物を単独
配合しても十分な効果はないものであるが、ヒユームド
シリカと１分子中にポリオキシアルキレンブロックを２
０重量％以上有する有機化合物とを併用した場合、これ
ら同成分が相乗的に作用し、ヒユームドシリカ単独配合
のものより低粘度で優れたチクソトロピック性を付与し
得、しかもこのチクソトロピック性は、例えば５℃で３
ケ月間保存した後でも全くその性質が変化せず、極めて
安定であることを見い出し１本発明をなすに至ったもの
である。In other words, simply adding fumed silica to a liquid epoxy resin can impart some thixotropic properties to the liquid epoxy resin, but the thixotropic properties are insufficient, and furthermore, the viscosity increases and changes over time are slow. Thixotropic properties deteriorate significantly during storage. On the other hand, even if an organic compound containing 20% by weight or more of polyoxyalkylene blocks in one molecule is blended alone, there is no sufficient effect;
When used in combination with an organic compound containing 0% by weight or more, these same components act synergistically to provide superior thixotropic properties with a lower viscosity than those containing fumed silica alone. 3 at 5℃
The present invention was based on the discovery that its properties do not change at all even after storage for several months, and it is extremely stable.
従って１本発明は
（Ａ）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。Therefore, the present invention provides (A) an epoxy resin having two or more epoxy groups in one molecule.
（Ｂ）上記エポキシ樹脂の硬化剤、
（Ｃ）１分子中にポリオキシアルキレンブロックを２０
重量％以上有する有機化合物、及び（Ｄ）ヒユームドシ
リカ
を配合してなり、２５℃におけるＢＨ型回転粘度計での
２Ｏｒｐｍの粘度が２０００ポイズ以下である液状エポ
キシ樹脂組成物、及びこの液状エポキシ樹脂組成物を硬
化させた硬化物を提供する。(B) A curing agent for the above epoxy resin, (C) 20 polyoxyalkylene blocks in one molecule.
A liquid epoxy resin composition containing an organic compound having at least % by weight and (D) fumed silica, and having a viscosity of 2000 poise or less at 2000 poise in a BH-type rotational viscometer at 25°C, and this liquid epoxy resin composition. Provides a cured product obtained by curing.
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、本発明の組成物の（Ａ）成分を構成するエポキシ
樹脂は１分子中に２個以上のエポキシ基を有するエポキ
シ樹脂であって、このエポキシ樹脂は後述するような各
種硬化剤によって硬化させることが可能な限り分子構造
、分子量等に特に制限はなく、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る。これには、例えばエ
ピクロルヒドリンとビスフェノールをはじめとする各種
ノボラック樹脂とから合成されるエポキシ樹脂。First, the epoxy resin constituting component (A) of the composition of the present invention is an epoxy resin having two or more epoxy groups in one molecule, and this epoxy resin is cured with various curing agents as described below. There are no particular restrictions on the molecular structure, molecular weight, etc., as long as it is possible, and various conventionally known ones can be used. This includes, for example, epoxy resins synthesized from epichlorohydrin and various novolac resins including bisphenol.
脂環式エポキシ樹脂或いは塩素や臭素原子等のハロゲン
原子を導入したエポキシ樹脂などを挙げることができる
。Examples include alicyclic epoxy resins and epoxy resins into which halogen atoms such as chlorine and bromine atoms are introduced.
これらのうちで、常温で液状の組成物を得るためにはビ
スフェノールＡ又はビスフェノールＦのグリシジルエー
テル誘導体が好適に泪いられる。Among these, glycidyl ether derivatives of bisphenol A or bisphenol F are preferably used to obtain a composition that is liquid at room temperature.
また、エポキシ樹脂は後述する硬化剤との混合物の軟化
点が３０℃以下であり、かつ２５℃における粘度が５０
０ポイズ以下であることが液状のエポキシ樹脂組成物と
する点で好ましい。In addition, the epoxy resin has a softening point of 30°C or less when mixed with a curing agent described below, and a viscosity of 50°C at 25°C.
It is preferable that the epoxy resin composition is 0 poise or less in order to form a liquid epoxy resin composition.
