JPH02170819A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH02170819A JPH02170819A JP32708288A JP32708288A JPH02170819A JP H02170819 A JPH02170819 A JP H02170819A JP 32708288 A JP32708288 A JP 32708288A JP 32708288 A JP32708288 A JP 32708288A JP H02170819 A JPH02170819 A JP H02170819A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- modified
- resin composition
- organopolysiloxane
- cured product
- 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
- 239000000203 mixture Substances 0.000 title abstract description 22
- 239000003822 epoxy resin Substances 0.000 title description 28
- 229920000647 polyepoxide Polymers 0.000 title description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 12
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 238000000465 moulding Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000005452 bending Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- -1 laminates Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 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
- 239000000049 pigment Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 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〕
この発明は、たとえば半導体素子の樹脂封止等に用いら
れる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 an epoxy resin composition used, for example, for resin encapsulation of semiconductor elements.
エポキシ樹脂組成物は、電子機器や電子部品などを構成
するために、接着剤、積層板、半導体素子封止材料など
として、従来から使用されてきている。特に最近では、
エレクトロニクスの分野におけるＩＣ用、さらにはＬＳ
Ｉ用封止材料としての需要が拡大している。Epoxy resin compositions have conventionally been used as adhesives, laminates, semiconductor element sealing materials, and the like in order to construct electronic devices, electronic components, and the like. Especially recently,
For IC in the field of electronics, and even for LS
Demand as a sealing material for I is expanding.
今日の半導体素子では、配線の高密度化とともに、チッ
プサイズの大型化が進んでいるが、この大型のチップを
エポキシ樹脂組成物で封止した場合、その硬化物の内部
応力により、アルミ配線のずれ（スライド）、パッシベ
ーション層におけるクラック発生等の問題が起こってい
る。このために、現在、エポキシ樹脂組成物の硬化物の
低応力化が大きな課題の一つになっている。In today's semiconductor devices, the wiring density is increasing and the chip size is increasing, but when these large chips are encapsulated with an epoxy resin composition, the internal stress of the cured product causes the aluminum wiring to become larger. Problems such as shifting (sliding) and cracking in the passivation layer are occurring. For this reason, reducing stress in cured products of epoxy resin compositions is currently one of the major challenges.
そこで、エポキシ樹脂組成物に通常のシリコ−ン弾性体
を添加することにより、その硬化物に可撓性を付与して
弾性率を低下させ、内部応力を緩和することが試みられ
てきた。Therefore, attempts have been made to add flexibility to the cured product by adding a common silicone elastomer to the epoxy resin composition, thereby lowering the elastic modulus and relieving the internal stress.
しかし、通常のシリコーン弾性体を含有するエポキシ樹
脂組成物は、成形時にパリが生じたり、硬化物のガラス
転移点（Ｔｇ）が低下したり、さらには曲げ強度が低下
したりする、という問題点を有していた。However, epoxy resin compositions containing ordinary silicone elastomers have problems such as cracking during molding, a decrease in the glass transition point (Tg) of the cured product, and a decrease in bending strength. It had
こうした事情に鑑み、この発明は、成形性を損なわず、
しかも、硬化物のＴｇおよび曲げ強度を低下させずに、
硬化物の低応力化を図ることができたエポキシ樹脂組成
物を提供することを課題とする。In view of these circumstances, this invention does not impair moldability,
Moreover, without reducing the Tg and bending strength of the cured product,
An object of the present invention is to provide an epoxy resin composition that can reduce stress in a cured product.
上記課題を解決するため、この発明にかかるエポキシ樹
脂組成物では、硬化物の低応力化を図る改質剤として、
下記（２）および（Ｂ）が含まれているようにする。In order to solve the above problems, in the epoxy resin composition according to the present invention, as a modifier to reduce the stress of the cured product,
Make sure that the following (2) and (B) are included.
