JPH0572406B2 - - Google Patents
Info
- Publication number
- JPH0572406B2 JPH0572406B2 JP59262976A JP26297684A JPH0572406B2 JP H0572406 B2 JPH0572406 B2 JP H0572406B2 JP 59262976 A JP59262976 A JP 59262976A JP 26297684 A JP26297684 A JP 26297684A JP H0572406 B2 JPH0572406 B2 JP H0572406B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- aromatic polyimide
- polyimide
- solution
- mol
- 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 - Lifetime
Links
- 125000003118 aryl group Chemical group 0.000 claims description 56
- 239000004642 Polyimide Substances 0.000 claims description 53
- 229920001721 polyimide Polymers 0.000 claims description 53
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 28
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 150000003457 sulfones Chemical class 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical class C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 15
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- NHJNWRVCOATWGF-UHFFFAOYSA-N 3-(3-amino-2-phenoxyphenyl)sulfonyl-2-phenoxyaniline Chemical class NC1=CC=CC(S(=O)(=O)C=2C(=C(N)C=CC=2)OC=2C=CC=CC=2)=C1OC1=CC=CC=C1 NHJNWRVCOATWGF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000002966 varnish 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
〔本発明の技術分野〕
この発明は、有機極性溶媒に可溶性であり、し
かも透明性および非着色性が優れている特定の芳
香族ポリイミドに係るものである。
この発明の透明な芳香族ポリイミドは、電気的
性質、機械的性質および耐熱性などにおいて優れ
ていると共に、光などの透過性、非着色性および
有機溶媒に対する溶解性（可溶性）が優れている
ので、種々の電気または電子部品の電気絶縁用の
保護膜を形成するための芳香族ポリイミド組成物
（ワニス）を容易に調製することができ、さらに、
その芳香族ポリイミの溶液組成物を種々の電気ま
たは電子部品の表面に塗布して電気絶縁用の保護
膜を形成することができる。
〔従来技術の説明〕
芳香族ポリイミドを、電気絶縁性の保護膜（層
間絶縁膜など）として使用することは、電気また
は電子材料工業において、例えば、特開昭48−
34686号公報、特開昭49−40077号公報などに示さ
れているように、固体素子への絶縁膜、パツシベ
ーシヨン膜の形成材料、半導体集積回路などの層
間絶縁膜などにおいて、耐熱性および絶縁性など
の優れた性質からポリイミドで形成することが、
すでに種々提案されている。
しかしながら、一般的に、芳香族ポリイミド
は、有機溶媒に溶解しにくいために、芳香族ポリ
イミドの前駆体（芳香族ポリアミツク酸）の溶液
を使用して、塗布膜を形成し、次いで、乾燥とイ
ミド化のために塗布膜を、かなりの高温で長時
間、加熱処理して、芳香族ポリイミド製の保護膜
を形成する必要があり、芳香族ポリイミド製の保
護膜を比較的低温で再現性よく形成できるもので
はなかつたので、保護すべき電気または電子材料
自体が熱的に劣化してしまうという問題があつ
た。
一方、有機極性溶媒に可溶性の芳香族ポリイミ
ドは、例えば、特公昭57−41491号公報に記載さ
れているようなポリイミドが知られているが、こ
れらの芳香族ポリイミドは、一般に黄色、褐色、
赤褐色などに着色しており、可視光線などの透過
性が充分ではなかつたので、画像形成用の材料に
使用したり、光センサー、太陽電池などの保護膜
として使用する場合に不適当であつた。
〔本発明の要件およびその効果〕
この発明者らは、前述のような欠点を有してい
ない芳香族ポリイミド、すなわち、優れた透明性
および可溶性を共に有している芳香族ポリイミド
について鋭意研究した結果、２，３，3′，4′−ビ
フエニルテトラカルボン酸類を主成分とする芳香
族テトラカルボン酸成分と、ビス（アミノフエノ
キシ−フエニル）スルホン類を主成分とする芳香
族ジアミン成分との略等モルを、重合およびイミ
ド化して得られた芳香族ポリイミドが、有機極性
溶媒に対るす優れた溶解性を有しており、しか
も、可視光線に対して優れた透過性を有している
ことを見出し、この発明を完成した。
すなわち、この発明は、２，３，3′，4′−ビフ
エニルテトラカルボン酸類を80モル％以上含有す
る芳香族テトラカルボン酸成分と、一般式
[Technical Field of the Invention] The present invention relates to a specific aromatic polyimide that is soluble in organic polar solvents and has excellent transparency and non-coloring properties. The transparent aromatic polyimide of the present invention has excellent electrical properties, mechanical properties, heat resistance, etc., as well as excellent transparency for light, non-coloring property, and solubility in organic solvents. , an aromatic polyimide composition (varnish) for forming a protective film for electrical insulation of various electrical or electronic components can be easily prepared, and further,