なお、上記エポキシ樹脂は、その１種を単独で又は２種
以上を混合して使用することができる。In addition, the said epoxy resin can be used individually or in mixture of 2 or more types.
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。When using the above epoxy resin, there is no problem in using a monoepoxy compound as appropriate. Examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether,
Ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide,
Examples include dodecene oxide.
上記エポキシ樹脂の硬化に用いられる（Ｂ）成分の硬化
剤としては、ジアミノジフェニルメタン。The curing agent for component (B) used for curing the epoxy resin is diaminodiphenylmethane.
ジアミノジフェニルスルホン、メタフェニレンジアミン
等のアミン系硬化剤、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、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
ノボラック系硬化剤などが例示されるが、これらのなか
で常温で液状の酸無水物系硬化剤が好適に用いられる。Amine curing agents such as diaminodiphenylsulfone and metaphenylene diamine, acid anhydride curing agents such as phthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, phenol novolak, cresol novolac, etc. 2 in one molecule Examples include the above-mentioned phenol novolac curing agents having a hydroxyl group, and among these, acid anhydride curing agents that are liquid at room temperature are preferably used.
更に１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
ミダゾール或いはその誘導体、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し１゜
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。Furthermore, in the present invention, various curing accelerators such as imidazole or its derivatives, tertiary amine derivatives, phosphine derivatives, cycloamidine derivatives, etc. may be used in combination for the purpose of promoting the reaction between the above-mentioned curing agent and the epoxy resin. There is no problem with 1゜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.
本発明の液状エポキシ樹脂組成物を構成する（Ｃ）成分
と（Ｄ）成分は本発明の主目的であるチクソトロピック
性を付与するためのもので、これら（Ｃ）成分と（Ｄ）
成分を併用することにより、エポキシ樹脂組成物に低粘
度で優れたチクソトロピック性を付与することができる
。Component (C) and component (D) constituting the liquid epoxy resin composition of the present invention are for imparting thixotropic properties, which is the main objective of the present invention.
By using these components in combination, it is possible to impart low viscosity and excellent thixotropic properties to the epoxy resin composition.
ここで、（Ｃ）成分は１分子中にポリオキシアルキレン
ブロックを２０重量％以上、好ましくは４０重量％以上
有する有機化合物であり、このような有機化合物として
は１例えばＨＯ−ｆｃ２Ｈ４０）、Ｈ。Here, component (C) is an organic compound having 20% by weight or more, preferably 40% by weight or more of polyoxyalkylene blocks in one molecule, and examples of such organic compounds include 1, for example, HO-fc2H40), H.
ＨＯ！ Ｃ，Ｈ，ｏ ） ｔｓ Ｈ−Ｃ−Ｈ，ｏ ＋
ｃｓ ｎ−０） ２゜Ｃ，Ｈ。HO! C,H,o ) ts H-C-H,o +
cs n-0) 2°C,H.
等が挙げられるが、特にポリオキシアルキレンブロック
を２０重量％以上含有するポリオルガノシロキサンが好
適に用いられる。このようなポリオルガノシロキサンと
しては、例えば下記一般式％式％
（但し Ｒ１は水素原子又は炭素数１〜８の置換又は非
置換の一価炭化水素基、Ｒ２は炭素数１〜８の置換又は
非置換の一価炭化水素基、又はアミノプロピル基又はグ
リシドキシプロビル基を示す。In particular, polyorganosiloxane containing 20% by weight or more of polyoxyalkylene blocks is preferably used. Such polyorganosiloxanes include, for example, the following general formula % (where R1 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and R2 is a substituted or It represents an unsubstituted monovalent hydrocarbon group, or an aminopropyl group or a glycidoxyprobyl group.
ｎは２〜１００の整数、ｃ、ｄ、ｅはそれぞれ０．０５
＜ｃ＜１．０．１．８＜ｄ＜２．５゜０≦ｅ≦０．５．
１．８＜ｃ＋ｄ＋ｅ≦３の正数である。）
で示されるポリオキシプロピレン含有シロキサンを好適
に使用することができ、具体的には下記式で示される化
合物などが挙げられる。n is an integer from 2 to 100, c, d, and e are each 0.05
<c<1.0.1.8<d<2.5゜0≦e≦0.5.