（２）下記−儀式（１）で表されるポリエーテルエポキ
シ変性シリコーン重合体Ａ６
〔式中、Ｒ’、 Ｒ”はそれぞれ独立に炭素数１〜４の
２価の炭化水素基、
（Ｂ）両末端アミノ変性オルガノポリシロキサンＢ、お
よび／または両末端メルカプト変性オルガノポリシロキ
サンＢ２゜
なお、この発明において、上記（２）および（８）は、
両者が反応した形で、すなわち（Ａ）と（ト））の反応
生成物として含まれていてもよい。(2) Polyether epoxy modified silicone polymer A6 represented by the following formula (1) [wherein R' and R'' are each independently a divalent hydrocarbon group having 1 to 4 carbon atoms, (B) Both terminal amino-modified organopolysiloxane B and/or both terminal mercapto-modified organopolysiloxane B2゜In this invention, the above (2) and (8) are
It may be contained in a form in which both of them have reacted, that is, as a reaction product of (A) and (g)).
この発明のエポキシ樹脂組成物は、改質剤として、上記
（Ａ）および（Ｂ）を含んでいることにより、硬化物の
内部応力を低減することができ、しがも、成形時にパリ
が発生したり、硬化物のＴｇや曲げ強度が低下したりす
るのを防ぐことができる。By containing the above (A) and (B) as modifiers, the epoxy resin composition of the present invention can reduce the internal stress of the cured product, but it also causes flaking during molding. It is possible to prevent the Tg and bending strength of the cured product from decreasing.
以下に、この発明の詳細な説明する。 The present invention will be explained in detail below.
この発明のエポキシ樹脂組成物は、少なくともエポキシ
樹脂、その硬化剤、上記低応力化のための改質剤を含む
。The epoxy resin composition of the present invention contains at least an epoxy resin, a curing agent for the epoxy resin, and a modifier for reducing stress.
ポリエーテルエポキシ変性シリコーン重合体Ａは、上記
−儀式（１）に示す通りであり、側鎖として、炭素数１
〜４の２価の炭化水素基Ｒ’、 Ｒ”を介して、それぞ
れポリオキシアルキレン基Ｚ。The polyether epoxy modified silicone polymer A is as shown in the above-mentioned formula (1), and has 1 carbon number as a side chain.
~4 divalent hydrocarbon groups R', R'', respectively, to a polyoxyalkylene group Z.
エポキシ基Ｙを含んでいる。Contains an epoxy group Y.
両末端がアミノ基により封鎖された両末端アミノ変性オ
ルガノポリシロキサンＢｌ、および両末端がメルカプト
基により封鎖された両末端メルカプト変性オルガノポリ
シロキサンＢ、としては、それぞれ、たとえば下記−儀
式（Ｉｆ）、 （’Ｉ［［） ：で示されるポリジメ
チルシロキサン骨格を有するものなどが好例として挙げ
られる。ただし、側鎖のメチル基は、たとえばフェニル
基等により、その一部が置き換えられていてもよい。The both terminal amino-modified organopolysiloxane Bl whose both terminals are capped with amino groups and the mercapto-modified organopolysiloxane B whose both terminals are capped with mercapto groups are, for example, the following formula (If), respectively. A good example is one having a polydimethylsiloxane skeleton represented by ('I[[):]. However, a part of the methyl group in the side chain may be replaced by, for example, a phenyl group.
上記式（Ｉ）中の繰り返し数３． ｂ＋ ｅ、 ｍ
ｔ＋ｍ、については、特に限定されないが、それぞれ、
ａ＝２〜５００． ｂ＝２〜１００゜ｃ＝２〜ｉｏ
ｏ、ｍ、≦２０． ｍ−≦２０゜の範囲にあることが
好ましい。ただし、ｍｌ＋ ｍｔのうちいずれか一方は
０であってもよい。また、上記式（Ｉｆ）および（ＩＩ
Ｉ）中の繰り返し数ｄ、 ｅについても、特に限定は
されないが、それぞれ、ｄ＝５〜５０． ｅ＝５〜
５０
の範囲にあることが好ましい。ここで、上記ａ。Number of repeats in the above formula (I) 3. b+ e, m
Regarding t+m, there is no particular limitation, but respectively,
a=2-500. b=2~100°c=2~io
o, m, ≦20. It is preferable that m-≦20°. However, either one of ml+mt may be 0. In addition, the above formulas (If) and (II
The repeat numbers d and e in I) are also not particularly limited, but d=5 to 50. e=5~
It is preferably in the range of 50. Here, the above a.
