JPH0553180B2 - - Google Patents
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- Publication number
- JPH0553180B2 JPH0553180B2 JP3042487A JP3042487A JPH0553180B2 JP H0553180 B2 JPH0553180 B2 JP H0553180B2 JP 3042487 A JP3042487 A JP 3042487A JP 3042487 A JP3042487 A JP 3042487A JP H0553180 B2 JPH0553180 B2 JP H0553180B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- polyimide precursor
- modulus
- young
- present
- 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.)
- Expired - Fee Related
Links
- 229920001721 polyimide Polymers 0.000 claims description 59
- 239000004642 Polyimide Substances 0.000 claims description 54
- 239000002243 precursor Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 20
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 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 8
- 238000002156 mixing Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- -1 aliphatic diamines Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 3
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- BATVGDQMONZKCV-UHFFFAOYSA-N 2-[3-(2-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC(OC=2C(=CC=CC=2)N)=C1 BATVGDQMONZKCV-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 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
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
［産業上の利用分野］
本発明はポリイミド組成物に関するものであ
り、さらに詳しくは、ヤング率の低いポリイミド
を得ることのできるポリイミド組成物に関するも
のである。
［従来の技術］
近年、半導体業界では、半導体素子の集積化が
急速に進んでおり、DRAMの分野では4Mビツト
レベルの製品が試作されるに及んでいる。しか
し、このような高集積化に伴ないシリコン基板と
樹脂封止剤との線膨張係数の差に起因する熱応力
の問題が大きくなり、パツシベーシヨン膜にクラ
ツクが入る、アルミ配線が切断されるといつた事
態が生じている。これらの問題点を解決できない
と品質の安定した製品は得られない。そのため、
熱応力を弱めるために低いヤング率で耐熱性を有
した樹脂コート剤の開発が望まれているが、従来
のポリイミドの場合、ヤング率は最低でも250
Kg／mm2であるというのが実状である。
本発明者等はこのような事情に鑑み、ポリイミ
ドの低ヤング率化対策について鋭意検討の結果、
ポリイミド組成物を２種の特定のジアミン成分と
酸成分からなるもので構成した場合にはヤング率
の著しく低く、しかも強伸度特性の優れたポリイ
ミドが得られることを知見し、本発明に到達した
ものである。
［発明が解決しようとする問題点］
したがつて、本発明の目的は低いヤング率で、
かつ強度、伸度に優れたポリイミドを得ることの
できるポリイミド組成物を提供することにある。
［問題点を解決するための手段］
かかる本発明の目的は、４，4′−ジアミノジフ
エニルスルフイドとピロメリツト酸二無水物を反
応させて得られるポリイミド前駆体（）と、
４，4′−ジアミノジフエニルエーテルとピロメリ
ツト酸二無水物を反応させて得られるポリイミド
前駆体（）との混合物からなり、かつ該ポリイ
ミド前駆体（）および（）がモル比で
（）／（）＝95／５〜５／95となるように配合
されてなるポリイミド組成物により達成される。
本発明におけるポリイミド組成物（）は、
４，4′−ジアミノジフエニルスルフイド（以下
DASという）とピロメリツト酸二無水物（以下
PMDAという）を反応させて得られるものであ
り、またポリイミド（）は４，4′−ジアミノジ
フエニルエーテル（以下DAEという）とPMDA
を反応させて得られるものである。
また、本発明のポリイミド組成物は、上述のよ
うなポリイミド前駆体（）および（）を含有
するとともに、該前駆体（）および（）が、
モル比で（）／（）＝95／５〜５／95となる
ように配合されてなるものである。
ポリイミド前駆体（）および（）のモル比
が、95／５より多くなると、得られるフイルムの
強度、伸度が小さくなるため好ましくなく、また
モル比が５／95より少なくなるとヤング率の低い
ものが得られなくなる。特に好ましい範囲は、
１／９〜４／１の範囲である。
本発明のポリイミド組成物は、ヤング率に影響
を与えない範囲で、他のジアミンやテトラカルボ
ン酸を配合させることができる。このようなジア
ミンの例としては、ｍ−フエニレンジアミン、
４，4′−ジアミノジフエニルメタン、３，3′−ジ
アミノジフエニルスルホン、ベンチジン、４，
4′−ジアミノターフエニル、１，３−ビス（アミ
ノフエノキシ）ベンゼンのような芳香族ジアミ
ン、ヘキサメチレンジアミン、ヘプタメチレンジ
アミンのような脂肪族ジアミンが挙げられる。ま
たテトラカルボン酸の例としては、３，3′，４，
4′−ベンゾフエノンテトラカルボン酸、３，3′，
４，4′−ビフエニルテトラカルボン酸、３，3′，
４，4′−ジフエニルエーテルテトラカルボン酸の
ような芳香族テトラカルボン酸、１，２，３，４
−ブタンテトラカルボン酸、１，２，３，４−シ
クロペンタンテトラカルボン酸のような脂肪族テ
トラカルボン酸が挙げられる。
さらに接着性を改良するために、１，３−ビス
（３−アミノプロピル）テトラメチルジシロキサ
ンのようなシロキサンジアミンを全アミノ量の１
〜６モル％配合させることもできる。
次に本発明のポリイミド組成物の製造方法の一
例を説明する。すなわち、溶媒中でDASに対し
てPMDAをモル比で好ましくは90〜110モル％、
より好ましくは等モルの配合比で、−20℃〜100℃
で反応させることにより、PMDAとDASのポリ
イミド前駆体（）を製造する。また、溶媒中で
DAEに対してPMDAをモル比で好ましくは90〜
110モル％、より好ましくは等モルの配合比で、−
20℃〜100℃で反応させることにより、PMDAと
DAEのポリイミド前駆体（）を製造すること
ができる。以上のようにして製造したポリイミド
前駆体（）と（）の溶液を５／95〜95／５の
割合（モル比）で混合することにより、本発明の
ポリイミド前駆体のワニスを得ることができる。
