JP3551030B2 - Polyamic acid solution giving low moisture absorption polyimide and process for preparing polyimide - Google Patents
Polyamic acid solution giving low moisture absorption polyimide and process for preparing polyimide Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
この発明は、新規な低吸湿ポリイミドおよびポリアミック酸溶液に関し、さらに詳しくは３，３’，４，４’−ビフェニルテトラカルボン酸二無水物や２，３，３’，４’−ビフェニルテトラカルボン酸二無水物などのビフェニルテトラカルボン酸類と４，４’−ビス（４−アミノフェノキシ）ビフェニルとを重合、イミド化して得られる低吸湿のポリイミドおよびそのポリアミック酸溶液に関するものである。
【０００２】
【従来の技術】
従来、公知の芳香族テトラカルボン酸二無水物と芳香族ジアミンとを用いて製造されている芳香族ポリイミドは、耐熱性や電気絶縁性は優れているものの吸湿率が高いことが知られている。
例えば、一般的に使用されているピロメリット酸二無水物と４，４’−ジアミノジフェニルエ−テルとから得られるポリイミドフィルムでは吸湿率が２−２．５％（２５℃、８０Ｒ．Ｈ．）程度であり、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物とパラフェニレンジアミンとから得られるポリイミドフィルムでは吸湿率が１．５−２％（２５℃、８０Ｒ．Ｈ．）程度である。
【０００３】
また、吸湿率が１％以下であるポリイミドとして、２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパンや２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕ヘキサフルオロプリパンなどと３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物やピロメリット酸二無水物とを重合、イミド化して得られるポリイミドが特公平３−１５３４０号公報に記載されている。
しかし、これらの低吸湿ポリイミドといわれるものも、吸湿率が０．５％程度であり、さらに低吸湿率のポリイミドが求められる。
【０００４】
【発明が解決しようとする課題】
この発明の目的は、耐熱性を有しかつ低吸湿率の芳香族ポリイミドを与えるポリアミック酸溶液およびポリイミドの製法を提供することである。
【０００５】
【課題を解決するための手段】
すなわち、この発明は、有機溶媒中に３，３ ' ，４，４ ' −または２，３，３ ' ，４ ' −ビフェニルテトラカルボン酸、その酸エステルまたはその酸二無水物と４，４ ' −ビス（４−アミノフェノキシ）ビフェニルとを重合して得られるポリアミック酸を５−５０重量％含有し、ポリアミック酸のアミック酸単位に対して０．０１−２５モル％のイミド化触媒を添加してなるポリアミック酸溶液に関するものである。
また、この発明は、前記のポリアミック酸溶液を基材に塗布し、加熱乾燥するポリイミドの製法に関するものである。
【０００８】
この明細書において吸湿率とは、５０℃で２４時間乾燥させた乾燥状態のフィルムを、一定の湿度条件（２５℃、８０％Ｒ．Ｈ．）で飽和させ、その前後の重量変化から次式により求められるものである。
この発明のポリイミドは、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（特に好ましい。）や２，３，３’，４’−ビフェニルテトラカルボン酸二無水物などのビフェニルテトラカルボン酸類と４，４’−ビス（４−アミノフェノキシ）ビフェニルとを有機極性溶媒中で重合させたポリアミック酸溶液（ポリアミック酸の割合が溶液中５重量％以上５０重量％以下、好ましくは１０重量％以上３０重量％以下）を支持体または基板上に塗布し、加熱・乾燥しイミド化して得ることができる。
【００１０】
前記のポリアミック酸溶液は、芳香族カルボン酸二無水物成分と芳香族ジアミン成分とをそれぞれ等モル量反応させてもよく、いずれかを酸過剰またはジアミン過剰にしてもよい。
この場合、テトラカルボン酸二無水物／ジアミン（モル比）が、１．０５−０．９５の範囲内であることが好ましい。
【００１１】