ｂ、ｃ、ｄ、ｅのうち少なくとも一つが上記範囲を下回
ると、成形性、硬化物の低応力物性などの性能を向上さ
せられないことがある。また、ａ。If at least one of b, c, d, and e is below the above range, performance such as moldability and low stress physical properties of the cured product may not be improved. Also, a.
ｂ、ｃ、ｄ、ｅ、ｍｔ＋ ｍｚのうちの少なくとも一つ
が上記範囲を上回ると、成形性、硬化物の低応力物性な
どの性能が低下する恐れがある。If at least one of b, c, d, e, and mt+ mz exceeds the above range, there is a risk that performance such as moldability and low stress physical properties of the cured product may deteriorate.
上述したように、上記（Ａ）：ポリエーテルエポキシ変
性シリコーン重合体Ａと、（Ｂ）：両末端アミノ変性オ
ルガノポリシロキサンＢｌおよび／または両末端メルカ
プト変性オルガノポリシロキサン８つは、両者が反応し
た形で含まれていてもよく、（Ａ）と（９）の反応生成
物（ゲルまたはゴム状エラストマー）を得るには、たと
えば以下のように行うことができる。すなわち、使用す
るエポキシ樹脂および／または硬化剤としてのフェノー
ル樹脂等を熱熔融させた中に上記（Ａ）と（９）を所定
量配合し、高速デイスパーで加熱攪拌を行う。反応は、
８０〜１５０℃で５〜１２０分間程度行うことが好まし
いが、これに限定されることはない。（Ａ）と（９）の
配合割合については、（Ｎのエポキシ基当量／（ト））
のアミノ基および／またはメルカプト基当量が０．２〜
５程度になっていることが好ましい。また、（Ａ）と領
）の合計配合量は、特に限定はされないが、エポキシ樹
脂組成物全体中の１〜５重量％の範囲が好ましい。この
範囲を外れると、硬化物の低応力化という効果が充分に
得られなくなったり、硬化物物性や成形性等のバランス
が悪くなったりする恐れがある。As described above, (A): polyether epoxy-modified silicone polymer A and (B): both terminal amino-modified organopolysiloxane Bl and/or both terminal mercapto-modified organopolysiloxane 8 were reacted. The reaction product (gel or rubbery elastomer) of (A) and (9) can be obtained, for example, as follows. That is, a predetermined amount of the above (A) and (9) are blended into a hot melt of the epoxy resin to be used and/or the phenol resin as a curing agent, and the mixture is heated and stirred using a high-speed disperser. The reaction is
It is preferable to carry out the treatment at 80 to 150°C for about 5 to 120 minutes, but the method is not limited thereto. Regarding the blending ratio of (A) and (9), (epoxy group equivalent of N/(t))
The amino group and/or mercapto group equivalent of is 0.2 to
It is preferable that it is about 5. The total amount of (A) and (A) is not particularly limited, but is preferably in the range of 1 to 5% by weight based on the entire epoxy resin composition. If it is outside this range, the effect of reducing stress in the cured product may not be sufficiently achieved, or the physical properties and moldability of the cured product may become unbalanced.
この発明で用いるエポキシ樹脂としては、たとえば、ビ
スフェノールＡ系エポキシ樹脂、ビスフェノールＦ系エ
ポキシ樹脂、ノボラック系エポキシ樹脂、脂環式エポキ
シ樹脂等が挙げられ、特に限定はされない。これらは単
独で、あるいは複数種を併せて使用される。ただし、半
導体素子等を封止する成形材料として、この発明のエポ
キシ樹脂組成物を用いる場合には、硬化物のＴｇ、耐湿
性等の物性に鑑みて、ノボラック系エポキシ樹脂を用い
ることが好ましい。Examples of the epoxy resin used in the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, alicyclic epoxy resin, and the like, but are not particularly limited. These may be used alone or in combination. However, when using the epoxy resin composition of the present invention as a molding material for sealing a semiconductor element or the like, it is preferable to use a novolac-based epoxy resin in view of physical properties such as Tg and moisture resistance of the cured product.