It is a positive number such that 1.8<c+d+e≦3. ) Polyoxypropylene-containing siloxanes represented by the following formulas can be suitably used, and specific examples thereof include compounds represented by the following formulas.
また、（Ｄ）成分のヒユームドシリカは特に制限されず
、一般的な各種ヒユームドシリカを使用でざるが、ＢＥ
Ｔ比表面積が５０〜４００ｒｄ／ｇのものが好ましく、
更に、ヒユームドシリカをジメチルジクロロシランやヘ
キサメチルジシラザン等の有機けい素化合物で表面処理
したものが好適に使用できる。Further, the fumed silica of component (D) is not particularly limited, and various common fumed silicas may be used, but BE
It is preferable that the T specific surface area is 50 to 400rd/g,
Furthermore, fumed silica surface-treated with an organic silicon compound such as dimethyldichlorosilane or hexamethyldisilazane can be suitably used.
ここで、（Ｃ）成分、（Ｄ）成分の配合量は（Ａ）成分
とＣＢ）成分との合計量１．００重量部に対していずれ
も好ましくは０．５〜４重量部、より好ましくは１〜３
重量部であり、この範囲内で適当量用いることにより良
好な任意のチクソトロビック性を得ることができる。こ
れに対し、（Ｃ）成分、（Ｄ）成分の配合量のいずれか
又は両方が０．５′重量部より少ないと十分なチクソト
ロピック性が得られない場合があり、一方４重量部より
多く配合すると組成物の粘度が高くなりすぎたり、十分
な接着力が得られない場合が生じる。Here, the blending amounts of component (C) and component (D) are preferably 0.5 to 4 parts by weight, more preferably 0.5 to 4 parts by weight, based on 1.00 parts by weight of the total amount of components (A) and CB). is 1-3
By using an appropriate amount within this range, good thixotropic properties can be obtained. On the other hand, if either or both of the amounts of component (C) and (D) are less than 0.5 parts by weight, sufficient thixotropic properties may not be obtained; If blended, the viscosity of the composition may become too high or sufficient adhesive strength may not be obtained.
本発明の組成物には、上記成分に加え、硬化物の低応力
性を向上させるために、オルガノポリシロキサン含有化
合物などの低応力化剤を配合することが好ましい
ここで、低応力化剤としては、１分子中に２個以上のエ
ポキシ基及び１個以上のアルケニル基を官有する芳香族
重合体（アルケニル基官有エポキシ樹脂）と下記式
％式％
（但し、式中Ｒは置換又は非置換の一価炭化水素基、ａ
は０．０１〜０．１、ｂは１．８〜２．２の正数で、１
．８１＜ａ＋ｂ＜２．３であり、１分子中のけい素原子
の数は２０〜４００．１分子中のけい素原子に直結した
水素原子の数は１〜５である。）
で示されるオルガノポリシロキサンとの付加反応により
得られる共重合体を特に好適に使用できる。In addition to the above-mentioned components, the composition of the present invention preferably contains a stress reducing agent such as an organopolysiloxane-containing compound in order to improve the low stress properties of the cured product. is an aromatic polymer having two or more epoxy groups and one or more alkenyl groups in one molecule (alkenyl group-functionalized epoxy resin) and the following formula % formula % (However, in the formula, R is substituted or unsubstituted. substituted monovalent hydrocarbon group, a
is 0.01 to 0.1, b is a positive number of 1.8 to 2.2, and 1
．． 81<a+b<2.3, and the number of silicon atoms in one molecule is 20 to 400. The number of hydrogen atoms directly bonded to silicon atoms in one molecule is 1 to 5. ) A copolymer obtained by an addition reaction with an organopolysiloxane shown in the formula below can be particularly preferably used.
なお、上記アルケニル基含有エポキシ樹脂及び上記式で
示されるオルガノポリシロキサンとしては、例えば特開
昭６３−２４８８２１号公報に記載されたものを使用す
ることができる。As the alkenyl group-containing epoxy resin and the organopolysiloxane represented by the above formula, for example, those described in JP-A-63-248821 can be used.