この発明においては、芳香族テトラカルボン酸成分として３，３’，４，４’−ビフェニルテトラカルボン酸、２，３，３’，４’−ビフェニルテトラカルボン酸またはこれらの酸のエステルまたは酸の二無水物を、芳香族ジアミン成分として４，４’−ビス（４−アミノフェノキシ）ビフェニルをそれぞれ使用することが必要あり、さらに他の物性に悪影響を及ぼさない範囲で他のジアミン成分、例えば２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン、２，２−ビス〔４−（３−アミノフェノキシ）フェニル〕プロパン、２，２−ビス〔４−（３−アミノフェノキシ）フェニル〕ヘキサフルオロプロパン、４，４’−ジアミノジフェニルスルフィド、４，４’−ジアミノジフェニルメタンなどの芳香族ジアミン、ビス（３−アミノプロピル）テトラメチルジシロキサンなどのジアミノシロキサンや他の芳香族テトラカルボン酸成分、例えば３，３’，４，４’−ビフェニルエ−テルテトラカルボン酸二無水物、ピロメリット酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物などを使用してもよい。
これらの他の芳香族テトラカルボン酸成分およびジアミン成分は、全テトラカルボン酸成分およびジアミン成分中それぞれ４０モル％以下であることが好ましい。
【００１２】
また、ポリアミック酸溶液に、ポリアミック酸のアミン末端を封止するため、ジカルボン酸無水物、例えば無水フタル酸およびその置換体（例えば３−メチル又は４−メチルフタル酸無水物）、ヘキサヒドロ無水フタル酸およびその置換体、無水コハク酸およびその置換体などを添加してもよい。
【００１３】
前記のポリアミック酸を得るために使用する有機溶媒は、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、Ｎ，Ｎ−ジエチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホルアミド、Ｎ−メチルカプロラクタムなどが挙げられる。これらの有機溶媒は単独で用いてもよく、２種以上を併用してもよい。
【００１４】
この発明のポリアミック酸溶液は、前記各成分を使用し、前記のジアミン成分とテトラカルボン酸二無水物とを、それぞれ有機溶媒中で０−１００℃、好ましくは５−５０℃程度の温度で重合させてポリアミック酸の溶液（均一な溶液状態が保たれていれば一部がイミド化されていてもよい）とし、そのまま、あるいは一旦ポリアミック酸を分離した後有機溶媒（前記の有機溶媒と同一でもよく、あるいはテトラヒドロフランやジエチレングリコ−ルジメチルエ−テルのように低沸点含酸素有機溶媒でもよい。）に溶解して得ることができる。
【００１５】
この発明のポリアミック酸溶液には、ポリアミック酸のアミック酸単位に対して０．０１モル％以上、特に０．１モル％以上で、５０モル％以下、特に２５モル％以下のイミド化触媒、例えば、ピリジン、ピコリン類、イミダゾ−ル類、キノリン類、トリエチルアミンなどを添加することが好ましい。
また、この発明のポリアミック酸溶液には、無機フィラ−、導電性フィラ−、無機・有機顔料などを添加してもよい。
【００１６】
この発明のポリイミドは、前記のポリアミック酸溶液を基材に塗布し、加熱乾燥して得ることができる。
この発明のポリイミドは、コ−ティング膜やフィルム（未キュアフィルムをピンテンタ−などを使用して熱処理する。）のいずれにも適用可能である。
好適には、ガラス基板、炭素基板やシリコンウエハ−に直接（これらの表面はアミノシランカップリング剤、エポキシシランカップリング剤、メルカプトシランカップリング剤などのカップリング剤で処理しておいてもよい。）、あるいは有機あるいは無機膜を形成した後、その表面に前記のポリアミック酸溶液をスピンコ−トなどによって、厚み１−５００μｍに塗布し、５０−３００℃、好ましくは７５−３００℃程度の温度で５−３００分程度、好適には多段加熱（例えば７５℃以上１２５℃未満で１−１２０分、１２５℃以上２００℃未満で１−１２０分、２００℃以上２５０℃未満で０．１−１２０分、２５０℃以上３００℃以下で０．１−６０分それぞれの段で加熱のうち、３段以上を組み合わせ）によって加熱・乾燥してポリイミド膜を得ることができる。
【００１７】
【実施例】
以下、この発明を実施例および比較例によりさらに詳細に説明する。
また、ポリイミドフィルムの評価は次の試験方法による。
ポリイミドフィルムを５０℃の熱風乾燥機中で２４時間乾燥させ、１０ｃｍ×１０ｃｍの大きさにして秤量したのち、２５℃、８０％Ｒ．Ｈ．に湿度調整された恒温恒湿装置内に２４時間放置して秤量し、重量変化から吸湿率を求めた。
