JP2584634B2 - Manufacturing method of high molecular weight polyimide - Google Patents
Manufacturing method of high molecular weight polyimideInfo
- Publication number
- JP2584634B2 JP2584634B2 JP62195332A JP19533287A JP2584634B2 JP 2584634 B2 JP2584634 B2 JP 2584634B2 JP 62195332 A JP62195332 A JP 62195332A JP 19533287 A JP19533287 A JP 19533287A JP 2584634 B2 JP2584634 B2 JP 2584634B2
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- JP
- Japan
- Prior art keywords
- polyimide
- bismaleimide
- reaction
- molecular weight
- formula
- 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.)
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明はポリイミドの製造法に関する。さらに詳しく
はフィルム用等に好ましい高分子量ポリイミドの製造法
に関する 従来の技術 ビスマレイミドとジアミンを反応させポリイミドを製
造する方法は公知であり多くの報告がなされている。例
えばフランス国特許第1555564号及び特開昭46−3845号
等がある。前者は極性溶媒中または塊状で触媒の不存在
下にビスマレイミドとジアミンとを反応させる方法を、
一方後者は酸触媒の存在下、酸を溶媒として兼ねるかあ
るいは有機溶媒中で前記の両原料を反応させる方法をそ
れぞれ開示している。しかしながらこれ等に開示されて
いるポリイミドの製造法は比較的低分子量のポリイミド
を得ることを目的としたものであり、それらに開示され
た方法で得られたポリイミドはせいぜい200℃程度まで
の融点を有しており、これらは主として他の化合物例え
ばエポキシ樹脂等との組合せにより、成形加工した後30
0℃程度まで再加熱することにより不融不溶の高分子量
ポリイミドを得るのに適している。The present invention relates to a method for producing polyimide. More specifically, a conventional technique relating to a method for producing a high-molecular-weight polyimide which is preferable for films and the like A method for producing a polyimide by reacting bismaleimide and a diamine is known and many reports have been made. For example, there are French Patent No. 1555564 and JP-A-46-3845. The former is a method of reacting bismaleimide and diamine in a polar solvent or in the absence of a catalyst in a lump,
On the other hand, the latter discloses a method in which both the above-mentioned raw materials are reacted in the presence of an acid catalyst, both using an acid as a solvent or in an organic solvent. However, the polyimide production methods disclosed therein are intended to obtain polyimides having a relatively low molecular weight, and the polyimides obtained by the methods disclosed therein have a melting point of up to about 200 ° C at most. These are mainly used in combination with other compounds such as epoxy resins, etc.
It is suitable for obtaining insoluble and insoluble high molecular weight polyimide by reheating to about 0 ° C.
ところでポリイミドについてはフレキシブル配線基板
あるいは液晶の配向制御膜などフィルムとしての需要が
最近増大しているがフィルムを製造するためのワニスは
製膜時の作業性から適度の粘度が必要なことは衆知の通
りで、特に極めて薄いフィルムを得たい場合にはポリイ
ミドの含有量が小さくかつ粘度の高いワニスが必要であ
り、かかるワニスを得るためには高分子量のポリイミド
が必要である。前記した公知の製造法で得られたポリイ
ミドを使用したワニスは粘度が低く均一で薄いフィルム
を得るためのポリイミドとしては不適当なものである。By the way, the demand for polyimide as a film such as a flexible wiring board or a liquid crystal alignment control film has recently been increasing, but it is well known that a varnish for producing a film requires an appropriate viscosity due to workability during film formation. In particular, when it is desired to obtain a very thin film, a varnish having a low polyimide content and a high viscosity is required, and a high molecular weight polyimide is required to obtain such a varnish. A varnish using a polyimide obtained by the above-mentioned known production method is unsuitable as a polyimide for obtaining a uniform and thin film having a low viscosity.
また前記した特許等の実施例を見ると使用されている
ビスマレイミドは芳香核に置換基を有さないビスマレイ
ミドであり、芳香核に置換基を有するビスマレイミドを
用いたポリイミドの製造法については充分に検討されて
いるとは言えない。The bismaleimide used in the examples of the patents described above is a bismaleimide having no substituent on the aromatic nucleus, and a method for producing a polyimide using bismaleimide having a substituent on the aromatic nucleus is described below. It is not considered enough.