本発明の組成物中に無機質充填剤を配合することは差支
えなく、無機質充填剤としては、エポキシ樹脂組成物の
用途等に応じて適宜選択される。There is no problem in incorporating an inorganic filler into the composition of the present invention, and the inorganic filler is appropriately selected depending on the intended use of the epoxy resin composition.
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
、窒化けい素、ボロンナイトライド、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。そ
の配合量としては必ずしも制限されないが、（Ａ）成分
と（Ｂ）成分の合計量１００重量部に対して５０〜４０
０重量部とすることが好ましく、より好ましくは１００
〜３００重量部である。５０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、耐クランク性な
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、４００重量部を超えると粘度が極端に高くなって
しまう場合がある。For example, one or more types selected from natural silica such as crystalline silica and amorphous silica, synthetic high-purity silica, synthetic spherical silica, talc, mica, silicon nitride, boron nitride, alumina, etc. are used. be able to. The blending amount is not necessarily limited, but is 50 to 40 parts by weight per 100 parts by weight of the total amount of components (A) and (B).
It is preferably 0 parts by weight, more preferably 100 parts by weight.
~300 parts by weight. If it is less than 50 parts by weight, the expansion coefficient of the resulting epoxy resin composition will be large, and satisfactory results may not be obtained in terms of physical properties such as crank resistance.
On the other hand, if it exceeds 400 parts by weight, the viscosity may become extremely high.
本発明の組成物には、更に接着向上用炭素官能性シラン
、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、表面処理剤（γ−グリシドキシプロピルトリメ
トキシシラン等）、各種導電性充填材、その他の添加剤
を配合することもできる。The composition of the present invention may further include carbon-functional silanes for improving adhesion, waxes, mold release agents such as fatty acids such as stearic acid and metal salts thereof, pigments such as carbon black, dyes, antioxidants, and surface treatment agents. (gamma-glycidoxypropyltrimethoxysilane, etc.), various conductive fillers, and other additives can also be blended.
本発明の液状エポキシ樹脂組成物の粘度は、低粘度とす
るため２５℃においてＢＨ型回転粘度計で２０ｒρｍ値
が２０００ボイズ以下であり、この低粘度を保つよう上
記必須成分及び任意成分を選択する。The viscosity of the liquid epoxy resin composition of the present invention is such that the 20rρm value measured by a BH type rotational viscometer at 25° C. is 2000 voids or less in order to have a low viscosity, and the above-mentioned essential components and optional components are selected to maintain this low viscosity. .
なお、チクソトロピック性は、Ｂ Ｉ−Ｔ型回転粘度計
において回転数２ ｒｐｍの粘度／回転数２Ｏｒｐｍの
粘度の比（粘度比）と相関があり、この粘度比が好まし
くは２．５〜４となるような範囲とすると、良好なチク
ソトロビック性を示す。The thixotropic property is correlated with the ratio (viscosity ratio) of viscosity at a rotational speed of 2 rpm/viscosity at a rotational speed of 20 rpm in a B I-T rotational viscometer, and this viscosity ratio is preferably 2.5 to 4. When the range is such that it shows good thixotropic properties.
本発明のエポキシ樹脂組成物は、上述した成分の所定量
を均一に撹拌、混合することにより得ることができる。The epoxy resin composition of the present invention can be obtained by uniformly stirring and mixing predetermined amounts of the above-mentioned components.
また、必要に応じてアセトン、トルエン、キシレンなど
の有機溶剤で希釈して使用することも差し支えない。な
お、成分の配合順序に特に制限はない。Further, it may be used after being diluted with an organic solvent such as acetone, toluene, or xylene, if necessary. Note that there is no particular restriction on the order of blending the components.
本発明の液状エポキシ樹脂組成物は、低粘度でチクソト
ロビック性を有するので、ＩＣ，ＬＳＩ。The liquid epoxy resin composition of the present invention has low viscosity and thixotropic properties, so it is suitable for IC, LSI.