また、熱分析装置によりガラス転移温度を測定し、ＡＳＴＭ Ｄ８８２によって伸びおよび弾性率を測定した。
【００１８】
実施例１（参考のため示す）
撹拌機を備えた５００ｍｌのフラスコに４，４'−ビス（４−アミノフェノキシ）ビフェニル（０．１モル）及び反応溶媒としてＮ−メチル−２−ピロリドン（使用料は固形分濃度が１８重量％となる量）を加え、室温で撹拌溶解させた。これに３，３'，４，４'−ビフェニルテトラカルボン酸二無水物（０．１モル）を徐々に加え、室温（２５℃）で５時間撹拌した。この間、反応時間の経過と共にポリアミック酸反応液の粘度は上昇し、５時間撹拌後の反応液の粘度は１６００ポイズであった。得られたポリアミック酸溶液をガラス板上に塗布して被膜を形成し、熱風乾燥機中で８０−３００℃に段階的に昇温させて熱処理して５０±５μｍ厚さのポリイミドフィルムを得た。このポリイミドフィルムについて評価した結果、吸湿率が０．２２％で、ガラス転移温度が２６９℃で、伸びが３１％で、弾性率が３９９ｋｇ／ｍｍ2 であった。
【００１９】
実施例２
ポリアミック酸溶液１００重量部に対して０．２７５重量部の割合（ポリアミック酸のユニットに対して１０モル％）で１，２−ジメチルイミダゾ−ルを添加・溶解させた他は、実施例１と同様に実施した。
このポリイミドフィルムは、吸湿率がほとんど変わらず、伸びが６８％と改良された。
【００２０】
比較例１
４，４’−ジアミノジフェニルエ−テル、３，３’、４，４’−ビフェニリテトラカルボン酸二無水物およびＮ−メチル−２−ピロリドンを使用し実施例１と同様にして得たポリアミック酸溶液を、８０−４５０℃で熱処理してポリイミドフィルムを得た。
このポリイミドフィルムは、吸湿率が１．８％で、ガラス転移温度が２８５℃であった。
【００２１】
比較例２
２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン、３，３’，４，４’−ビフェニリテトラカルボン酸二無水物およびＮ−メチル−２−ピロリドンを使用し実施例１と同様にして得たポリアミック酸溶液を、８０−３００℃で熱処理してポリイミドフィルムを得た。
このポリイミドフィルムは、吸湿率が０．３３％で、ガラス転移温度が２４６℃であった。
【００２２】
実施例３（参考のため示す）
３，３'，４，４'−ビフェニルテトラカルボン酸二無水物、４，４'−ビス（４−アミノフェノキシ）ビフェニル及び反応溶媒としてＮ−メチル−２−ピロリドンを使用して重合し、固形分濃度１８重量％、粘度が５０ポイズのポリアミック酸溶液を得た。これを、アルミニウム（Ａｌ）箔、ＳＵＳ、銅箔に乾燥膜厚みが３０μｍとなるようにキャストし、最高温度３００℃（８０℃ｘ１０分、１３０℃ｘ１０分、１８０℃ｘ１０分、２５０℃ｘ１０分、３００℃ｘ１０分）でキュアした。得られたサンプルについて９０°剥離、及び１８０°剥離させた。結果は次のようになった。剥離強度を示す。
Ａｌ ３００ｇ／ｃｍ（１８０°剥離）、７００ｇ／ｃｍ（９０°剥離）
ＳＵＳ ６００ｇ／ｃｍ（１８０°剥離）、８５０ｇ／ｃｍ（９０°剥離）
銅（光沢面） １５０ｇ／ｃｍ（９０°剥離）
銅（マット面）剥離せず
また、ガラス基板上にアミノシランカップリング剤で処理した後、同様にキャストしてキュアした。碁盤目剥離試験では剥離は全く認められず、水中に浸けても剥離しなかった。なお、各サンプルの吸湿率、他の物性は実施例１のものと同等であった。
【００２３】
【発明の効果】
この発明のポリイミドは、機械的物性および耐熱性が良好で、しかも従来公知の低吸湿ポリイミドに比べてさらに低吸湿率である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel low moisture absorption polyimide and polyamic acid solution, and more particularly, to 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 2,3,3', 4'-biphenyltetracarboxylic acid The present invention relates to a low moisture-absorbing polyimide obtained by polymerizing and imidizing biphenyltetracarboxylic acids such as dianhydride and 4,4′-bis (4-aminophenoxy) biphenyl, and a polyamic acid solution thereof.
