JPH01108255A - Curable epoxy resin composition - Google Patents
Curable epoxy resin compositionInfo
- Publication number
- JPH01108255A JPH01108255A JP26513687A JP26513687A JPH01108255A JP H01108255 A JPH01108255 A JP H01108255A JP 26513687 A JP26513687 A JP 26513687A JP 26513687 A JP26513687 A JP 26513687A JP H01108255 A JPH01108255 A JP H01108255A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- modified organopolysiloxane
- amine
- curable epoxy
- group
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 52
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 27
- 239000002075 main ingredient Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229920003986 novolac Polymers 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002252 acyl group Chemical group 0.000 abstract description 2
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- 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 6
- 239000002245 particle Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 polysiloxane Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000003756 stirring Methods 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
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000004593 Epoxy Substances 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
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive 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
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229930003836 cresol Natural products 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
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-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
- 239000006185 dispersion Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000001879 gelation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 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
- 238000012360 testing method Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、硬化性エポキシ樹脂組成物に関し、特に耐衝
撃性及び耐湿性に優れた硬化性エポキシ樹脂組成物に関
する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a curable epoxy resin composition, and particularly to a curable epoxy resin composition having excellent impact resistance and moisture resistance.
（従来の技術）
エポキシ樹脂組成物は、誘電特性、体積抵抗率、絶縁破
壊強度等の電気特性のみならず、曲げ強度、圧縮強度、
衝撃強度等の機械特性、耐熱性、接着性等に優れている
ことから、接着剤や各種の複合材料はもとより、各種の
電気・電子部品の絶縁材料として賞月されている。(Prior art) Epoxy resin compositions have not only electrical properties such as dielectric properties, volume resistivity, and dielectric breakdown strength, but also bending strength, compressive strength,
Due to its excellent mechanical properties such as impact strength, heat resistance, and adhesive properties, it is prized not only for adhesives and various composite materials, but also as an insulating material for various electrical and electronic parts.
しかしながら最近、電子部品の薄層化や小型化、半導体
集積度の増大による半導体チップの大型化が進行する中
で、パッケージ材料のクラック、シリコンチップのクラ
ック、パッシベーションクラック、配線移動、エポキシ
樹脂自身のクラックや電気・電子部品とエポキシ樹脂と
の間にすき間が生じ、そのすき間から水分が侵入するた
めに生じる故障等の問題が大きくなってきている。However, recently, as electronic components have become thinner and smaller, and semiconductor chips have become larger due to increased semiconductor integration, cracks in package materials, silicon chip cracks, passivation cracks, wiring movement, and epoxy resin itself Problems such as cracks and failures caused by gaps occurring between electric/electronic components and epoxy resins and moisture infiltrating through these gaps are becoming more and more serious.
このような欠点を改良する方法として、従来、（１）エ
ポキシ樹脂中に、可撓性を付与するような樹脂を添加す
る方法（例えば特開昭５４−８１３６０号、特開昭５７
−５６９５４号）（２）熱膨張係数の小さいシリカやア
ルミナ等の無機質充填材を多量に配合する方法、（３）
硬化可能なエポキシ樹脂に、硬化可能なシリコーンゴム
とカーボンファンクシシナルシランを添加して混合し、
同時に硬化させることによりエポキシ樹脂硬化物の耐ク
ラツク性を改良する（特開昭５５−３４１２号）等の方
法が採用されている。Conventionally, as a method to improve such defects, (1) a method of adding a resin that imparts flexibility to an epoxy resin (for example, JP-A-54-81360, JP-A-57
-56954) (2) A method of blending a large amount of inorganic filler such as silica or alumina with a small coefficient of thermal expansion, (3)
Add and mix curable silicone rubber and carbon funccinal silane to curable epoxy resin,
A method has been adopted in which the crack resistance of a cured epoxy resin is improved by curing at the same time (Japanese Unexamined Patent Publication No. 55-3412).
