JPH01299816A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH01299816A JPH01299816A JP12863888A JP12863888A JPH01299816A JP H01299816 A JPH01299816 A JP H01299816A JP 12863888 A JP12863888 A JP 12863888A JP 12863888 A JP12863888 A JP 12863888A JP H01299816 A JPH01299816 A JP H01299816A
- Authority
- JP
- Japan
- Prior art keywords
- modified silicone
- silicone polymer
- epoxy resin
- component
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims description 21
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 39
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 18
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 239000000945 filler Substances 0.000 abstract description 6
- 238000005452 bending Methods 0.000 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract description 3
- 239000007822 coupling agent Substances 0.000 abstract description 3
- 239000005011 phenolic resin Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 229920000570 polyether Polymers 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 description 16
- 238000000465 moulding Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000000463 material Substances 0.000 description 4
- 239000006082 mold release agent Substances 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- -1 laminates Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-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
- 239000006229 carbon black Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- 125000002947 alkylene 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
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical group [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000017525 heat dissipation Effects 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
- 238000000034 method Methods 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
- 238000002161 passivation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (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、エポキシ樹脂組成物に関する。[Detailed description of the invention] [Industrial application field] TECHNICAL FIELD This invention relates to epoxy resin compositions.
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、半導体素子封止用材料な
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、ｒｃ用、さらに
は、ＬＳＩ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. Particularly, recently, the demand for encapsulating materials for RC and LSI in the electronics field has been increasing.
半導体素子は、高密度化するとともに、チップサイズが
大型化している。大型のチップをエポキシ樹脂組成物で
封止した場合、その硬化物の応力にヨリ、アルミ配線の
ずれ、パッシベーション層のクランクなどが発生すると
いう問題が生じている。このため、エポキシ樹脂組成物
の硬化物を低応力化させるということが大きな課題のひ
とつになっている。Semiconductor devices are becoming denser and have larger chip sizes. When a large chip is encapsulated with an epoxy resin composition, problems such as twisting of the cured product, displacement of aluminum wiring, and cranking of the passivation layer occur due to the stress of the cured product. Therefore, one of the major challenges is to reduce the stress in the cured product of the epoxy resin composition.
そこで、エポキシ樹脂組成物に通常のシリコーン弾性体
を導入することにより、その硬化物の弾性率を低減する
ことが考えられた。Therefore, it has been considered to reduce the elastic modulus of the cured product by introducing a common silicone elastomer into the epoxy resin composition.
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、成形時にパリを生じたり、硬化物のＴｇお
よび曲げ強度を低下させたりするという問題点を有する
。However, epoxy resin compositions containing ordinary silicone elastomers have problems in that they cause flaking during molding and reduce the Tg and bending strength of the cured product.
そこで、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るエポキシ樹脂組成物を提供する
ことを課題とする。Therefore, an object of the present invention is to provide an epoxy resin composition that can reduce the stress of a cured product without impairing moldability or reducing the Tg and bending strength of the cured product. .
この発明にかかるエポキシ樹脂組成物は、上記課題を解
決するため、硬化物の低応力化を図る改質剤として、下
記（２）式で表されるポリエーテル変性シリコーン重合
体、下記（司式で表されるビニル基変性シリコーン重合
体、および、同ビニル基変性シリコーン重合体を架橋さ
せる架橋剤を含んでいる。In order to solve the above problems, the epoxy resin composition according to the present invention uses a polyether-modified silicone polymer represented by the following formula (2) as a modifier to reduce stress in the cured product, and a polyether-modified silicone polymer represented by the following formula (2). It contains the vinyl group-modified silicone polymer shown above and a crosslinking agent that crosslinks the vinyl group-modified silicone polymer.