トプンジスタ、サイリスタ、ダイオード等の半導体装置
の封止材、プリント回路板の製造などに有効に使用でき
、具体的にはフリップチップの封止、テープオートメ−
ティドボンディング（ＴＡＢ）。It can be effectively used as a sealing material for semiconductor devices such as topunjistors, thyristors, and diodes, and in the production of printed circuit boards.Specifically, it can be used for flip chip sealing and tape automation.
Tidbonding (TAB).
チップオンボード（ＣＯＢ）などの半導体の封止。Encapsulation of semiconductors such as chip-on-board (COB).
ハイブリッドＩＣのスポット封止、外装封止、液晶用の
接着材、セラミックパッケージ用接着材などに特に有効
であるほか、各種産業分野における外装材、接着材、シ
ール材としても好適に使用することができる。It is particularly effective for spot encapsulation of hybrid ICs, exterior encapsulation, adhesives for liquid crystals, adhesives for ceramic packages, etc., and can also be suitably used as exterior materials, adhesives, and sealants in various industrial fields. can.
本発明の液状エポキシ樹脂組成物を上記用途に使用する
に際しては、一般的なディッピングやディスペンサーに
よる注型等の方法を用いることができ、この場合、必要
に応じて組成物や被塗覆材料を予め３０〜８０℃に加熱
することもできる。When using the liquid epoxy resin composition of the present invention for the above-mentioned purposes, general methods such as dipping or casting using a dispenser can be used. It can also be preheated to 30 to 80°C.
また、硬化させる際、成形表面や内部の気泡発生を抑え
るため、１段階のみの加熱だけでなく。In addition, during curing, in order to suppress the generation of air bubbles on the molded surface and inside, not only one stage of heating is used.
２段階以上に加熱温度を変えて硬化するいわゆるステッ
プキュアーを行なうこともできる。It is also possible to perform so-called step curing in which curing is performed by changing the heating temperature in two or more stages.
以上説明したように５本発明の液状エポキシ樹脂組成物
は、エポキシ樹脂組成物に１分子中にポリオキシアルキ
レンブロックを２０重量％以上有する有機化合物とヒユ
ームドシリカを併用して配合したことにより、低粘度で
良好なチクソトロビック性を有し、しかも保存安定性に
優れたものである。As explained above, the liquid epoxy resin composition of the present invention has a low viscosity due to the combination of an organic compound having 20% by weight or more of polyoxyalkylene blocks in one molecule and fumed silica. It has good thixotropic properties and excellent storage stability.
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
。なお、下記の例において部は重量部を示す。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. In addition, in the following examples, parts indicate parts by weight.
まず、実施例、比較例の説明に先立ち、同側で使用した
共重合体の製造例を参考例により示す。First, prior to explaining the Examples and Comparative Examples, a reference example will be shown to describe a production example of the copolymer used on the same side.
〔参考例１〕
リフラッグスコンデンサー、温度計、撹拌機及び滴下ロ
ートを具備した内容積ＩＱの四つロフラスコに軟化点８
０℃のエポキシ化フェノールノボラック樹脂（エポキシ
当量１９５）３００ｇを入れ、温度１１０℃で撹拌しな
から２−アリルフェノール３２ｇとトリブチルアミン１
ｇとの混合物を滴下時間１０分にて滴下し、更に温度１
１０℃にて２時間撹拌を続けた。得られた内容物から未
反応の２−アリルフェノール及びトリブチルアミンを減
圧下に留去し、アリル基含有エポキシ樹脂（アリル当量
１４９０、エポキシ当量２３５）を得た。[Reference Example 1] A four-loaf flask with an internal volume of IQ equipped with a Reflags condenser, a thermometer, a stirrer, and a dropping funnel had a softening point of 8.
Add 300 g of epoxidized phenol novolac resin (epoxy equivalent: 195) at 0°C, stir at 110°C, and add 32 g of 2-allylphenol and 1 tributylamine.
The mixture with g was added dropwise for 10 minutes, and the temperature
Stirring was continued for 2 hours at 10°C. Unreacted 2-allylphenol and tributylamine were distilled off from the resulting contents under reduced pressure to obtain an allyl group-containing epoxy resin (allyl equivalent: 1490, epoxy equivalent: 235).