しかしながら、第１番目の方法は、エポキシ樹脂自身の
クラック発生防止方法として有効ではあるが、エポキシ
樹脂本来の優れた特性である、熱時硬度やガラス転移点
温度の低下をもたらし、エポキシ樹脂の高温特性を損な
うという欠点があった。一方、第２番目の方法は、所望
の熱膨張係数−に近い硬化物が得られるものの、エポキ
シ樹脂組成物の流動性が著しく低下するために、注型や
トランスファー成形、ボッティング、粉末塗装、滴下等
の作業が実質的に不可能となる上、エポキシ樹脂のヤン
グ率が増大するため熱膨張係数の低下による内部応力の
低下をあまり期待することができないという欠点があっ
た。However, although the first method is effective as a method for preventing the occurrence of cracks in the epoxy resin itself, it lowers the hardness and glass transition temperature when heated, which are the excellent properties of epoxy resin, and the high temperature of the epoxy resin. It had the disadvantage of impairing its characteristics. On the other hand, in the second method, although a cured product with a coefficient of thermal expansion close to the desired value is obtained, the fluidity of the epoxy resin composition is significantly reduced, so it is difficult to use casting, transfer molding, botting, powder coating, etc. There are disadvantages in that it becomes virtually impossible to carry out operations such as dripping, and in addition, because the Young's modulus of the epoxy resin increases, it is difficult to expect much reduction in internal stress due to a reduction in the coefficient of thermal expansion.
又、第３番目の方法は、硬化可能なシリコーンゴムを硬
化可能なエポキシ樹脂中に分散させた状態で硬化させる
ので硬化反応が完全には進行せず未反応物が残存するた
め、金型成形時に金型汚れを起こしたり、硬化物への印
字性が低下したり、或いは、重ね塗りをすることができ
ないという欠点があった。このような欠点は、熱硬化性
樹脂組成物のゲル化を抑制した状態で、攪拌下に熱硬化
性シリコーン樹脂組成物を分散粒子状としてゲル化し、
その後に前記熱硬化性樹脂組成物を硬化することにより
大巾に改善することができる（特開昭５６−１４５５６
号）、この方法は熱硬化性樹脂中に、シリコーン樹脂を
微分散することができる点で優れているものの、所詮、
熱硬化性樹脂とシリコーン樹脂の相溶性が悪いことから
、後者が徐々に浮上するので、硬化物全体としての均一
性には自ずから限界があるという欠点があった。このよ
うな欠点は、エポキシ樹脂と硬化剤並びに、あらかじめ
硬化させた線状オルガノポリシロキサンブロックを１０
重量％以上含むポリマー硬化物からなる熱硬化性エポキ
シ樹脂組成物（特開昭５８−２１９２１８号）について
も同様に存在する。In addition, in the third method, the curable silicone rubber is cured after being dispersed in the curable epoxy resin, so the curing reaction does not proceed completely and unreacted materials remain. There are disadvantages in that mold stains sometimes occur, printing performance on cured products deteriorates, and overcoating cannot be performed. These drawbacks are due to the fact that the thermosetting silicone resin composition is gelled in the form of dispersed particles under stirring while the gelation of the thermosetting resin composition is suppressed.
By subsequently curing the thermosetting resin composition, significant improvements can be made (Japanese Patent Application Laid-Open No. 56-14556
Although this method is excellent in that it can finely disperse the silicone resin in the thermosetting resin,
Since the thermosetting resin and the silicone resin have poor compatibility, the latter gradually floats to the surface, which naturally limits the uniformity of the cured product as a whole. These drawbacks are due to the fact that the epoxy resin and curing agent as well as the pre-cured linear organopolysiloxane blocks are
A thermosetting epoxy resin composition (Japanese Patent Application Laid-Open No. 58-219218) consisting of a cured polymer containing at least % by weight also exists.