The aromatic polyimide solution composition can be applied to the surfaces of various electrical or electronic parts to form a protective film for electrical insulation. [Description of the Prior Art] The use of aromatic polyimide as an electrically insulating protective film (such as an interlayer insulating film) is known in the electrical or electronic materials industry, for example, as disclosed in JP-A-48-
As shown in Publication No. 34686 and Japanese Unexamined Patent Publication No. 49-40077, heat resistance and insulation properties are required for insulating films for solid-state devices, materials for forming passivation films, interlayer insulating films for semiconductor integrated circuits, etc. It is possible to form polyimide due to its excellent properties such as
Various proposals have already been made. However, since aromatic polyimides are generally difficult to dissolve in organic solvents, a coating film is formed using a solution of an aromatic polyimide precursor (aromatic polyamic acid), and then dried and imide coated. In order to form a protective film made of aromatic polyimide, it is necessary to heat-treat the coated film at a fairly high temperature for a long time to form a protective film made of aromatic polyimide at a relatively low temperature. However, there was a problem in that the electrical or electronic materials themselves to be protected would be thermally degraded. On the other hand, examples of aromatic polyimides soluble in organic polar solvents include those described in Japanese Patent Publication No. 57-41491, but these aromatic polyimides are generally yellow, brown,
It was colored reddish-brown and did not have sufficient transparency for visible light, making it unsuitable for use as an image-forming material or as a protective film for optical sensors, solar cells, etc. . [Requirements of the present invention and its effects] The inventors have conducted intensive research on aromatic polyimides that do not have the above-mentioned drawbacks, that is, aromatic polyimides that have both excellent transparency and solubility. As a result, an abbreviation for an aromatic tetracarboxylic acid component mainly composed of 2,3,3',4'-biphenyltetracarboxylic acids and an aromatic diamine component mainly composed of bis(aminophenoxy-phenyl)sulfones. The aromatic polyimide obtained by polymerizing and imidizing equimolar amounts has excellent solubility in organic polar solvents and excellent transparency to visible light. He discovered this and completed this invention. That is, this invention provides an aromatic tetracarboxylic acid component containing 80 mol% or more of 2,3,3',4'-biphenyltetracarboxylic acids, and a compound of the general formula
【化】
で示されるビス（アミノフエノキシ−フエニル）
スルホン類を80モル％以上含有する芳香族ジアミ
ン成分との略等モルから、重合及びイミド化によ
つて得られた、一般式Bis(aminophenoxy-phenyl) represented by
A general formula obtained by polymerization and imidization from approximately equimolar amounts with an aromatic diamine component containing 80 mol% or more of sulfones.