エポキシ樹脂組成物が、上記（４）式で表されるポリエ
ーテル変性シリコーン重合体、上記（Ｂｌで表されるビ
ニル基変性シリコーン重合体、および、同ビニル基変性
シリコーン重合体を架橋させる架橋剤を改質剤として含
むことにより、硬化物の内部応力を低減することができ
、しかも、成形時にパリが発生したり、硬化物のＴｇお
よび曲げ強度が低下したりするのを防ぐことができる。The epoxy resin composition is a polyether-modified silicone polymer represented by the above formula (4), a vinyl group-modified silicone polymer represented by (Bl), and a crosslinking agent that crosslinks the vinyl group-modified silicone polymer. By including as a modifier, it is possible to reduce the internal stress of the cured product, and moreover, it is possible to prevent the occurrence of flashing during molding and a decrease in the Tg and bending strength of the cured product.
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、硬化剤、ポリエーテル変性シリコーン重合体、
ビニル基変性シリコーン重合体、および、同ビニル基変
性シリコーン重合体を架橋させる架橋剤を含む。The epoxy resin composition of this invention comprises at least an epoxy resin, a curing agent, a polyether-modified silicone polymer,
It includes a vinyl group-modified silicone polymer and a crosslinking agent that crosslinks the vinyl group-modified silicone polymer.
ポリエーテル変性シリコーン重合体は、上記（４）式で
表される。基Ｒは、炭素数１〜４の２価の炭化水素基で
ある。基Ｚは、上記化学式で表されるポリオキシアルキ
レンである。この重合体を改質剤に用いると、エポキシ
基を含む重合体を用いる場合に比べて、硬化物の物性が
改善される。The polyether-modified silicone polymer is represented by the above formula (4). The group R is a divalent hydrocarbon group having 1 to 4 carbon atoms. The group Z is a polyoxyalkylene represented by the above chemical formula. When this polymer is used as a modifier, the physical properties of the cured product are improved compared to when a polymer containing an epoxy group is used.
（４）式中、繰り返し数ｘ、ｙ、ｍ、ｎは、それぞれ、
ｘ＝２〜５００、ｙ＝２〜１００、ｍ≦２０、ｎ≦２０
の範囲が好ましい。ただし、ｍおよびｎのうちいずれか
一方はゼロであってもよい。Ｘおよびｙのうち少なくと
も１つが前記範囲を下回ると、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、
ｘ、 ｙ、 ｍ、ｎのうち少なくとも１つが前記範囲
を上回ると、成形性、硬化物の低応力物性などの性能が
低下することがある。(4) In the formula, the number of repetitions x, y, m, and n are, respectively,
x=2-500, y=2-100, m≦20, n≦20
A range of is preferred. However, either one of m and n may be zero. If at least one of X and y is below the above range, performance such as moldability and low stress physical properties of the cured product may not be improved. Also,
When at least one of x, y, m, and n exceeds the above range, performances such as moldability and low stress physical properties of the cured product may deteriorate.
ポリエーテル変性シリコーン重合体の添加割合は、特に
限定はないが、エポキシ樹脂組成物全体中の０．０５〜
３．００重量％の範囲が好ましい。０゜０５重量％未満
だと、硬化物を低応力化するという効果が得られないこ
とがある。３．００重量％よりも多いと、硬化物のＴｇ
が低下したり、成形時にパリが発生したりすることがあ
る。The proportion of the polyether-modified silicone polymer added is not particularly limited, but it is from 0.05 to 0.05 in the entire epoxy resin composition.
A range of 3.00% by weight is preferred. If it is less than 0.05% by weight, the effect of reducing stress in the cured product may not be achieved. If it is more than 3.00% by weight, the Tg of the cured product
This may result in a decrease in the temperature or the occurrence of cracks during molding.