上記製造方法で用いる溶媒としては、ポリマー
の溶解性の点から極性溶媒を使用するのが好まし
く、特に非プロトン性極性溶媒が好適である。非
プロトン性極性溶媒としては、Ｎ−メチル−２−
ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、
Ｎ，Ｎ−ジメチルアセトアミド、ヘキサメチルホ
スホロトリアミド、ジメチルスルホキシド、γ−
ブチロラクトンなどが好ましく用いられる。
次に、以上のようにして得たポリイミド前駆体
のワニスを適当な支持体上に塗布し、50〜100℃
で乾燥し、ポリイミド前駆体のフイルムを得る。
このようにして得たポリイミド前駆体のフイル
ムを化学的あるいは熱的に処理して脱水閉環する
ことによりポリイミド製フイルムが得られる。
化学的に処理する場合は、ポリイミド前駆体の
フイルムを、無水酢酸とピリジンの混合溶液に浸
漬処理することにより、ポリイミドフイルムを得
る。また熱的に処理する場合は、ポリイミド前駆
体のフイルムを室温から450℃の範囲で数段階の
温度を選び段階的に昇温するか、ある温度範囲を
選び連続的に昇温しながら、５分〜５時間実施す
るのがよい。例えば、130℃、200℃、300℃、400
℃各々30分づつ熱処理するか、または室温から
400℃まで２時間かけて直線的に昇温してもよい。
（特性の測定方法）
ヤング率
本発明のヤング率の測定方法は、JIS−
Z1702に基づき、試料幅10mm、試験長50mmの試
験片を東洋ボールドウイン社製テンシロンデ20
mm／分の引張速度で測定した。また同時に強度
と伸度を算出した。
耐湿接着性
シリコンウエハー上に形成したポリイミド膜
に、カツターで２mm間隔の切れ目を縦横６本づ
つ形成して25個の碁盤目を作る。これを120℃、
2.0気圧の飽和水蒸気下、所定の時間湿熱処理
を行なう。この試料にセロハン粘着テープ（ニ
チバン(株)製）を貼りつけ、JIS D0202表13、１
に記載の方法に準じて引き剥す。
［実施例］
以下本発明を実施例に基づいて具体的に説明す
る。
実施例１〜３、比較例１、２
PMDA 104.7ｇ、DAE 100.1ｇをＮ−メチル
−２−ピロリドン（NMP）1182.1ｇ中で、30℃
で１時間、続いて70℃で２時間反応を行ない、Ｅ
型回転粘度計による25℃での測定が30ポイズのポ
リイミド前駆体溶液(1)を得た。
また、PMDA 107.9ｇ、DAS 108.1ｇをNMP
1227.4ｇ中で、30℃で１時間、続いて70℃で２時
間反応を行ない、Ｅ型回転粘度計による25℃での
測定が30ポイズのポリイミド前駆体溶液(2)を得
た。
以上のようにして作成したポリイミド前駆体溶
液(1)と(2)を表１に示す割合でそれぞれ混合してポ
リイミド前駆体のブレンド溶液を得た。
得られたポリイミド前駆体のブレンド溶液をシ
リコンウエハー上にスピナーを用いてイミド化後
の厚さが20μ±2μとなるように塗布した。これを
80℃、200℃、300℃、350℃で各々30分づつ熱処
理してポリイミドのフイルムを得、ヤング率およ
び強伸度特性を測定した。結果を表１に示す。
表１において、実施例１〜３が本発明のポリイ
ミド前駆体（）とポリイミド前駆体（）との
混合物からなるポリイミド組成物、比較例１がポ
リイミド前駆体（）のみからなるポリイミド組
成物の場合、比較例２がポリイミド前駆体（）
のみからなるポリイミド組成物の場合である。
[Industrial Field of Application] The present invention relates to a polyimide composition, and more particularly, to a polyimide composition capable of obtaining a polyimide having a low Young's modulus. [Prior Art] In recent years, in the semiconductor industry, the integration of semiconductor elements has progressed rapidly, and in the DRAM field, 4M bit level products are being prototyped. However, with this increase in integration, the problem of thermal stress caused by the difference in linear expansion coefficient between the silicon substrate and the resin encapsulant increases, causing cracks in the passivation film and breakage of the aluminum wiring. A strange situation is occurring. Unless these problems are resolved, products with stable quality cannot be obtained. Therefore,
It is desired to develop a heat-resistant resin coating agent with a low Young's modulus to weaken thermal stress, but in the case of conventional polyimide, the Young's modulus is at least 250.
The actual situation is that it is Kg/mm 2 . In view of these circumstances, the inventors of the present invention have conducted intensive studies on measures to reduce the Young's modulus of polyimide.
It was discovered that when a polyimide composition is composed of two specific diamine components and an acid component, a polyimide with a significantly low Young's modulus and excellent strength and elongation properties can be obtained, and the present invention has been achieved. This is what I did. [Problems to be Solved by the Invention] Therefore, an object of the present invention is to achieve a low Young's modulus,
Another object of the present invention is to provide a polyimide composition from which a polyimide having excellent strength and elongation can be obtained. [Means for Solving the Problems] The object of the present invention is to provide a polyimide precursor () obtained by reacting 4,4'-diaminodiphenyl sulfide and pyromellitic dianhydride;