この発明の芳香族ポリイミドは、２，３，3′，
4′−ビフエニルテトラカルボン酸類を80モル％以
上、好ましくは90モル％以上含有している芳香族
テトラカルボン酸成分と、一般式
The aromatic polyimide of this invention has 2,3,3′,
An aromatic tetracarboxylic acid component containing 80 mol% or more, preferably 90 mol% or more of 4'-biphenyltetracarboxylic acids, and a compound having the general formula
【化】
で示されるビス（アミノフエノキシ−フエニル）
スルホン類を80モル％以上、好ましくは90モル％
以上含有している芳香族ジアミン成分とを、略等
モル、有機極性溶媒中で、かなりの高温（好まし
くは約100〜300℃の温度）に加熱して、一段で重
合およびイミド化することによつて製造される
か、あるいは、前記の二成分を、略等モル、有機
極性溶媒中で、好ましくは約80℃以下の温度で、
特に０〜60％の温度で重合して芳香族ポリアミツ
ク酸（芳香族ポリイミドの前駆体）を製造し、そ
の芳香族ポリアミツク酸を適当な条件でイミド化
して製造される透明な可溶性芳香族ポリイミドで
ある。
すなわち、この発明の芳香族ポリイミドは、一
般式Bis(aminophenoxy-phenyl) represented by
80 mol% or more of sulfones, preferably 90 mol%
The aromatic diamine components contained above are heated in approximately equimolar amounts to a considerably high temperature (preferably at a temperature of about 100 to 300°C) in an organic polar solvent to polymerize and imidize in one step. Alternatively, the two components described above are prepared in approximately equimolar amounts in an organic polar solvent, preferably at a temperature below about 80°C.
In particular, it is a transparent soluble aromatic polyimide produced by polymerizing at a temperature of 0 to 60% to produce aromatic polyamic acid (precursor of aromatic polyimide), and then imidizing the aromatic polyamic acid under appropriate conditions. be. That is, the aromatic polyimide of this invention has the general formula
実施例 １
Ｎ−メチル−２−ピロリドン（NMP）18.0ml
に、２，３，3′，4′−ビフエニルテトラカルボン
酸二無水物1.64ｇおよびビス〔４−（4′−アミノ
フエノキシ）フエニル〕スルホン2.43ｇを加え、
窒素ガスを流通し撹拌しながら、その反応液を20
℃の反応温度で、５時間保持して、重合を行い、
芳香族ポリアミツク酸を生成した。
次に、この芳香族ポリアミツク酸の溶液をさら
にNMP55.8mlを加えて希釈した後、無水酢酸
11.14ｇおよびピリジン4.26ｇを加えて、50℃で
３時間イミド化反応させて、芳香族ポリイミドを
生成させ、さらにこの溶液にメタノールを添加し
て、生成している芳香族ポリイミドを析出させ濾
過して、芳香族ポリイミド粉末を得た。
前述のようにして得られた芳香族ポリイミドに
ついて、NMPに約30℃に溶解して、そのポリイ
ミドの溶解性（前記芳香族ポリイミド粉末が、
NMP溶媒に30℃で溶解する最大の濃度、およ
び、前記芳香族ポリイミド粉末が14重量％の濃度
にまで30℃でNMP溶媒に溶解するのにようした
溶解時間で示す。）、およびこのポリイミドの対数