ビニル基変性シリコーン重合体は、上記（ト））式で表
される。（６）式中、繰り返し数ａは、ａ＝ｌ Ｏ〜５
００の範囲が好ましい。ａが１０未満だと、硬化物のＴ
ｇが低下することがある。ａが５００よりも大きいと、
次に示す架橋剤との反応性に乏しく、成形時にパリを生
じることがある。The vinyl group-modified silicone polymer is represented by the above formula (g). (6) In the formula, the number of repetitions a is a=l O~5
A range of 00 is preferred. If a is less than 10, T of the cured product
g may decrease. If a is larger than 500,
It has poor reactivity with the following crosslinking agents and may cause flaking during molding.
前記架橋剤は、前記ビニル基変性シリコーン重合体のビ
ニル基とラジカル重合し、ゲル状物または硬化物を生成
するものであれば特に限定は、ない。たとえば、末端に
５ｉ−Ｈを有するものが使用される。このような架橋剤
として、たとえば、下式（Ｑで表されるものが挙げられ
る。The crosslinking agent is not particularly limited as long as it radically polymerizes with the vinyl group of the vinyl group-modified silicone polymer to produce a gel-like material or a cured product. For example, one having 5i-H at the end is used. Examples of such crosslinking agents include those represented by the following formula (Q).
上記（０式中、繰り返し数Ｃは、ｃ＝５〜２０の範囲が
好ましい。Ｃが５未満であるか、または、２０よりも大
きいと、成形性が低下することがある。In the above formula (0), the repeating number C is preferably in the range of c=5 to 20. If C is less than 5 or greater than 20, moldability may decrease.
なお、上記ビニル基変性シリコーン重合体と上記架橋剤
との反応には、触媒が使用される。この触媒としては、
たとえば、塩化白金酸が使用される。触媒は、たとえば
、ｐｐｍオーダーで使用される。Note that a catalyst is used for the reaction between the vinyl group-modified silicone polymer and the crosslinking agent. This catalyst is
For example, chloroplatinic acid is used. The catalyst is used, for example, on the order of ppm.
上記ポリエーテル変性シリコーン重合体と上記ビニル基
変性シリコーン重合体の使用割合は、両者の重量比（（
Ａ）／（Ｂ））が、（２）／（６）＝０．１〜１０の範
囲となるようにするのが好ましい。同重量比が０．１未
満だと、硬化物の強度低下を生じることがあり、１０よ
りも大きいと、成形時にパリが発生したり、硬化物のＴ
ｇが低下したりすることがある上記ビニル基変性シリコ
ーン重合体と上記架橋剤の使用割合は、両者の重量比〔
架橋剤／帥）〕が、架橋剤／ＣＢｌ＝０．０１〜０．２
の範囲となるようにするのが好ましい。同重量比が０．
０１未満だと、成形時にパリが発生することがあり、０
．２よりも大きいと、硬化物の強度低下を招くことがあ
る。The proportion of the polyether-modified silicone polymer and the vinyl-modified silicone polymer used is their weight ratio ((
It is preferable that A)/(B)) is in the range of (2)/(6)=0.1 to 10. If the weight ratio is less than 0.1, the strength of the cured product may decrease; if it is greater than 10, flakes may occur during molding, or the T of the cured product may decrease.
The proportion of the vinyl group-modified silicone polymer and the crosslinking agent, which may cause a decrease in g, should be determined by their weight ratio [
crosslinking agent/CBl)] is crosslinking agent/CBl=0.01 to 0.2
It is preferable to set it within the range of . The same weight ratio is 0.
If it is less than 01, cracks may occur during molding, and
．． If it is larger than 2, the strength of the cured product may decrease.
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、ノボラック系エポキシ
樹脂、脂環式エポキシ樹脂などが挙げられる。半導体素
子などを封止する成形材料としてエポキシ樹脂組成物を
用いる場合には、硬化物のＴｇ、耐湿性等の物性を考慮
すると、ノボラック系エポキシ樹脂を用いるのが好まし
いが、これに限定するものではない。Examples of the epoxy resin used in the present invention include bisphenol A-based epoxy resins, novolak-based epoxy resins, and alicyclic epoxy resins. When using an epoxy resin composition as a molding material for encapsulating semiconductor elements, etc., it is preferable to use a novolac-based epoxy resin in consideration of physical properties such as Tg and moisture resistance of the cured product, but it is not limited to this. isn't it.