更に、この場合には、分散せしめる粒子状分散物は、硬
化物を粒子状に粉砕することによって得なければならず
煩雑であるのみならず、その粒径分布を狭くすることも
困難であるのでその意味においても、上記組成物からな
る熱硬化性エポキシ樹脂の硬化物の均質性が必ずしも十
分ではないということ、及びエポキシ樹脂とのなじみ性
を良くするためには、線状オルガノポリシロキサンブロ
ックの重合度や含有量を制限しなければならないという
点からも、エポキシ樹脂組成物の改質には自ずから限度
が生ずるいう欠点があった。Furthermore, in this case, the particulate dispersion to be dispersed must be obtained by pulverizing the cured product into particles, which is not only complicated but also difficult to narrow the particle size distribution. In that sense, the homogeneity of the cured product of the thermosetting epoxy resin made from the above composition is not necessarily sufficient, and in order to improve the compatibility with the epoxy resin, it is necessary to prepare a linear organopolysiloxane block. There is also a drawback that there is a limit to the modification of epoxy resin compositions because the degree of polymerization and content must be limited.
（発明が解決しようとする問題点）
そこで、本発明者等は、かかる従来の欠点を解決すべく
鋭意検討した結果、硬化性エポキシ樹脂にポリエーテル
変性オルガノポリシロキサンとアミン変性オルガノポリ
シロキサンを添加せしめた場合には、均質で耐衝撃性及
び耐湿性に優れたエポキシ樹脂組成物を得ることができ
ることを見出し本発明に到達した。(Problems to be Solved by the Invention) Therefore, as a result of intensive studies to solve these conventional drawbacks, the present inventors added polyether-modified organopolysiloxane and amine-modified organopolysiloxane to a curable epoxy resin. The present inventors have discovered that a homogeneous epoxy resin composition with excellent impact resistance and moisture resistance can be obtained when the epoxy resin composition is increased.
従って、本発明の目的は、耐衝撃性、耐湿性を改善した
均質な硬化性エポキシ樹脂組成物を提供することにある
。Therefore, an object of the present invention is to provide a homogeneous curable epoxy resin composition with improved impact resistance and moisture resistance.
（問題を解決するための手段）
本発明の上記の目的は、硬化性エポキシ樹脂、ポリエー
テル変性オルガノポリシロキサン及びアミン変性オルガ
ノポリシロキサンを主剤とする硬化性エポキシ樹脂組成
物によって達成された。(Means for Solving the Problems) The above objects of the present invention have been achieved by a curable epoxy resin composition containing a curable epoxy resin, a polyether-modified organopolysiloxane, and an amine-modified organopolysiloxane as main ingredients.
本発明において使用する第１成分としての硬化性エポキ
シ樹脂は、１分子中に２個以上のエポキシ基を有するエ
ポキシ樹脂と各種硬化剤とからなる硬化可能なエポキシ
樹脂であって、このエポキシ樹脂は後述するような各種
の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
種々のエポキシ樹脂の中から適宜選択して使用すること
ができる。このようなものとして、例えば、ビスフェノ
ールＡのジグリシジルエーテルや、その多量体であるエ
ビビスタイプのエポキシ樹脂、ビスフェノールＦ型エポ
キシ樹脂、レゾルシン型エポキシ樹脂、テトラヒドロキ
シフェニルエタン型エポキシ樹脂、タレゾールノボラッ
ク型エポキシ樹脂、ポリオレフィン型エポキシ樹脂、脂
環型エポキシ樹脂およびそれらのハロゲン化物等を挙げ
ることができる。The curable epoxy resin as the first component used in the present invention is a curable epoxy resin composed of an epoxy resin having two or more epoxy groups in one molecule and various curing agents. As long as it can be cured with various curing agents as described below, there are no particular restrictions on the molecular structure, molecular weight, etc., and it can be used by appropriately selecting from various conventionally known epoxy resins. . Examples of such materials include diglycidyl ether of bisphenol A, Ebibis type epoxy resin which is a polymer thereof, bisphenol F type epoxy resin, resorcinol type epoxy resin, tetrahydroxyphenylethane type epoxy resin, Talesol novolac. Examples include type epoxy resins, polyolefin type epoxy resins, alicyclic type epoxy resins, and their halides.
なお、上記した第１成分の使用にあたって、モノエポキ
シ化合物を適宜併用することは差し支えなく、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。この第
１成分はその使用にあたっては必ずしも１種類のみに限
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 first component, there is no problem in using a monoepoxy compound in combination as appropriate, and examples of this monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, Examples include allyl glycidyl ether, octylene oxide, and dodecene oxide. The first component is not necessarily limited to only one type, but may be used in combination of two or more types.