発明が解決しようとする問題点 成膜性に優れた高分子量のポリイミドの簡単な製造法
の確立が要望されている。Problems to be Solved by the Invention It is desired to establish a simple method for producing a high-molecular-weight polyimide having excellent film-forming properties.
問題点を解決するための手段 本発明者等は前記した問題点を解決すべく鋭意研究を
重ねた結果本発明に到った。すなわち本発明はクレゾー
ル溶媒中、式（１） （式（１）中、Ｒは を、Ａはメチル、エチル、メトキシ又はクロルを、又Ｂ
は水素又はＡと同じ意味をそれぞれ表す） で示されるビスマレイミドと式（２） （式（２）中、Ｙは−Ｏ−又は−CH2−を、又Ｃ及びＤ
はそれぞれ独立に水素、メチル又はエチルを表す） で示されるジアミンを該ビスマレイミドとジアミンの総
重量の１〜10重量％の酸触媒の存在下、50〜65℃で反応
させることを特徴とする高分子量ポリイミドの製造法を
提供する。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have arrived at the present invention. That is, the present invention provides a compound of the formula (1) (In the formula (1), R is A is methyl, ethyl, methoxy or chloro;
Represents the same meaning as hydrogen or A) and a bismaleimide represented by the formula (2): (In the formula (2), Y represents —O— or —CH 2 —, and C and D
Each independently represents hydrogen, methyl or ethyl) wherein bismaleimide is reacted at 50 to 65 ° C. in the presence of an acid catalyst in an amount of 1 to 10% by weight based on the total weight of the diamine. Provided is a method for producing a high molecular weight polyimide.
本発明の製法につき詳細に説明する。 The production method of the present invention will be described in detail.
本発明の製法はクレゾール溶媒中好ましくは窒素ガス
のような不活性ガス雰囲気下で行われる。ポリイミドを
製造する際に通常使用されるジメチルホルムアミド、Ｎ
−メチルピロリドン等の極性溶媒は高分子量のポリイミ
ドを得るためには不適当であり、クレゾールが最も好ま
しい溶媒である。The process of the present invention is carried out in a cresol solvent, preferably under an inert gas atmosphere such as nitrogen gas. Dimethylformamide, commonly used in producing polyimide, N
Polar solvents such as -methylpyrrolidone are unsuitable for obtaining high molecular weight polyimides, and cresol is the most preferred solvent.
クレゾールはオルソクレゾール、パラクレゾール、メ
タクレゾールあるいはo,m,p−の混合クレゾールのいず
れでも良くその使用量は、任意であるが通常ビスマレイ
ミドとジアミンの総重量の３〜10倍量好ましくは３〜６
倍量である。反応に使用する酸触媒としては塩酸等の鉱
酸又は酢酸、プロピオン酸等の脂肪族カルボン酸等を用
いることができるが、中でも酢酸が最も好ましい触媒で
ある。その使用量はビスマレイミドとジアミンの総重量
の１〜10重量％である。The cresol may be any of ortho-cresol, para-cresol, meta-cresol or a mixed cresol of o, m, p-, and the amount of cresol used is arbitrary, but is usually 3 to 10 times the total weight of bismaleimide and diamine, and preferably 3 to 10 times. ~ 6
Double the amount. As the acid catalyst used in the reaction, a mineral acid such as hydrochloric acid or acetic acid, or an aliphatic carboxylic acid such as propionic acid can be used. Among them, acetic acid is the most preferable catalyst. The amount used is 1 to 10% by weight of the total weight of bismaleimide and diamine.