粘度（濃度；0.5ｇ／100ml溶媒、測定温度；30
℃）を測定した。その結果を第１表に示す。
前述のようにして得られた芳香族ポリイミドを
NMPに約30℃で溶解して、濃度約14重量％の均
一な芳香族ポリイミド溶液を調製した。
前述のようにして調製された芳香族ポリイミド
溶液について、回転粘度（25℃）を測定して、そ
の結果を第１表に示す。
さらに、この芳香族ポリイミド溶液をSiO2が
コーテイングされているガラス上に、回転塗布機
（1000〜3000rpm）を使用して塗布し、80℃で60
分間加熱し乾燥させ、約5μの厚さの芳香族ポリ
イミド製の薄膜を形成させた。
この薄膜のそのまま、あるいはこの薄膜を空気
中で350℃で30分間熱処理した膜について、自記
分光光度計（日立製作所(株)製、330型）を使用し
て、400nｍおよび440nｍの波長の光線の光透過
性を測定した。また、前記の芳香族ポリイミド製
の薄膜（熱処理膜）についての、膜の色調を観察
し、次いで、熱量分析器（デユポン社製、951型）
を使用して、熱分解開始温度を測定した。前記の
測定結果を第１表に示す。
比較例 １
Ｎ−メチル−２−ピロリドン（NMP）23.6ml
に、３，3′，４，4′−ビフエニルテトラカルボン
酸二無水物2.15ｇおよびビス〔４−（4′−アミノ
フエノキシ）フエニル〕スルホン3.17ｇを加え窒
素雰囲気、20℃の反応温度で、５時間撹拌して重
合を行い、芳香族ポリアミツク酸を生成した。
次に、この芳香族ポリアミツク酸の溶液にさら
にNMP66.0mlを加えて希釈した後、無水酢酸
15.06ｇおよびピリジン5.76ｇを加えて、50℃で
３時間イミド化反応させて、芳香族ポリイミドを
生成させ、さらにこの溶液にメタノールを添加し
て、生成している芳香族ポリイミドを析出させ濾
過して、芳香族ポリイミド粉末を得た。
この芳香族ポリイミドについて、溶解性および
対数粘度を実施例１と同様にして測定し、その結
果を第１表に示す。
前述のようにして得られた芳香族ポリイミドを
NMPに約30℃で溶解して、濃度14重量％の均一
な芳香族ポリイミド溶液を調製した。
前述のようにして調製された芳香族ポリイミド
溶液について、回転粘度（25℃）を測定して、そ
の結果を第１表に示す。
さらに、この芳香族ポリイミド溶液を使用した
ほかは、実施例１と同様にして、芳香族ポリイミ
ド性の薄膜を製造した。
この薄膜について、実施例１と同様にして、光
透過性および熱分解開始温度を測定し、その結果
を第１表に示す。
この比較例１で得られた芳香族ポリイミド溶液
は、２日後にカンテン状となり、流動性が著しく
悪くなつた。従つて、この比較例１で得られた芳
香族ポリイミド溶液は、第１表に示すように25℃
の溶液粘度が極めて高いと共に、２日程度で流動
性がなくなつてしまうものであるので、保護膜形
成用のポリイミド溶液組成物として実用的なもの
ではなかつた。また、前記の比較例１で得られた
芳香族ポリイミドは溶解性において、溶解時間が
大きく、前記の芳香族ポリイミドの調製において
も問題があつた。
実施例 ２
Ｎ−メチル−２−ピロリドン（NMP）24.0ml
に、２，３，3′，4′−ビフエニルテトラカルボン
酸二無水物1.85ｇおよびビス〔４−（4′−アミノ
フエノキシ）フエニル〕スルホン2.76ｇを加え、
窒素雰囲気で180℃の重合反応温度で５時間撹拌
し、重合およびイミド化を一段で行い、回転粘度
（25℃）が110ポイズである芳香族ポリイミド溶液
を得た。
前記の溶液から、含有されている芳香族ポリイ
ミドを回収し、その芳香族ポリイミの溶解性およ
び対数粘度を、実施例１と同様にして測定し、そ
の結果を第１表に示す。
また、前記の芳香族ポリイミド溶液を使用した
ほかは、実施例１と同様にして、芳香族ポリイミ
ド製の薄膜を製造した。この薄膜について、実施
例１と同様にして、光透過性および熱分解開始温
度を測定し、その結果を第１表に示す。
Example 1 N-methyl-2-pyrrolidone (NMP) 18.0ml
To this, 1.64 g of 2,3,3',4'-biphenyltetracarboxylic dianhydride and 2.43 g of bis[4-(4'-aminophenoxy)phenyl]sulfone were added,
While flowing nitrogen gas and stirring, the reaction solution was heated for 20 min.