エポキシ樹脂の硬化剤としては、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を挙げる
ことができる。これらの硬化剤は単独で使用しても、２
種以上を同時に使用しても良いが、何れにしても、エポ
キシ樹脂を硬化させるに十分な量を使用する。Examples of curing agents for epoxy resins include amine-based curing agents such as diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylenediamine, phthalic anhydride,
Examples include acid anhydride curing agents such as pyromellitic anhydride and benzophenonetetracarboxylic anhydride, and phenol novolac curing agents having two or more hydroxyl groups in one molecule such as phenol novolak and cresol novolak. Even when used alone, these curing agents
More than one species may be used at the same time, but in any case, a sufficient amount is used to cure the epoxy resin.
本発明においては更に、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
ることができる。In the present invention, various curing accelerators such as imidazole or its derivatives, tertiary amine derivatives,
Phosphine derivatives, cycloamidine derivatives, etc. can be used in combination.
本発明で使用するアミン変性オルガノポリシロキサン及
びポリエーテル変性オルガノポリシロキサンは、公知の
ものの中から適宜選択することができるが特に下記のも
のが好ましい。The amine-modified organopolysiloxane and polyether-modified organopolysiloxane used in the present invention can be appropriately selected from known ones, but the following are particularly preferred.
−数式、 Ｒ’ ｂ Ｒ’ ａ Ｓ ｉＱユ、ユ。-mathematical formula, R' b R' a S iQ Yu, Yu.
［式中、Ｒ４は、ポリエーテル変性オルガノポリシロキ
サンの場合には
（ＣＨｚ ）ｌ ＯイＣｔ Ｈａ Ｏ）ｈイＣ３Ｈｂ
Ｏ）Ｌ Ｒ’で示され、ＲＳは水素原子、低級アルキル
基、アシル基から選択される原子または基、ｋおよび２
はそれぞれＯまたは正の整数、ｋ＋’ｆｆｉ≠０で示さ
れる基であり、アミン変性オルガノポリシロキサンの場
合には、Ｒ’ Ｘよ
（ＣＨｚ ）ｓ （ＮＨＣＨ２ＧＨｚ ）−ＮＨオ
（但し、ｍはＯまたは１）で示される基であり、Ｒ１は
メチル基、エチル基、プロピル基、ブチル基などのアル
キル基、ビニル基、アリル基などのアルケニル基、フェ
ニル基などのアリール基、シクロヘキシル基などのシク
ロアルキル基あるいはこれらの基の炭素原子に結合した
水素原子の一部または全部をハロゲン原子、シアノ基な
どで置換した基から選択される同種または異種の非置換
または置換１価炭化水素基、ａ及びｂは正の数（但しＱ
＜ａ＋ｂ＜４）である、〕で示されるオルガノポリシロ
キサンを使用することが好ましい。[In the formula, R4 is (CHz)lOiCtHaO)hiC3Hb in the case of polyether-modified organopolysiloxane
O)L R', where RS is an atom or group selected from a hydrogen atom, a lower alkyl group, an acyl group, k and 2
are each a group represented by O or a positive integer, k+'ffi≠0, and in the case of amine-modified organopolysiloxane, R' or 1), where R1 is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group, or a cyclo group such as a cyclohexyl group. The same or different unsubstituted or substituted monovalent hydrocarbon groups selected from alkyl groups or groups in which part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc.; b is a positive number (however, Q
It is preferable to use an organopolysiloxane represented by ], where <a+b<4).
アミン変性オルガノポリシロキサンは、特に直鎖状ポリ
シロキサンの両末端にアミノ基の結合しているものが好
ましい。The amine-modified organopolysiloxane is particularly preferably a linear polysiloxane with amino groups bonded to both ends.
これらの添加剤は単独で使用することも、２種以上を混
合して使用することもできる。These additives can be used alone or in combination of two or more.