次に、上記と同様に、四つ目フラスコに上記方法で得た
アリル基含有のエポキシ樹脂１２０ｇ、メチルイソブチ
ルケトン１００ｇ、トルエン２００ｇ、２％の白金濃度
の２−エチルヘキサノール変性塩化白金酸溶液０．０４
ｇをそれぞれ入れ、１時間の共沸脱水を行ない、還流温
度にて下記式で示されるオルガノポリシロキサン８０ｇ
を３０分にて滴下し、更に同一温度で４時間撹拌して反
応させた後、得られた内容物を水洗し、溶剤を減圧下で
留去することにより、粗反応生成物を得た。Next, in the same manner as above, 120 g of the allyl group-containing epoxy resin obtained by the above method, 100 g of methyl isobutyl ketone, 200 g of toluene, and 2-ethylhexanol-modified chloroplatinic acid solution with a platinum concentration of 2% were placed in a fourth flask. .04
g respectively, and subjected to azeotropic dehydration for 1 hour to produce 80 g of organopolysiloxane represented by the following formula at reflux temperature.
was added dropwise over 30 minutes, and the mixture was further stirred at the same temperature for 4 hours to react.The resulting contents were washed with water, and the solvent was distilled off under reduced pressure to obtain a crude reaction product.
この粗反応生成物１００ｇをアセトン３８０ｇに溶解し
、これに水１４０ｇを加えて放置することにより、二層
分離した溶液を得、この溶液の上層を廃棄した後、再び
アセトン２００ｇを加えて混合し、これに水５０ｇを加
えて放置した。得られた二層分離の溶液よりその下層を
採取し、アセトン及び水を減圧留去して第１表に示すシ
リコーン変性エポキシ樹脂を得た。100 g of this crude reaction product was dissolved in 380 g of acetone, 140 g of water was added thereto, and the mixture was left to stand to obtain a solution that separated into two layers. After discarding the upper layer of this solution, 200 g of acetone was added again and mixed. , 50 g of water was added to this and left to stand. The lower layer was collected from the resulting two-layer separated solution, and acetone and water were distilled off under reduced pressure to obtain the silicone-modified epoxy resin shown in Table 1.
第 １ 表
〔実施例１〜６．比較例１〜６〕
エポキシ当量１７３のエポキシ化ビスフェノールＦ（エ
ポキシ樹脂）、４−メチルへキサヒドロ無水フタル酸（
酸無水物）、ポリエーテル化合物（Ｃ成分）、ヒユーム
ドシリカ（Ｄ成分）及び参考例で得たシリコーン変性エ
ポキシ樹脂を第２表に示す配合量で使用し、これに石英
粉末１５０部、トリメトキシシラン０．３部、γ−グリ
シドキシプロピルトリメトキシシラン０．３部及び１，
８−ジアザビシクロウンデセン−７のトリフェニルベン
ジルボレート塩２部を配合し、５０℃で１時間混合し、
１０種のエポキシ樹脂組成物を得た。Table 1 [Examples 1 to 6. Comparative Examples 1 to 6] Epoxidized bisphenol F (epoxy resin) with an epoxy equivalent of 173, 4-methylhexahydrophthalic anhydride (
Acid anhydride), polyether compound (component C), fumed silica (component D), and silicone-modified epoxy resin obtained in the reference example were used in the amounts shown in Table 2, and 150 parts of quartz powder and trimethoxysilane were used. 0.3 parts, 0.3 parts of γ-glycidoxypropyltrimethoxysilane and 1,
2 parts of triphenylbenzylborate salt of 8-diazabicycloundecene-7 was blended and mixed at 50°C for 1 hour.
Ten types of epoxy resin compositions were obtained.
これらのエポキシ樹脂組成物につき、粘度比及び流動性
を下記方法により求めた。また、これらの組成物を５℃
で３ケ月間保存した後の粘度比と流動性を同様に測定し
た。The viscosity ratio and fluidity of these epoxy resin compositions were determined by the following methods. In addition, these compositions were heated at 5°C.
After storage for 3 months, the viscosity ratio and fluidity were measured in the same manner.
結果を第１表に併記する。The results are also listed in Table 1.