硬化剤としては、たとえば、フェノールノボラック樹脂
、酸無水物、アミン類などを、単独で、あるいは複数種
を併せて使用できる。上記エポキシ樹脂の場合と同様の
理由から、硬化剤としてはフェノールノボラック樹脂等
のフェノール樹脂を用いることが好ましいが、これに限
定されることはない。また、硬化剤の配合割合に、特に
制限はなく、必要量を適宜設定すればよい。As the curing agent, for example, phenol novolak resin, acid anhydride, amines, etc. can be used alone or in combination. For the same reason as in the case of the epoxy resin described above, it is preferable to use a phenol resin such as a phenol novolac resin as the curing agent, but the curing agent is not limited thereto. Further, there is no particular restriction on the blending ratio of the curing agent, and the necessary amount may be set as appropriate.
以上述べてきた必須成分を含むこの発明のエポキシ樹脂
組成物は、さらに必要に応じて、下記のその他の成分を
１種以上含んでいてもよい。同成分としては、たとえば
、硬化助剤または硬化促進剤（第３級アミン、イミダゾ
ール類、有機リン化合物等）、充填材または補強材（シ
リカ粉末、アルミナ粉末、炭酸カルシウム粉末、ガラス
繊維炭素繊維等）、難燃化剤（三酸化アンチモン、臭素
化エポキシ樹脂、水和アルミナ等）、離型剤（ワックス
、ステアリン酸、ステアリン酸塩等）、着色剤（カーボ
ンブラック、金属酸化物等の顔料）などが挙げられるが
、これらの種類および配合割合等は、特に限定されるも
のではない。なお、充填材を用いる場合には、エポキシ
樹脂組成物全体１００重量部（以下、単に「部」と記す
）に対して１０〜８０部となるように設定するのが好ま
しい。１０部以上の充填材を加えることにより、線膨張
係数を小さくして熱放散性を良好に保つことができるが
、８０部を越えると、キャビティーに完全に充愼されな
くなり、成形性が悪くなる恐れがある。The epoxy resin composition of the present invention containing the essential components described above may further contain one or more of the following other components, if necessary. The same components include, for example, curing aids or curing accelerators (tertiary amines, imidazoles, organic phosphorus compounds, etc.), fillers or reinforcing materials (silica powder, alumina powder, calcium carbonate powder, glass fiber carbon fiber, etc.). ), flame retardants (antimony trioxide, brominated epoxy resin, hydrated alumina, etc.), mold release agents (wax, stearic acid, stearate, etc.), colorants (carbon black, pigments such as metal oxides) These types and blending ratios are not particularly limited. In addition, when using a filler, it is preferable to set it so that it may be 10-80 parts with respect to 100 parts by weight (hereinafter simply referred to as "parts") of the entire epoxy resin composition. By adding 10 parts or more of filler, it is possible to reduce the linear expansion coefficient and maintain good heat dissipation, but if it exceeds 80 parts, the cavity will not be completely filled, resulting in poor moldability. There is a risk that it will happen.
上記構成成分（必須成分および必要に応じてはその他の
成分を含む）を、たとえばミキサ、ブレンダーなどで混
合し、ニーダ、ロールなどを使用して混練することによ
り、成形材料としてのエポキシ樹脂組成物を得ることが
できる。混線後に、必要に応じて冷却固化し、粉砕して
粒状等としてもよい。An epoxy resin composition as a molding material is produced by mixing the above components (including essential components and other components as necessary) using a mixer, blender, etc., and kneading using a kneader, roll, etc. can be obtained. After cross-wiring, the mixture may be cooled and solidified as required, and crushed to form granules.
以下に、この発明のさらに詳しい実施例を、比較例と併
せて示すが、この発明は、下記実施例に限定されるもの
ではない。More detailed examples of the present invention will be shown below together with comparative examples, but the invention is not limited to the following examples.
一実施例１〜３、比較例１．２−
下記の改質剤Ａ、Ｂ＋、Ｂｉ ：
Ａ：ポリエーテルエポキシ変性シリコーン重合体〔ただ
し、上記（１）式中、ａ＝２００゜ｂ ＝ ｃ ＝ ２
０． ｍ＋＝ｍｔ＝ ５）ＢＩ ：両末端アミノ変性オ
ルガノボリシロキサン（ただし、上記（ＩＩ）式中、ｄ
＝２０）Ｂ、：両末端メルカプト変性オルガノポリシロ
キサン〔ただし、上記（ＴＩ［）式中、ｅ＝２０）を用
いて、以下の各成分からなるエポキシ樹脂組成物を調製
した（数字は配合部を表す）。Examples 1 to 3, Comparative Example 1.2 - The following modifiers A, B+, Bi: A: Polyether epoxy modified silicone polymer [However, in the above formula (1), a = 200 ° b = c = 2
0. m+=mt=5) BI: both terminal amino-modified organoborisiloxane (however, in the above formula (II), d
= 20) B,: Organopolysiloxane modified with mercapto at both terminals [However, e = 20 in the above (TI[) formula] was used to prepare an epoxy resin composition consisting of the following components (numbers indicate blending parts). ).