[0002]
[Prior art]
Conventionally, aromatic polyimides manufactured using a known aromatic tetracarboxylic dianhydride and an aromatic diamine are known to have high heat absorption and high electrical absorption, but high moisture absorption. .
For example, a polyimide film obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether, which are generally used, has a moisture absorption of 2-2.5% (at 25 ° C., 80 RH). ), And a polyimide film obtained from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and paraphenylenediamine has a moisture absorption of 1.5-2% (25 ° C., 80 RH). ).
[0003]
In addition, as a polyimide having a moisture absorption of 1% or less, 2,2-bis [4- (4-aminophenoxy) phenyl] propane or 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropril A polyimide obtained by polymerizing bread and the like with 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride or pyromellitic dianhydride and imidizing is described in JP-B-3-15340. .
However, these low moisture absorption polyimides also have a moisture absorption of about 0.5%, and further require a polyimide having a low moisture absorption.
[0004]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamic acid solution and a method for producing polyimide, which provide an aromatic polyimide having heat resistance and low moisture absorption.
[0005]
[Means for Solving the Problems]
That is, the present invention is in an organic solvent of 3,3 ', 4,4' - or 2,3,3 ', 4' - biphenyltetracarboxylic acid, its ester or its dianhydride and 4,4 ' Polyamic acid obtained by polymerizing -bis (4-aminophenoxy) biphenyl is contained in an amount of 5 to 50% by weight, and an imidization catalyst is added in an amount of 0.01 to 25 mol% based on the amic acid unit of the polyamic acid. The present invention relates to a polyamic acid solution comprising:
The present invention also relates to a method for producing a polyimide in which the above-mentioned polyamic acid solution is applied to a substrate and dried by heating .
[0008]
In this specification, the moisture absorption means that a film in a dry state dried at 50 ° C. for 24 hours is saturated under a constant humidity condition (25 ° C., 80% RH), and the weight change before and after the saturation is expressed by the following formula. Is required by
The polyimide of the present invention may be a biphenyltetracarboxylic acid such as 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (particularly preferable) or 2,3,3', 4'-biphenyltetracarboxylic dianhydride. Polyamic acid solution obtained by polymerizing carboxylic acids and 4,4'-bis (4-aminophenoxy) biphenyl in an organic polar solvent (the ratio of polyamic acid is 5% by weight or more and 50% by weight or less, preferably 10% by weight in the solution) % Or more and 30% by weight or less) on a support or a substrate, followed by heating, drying and imidization.
[0010]
In the polyamic acid solution, the aromatic carboxylic dianhydride component and the aromatic diamine component may be reacted with each other in an equimolar amount, or either of them may be in excess of acid or in excess of diamine.
In this case, the tetracarboxylic dianhydride / diamine (molar ratio) is preferably in the range of 1.05 to 0.95.