硬化剤は、たとえば、フェノールノボラック樹脂、酸無
水物、アミン類などが使用される。エポキシ樹脂の場合
と同様の理由から、硬化剤として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のが好ましいが、これ
に限定するものではない。硬化剤としてフェノール樹脂
と他の硬化剤とを併用してもよい。硬化剤の配合割合は
、特に制限はなく、適宜設定すればよい。As the curing agent, for example, phenol novolak resin, acid anhydride, amines, etc. are used. For the same reason as in the case of epoxy resins, it is preferable to use phenol resins such as phenol novolac resins as the curing agent, but the invention is not limited thereto. As a curing agent, a phenol resin and another curing agent may be used together. The blending ratio of the curing agent is not particularly limited and may be set as appropriate.
この発明のエポキシ樹脂組成物は、エポキシ樹脂、硬化
剤、上記（Ｎ式で表されるポリエーテル変性シリコーン
重合体、上記（６）で表されるビニル基変性シリコーン
重合体、および、上記架橋剤以外にも、必要に応じてそ
の他の物質を含むことができる。たとえば、硬化助剤（
または硬化促進剤）、充填材、難燃剤、カップリング剤
、離型剤、着色剤などのうちのいずれか１つまたは２つ
以上が配合される。The epoxy resin composition of the present invention comprises an epoxy resin, a curing agent, the polyether-modified silicone polymer represented by the formula (N), the vinyl-modified silicone polymer represented by (6) above, and the crosslinking agent. In addition to this, other substances may be included if necessary.For example, curing aids (
or a curing accelerator), a filler, a flame retardant, a coupling agent, a mold release agent, a coloring agent, and the like.
硬化助剤としては、たとえば、第３級アミンなどが使用
される。As the curing aid, for example, tertiary amine is used.
充填材としては、たとえば、シリカ粉末、アルミナ粉末
、炭酸カルシウム粉末などが使用される、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
部に対して１０〜８０ｆｆｉ量部となるようにするのが
好ましい。８０重量部よりも多いと、キャビティーに完
全に充填されなくなり、成形性が悪くなることがある。As the filler, for example, silica powder, alumina powder, calcium carbonate powder, etc. are used. When a filler is used, the amount is 10 to 80 parts by weight based on 100 parts by weight of the entire epoxy resin composition. It is preferable to do so. If the amount is more than 80 parts by weight, the cavity may not be completely filled, resulting in poor moldability.
また、１０重量部よりも少ないと、線膨張係数（α、）
が大きくなり、熱放散性が悪くなることがある。In addition, if it is less than 10 parts by weight, the coefficient of linear expansion (α,)
may become large, resulting in poor heat dissipation.
難燃剤としては、たとえば、ブロム化エポキシ、三酸化
アンチモン、水和アルミナなどが使用される。Examples of flame retardants used include brominated epoxy, antimony trioxide, and hydrated alumina.
カップリング剤としては、たとえば、アミノシラン、エ
ポキシ樹脂ン、メルカプトシランなどが使用される。As the coupling agent, for example, aminosilane, epoxy resin, mercaptosilane, etc. are used.
離型剤としては、たとえば、ワックス、ステアリン酸、
ステアリン酸塩などが使用される。Examples of mold release agents include wax, stearic acid,
Stearates, etc. are used.
着色剤としては、たとえば、カーボンブラック、金属酸
化物などの顔料が使用される。As the coloring agent, for example, pigments such as carbon black and metal oxides are used.
上記の必須材料およびその他の添加剤は、上記のものに
限定されず、上記のもの以外のものも適宜使用すること
ができる。The above-mentioned essential materials and other additives are not limited to those mentioned above, and those other than those mentioned above can also be used as appropriate.