本発明で使用されるビスマレイミドの例としてはジ
（３−メチル−４−Ｎ−マレイミドフエニル）メタン、
ジ（３−エチル−４−Ｎ−マレイミドフエニル）メタ
ン、ジ（3,5−ジエチル−４−Ｎ−マレイミドフエニ
ル）メタン、ジ（３−エチル−５−メチル−４−Ｎ−マ
レイミドフエニル）メタン、N,N′−（3,3′−ジメチル
−4,4′−ビフエニレン）ビスマレイミド、N,N′−（3,
3′−ジメトキシ−4,4′−ビフエニレン）ビスマレイミ
ド、N,N′−（3,3′−ジクロル−4,4′−ビフエニレ
ン）ビスマレイミド、N,N′−（3,3′,5,5′−テトラメ
チル−4,4′−ビフエニレン）ビスマレイミド等があげ
られる。これ等のビスマレイミドは公知の方法例えば特
公昭49−40231の方法によって安易に製造することがで
きる。Examples of the bismaleimide used in the present invention include di (3-methyl-4-N-maleimidophenyl) methane,
Di (3-ethyl-4-N-maleimidophenyl) methane, di (3,5-diethyl-4-N-maleimidophenyl) methane, di (3-ethyl-5-methyl-4-N-maleimide) Enyl) methane, N, N '-(3,3'-dimethyl-4,4'-biphenylene) bismaleimide, N, N'-(3,
3'-dimethoxy-4,4'-biphenylene) bismaleimide, N, N '-(3,3'-dichloro-4,4'-biphenylene) bismaleimide, N, N'-(3,3 ', 5 , 5'-tetramethyl-4,4'-biphenylene) bismaleimide and the like. These bismaleimides can be easily produced by a known method, for example, the method of JP-B-49-40231.
また、本発明で使用されるジアミンの例としては、4,
4′−ジアミノジフエニルメタン、4,4′−ジアミノジフ
エニルエーテル、メチレンビス（オルソトルイジン）、
メチレンビス（オルソエチルアニリン）、メチレンビス
（2,6−ジエチルアニリン）、メチレンビス（２−エチ
ル−６−エチルアニリン）等があげられる。Examples of the diamine used in the present invention include 4,4
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, methylenebis (orthotoluidine),
Examples include methylene bis (orthoethylaniline), methylenebis (2,6-diethylaniline), and methylenebis (2-ethyl-6-ethylaniline).
ビスマレイミド対ジアミンの使用モル比は0.9〜1.1で
あり、等モル（モル比1.0）で使用するのが最も好まし
い。The molar ratio of bismaleimide to diamine used is from 0.9 to 1.1, most preferably in equimolar (molar ratio 1.0).
本発明の製造法における反応温度は50〜65℃、さらに
好ましくは50〜60℃である。この反応温度より高い温度
で反応を行うと低い重合度で反応が停止してしまいもは
やそれ以上反応が進行せず、一方反応温度が50℃より低
いと反応時間が極端に長くなる。このような事実は今ま
でにまったく予想されなかった全く新しい知見である。The reaction temperature in the production method of the present invention is 50 to 65 ° C, more preferably 50 to 60 ° C. If the reaction is carried out at a temperature higher than this reaction temperature, the reaction stops at a low degree of polymerization and the reaction no longer proceeds, while when the reaction temperature is lower than 50 ° C., the reaction time becomes extremely long. Such facts are completely new findings that have never been expected before.
本発明の製造法における反応時間は反応条件によって
も異なるが通常50〜150時間である。また本発明の製造
法で得られるポリイミドは重量平均分子量で８万〜15万
の分子量を有したポリイミドである。The reaction time in the production method of the present invention varies depending on the reaction conditions, but is usually 50 to 150 hours. The polyimide obtained by the production method of the present invention is a polyimide having a weight average molecular weight of 80,000 to 150,000.
本発明で得られたポリイミドは反応液そのままで又必
要であれば反応液をメタノール等にとり再沈澱させ乾燥
後Ｎ−メチルピロリドン等の極性溶媒に溶解しワニスと
してフィルムあるいは電線等の被膜として利用できる。The polyimide obtained in the present invention can be used as a varnish as a coating of a film or an electric wire as a varnish after dissolving in a polar solvent such as N-methylpyrrolidone after drying and reprecipitating the reaction solution in methanol or the like, if necessary, and reprecipitating and drying the reaction solution. .
本発明の製造法でえられるポリイミドは分子量が十分
にたかいのでフィルム用、成膜用としてすぐれている。Since the polyimide obtained by the production method of the present invention has a sufficiently high molecular weight, it is excellent for film and film formation.
実施例 以下実施例により本発明の製造法を具体的に説明す
る。EXAMPLES Hereinafter, the production method of the present invention will be specifically described with reference to examples.