（イ）粘度比
ＢＨ型回転粘度計を用いて２ ｒｐｍ及び２Ｑｒｐｍの
回転数で２５℃における粘度を測定し１両者の比率を
粘度比＝２ｒｐｎ＋の粘度／２０ｒｐｍの粘度として求
めた。(a) Viscosity ratio Using a BH type rotational viscometer, the viscosity at 25°C was measured at rotational speeds of 2 rpm and 2Q rpm, and the ratio of the two was determined as viscosity ratio = viscosity of 2rpn+/viscosity of 20 rpm.
（ロ）流動性
組成物を１０−シリンジへ入れ、ガラス基板上へ〇、Ｌ
ｏｇ滴下して、１２０℃で２時間硬化させたときの滴下
硬化物の最大厚さを測定した。(b) Put the fluid composition into the 10-syringe and place it on the glass substrate.
og dropwise and cured at 120° C. for 2 hours, and the maximum thickness of the cured product was measured.
注：
（１）ポリエーテルＡ化合物；
ＨＯ（Ｃ□Ｈ，○后Ｈ
（２）ポリエーテルＢ化合物；
（３）ヒユームドシリカム８日本アエロジル社製エロジ
ル２００
（４）ヒユームドシリカＢ：テグッサ社１１Ｒ９７２第
２表の結果より、本発明のエポキシ樹脂組成物は良好な
チクソトロピック性を有し、しかもこのチクソトロビッ
ク性は保存後もほとんど変化がみられない。Note: (1) Polyether A compound; HO(C□H,○H) (2) Polyether B compound; (3) Humid silica 8 Erosil 200 manufactured by Nippon Aerosil Co., Ltd. (4) Humid silica B: Tegussa Co., Ltd. From the results shown in Table 2 of 11R972, the epoxy resin composition of the present invention has good thixotropic properties, and this thixotropic property hardly changes after storage.
これに対して、ポリエーテル化合物とヒユームドシリカ
の両方を配合しないもの（比較例１）、ポリエーテル化
合物のみを配合し、ヒユームドシリカを配合しないもの
（比較例２，３）及びポリエーテル化合物を配合せず、
ヒユームドシリカのみを配合したもの（比較例４，５）
ではチクソトロピック性に劣る。また、ヒユームドシリ
カのみを４部配合したもの（比較例６）は製造直後のチ
クソトロピック性は比較的良いが、保存性が悪いことが
認められる。On the other hand, those that do not contain both a polyether compound and fumed silica (Comparative Example 1), those that contain only a polyether compound and no fumed silica (Comparative Examples 2 and 3), and those that do not contain a polyether compound ,
Formulated with only humid silica (Comparative Examples 4 and 5)
It is less thixotropic. In addition, it was found that the product containing only 4 parts of fumed silica (Comparative Example 6) had relatively good thixotropic properties immediately after production, but had poor storage stability.
出願人 信越化学工業 株式会社
代理人 弁理士 小 島 隆 司
（他１名）
手続補正帯（自発）
１．事件の表示
平成１年特許願第１２７０７４号
２、発明の名称
住 所 東京都千代田区大手町二丁目６番１号氏
、名 （２０６）信越化学工業 株式会社代表者 小
坂雄太部
４、代理人 〒１０４
住 所 東京都中央区銀座３丁目１１番１４号ダパ
クリエートビル５階 電話（５４５）６４５４明細書の
「発明の詳細な説明」の欄。Applicant Shin-Etsu Chemical Co., Ltd. Agent Patent attorney Takashi Kojima (and one other person) Procedural amendment band (voluntary) 1. Case description 1999 Patent Application No. 127074 2 Name of invention Address Mr. 6-1 Otemachi 2-chome, Chiyoda-ku, Tokyo
(206) Shin-Etsu Chemical Co., Ltd. Representative Yutabe Kosaka 4, Agent 104 Address 5th floor, Dapa Create Building, 3-11-14 Ginza, Chuo-ku, Tokyo Telephone: (545) 6454 'Detailed explanation' column.
６、補正の内容 （１）明細書第２０頁の第２表を次の通り訂正する。6. Contents of correction (1) Table 2 on page 20 of the specification is corrected as follows.