上記の必須材料、および、その他必要に応じて添加する
添加剤を、たとえば、ミキサなどで混合し、ニーダ、ロ
ールなどを使用して混練することにより、エポキシ樹脂
組成物を成形材料として得ることができる。混練後に、
必要に応じて冷却固化し、粉砕して粒状などにしてもよ
い。なお、ポリエーテル変性シリコーン重合体、ビニル
基変性シリコーン重合体、架橋剤、触媒を、熱熔融した
エポキシ樹脂と予め混合しておき、その他の成分と混合
するようにしてもよい。このようにすれば、ポリエーテ
ル変性シリコーン重合体、ビニル基変性シリコーン重合
体、架橋剤、触媒と樹脂とを均一に混合するという点か
ら好ましい。An epoxy resin composition can be obtained as a molding material by mixing the above-mentioned essential materials and other additives added as necessary, for example, in a mixer, and kneading them using a kneader, rolls, etc. can. After kneading,
If necessary, it may be cooled and solidified, and then pulverized into granules. Note that the polyether-modified silicone polymer, the vinyl group-modified silicone polymer, the crosslinking agent, and the catalyst may be mixed in advance with the hot-melted epoxy resin, and then mixed with other components. This is preferable because the polyether-modified silicone polymer, the vinyl-modified silicone polymer, the crosslinking agent, the catalyst, and the resin are uniformly mixed.
以下に、この発明のより具体的な実施例および比較例を
示すが、この発明は、下記実施例に限定されない。More specific examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following examples.
一実施例１〜３−
上記（Ａ）式で表されるポリエーテル変性シリコーン重
合体、上記＠氏で表されるビニル基変性シリコーン重合
体、上記（ａｉ−ｔ：表される架橋剤、および、触媒を
、予め１１０〜１３０度で熱熔融したタレゾールノボラ
ック型エポキシ樹脂（ＷＰＥ＝２００、平均重合度ｎ＝
４）に、第１表に示す割合で投入し、約１時間混合した
後、冷却してから微粉砕した。Examples 1 to 3 - A polyether-modified silicone polymer represented by the above formula (A), a vinyl group-modified silicone polymer represented by the above @, a crosslinking agent represented by the above (ai-t), and , a Talesol novolak type epoxy resin (WPE=200, average degree of polymerization n=
4) in the ratio shown in Table 1, mixed for about 1 hour, cooled, and finely ground.
この微粉砕粉、硬化剤、硬化助剤、離型剤、充填材、顔
料および難燃剤をそれぞれ第１表に示す割合でミキサに
より混合し、ニーダを使用して混練し、成形材料を得た
。This finely pulverized powder, a curing agent, a curing aid, a mold release agent, a filler, a pigment, and a flame retardant were mixed in a mixer in the proportions shown in Table 1, and kneaded using a kneader to obtain a molding material. .
この成形材料を常法に従って、圧力５０ｋｓｒ／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。This molding material was molded according to a conventional method at a pressure of 50 ksr/d and a temperature of 170° C. for 3 minutes, and after-cured at 170° C. for 5 hours to harden it.
ポリエーテル変性シリコーン重合体は、上記（Ａ１式に
おいて、ｘ＝２００．ｙ＝２０．ｍ＝５．ｎ＝５．Ｒ＝
炭素数１〜４のアルキレンというものを用いた。The polyether-modified silicone polymer has the above (in formula A1, x=200.y=20.m=5.n=5.R=
An alkylene having 1 to 4 carbon atoms was used.
ビニル基変性シリコーン重合体は、上記（８）式におい
て、ａ＝２５０というものを用いた。The vinyl group-modified silicone polymer used was one in which a=250 in the above formula (8).
架橋剤は、上記（０式において、ｃ＝１３というものを
用いた。As the crosslinking agent, the one in which c=13 in the above formula (0) was used.