（作用）
硬化性エポキシ樹脂とアミン変性オルガノポリシロキサ
ンの相溶性は極めて悪いがポリエーテル変性オルガノポ
リシロキサンが存在するために、両者は均一分散状態を
維持する。これは、ポリエーテル部分がエポキシ樹脂と
強い親和性を有する一方、ポリジメチルシロキサン部分
がアミン変性オルガノポリシロキサン部分と相溶するか
らと考えられる。(Function) Although the compatibility between the curable epoxy resin and the amine-modified organopolysiloxane is extremely poor, the presence of the polyether-modified organopolysiloxane allows them to maintain a uniformly dispersed state. This is thought to be because the polyether part has a strong affinity with the epoxy resin, while the polydimethylsiloxane part is compatible with the amine-modified organopolysiloxane part.
このポリエーテル変性オルガノポリシロキサンの使用量
は、その相溶化剤の種類によって適宜調節することがで
きるが、エポキシ樹脂に対して、０．１重量％〜１０重
量％添加する。０．１重量％より少ない場合には、相溶
化剤としての効果が不足し、１０重量％より多い場合に
は硬化後に相溶化剤かにじみ出たり、硬化物の物性が低
下するので好ましくない。特に好ましい添加量は、０゜
５重量％〜５重量％である。The amount of this polyether-modified organopolysiloxane to be used can be appropriately adjusted depending on the type of compatibilizing agent, but it is added in an amount of 0.1% to 10% by weight based on the epoxy resin. If it is less than 0.1% by weight, the effect as a compatibilizer is insufficient, and if it is more than 10% by weight, the compatibilizer may ooze out after curing or the physical properties of the cured product may deteriorate, which is not preferable. A particularly preferable addition amount is 0.5% to 5% by weight.
以上の如（して、製造したエポキシ硬化物は、従来のも
のに比して、耐衝撃性及び耐湿性が改善されるので、半
導体封止材料として特に有用である。The cured epoxy product produced as described above has improved impact resistance and moisture resistance compared to conventional products, and is therefore particularly useful as a semiconductor encapsulation material.
（発明の効果）
本発明によれば、アミン変性オルガノポリシロキサンと
硬化性エポキシ樹脂及び未変性のエポキシ樹脂を均一に
含有せしめることができるから、耐衝撃性や耐湿性の観
点から、用途に応じた木目の細かい設計をすることがで
きる。(Effects of the Invention) According to the present invention, it is possible to uniformly contain the amine-modified organopolysiloxane, the curable epoxy resin, and the unmodified epoxy resin. It is possible to create detailed wood grain designs.
（実施例）
以下に、本発明を実施例によって更に詳述するが本発明
はこれによって限定されるものではない。(Examples) The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.
実施例
ＫＦ６１５Ａポリエーテル変性オルガノポリシロキサン
を相溶化剤とし、硬化性エポキシ樹脂としてエピコート
８２８、その硬化剤としてビス−ｐ−アミノジクロルヘ
キシルメタン（ＰＡＣＭ）と、４．４′−ジアミノジフ
ェニルメタン（ＤＤＭ）を用い、アミン変性オルガノポ
リシロキサンとしてシリコーン−Ｘ−２２−１６ＩＣ（
信越化学■製）を用い、次のようにしてブレンドを作製
した。Example KF615A polyether-modified organopolysiloxane was used as a compatibilizer, Epicoat 828 was used as a curable epoxy resin, and its curing agents were bis-p-aminodichlorohexylmethane (PACM) and 4,4'-diaminodiphenylmethane (DDM). Silicone-X-22-16IC (
(manufactured by Shin-Etsu Chemical) as follows.
硬化性エポキシ樹脂（エピコート８２８）４９゜５ｇに
相溶化剤として前記ＫＦ６１５Ａ０．５ｇ（１重量％）
を加え、十分攪拌して脱泡した後、５０゛Ｃに加温して
スターラーで激しく攪拌しながら、触媒を含有するアミ
ン変性オルガノポリシロキサン９ｇを添加したところ、
アミン変性オルガノポリシロキサンによって変性された
エポキシ樹脂が分散して乳白色の粘稠な液体となった。Add 0.5 g (1% by weight) of the above KF615A as a compatibilizer to 49.5 g of curable epoxy resin (Epicoat 828).
was added, thoroughly stirred to defoam, heated to 50°C, and while stirring vigorously with a stirrer, 9 g of amine-modified organopolysiloxane containing a catalyst was added.