実施例1. 500mlコルベンにメタクレゾール200ml、N,N′−（3,
3′−ジメチル−4,4′−ビフエニレンビスマレイミド3
7.2g、4,4′−ジアミノジフエニルエーテル20.0g及び酢
酸2.0gを加え撹拌下、窒素ガスを吹き込みながら60℃に
昇温し、同温度で６日間（144時間）反応させた。その
間少量の反応液をサンプリングして反応時間と粘度の関
係を調べた。その結果を第１図に示す。反応後反応液を
２のメタノール中に注ぎ込み沈澱させ析出した結晶を
取乾燥してポリイミド55gを得たこれは理論収率の96.
2％であり、又その対数粘度は、メタクレゾール中30℃
で1.01（dl/g）であった。Example 1. 200 ml of metacresol was added to 500 ml of colben, and N, N '-(3,
3'-dimethyl-4,4'-biphenylenebismaleimide 3
7.2 g, 2,4 g of 4,4'-diaminodiphenyl ether and 2.0 g of acetic acid were added, and the mixture was heated to 60 ° C. while blowing nitrogen gas with stirring, and reacted at the same temperature for 6 days (144 hours). During that time, a small amount of the reaction solution was sampled to examine the relationship between the reaction time and the viscosity. The result is shown in FIG. After the reaction, the reaction solution was poured into methanol (2) and precipitated. The precipitated crystals were dried to obtain 55 g of polyimide, which had a theoretical yield of 96.
2% and its logarithmic viscosity is 30 ° C in metacresol
Was 1.01 (dl / g).
比較例1. 実施例１において反応温度を100℃とした以外はすべ
て実施例１と同様にして反応させた時の反応時間と粘度
の関係を第１図に示した。第１図から明らかなように10
0℃での反応では、対数粘度が上昇せず重合が頭打ちに
なっている。Comparative Example 1. FIG. 1 shows the relationship between the reaction time and the viscosity when the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 100 ° C. As is clear from FIG.
In the reaction at 0 ° C., the logarithmic viscosity did not increase and the polymerization leveled off.
実施例2. 実施例１においてN,N′−（3,3′−ジメチル−4,4′
−ビフエニレン）ビスマレイミド37.2gの代りにジ（３
−メチル−４−Ｎ−マレイミドフエニル）メタン38.6g
を用いる他は実施例１と同様にして55℃で６日間（144
時間）反応させた。２のメタノール中に反応液を加え
目的物を沈澱させ、析出した結晶を取した。ポリイミ
ドの収量は57gで定量的収率であった。このポリイミド
の対数粘度は0.90（dl/g）であった。Example 2 In Example 1, N, N '-(3,3'-dimethyl-4,4'
-(Biphenylene) bismaleimide instead of 37.2g di (3)
-Methyl-4-N-maleimidophenyl) methane 38.6 g
6 days at 55 ° C. (144
Time). The reaction solution was added to methanol of No. 2 to precipitate the desired product, and the precipitated crystals were collected. The yield of the polyimide was 57 g, which was a quantitative yield. The logarithmic viscosity of this polyimide was 0.90 (dl / g).
実施例3. 実施例１においてN,N′−（3,3′−ジメチル−4,4′
−ジフエニレン）ビスマレイミド37.2gの代りにジ（3,5
−ジエチル−４−Ｎ−マレイミドフエニル）メタン47.0
gを用いる他は実施例１と同様にして60℃で５日間（120
時間）反応させた。実施例１と同様に処理して67.0g
（収率100％）のポリイミドを得た。このポリイミドの
対数粘度はメタクレゾール中30℃で0.85（dl/g）であっ
た。Example 3 In Example 1, N, N '-(3,3'-dimethyl-4,4'
-Diphenylene) bismaleimide instead of 37.2g di (3,5
-Diethyl-4-N-maleimidophenyl) methane 47.0
g at 60 ° C. for 5 days (120 g
Time). 67.0g processed in the same manner as in Example 1.
(Yield 100%) polyimide was obtained. The logarithmic viscosity of this polyimide was 0.85 (dl / g) at 30 ° C. in metacresol.