It consists of a mixture of a polyimide precursor () obtained by reacting 4,4'-diaminodiphenyl ether and pyromellitic dianhydride, and the polyimide precursors () and () have a molar ratio of ()/( )=95/5 to 5/95. The polyimide composition () in the present invention is
4,4'-diaminodiphenyl sulfide (hereinafter
DAS) and pyromellitic dianhydride (hereinafter referred to as
Polyimide () is obtained by reacting 4,4'-diaminodiphenyl ether (hereinafter referred to as DAE) with PMDA.
It is obtained by reacting. Moreover, the polyimide composition of the present invention contains the polyimide precursors () and () as described above, and the precursors () and () are
They are blended in a molar ratio of ()/()=95/5 to 5/95. If the molar ratio of the polyimide precursors () and () is more than 95/5, the strength and elongation of the obtained film will decrease, which is undesirable, and if the molar ratio is less than 5/95, the film will have a low Young's modulus. will not be obtained. A particularly preferable range is
It is in the range of 1/9 to 4/1. The polyimide composition of the present invention can contain other diamines and tetracarboxylic acids as long as they do not affect the Young's modulus. Examples of such diamines include m-phenylenediamine,
4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, benzidine, 4,
Examples include aromatic diamines such as 4'-diaminoterphenyl and 1,3-bis(aminophenoxy)benzene, and aliphatic diamines such as hexamethylene diamine and heptamethylene diamine. Examples of tetracarboxylic acids include 3, 3', 4,
4'-Benzophenonetetracarboxylic acid, 3,3',
4,4'-biphenyltetracarboxylic acid, 3,3',
Aromatic tetracarboxylic acids such as 4,4'-diphenyl ether tetracarboxylic acid, 1,2,3,4
Examples include aliphatic tetracarboxylic acids such as -butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. To further improve adhesion, a siloxane diamine such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane may be added to
It is also possible to incorporate up to 6 mol%. Next, an example of a method for producing the polyimide composition of the present invention will be explained. That is, the molar ratio of PMDA to DAS in the solvent is preferably 90 to 110 mol%,
More preferably at an equimolar blending ratio, -20°C to 100°C
A polyimide precursor ( ) of PMDA and DAS is produced by reacting with . Also, in a solvent
The molar ratio of PMDA to DAE is preferably 90~
110 mol%, more preferably an equimolar blending ratio, -
By reacting at 20℃ to 100℃, PMDA and
DAE polyimide precursor () can be produced. The polyimide precursor varnish of the present invention can be obtained by mixing the solutions of the polyimide precursors () and () produced as described above at a ratio (molar ratio) of 5/95 to 95/5. . As the solvent used in the above production method, it is preferable to use a polar solvent from the viewpoint of solubility of the polymer, and an aprotic polar solvent is particularly preferable. As the aprotic polar solvent, N-methyl-2-
pyrrolidone, N,N-dimethylformamide,
N,N-dimethylacetamide, hexamethylphosphorotriamide, dimethyl sulfoxide, γ-
Butyrolactone and the like are preferably used. Next, the varnish of the polyimide precursor obtained as described above is applied onto a suitable support, and heated at 50 to 100°C.