The epoxy resin modified with the amine-modified organopolysiloxane was dispersed to form a milky white viscous liquid.
得られた液体を脱泡した後、当量の硬化剤４．４’ −
ジアミノジフェニルメタン（ＤＤＭ）を加え、更に攪拌
、脱泡して鋳型に流し込み、１６５°Ｃで２時間加熱し
硬化させた。After defoaming the resulting liquid, an equivalent amount of curing agent 4.4' −
Diaminodiphenylmethane (DDM) was added, and the mixture was further stirred and defoamed, poured into a mold, and heated at 165°C for 2 hours to harden.
得られた硬化物から、ＪＩＳＫ７１１０に準拠して１２
．７Ｘ１２．７Ｘ６３．６ｍｍの試験片を切り出し、そ
の中央に深さ２．５４ｍｍのノツチをつけ、アイゾツト
衝撃試験を行った結果、良好な結果が得られた。From the obtained cured product, 12
．． A test piece measuring 7 x 12.7 x 63.6 mm was cut out, a notch with a depth of 2.54 mm was made in the center, and an Izot impact test was conducted, and good results were obtained.
特許出願人 信越化学工業株式会社Patent applicant: Shin-Etsu Chemical Co., Ltd.
Claims (1)
リシロキサン及びアミン変性オルガノポリシロキサンを
主剤とする硬化性エポキシ樹脂組成物。1) A curable epoxy resin composition containing a curable epoxy resin, a polyether-modified organopolysiloxane, and an amine-modified organopolysiloxane as main ingredients.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26513687A JPH01108255A (en) | 1987-10-20 | 1987-10-20 | Curable epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26513687A JPH01108255A (en) | 1987-10-20 | 1987-10-20 | Curable epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01108255A true JPH01108255A (en) | 1989-04-25 |
Family
ID=17413121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26513687A Pending JPH01108255A (en) | 1987-10-20 | 1987-10-20 | Curable epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01108255A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0493363A (en) * | 1990-08-10 | 1992-03-26 | Shin Etsu Chem Co Ltd | Synthetic resin composition |
| JP2011506750A (en) * | 2007-12-18 | 2011-03-03 | ダウ グローバル テクノロジーズ インコーポレイティド | Thermosetting compositions containing silicone polyethers, their manufacture and use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6263452A (en) * | 1985-09-13 | 1987-03-20 | Nitto Electric Ind Co Ltd | Semiconductor device |
| JPS6263453A (en) * | 1985-09-13 | 1987-03-20 | Nitto Electric Ind Co Ltd | Semiconductor device |
| JPS62158716A (en) * | 1985-12-30 | 1987-07-14 | ダウ コ−ニング コ−ポレ−シヨン | Silicone modifier dispersion and modifying method |
-
1987
- 1987-10-20 JP JP26513687A patent/JPH01108255A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6263452A (en) * | 1985-09-13 | 1987-03-20 | Nitto Electric Ind Co Ltd | Semiconductor device |
| JPS6263453A (en) * | 1985-09-13 | 1987-03-20 | Nitto Electric Ind Co Ltd | Semiconductor device |
| JPS62158716A (en) * | 1985-12-30 | 1987-07-14 | ダウ コ−ニング コ−ポレ−シヨン | Silicone modifier dispersion and modifying method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0493363A (en) * | 1990-08-10 | 1992-03-26 | Shin Etsu Chem Co Ltd | Synthetic resin composition |
| JP2011506750A (en) * | 2007-12-18 | 2011-03-03 | ダウ グローバル テクノロジーズ インコーポレイティド | Thermosetting compositions containing silicone polyethers, their manufacture and use |
| US8535793B2 (en) | 2007-12-18 | 2013-09-17 | Dow Global Technologies Llc | Thermosetting compositions comprising silicone polyethers, their manufacture, and uses |
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