ここで、上記各成分の配合は、以下の手順に沿って行っ
た。まず、約１５０ ’Ｃで熱熔融した上記フェノール
樹脂中に、第１表に示した改質剤を投入して、約１時間
混合反応させた。その後、冷却。Here, the above-mentioned components were blended according to the following procedure. First, the modifier shown in Table 1 was added to the above phenol resin which had been thermally melted at about 150'C, and mixed and reacted for about 1 hour. Then cool.
微粉砕し、得られた微粉砕粉と上記その他の成分を合わ
せ、これらをミキサで混合し、ニーダを使用して混練し
て成形材料を得た。The resulting finely pulverized powder was combined with the other components mentioned above, mixed in a mixer, and kneaded using a kneader to obtain a molding material.
同成形材料を常法に従って、圧力５０ｋｇ／ｄ。The same molding material was molded using a conventional method at a pressure of 50 kg/d.
温度１７０℃で３分間成形し、１７０℃で５時間アフタ
キュアさせて硬化させた。It was molded at a temperature of 170° C. for 3 minutes, and after-cured at 170° C. for 5 hours to be cured.
一比較例３−
上記の改質剤のいずれをも用いず、充填材配合量を７０
．６部とする他は、上記と同様に処理して硬化物を得た
。Comparative Example 3 - Without using any of the above modifiers, the filler loading was 70%.
．． A cured product was obtained by processing in the same manner as above except that the amount was changed to 6 parts.
上記実施例および比較例の各エポキシ樹脂組成物につい
て、成形時のパリの発生、線膨張係数（αｌ）、曲げ弾
性率（Ｅ）、曲げ強度（σｆ）、Ｔｇをそれぞれ調べ、
さらにヒートサイクル試験を行った。For each of the epoxy resin compositions of the above examples and comparative examples, the occurrence of flakes during molding, linear expansion coefficient (αl), flexural modulus (E), flexural strength (σf), and Tg were investigated,
Furthermore, a heat cycle test was conducted.
成形時のパリの発生は、１０〜１００ｎの金型スリット
間からのしみ出しの有（×）無（○）を観察し、Ｑ、×
、△で評価した。線膨張係数およびＴｇは、ＴＭＡ法に
より求め、曲げ弾性率および曲げ強度は、曲げ強度試験
機を用いて測定した。ヒートサイクル試験は、ΔＴ＝２
００℃のヒートサイクル温度試験幅で行い、その結果を
、優秀（◎）、良い（○）、悪い（×）で評価した。The occurrence of paris during molding was determined by observing the presence (x) and absence (○) of seepage from between the 10 to 100n mold slits, and
, △ was evaluated. The linear expansion coefficient and Tg were determined by the TMA method, and the flexural modulus and flexural strength were measured using a flexural strength tester. Heat cycle test is ΔT=2
The heat cycle temperature test was conducted at a temperature of 00° C., and the results were evaluated as excellent (◎), good (◎), and poor (x).
以上の結果を、同じく第１表に示す。The above results are also shown in Table 1.
第１表にみるように、実施例のものは比較例に比べ、パ
リの発生がなく、Ｔｇおよび曲げ強度σｆが低下するこ
となく、線膨張係数α１と曲げ弾性率Ｅが一層低下して
いる。すなわち、低応力化されている。また、ヒートサ
イクル試験結果も、実施例のものは非常に良好であった
。As shown in Table 1, compared to the comparative example, the example has no occurrence of flash, Tg and bending strength σf have not decreased, and the linear expansion coefficient α1 and bending modulus E have further decreased. . In other words, the stress is reduced. Further, the heat cycle test results of the examples were also very good.