[0011]
In the present invention, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid or an ester or acid of these acids is used as the aromatic tetracarboxylic acid component. It is necessary to use 4,4'-bis (4-aminophenoxy) biphenyl as an aromatic diamine component for the dianhydride, and further, other diamine components such as 2 as long as they do not adversely affect other physical properties. , 2-Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl Aromatic diamines such as hexafluoropropane, 4,4'-diaminodiphenyl sulfide, and 4,4'-diaminodiphenylmethane, bis (3-amino Propyl) diaminosiloxanes such as tetramethyldisiloxane and other aromatic tetracarboxylic acid components such as 3,3 ′, 4,4′-biphenylethertetracarboxylic dianhydride, pyromellitic dianhydride and 3 , 3 ', 4,4'-benzophenonetetracarboxylic dianhydride may be used.
The content of these other aromatic tetracarboxylic acid components and diamine components is preferably 40 mol% or less in the total tetracarboxylic acid components and diamine components.
[0012]
Further, in order to seal the amine end of the polyamic acid in the polyamic acid solution, dicarboxylic acid anhydrides, for example, phthalic anhydride and a substituted product thereof (for example, 3-methyl or 4-methylphthalic anhydride), hexahydrophthalic anhydride and A substituted product thereof, succinic anhydride and a substituted product thereof may be added.
[0013]
The organic solvent used to obtain the above polyamic acid includes N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethylsulfoxide, hexamethylphosphoride Amides, N-methylcaprolactam and the like. These organic solvents may be used alone or in combination of two or more.
[0014]
The polyamic acid solution of the present invention uses each of the above components, and polymerizes the above diamine component and tetracarboxylic dianhydride in an organic solvent at a temperature of 0 to 100 ° C, preferably about 5 to 50 ° C. To form a solution of polyamic acid (may be partially imidized if a uniform solution state is maintained), or as it is or after once separating the polyamic acid, an organic solvent (even if the same as the above organic solvent) Or a low-boiling oxygen-containing organic solvent such as tetrahydrofuran or diethylene glycol dimethyl ether).
[0015]
The polyamic acid solution of the present invention contains 0.01 mol% or more, particularly 0.1 mol% or more, and 50 mol% or less, particularly 25 mol% or less of an imidation catalyst, based on the amic acid unit of the polyamic acid. , Pyridine, picolines, imidazoles, quinolines, triethylamine and the like are preferably added.
Further, an inorganic filler, a conductive filler, an inorganic / organic pigment, and the like may be added to the polyamic acid solution of the present invention.
[0016]
The polyimide of the present invention can be obtained by applying the above-mentioned polyamic acid solution to a substrate and drying by heating.
The polyimide of the present invention can be applied to any of a coating film and a film (an uncured film is heat-treated using a pin tenter or the like).
Preferably, a glass substrate, a carbon substrate, or a silicon wafer is directly applied (the surfaces thereof may be treated with a coupling agent such as an aminosilane coupling agent, an epoxysilane coupling agent, or a mercaptosilane coupling agent. ) Or after forming an organic or inorganic film, apply the above-mentioned polyamic acid solution to the surface thereof by spin coating or the like to a thickness of 1-500 μm, and at a temperature of 50-300 ° C., preferably about 75-300 ° C. About 5-300 minutes, preferably multi-stage heating (for example, 1-120 minutes at 75 ° C or more and less than 125 ° C, 1-120 minutes at 125 ° C or more and less than 200 ° C, 0.1-120 minutes at 200 ° C or more and less than 250 ° C) And heating at 250 ° C or more and 300 ° C or less and 300 ° C or less for 0.1-60 minutes in each stage. It is possible to obtain the bromide film.
[0017]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The evaluation of the polyimide film is based on the following test method.
The polyimide film is dried in a hot-air dryer at 50 ° C. for 24 hours, weighed to a size of 10 cm × 10 cm, and then weighed at 25 ° C. and 80% RH. H. The sample was allowed to stand for 24 hours in a thermo-hygrostat where the humidity was adjusted and weighed, and the moisture absorption was determined from the change in weight.