触媒は、塩化白金酸をｐｐｍのオーダーで用いた。As a catalyst, chloroplatinic acid was used in ppm order.
なお、硬化剤はフェノールノボラック樹脂を、硬化助剤
は２−エチルイミダゾールを、離型剤は天然カルナバワ
ックスを、充填材はシリカ粉末を、顔料はカーボンブラ
ックを、難燃剤は二酸化アンチモンおよびブロム化エポ
キシ樹脂をそれぞれ用いた。The curing agent is phenol novolac resin, the curing aid is 2-ethylimidazole, the mold release agent is natural carnauba wax, the filler is silica powder, the pigment is carbon black, and the flame retardant is antimony dioxide and brominated. Epoxy resin was used for each.
一比較例１一
実施例１において、ポリエーテル変性シリコーン重合体
の代わりに同じ重量のビニル基変性シリコーン重合体を
使用したこと以外は、実施例１と同様にして硬化物を得
た。Comparative Example 1 A cured product was obtained in the same manner as in Example 1, except that the same weight of vinyl group-modified silicone polymer was used instead of the polyether-modified silicone polymer.
一比較例２一
実施例１において、ビニル基変性シリコーン重合体の代
わりに同じ重量のポリエーテル変性シリコーン重合体を
使用したこと以外は、実施例１と同様にして硬化物を得
た。Comparative Example 2 A cured product was obtained in the same manner as in Example 1, except that the same weight of polyether-modified silicone polymer was used instead of the vinyl group-modified silicone polymer.
一比較例３一
実施例１において、ポリエーテル変性シリコーン重合体
およびビニル基変性シリコーン重合体を使用せず、配合
を第１表に示すようにしたこと以外は、実施例１と同様
にして硬化物を得た。Comparative Example 3 Curing was carried out in the same manner as in Example 1, except that the polyether-modified silicone polymer and vinyl group-modified silicone polymer were not used and the formulation was as shown in Table 1. I got something.
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（α１）、ガラス
転移温度（Ｔｇ） 、曲げ弾性率（Ｅ）、および、曲げ
強度（σｆ）をそれぞれ調べ、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 (α1), glass transition temperature (Tg), flexural modulus (E), and flexural strength (σf) were measured. Each was investigated and a heat cycle test was conducted.
成形時のパリの発生は、１０〜１００ｐの金型スリット
間からのしみ出しを観察して、無い（○）〜少しある（
△）〜多い（×）で示した。The generation of flakes during molding was determined by observing seepage between the mold slits of 10 to 100p, and the results were as follows: no (○) to a little (
Indicated by △) to many (x).
線膨張係数゛（α、）およびガラス転移温度（Ｔｇ）は
、ＴＭＡ法により求めた。曲げ弾性率（Ｅ）および曲げ
強度（σｆ）は、曲げ強度試験機により求めた。The coefficient of linear expansion (α,) and the glass transition temperature (Tg) were determined by the TMA method. The flexural modulus (E) and the flexural strength (σf) were determined using a flexural strength tester.
ヒートサイクル試験は、ΔＴ＝２００℃のヒートサイク
ル温度試験幅で行い、その結果が、優良（◎）〜良い（
０）〜悪い（×）で示した。The heat cycle test was conducted with a heat cycle temperature test width of ΔT = 200°C, and the results were evaluated as excellent (◎) to good (
0) to poor (×).
結果を、配合とともに第１表に示した。The results are shown in Table 1 along with the formulation.
第１表かられかるように、実施例のものはパリの発生が
なく、Ｔｇおよびσｆが低下することなく、α１および
Ｅが下がっている、すなわち、低応力化されている。ヒ
ートサイクル試験結果も、実施例のものは良好である。As can be seen from Table 1, in the examples, there is no occurrence of Paris, Tg and σf are not decreased, and α1 and E are decreased, that is, stress is reduced. The heat cycle test results of the examples were also good.