to obtain a polyimide precursor film. A polyimide film is obtained by chemically or thermally treating the polyimide precursor film thus obtained to undergo dehydration and ring closure. In the case of chemical treatment, a polyimide film is obtained by immersing a polyimide precursor film in a mixed solution of acetic anhydride and pyridine. In addition, when thermally processing the polyimide precursor film, the temperature can be increased stepwise by selecting several temperatures in the range from room temperature to 450°C, or by selecting a certain temperature range and increasing the temperature continuously. It is recommended that the treatment be carried out for 5 minutes to 5 hours. For example, 130℃, 200℃, 300℃, 400℃
Heat treatment for 30 minutes each, or from room temperature
The temperature may be increased linearly to 400°C over 2 hours. (Method for measuring properties) Young's modulus The method for measuring Young's modulus of the present invention is as follows:
Based on Z1702, a test piece with a sample width of 10 mm and a test length of 50 mm was
Measurements were made at a tensile rate of mm/min. At the same time, strength and elongation were calculated. Moisture-resistant adhesion A cutter is used to make 25 cuts in the polyimide film formed on a silicon wafer at 2 mm intervals, 6 in length and width, creating 25 grids. This is heated to 120℃.
Humid heat treatment is performed for a predetermined period of time under saturated steam at 2.0 atm. Attach cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) to this sample and
Peel off according to the method described in . [Examples] The present invention will be specifically described below based on Examples. Examples 1 to 3, Comparative Examples 1 and 2 104.7 g of PMDA and 100.1 g of DAE were heated at 30°C in 1182.1 g of N-methyl-2-pyrrolidone (NMP).
The reaction was carried out for 1 hour at 70°C, followed by 2 hours at 70°C, and
A polyimide precursor solution (1) with a measurement value of 30 poise at 25°C using a rotary viscometer was obtained. In addition, PMDA 107.9g and DAS 108.1g were added to NMP.
The reaction was carried out in 1227.4 g at 30°C for 1 hour and then at 70°C for 2 hours to obtain a polyimide precursor solution (2) with a measurement of 30 poise at 25°C using an E-type rotational viscometer. The polyimide precursor solutions (1) and (2) prepared as described above were mixed in the proportions shown in Table 1 to obtain a polyimide precursor blend solution. The obtained polyimide precursor blend solution was applied onto a silicon wafer using a spinner so that the thickness after imidization was 20μ±2μ. this
Polyimide films were obtained by heat treatment at 80°C, 200°C, 300°C, and 350°C for 30 minutes each, and their Young's modulus and strength/elongation properties were measured. The results are shown in Table 1. In Table 1, Examples 1 to 3 are polyimide compositions made of a mixture of the polyimide precursor () of the present invention and a polyimide precursor (), and Comparative Example 1 is a polyimide composition made only of the polyimide precursor (). , Comparative Example 2 is a polyimide precursor ()
This is the case of a polyimide composition consisting of only
【表】
表１から明らかなごとく、比較例１のポリイミ
ド前駆体（）のみからなるポリイミドの場合は
ヤング率が高いという欠点があり、また比較例２
のポリイミド前駆体（）のみからなるポリイミ
ドの場合は、強度、伸度が低く実用性能が劣ると
いう欠点がある。これに対して、実施例１〜３の
本発明のポリイミド組成物からなるフイルムは、
ヤング率が低い上、優れた強伸度特性を有するこ
とがわかる。
実施例 ４
PMDA 104.7ｇ、DAE 103.8ｇおよび１，３
−ビス（３−アミノプロピル）テトラメチルジシ
ロキサン5.0ｇをNMP 1227.9ｇ中で、30分で１
時間、続いて70℃で２時間反応を行い、Ｅ型回転
粘度計による25℃での測定が30ポイズのポリマー
溶液(3)を得た。
以上のようにして作成したポリマー溶液(3)を８
重量部とポリマー溶液(1)を２重量部混合撹拌して
所定のポリイミド前駆体溶液を得た。
得られたポリイミド前駆体のブレンド溶液をシ
リコンウエハー上にスピナーを用いてイミド化後
の厚さが20μ±2μとなるように塗布した。これを
80℃、200℃、300℃、350℃で各々30分づつ熱処
理してポリイミドのフイルムを得、ヤング率およ
び強伸度特性を測定した。