実施例4. 実施例１においてN,N′−（3,3′−ジメチル−4,4′
−ジフエニレン）ビスマレイミド37.2gの代りにN,N′−
（3,3′−ジメトキシ−4,4′−ジフエニレン）ビスマレ
イミド40.4gを、また4,4′−ジアミノジフエニルエーテ
ルの代りにメチレンジ（オルソエチルアニリン）25.4g
を用いる他は実施例１と同様の条件で反応及び処理を行
い65g（収率98.8％）のポリイミドを得た。このポリイ
ミドの対数粘度は実施例１と同一条件で0.95（dl/g）で
あった。Example 4. In Example 1, N, N '-(3,3'-dimethyl-4,4'
-N, N'- in place of 37.2 g of diphenylene) bismaleimide
40.4 g of (3,3'-dimethoxy-4,4'-diphenylene) bismaleimide and 25.4 g of methylene di (orthoethylaniline) in place of 4,4'-diaminodiphenyl ether
The reaction and treatment were carried out under the same conditions as in Example 1 except for using, to obtain 65 g (yield 98.8%) of polyimide. The logarithmic viscosity of this polyimide was 0.95 (dl / g) under the same conditions as in Example 1.
実施例5. 実施例１においてN,N′−（3,3′−ジメチル−4,4′
−ジフエニレン）ビスマレイミド37.2gの代りにジ（３
−エチル−４−Ｎ−マレイミドフエニル）メタン41.2g
を、また4,4′−ジアミノジフエニルエーテルの代りに
4,4′−ジアミノジフエニルメタン19.8gを用いる他は実
施例１と同様にして55℃で４日間（96時間）反応させ
た。実施例１と同様な処理を施して、61g（収率100％）
のポリイミドを得た。このポリイミドの対数粘度は、メ
タクレゾール中30℃で0.81（dl/g）であった。Example 5. In Example 1, N, N '-(3,3'-dimethyl-4,4'
-Diphenylene) bismaleimide instead of 37.2g di (3)
-Ethyl-4-N-maleimidophenyl) methane 41.2 g
And in place of 4,4'-diaminodiphenyl ether
The reaction was carried out at 55 ° C for 4 days (96 hours) in the same manner as in Example 1 except that 19.8 g of 4,4'-diaminodiphenylmethane was used. The same treatment as in Example 1 was performed to give 61 g (100% yield).
Of polyimide was obtained. The logarithmic viscosity of this polyimide was 0.81 (dl / g) at 30 ° C. in metacresol.
実施例6. 実施例１においてN,N′−（3,3′−ジメチル−4,4′
−ジフエニレン）ビスマレイミド37.2gの代りにN,N′−
（3,3′,5,5′−テトラメチル−4,4′−ジフエニレン）
ビスマレイミド40.0gを用いる他は実施例１と同様にし
て60℃で３日間（72時間）反応させた。実施例１と同様
な処理を施して60gのポリイミドを得た（収率100％）。
実施例１と同様に測定した対数粘度は0.55（dl/g）であ
った。Example 6. In Example 1, N, N '-(3,3'-dimethyl-4,4'
-N, N'- in place of 37.2 g of diphenylene) bismaleimide
(3,3 ', 5,5'-tetramethyl-4,4'-diphenylene)
The reaction was carried out at 60 ° C. for 3 days (72 hours) in the same manner as in Example 1 except that 40.0 g of bismaleimide was used. The same treatment as in Example 1 was performed to obtain 60 g of a polyimide (100% yield).
The logarithmic viscosity measured in the same manner as in Example 1 was 0.55 (dl / g).
発明の効果 フィルム成型、成膜にすぐれた高分子量ポリイミドの
簡便な製造法が確立された。Effect of the Invention A simple method for producing a high-molecular-weight polyimide excellent in film molding and film formation has been established.