（発明の効果〕
この発明にかかるエポキシ樹脂は、以上のように、成形
時にパリが発生しにくく、しかも、硬化物のＴｇおよび
曲げ強度を低下させずに、低応力化された硬化物を得る
ことができる。(Effects of the Invention) As described above, the epoxy resin according to the present invention is less likely to generate flakes during molding, and can provide a cured product with low stress without reducing the Tg and bending strength of the cured product. be able to.
代理人 弁理士 松 本 武 彦Agent: Patent Attorney Takehiko Matsumoto
Claims (1)
および（Ｂ）が含まれているエポキシ樹脂組成物。 （Ａ）下記一般式（Ｉ）で表されるポリエーテルエポキ
シ変性シリコーン重合体Ａ。 ▲数式、化学式、表等があります▼…（Ｉ） 〔式中、Ｒ＾１、Ｒ＾２はそれぞれ独立に炭素数１〜４
の２価の炭化水素基、 Ｚは▲数式、化学式、表等があります▼ Ｙは▲数式、化学式、表等があります▼ をそれぞれ表す。〕 （Ｂ）両末端アミノ変性オルガノポリシロキサンＢ＿１
および／または両末端メルカプト変性オルガノポリシロ
キサンＢ＿２。[Claims] 1. The following (A) is used as a modifier for reducing stress in a cured product:
and (B). (A) Polyether epoxy modified silicone polymer A represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) [In the formula, R^1 and R^2 each independently have a carbon number of 1 to 4
A divalent hydrocarbon group, Z represents ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ Y represents ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼. ] (B) Both terminal amino-modified organopolysiloxane B_1
and/or both terminal mercapto-modified organopolysiloxane B_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32708288A JPH02170819A (en) | 1988-12-23 | 1988-12-23 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32708288A JPH02170819A (en) | 1988-12-23 | 1988-12-23 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02170819A true JPH02170819A (en) | 1990-07-02 |
Family
ID=18195088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32708288A Pending JPH02170819A (en) | 1988-12-23 | 1988-12-23 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02170819A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194169A (en) * | 2012-01-10 | 2013-07-10 | 深圳市隆邦工业材料有限公司 | Dual-component condensed type organosilicone transparent electronic pouring sealant with high adhesion |
| JP2021120462A (en) * | 2016-04-20 | 2021-08-19 | 住友ベークライト株式会社 | Thermosetting resin composition, resin-sealed substrate, and electronic device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6013841A (en) * | 1983-07-04 | 1985-01-24 | Toray Silicone Co Ltd | Epoxy resin composition for molding |
| JPS62187721A (en) * | 1986-02-14 | 1987-08-17 | Shin Etsu Chem Co Ltd | Epoxy resin composition |
| JPS638008A (en) * | 1986-06-28 | 1988-01-13 | Daihatsu Motor Co Ltd | Suspension for automobile |
| JPS6381120A (en) * | 1986-09-24 | 1988-04-12 | Hitachi Ltd | Epoxy resin composition |
| JPS63241020A (en) * | 1987-03-27 | 1988-10-06 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing electronic component |
-
1988
- 1988-12-23 JP JP32708288A patent/JPH02170819A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6013841A (en) * | 1983-07-04 | 1985-01-24 | Toray Silicone Co Ltd | Epoxy resin composition for molding |
| JPS62187721A (en) * | 1986-02-14 | 1987-08-17 | Shin Etsu Chem Co Ltd | Epoxy resin composition |
| JPS638008A (en) * | 1986-06-28 | 1988-01-13 | Daihatsu Motor Co Ltd | Suspension for automobile |
| JPS6381120A (en) * | 1986-09-24 | 1988-04-12 | Hitachi Ltd | Epoxy resin composition |
| JPS63241020A (en) * | 1987-03-27 | 1988-10-06 | Hitachi Chem Co Ltd | Epoxy resin molding material for sealing electronic component |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194169A (en) * | 2012-01-10 | 2013-07-10 | 深圳市隆邦工业材料有限公司 | Dual-component condensed type organosilicone transparent electronic pouring sealant with high adhesion |
| JP2021120462A (en) * | 2016-04-20 | 2021-08-19 | 住友ベークライト株式会社 | Thermosetting resin composition, resin-sealed substrate, and electronic device |
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