Polymerization is carried out by holding at a reaction temperature of °C for 5 hours,
Aromatic polyamic acid was produced. Next, this solution of aromatic polyamic acid was further diluted by adding 55.8 ml of NMP, and then acetic anhydride was added.
11.14 g and 4.26 g of pyridine were added, and an imidization reaction was carried out at 50°C for 3 hours to produce aromatic polyimide. Methanol was further added to this solution to precipitate the produced aromatic polyimide, which was then filtered. Thus, aromatic polyimide powder was obtained. The aromatic polyimide obtained as described above was dissolved in NMP at about 30°C to determine the solubility of the polyimide (the aromatic polyimide powder was
The maximum concentration dissolved in NMP solvent at 30°C and the dissolution time required to dissolve the aromatic polyimide powder in NMP solvent at 30°C to a concentration of 14% by weight are shown. ), and the logarithmic viscosity of this polyimide (concentration: 0.5 g/100 ml solvent, measurement temperature: 30
℃) was measured. The results are shown in Table 1. The aromatic polyimide obtained as described above was
A homogeneous aromatic polyimide solution having a concentration of about 14% by weight was prepared by dissolving it in NMP at about 30°C. The rotational viscosity (25° C.) of the aromatic polyimide solution prepared as described above was measured and the results are shown in Table 1. Furthermore, this aromatic polyimide solution was applied onto the glass coated with SiO 2 using a spin coating machine (1000 to 3000 rpm), and then heated at 80°C for 60°C.
It was dried by heating for a minute to form a thin film made of aromatic polyimide with a thickness of about 5 μm. Using a self-recording spectrophotometer (manufactured by Hitachi, Ltd., Model 330), the thin film as it was or the film heat-treated in air at 350°C for 30 minutes was measured using a self-recording spectrophotometer (manufactured by Hitachi, Ltd., Model 330). Light transmittance was measured. In addition, the color tone of the aromatic polyimide thin film (heat-treated film) was observed, and then a calorimeter (manufactured by DuPont, Model 951) was used.
was used to measure the thermal decomposition onset temperature. The above measurement results are shown in Table 1. Comparative example 1 N-methyl-2-pyrrolidone (NMP) 23.6ml
2.15 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 3.17 g of bis[4-(4'-aminophenoxy)phenyl]sulfone were added to the mixture at a reaction temperature of 20°C in a nitrogen atmosphere. Polymerization was carried out by stirring for 5 hours to produce aromatic polyamic acid. Next, 66.0 ml of NMP was further added to this solution of aromatic polyamic acid to dilute it, and then acetic anhydride was added.
15.06 g and 5.76 g of pyridine were added, and an imidization reaction was carried out at 50°C for 3 hours to produce an aromatic polyimide. Furthermore, methanol was added to this solution to precipitate the produced aromatic polyimide, which was then filtered. Thus, aromatic polyimide powder was obtained. The solubility and logarithmic viscosity of this aromatic polyimide were measured in the same manner as in Example 1, and the results are shown in Table 1. The aromatic polyimide obtained as described above was
A homogeneous aromatic polyimide solution with a concentration of 14% by weight was prepared by dissolving it in NMP at about 30°C. The rotational viscosity (25° C.) of the aromatic polyimide solution prepared as described above was measured and the results are shown in Table 1. Furthermore, an aromatic polyimide thin film was produced in the same manner as in Example 1 except that this aromatic polyimide solution was used. The light transmittance and thermal decomposition onset temperature of this thin film were measured in the same manner as in Example 1, and the results are shown in Table 1. The aromatic polyimide solution obtained in Comparative Example 1 became agar-like after two days, and its fluidity became extremely poor. Therefore, the aromatic polyimide solution obtained in Comparative Example 1 was heated at 25°C as shown in Table 1.