Claims (1)
ポキシ樹脂、 （Ｂ）上記エポキシ樹脂の硬化剤、 （Ｃ）１分子中にポリオキシアルキレンブロックを２０
重量％以上有する有機化合物、及び （Ｄ）ヒュームドシリカ を配合してなり、２５℃におけるＢＨ型回転粘度計での
２０ｒｐｍの粘度が２０００ポイズ以下である液状エポ
キシ樹脂組成物。 ２、請求項１記載の液状エポキシ樹脂組成物を硬化させ
た硬化物。[Claims] 1. (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent for the above epoxy resin, (C) 20 polyoxyalkylene blocks in one molecule.
A liquid epoxy resin composition, which contains an organic compound having a weight percent or more, and (D) fumed silica, and has a viscosity of 2000 poise or less at 20 rpm at 25° C. using a BH type rotational viscometer. 2. A cured product obtained by curing the liquid epoxy resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12707489A JPH0611840B2 (en) | 1989-05-19 | 1989-05-19 | Liquid epoxy resin composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12707489A JPH0611840B2 (en) | 1989-05-19 | 1989-05-19 | Liquid epoxy resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02305848A true JPH02305848A (en) | 1990-12-19 |
| JPH0611840B2 JPH0611840B2 (en) | 1994-02-16 |
Family
ID=14950933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12707489A Expired - Fee Related JPH0611840B2 (en) | 1989-05-19 | 1989-05-19 | Liquid epoxy resin composition and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611840B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05287054A (en) * | 1992-04-07 | 1993-11-02 | Shin Etsu Chem Co Ltd | Liquid epoxy resin composition, its cured product, and semiconductor device sealed therewith |
| JPH10273644A (en) * | 1997-03-28 | 1998-10-13 | Nippon Kayaku Co Ltd | Liquid crystal sealer and liquid crystalline cell |
| JP2002241469A (en) * | 2001-02-14 | 2002-08-28 | Nitto Denko Corp | Thermosetting resin composition and semiconductor device |
| KR100497456B1 (en) * | 1996-12-19 | 2005-09-26 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Epoxy Resin Composition |
| JP2012057052A (en) * | 2010-09-09 | 2012-03-22 | Namics Corp | Epoxy resin composition |
| JP2012064952A (en) * | 2011-10-11 | 2012-03-29 | Sumitomo Bakelite Co Ltd | Insulating resin composition for multilayer printed circuit board, insulation sheet with substrate, multilayer printed circuit board, and semiconductor device |
| JP2013033994A (en) * | 2012-10-19 | 2013-02-14 | Sumitomo Bakelite Co Ltd | Insulation resin composition for multilayer printed wiring board, insulation sheet with base material, multilayer printed wiring board and semiconductor device |
-
1989
- 1989-05-19 JP JP12707489A patent/JPH0611840B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05287054A (en) * | 1992-04-07 | 1993-11-02 | Shin Etsu Chem Co Ltd | Liquid epoxy resin composition, its cured product, and semiconductor device sealed therewith |
| KR100497456B1 (en) * | 1996-12-19 | 2005-09-26 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Epoxy Resin Composition |
| JPH10273644A (en) * | 1997-03-28 | 1998-10-13 | Nippon Kayaku Co Ltd | Liquid crystal sealer and liquid crystalline cell |
| JP2002241469A (en) * | 2001-02-14 | 2002-08-28 | Nitto Denko Corp | Thermosetting resin composition and semiconductor device |
| JP2012057052A (en) * | 2010-09-09 | 2012-03-22 | Namics Corp | Epoxy resin composition |
| JP2012064952A (en) * | 2011-10-11 | 2012-03-29 | Sumitomo Bakelite Co Ltd | Insulating resin composition for multilayer printed circuit board, insulation sheet with substrate, multilayer printed circuit board, and semiconductor device |
| JP2013033994A (en) * | 2012-10-19 | 2013-02-14 | Sumitomo Bakelite Co Ltd | Insulation resin composition for multilayer printed wiring board, insulation sheet with base material, multilayer printed wiring board and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0611840B2 (en) | 1994-02-16 |
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