このフイルムは、ヤング率230Kg／mm2、強度13
Kg／mm2、伸度32％と良好な特性を示した。
また耐湿熱特性も良好で120℃、2.0気圧の耐湿
接着性試験で100時間後もセロテープによる剥離
は起らなかつた。
［発明の効果］
本発明のポリイミド組成物は、上述のごとく２
種の特定のポリイミド前駆体を特定の割合で配合
せしめたので、低ヤング率にして強度、伸度に優
れた高機能なポリイミドを得ることができたもの
である。[Table] As is clear from Table 1, the polyimide made only of the polyimide precursor () of Comparative Example 1 has the disadvantage of a high Young's modulus;
In the case of a polyimide made only of the polyimide precursor (), there is a drawback that the strength and elongation are low and the practical performance is poor. On the other hand, the films made of the polyimide compositions of the present invention in Examples 1 to 3 were
It can be seen that it has a low Young's modulus and excellent strength and elongation properties. Example 4 PMDA 104.7g, DAE 103.8g and 1,3
- 5.0 g of bis(3-aminopropyl)tetramethyldisiloxane in 1227.9 g of NMP in 30 minutes.
The reaction was then carried out at 70°C for 2 hours to obtain a polymer solution (3) with a measurement of 30 poise at 25°C using an E-type rotational viscometer. Polymer solution (3) prepared as above was added to 8
A predetermined polyimide precursor solution was obtained by mixing and stirring 2 parts by weight of the polymer solution (1). The obtained polyimide precursor blend solution was applied onto a silicon wafer using a spinner so that the thickness after imidization was 20μ±2μ. this
Polyimide films were obtained by heat treatment at 80°C, 200°C, 300°C, and 350°C for 30 minutes each, and their Young's modulus and strength/elongation properties were measured. This film has a Young's modulus of 230Kg/mm 2 and a strength of 13
It showed good properties with Kg/mm 2 and elongation of 32%. It also has good moisture and heat resistance properties, with no peeling caused by cellophane tape even after 100 hours in a moisture resistant adhesion test at 120°C and 2.0 atm. [Effect of the invention] As described above, the polyimide composition of the present invention has 2
By blending specific polyimide precursors in specific proportions, it was possible to obtain a highly functional polyimide with a low Young's modulus and excellent strength and elongation.
Claims (1)
ロメリツト酸二無水物を反応させて得られるポリ
イミド前駆体（）と、４，4′−ジアミノジフエ
ニルエーテルとピロメリツト酸二無水物を反応さ
せて得られるポリイミド前駆体（）との混合物
からなり、かつ該ポリイミド前駆体（）および
（）がモル比で（）／（）＝95／５〜５／95
となるように配合されてなるポリイミド組成物。1 Polyimide precursor () obtained by reacting 4,4'-diaminodiphenyl sulfide and pyromellitic dianhydride with 4,4'-diaminodiphenyl ether and pyromellitic dianhydride. It consists of a mixture with the obtained polyimide precursor (), and the molar ratio of the polyimide precursor () and () is ()/() = 95/5 to 5/95.
A polyimide composition that is formulated to have the following properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3042487A JPS63199238A (en) | 1987-02-12 | 1987-02-12 | Polyimide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3042487A JPS63199238A (en) | 1987-02-12 | 1987-02-12 | Polyimide composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5050892A Division JPH0578483A (en) | 1992-03-09 | 1992-03-09 | Polyimide copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63199238A JPS63199238A (en) | 1988-08-17 |
| JPH0553180B2 true JPH0553180B2 (en) | 1993-08-09 |
Family
ID=12303570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3042487A Granted JPS63199238A (en) | 1987-02-12 | 1987-02-12 | Polyimide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63199238A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113645A (en) * | 1995-10-17 | 1996-05-07 | Toray Ind Inc | Semiconductor-protecting polyimide film |
-
1987
- 1987-02-12 JP JP3042487A patent/JPS63199238A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63199238A (en) | 1988-08-17 |
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