第１図は実施例１及び比較例１における反応時間と対数
粘度との関係を示す。同図においてＡは実施例１におい
て、又Ｂは比較例１においてえられた反応時間と対数粘
度との関係を示す。FIG. 1 shows the relationship between the reaction time and the logarithmic viscosity in Example 1 and Comparative Example 1. In the same figure, A shows the relationship between the reaction time and the logarithmic viscosity obtained in Example 1 and B shows the relationship between the logarithmic viscosity obtained in Comparative Example 1.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−93159（ＪＰ，Ａ) 特開 昭62−50331（ＪＰ，Ａ) 特開 昭62−99358（ＪＰ，Ａ) 特開 昭63−289037（ＪＰ，Ａ) 特開 昭63−289036（ＪＰ，Ａ) 特開 昭63−77938（ＪＰ，Ａ) 特開 昭63−156827（ＪＰ，Ａ) 特公 昭48−43675（ＪＰ，Ｂ１) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-93159 (JP, A) JP-A-62-50331 (JP, A) JP-A-62-99358 (JP, A) JP-A-63-93 289037 (JP, A) JP-A-63-289036 (JP, A) JP-A-63-77938 (JP, A) JP-A-63-156827 (JP, A) JP-B-48-43675 (JP, B1)
Claims (1)
は水素又はＡと同じ意味をそれぞれ表す） で示されるビスマレイミドと式（２） （式（２）中、Ｙは−Ｏ−又は−CH2−を、Ｃ及びＤは
それぞれ独立に水素、メチル又はエチルをそれぞれ表
す） で示されるジアミンを該ビスマレイミドとジアミンの総
重量の１〜10重量％の酸触媒の存在下、50〜65℃で反応
させることを特徴とする高分子量ポリイミドの製造法1. A compound of the formula (1) in a cresol solvent. (In the formula (1), R is A is methyl, ethyl, methoxy or chloro;
Represents the same meaning as hydrogen or A) and a bismaleimide represented by the formula (2): (In the formula (2), Y represents —O— or —CH 2 —, and C and D each independently represent hydrogen, methyl or ethyl). The diamine represented by the formula (1) is defined as 1% of the total weight of the bismaleimide and the diamine. A method for producing a high molecular weight polyimide, wherein the reaction is carried out at 50 to 65 ° C. in the presence of an acid catalyst of 10 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62195332A JP2584634B2 (en) | 1987-08-06 | 1987-08-06 | Manufacturing method of high molecular weight polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62195332A JP2584634B2 (en) | 1987-08-06 | 1987-08-06 | Manufacturing method of high molecular weight polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6440529A JPS6440529A (en) | 1989-02-10 |
| JP2584634B2 true JP2584634B2 (en) | 1997-02-26 |
Family
ID=16339410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62195332A Expired - Fee Related JP2584634B2 (en) | 1987-08-06 | 1987-08-06 | Manufacturing method of high molecular weight polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2584634B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02274731A (en) * | 1989-04-17 | 1990-11-08 | Sumitomo Bakelite Co Ltd | Production of amine-modified maleimide resin |
| JPH0747638B2 (en) * | 1989-05-12 | 1995-05-24 | 松下電工株式会社 | Manufacturing method of laminated board for printed wiring board |
| JPH02298918A (en) * | 1989-05-12 | 1990-12-11 | Toppan Printing Co Ltd | Liquid crystal display element |
| JPH0431435A (en) * | 1990-05-28 | 1992-02-03 | Matsushita Electric Works Ltd | Addition type imide resin prepolymer and resin film prepared therefrom |
| JPH04202323A (en) * | 1990-11-29 | 1992-07-23 | Nitto Denko Corp | Powder composition for electrical insulation |
| TWI401252B (en) * | 2010-06-22 | 2013-07-11 | Chi Mei Corp | Liquid-crystal alignment formulation, and liquid-crystal aligning film and liquid-crystal display element prepared by using the same |
| CN102344816B (en) * | 2010-08-03 | 2014-02-19 | 奇美实业股份有限公司 | Liquid crystal aligning agent, liquid crystal aligning film prepared by using same and liquid crystal display element prepared by using liquid crystal aligning agent |
| TWI658068B (en) * | 2018-02-26 | 2019-05-01 | 臺灣塑膠工業股份有限公司 | Method of forming polymer for lithium battery, electrolyte and lithium battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS519630B2 (en) * | 1971-10-04 | 1976-03-29 | ||
| JPH0696638B2 (en) * | 1984-10-15 | 1994-11-30 | 三菱油化株式会社 | Method for manufacturing heat resistant material |
| JPS6250331A (en) * | 1985-08-29 | 1987-03-05 | Mitsubishi Petrochem Co Ltd | Heat-resistant resin composition |
| JPS6299358A (en) * | 1985-10-24 | 1987-05-08 | Mitsubishi Petrochem Co Ltd | Novel bismaleimide |
-
1987
- 1987-08-06 JP JP62195332A patent/JP2584634B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6440529A (en) | 1989-02-10 |
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