The glass transition temperature was measured by a thermal analyzer, and the elongation and elastic modulus were measured by ASTM D882.
[0018]
Example 1 (shown for reference)
In a 500 ml flask equipped with a stirrer, 4,4′-bis (4-aminophenoxy) biphenyl (0.1 mol) and N-methyl-2-pyrrolidone as a reaction solvent (the solid content of the used material is 18% by weight. ) And dissolved by stirring at room temperature. To this, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (0.1 mol) was gradually added, followed by stirring at room temperature (25 ° C.) for 5 hours. During this time, the viscosity of the polyamic acid reaction liquid increased with the elapse of the reaction time, and the viscosity of the reaction liquid after stirring for 5 hours was 1600 poise. The obtained polyamic acid solution was applied on a glass plate to form a coating, and the temperature was increased stepwise to 80 to 300 ° C. in a hot air drier, followed by heat treatment to obtain a 50 ± 5 μm thick polyimide film. . As a result of evaluating this polyimide film, the moisture absorption was 0.22%, the glass transition temperature was 269 ° C., the elongation was 31%, and the elastic modulus was 399 kg / mm 2 .
[0019]
Example 2
Example 1 was the same as Example 1 except that 1,2-dimethylimidazole was added and dissolved at a rate of 0.275 part by weight (10 mol% based on the polyamic acid unit) based on 100 parts by weight of the polyamic acid solution. The same was performed.
This polyimide film showed almost no change in moisture absorption, and its elongation was improved to 68%.
[0020]
Comparative Example 1
Polyamic obtained in the same manner as in Example 1 using 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-biphenylitetracarboxylic dianhydride and N-methyl-2-pyrrolidone The acid solution was heat-treated at 80-450 ° C to obtain a polyimide film.
This polyimide film had a moisture absorption of 1.8% and a glass transition temperature of 285 ° C.
[0021]
Comparative Example 2
Example 1 using 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3,3 ', 4,4'-biphenylitetracarboxylic dianhydride and N-methyl-2-pyrrolidone. The polyamic acid solution obtained in the same manner as described above was heat-treated at 80 to 300 ° C to obtain a polyimide film.
This polyimide film had a moisture absorption of 0.33% and a glass transition temperature of 246 ° C.
[0022]
Example 3 (shown for reference)
Polymerized using 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-bis (4-aminophenoxy) biphenyl and N-methyl-2-pyrrolidone as a reaction solvent, and solidified. A polyamic acid solution having a concentration of 18% by weight and a viscosity of 50 poise was obtained. This is cast on an aluminum (Al) foil, SUS, or copper foil so as to have a dry film thickness of 30 μm. (300 ° C. × 10 minutes). The obtained sample was peeled at 90 ° and 180 °. The result was as follows. It shows the peel strength.
Al 300g / cm (180 ° peel), 700g / cm (90 ° peel)
SUS 600g / cm (180 ° peel), 850g / cm (90 ° peel)
Copper (glossy surface) 150g / cm (90 ° peeling)
The copper (mat surface) was not peeled off, and the glass substrate was treated with an aminosilane coupling agent, and then cast and cured in the same manner. No peeling was observed in the cross-cut peeling test, and no peeling occurred even when immersed in water. The moisture absorption and other physical properties of each sample were the same as those of Example 1.
[0023]
【The invention's effect】
The polyimide of the present invention has good mechanical properties and heat resistance, and has a further lower moisture absorption rate than conventionally known low moisture absorption polyimides.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP21689498A JP3551030B2 (en) | 1998-07-31 | 1998-07-31 | Polyamic acid solution giving low moisture absorption polyimide and process for preparing polyimide |
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| JP21689498A JP3551030B2 (en) | 1998-07-31 | 1998-07-31 | Polyamic acid solution giving low moisture absorption polyimide and process for preparing polyimide |
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| JP2000044682A JP2000044682A (en) | 2000-02-15 |
| JP3551030B2 true JP3551030B2 (en) | 2004-08-04 |
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