この発明にかかるエポキシ樹脂組成物は、以上のように
、成形時にパリが生じにくく、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。As described above, the epoxy resin composition according to the present invention is less likely to cause flaking during molding, and can provide a cured product with low stress without reducing the Tg and bending strength of the cured product.
代理人 弁理士 松 本 武 彦Agent: Patent Attorney Takehiko Matsumoto
Claims (1)
式で表されるポリエーテル変性シリコーン重合体、下記
（Ｂ）式で表されるビニル基変性シリコーン重合体、お
よび、同ビニル基変性シリコーン重合体を架橋させる架
橋剤が含まれているエポキシ樹脂組成物。 ▲数式、化学式、表等があります▼…（Ａ） ここで、 ＲはＣを１〜４個含む２価の炭化水素基、 Ｚは▲数式、化学式、表等があります▼ である。 ▲数式、化学式、表等があります▼…（Ｂ）[Claims] 1. The following (A) is used as a modifier for reducing stress in a cured product:
An epoxy resin composition containing a polyether-modified silicone polymer represented by the formula, a vinyl-modified silicone polymer represented by the following formula (B), and a crosslinking agent that crosslinks the vinyl-modified silicone polymer. thing. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(A) Here, R is a divalent hydrocarbon group containing 1 to 4 carbon atoms, and Z is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ▲There are mathematical formulas, chemical formulas, tables, etc.▼…(B)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63128638A JPH0623236B2 (en) | 1988-05-26 | 1988-05-26 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63128638A JPH0623236B2 (en) | 1988-05-26 | 1988-05-26 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01299816A true JPH01299816A (en) | 1989-12-04 |
| JPH0623236B2 JPH0623236B2 (en) | 1994-03-30 |
Family
ID=14989767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63128638A Expired - Lifetime JPH0623236B2 (en) | 1988-05-26 | 1988-05-26 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0623236B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0481423A (en) * | 1990-07-24 | 1992-03-16 | Matsushita Electric Works Ltd | Epoxy resin composition for sealing |
| JP2007002233A (en) * | 2005-05-24 | 2007-01-11 | Shin Etsu Chem Co Ltd | Epoxy/silicone resin composition, its cured product and light-emitting semiconductor device encapsulated and protected with the 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS553412A (en) * | 1978-06-21 | 1980-01-11 | Hitachi Ltd | Epoxy resin composition |
| JPS6013841A (en) * | 1983-07-04 | 1985-01-24 | Toray Silicone Co Ltd | Epoxy resin composition for molding |
| JPS61185527A (en) * | 1985-02-13 | 1986-08-19 | Toray Silicone Co Ltd | Curable epoxy resin composition |
| JPS62187721A (en) * | 1986-02-14 | 1987-08-17 | Shin Etsu Chem Co Ltd | Epoxy resin composition |
-
1988
- 1988-05-26 JP JP63128638A patent/JPH0623236B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS553412A (en) * | 1978-06-21 | 1980-01-11 | Hitachi Ltd | Epoxy resin composition |
| JPS6013841A (en) * | 1983-07-04 | 1985-01-24 | Toray Silicone Co Ltd | Epoxy resin composition for molding |
| JPS61185527A (en) * | 1985-02-13 | 1986-08-19 | Toray Silicone Co Ltd | Curable epoxy resin composition |
| JPS62187721A (en) * | 1986-02-14 | 1987-08-17 | Shin Etsu Chem Co Ltd | Epoxy resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0481423A (en) * | 1990-07-24 | 1992-03-16 | Matsushita Electric Works Ltd | Epoxy resin composition for sealing |
| JP2007002233A (en) * | 2005-05-24 | 2007-01-11 | Shin Etsu Chem Co Ltd | Epoxy/silicone resin composition, its cured product and light-emitting semiconductor device encapsulated and protected with the 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0623236B2 (en) | 1994-03-30 |
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