The solution viscosity was extremely high and the fluidity disappeared in about two days, so it was not practical as a polyimide solution composition for forming a protective film. In addition, the aromatic polyimide obtained in Comparative Example 1 had a long dissolution time in terms of solubility, and there were also problems in the preparation of the aromatic polyimide. Example 2 N-methyl-2-pyrrolidone (NMP) 24.0ml
1.85 g of 2,3,3',4'-biphenyltetracarboxylic dianhydride and 2.76 g of bis[4-(4'-aminophenoxy)phenyl]sulfone were added,
Stirring was carried out in a nitrogen atmosphere at a polymerization reaction temperature of 180° C. for 5 hours to carry out polymerization and imidization in one step to obtain an aromatic polyimide solution having a rotational viscosity (25° C.) of 110 poise. The aromatic polyimide contained in the solution was recovered, and the solubility and logarithmic viscosity of the aromatic polyimide were measured in the same manner as in Example 1, and the results are shown in Table 1. Further, a thin film made of aromatic polyimide was produced in the same manner as in Example 1, except that the above-mentioned aromatic polyimide solution was used. The light transmittance and thermal decomposition onset temperature of this thin film were measured in the same manner as in Example 1, and the results are shown in Table 1.
Claims (1)
酸類を80モル％以上含有する芳香族テトラカルボ
ン酸成分と、一般式 【化】 で示されるビス（アミノフエノキシ−フエニル）
スルホン類を80モル％以上含有する芳香族ジアミ
ン成分との略等モルから、重合及びイミド化によ
つて得られた、一般式 【化】 で示される反復単位を主として含有するポリマー
であつて、対数粘度〔濃度；0.5ｇ／100ml溶媒
（Ｎ−メチル−２−ピロリドン）、測定温度；30
℃〕が0.2〜5.0である透明な可溶性芳香族ポリイ
ミド。[Scope of Claims] 1 An aromatic tetracarboxylic acid component containing 80 mol% or more of 2,3,3',4'-biphenyltetracarboxylic acids, and a bis(aminophenoxy-phenyl )
A polymer mainly containing repeating units represented by the general formula [Chemical formula] obtained by polymerization and imidization from approximately equimolar amounts with an aromatic diamine component containing 80 mol% or more of sulfones, Logarithmic viscosity [concentration: 0.5g/100ml solvent (N-methyl-2-pyrrolidone), measurement temperature: 30
A transparent soluble aromatic polyimide with a temperature of 0.2 to 5.0.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26297684A JPS61141731A (en) | 1984-12-14 | 1984-12-14 | Transparent aromatic polyimide and its composition |
| US06/809,528 US4696994A (en) | 1984-12-14 | 1985-12-16 | Transparent aromatic polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26297684A JPS61141731A (en) | 1984-12-14 | 1984-12-14 | Transparent aromatic polyimide and its composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28820391A Division JPH0532894A (en) | 1991-08-14 | 1991-08-14 | Solution composition of transparent aromatic polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61141731A JPS61141731A (en) | 1986-06-28 |
| JPH0572406B2 true JPH0572406B2 (en) | 1993-10-12 |
Family
ID=17383161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26297684A Granted JPS61141731A (en) | 1984-12-14 | 1984-12-14 | Transparent aromatic polyimide and its composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61141731A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS627733A (en) * | 1985-03-10 | 1987-01-14 | Nitto Electric Ind Co Ltd | Colorless clear polyimide formed body and its production |
| JPH0196246A (en) * | 1987-10-09 | 1989-04-14 | Ube Ind Ltd | Production of copper paste composition and electrically conductive wired material |
| JP2624724B2 (en) * | 1987-11-04 | 1997-06-25 | 宇部興産株式会社 | Polyimide siloxane composition |
| JP2624723B2 (en) * | 1987-11-04 | 1997-06-25 | 宇部興産株式会社 | Polyimide composition for printing |
| DE3738457A1 (en) * | 1987-11-12 | 1989-05-24 | Lentia Gmbh | NEW SOLUBLE AND / OR MELTABLE POLYIMIDES AND POLYAMIDE IMIDS |
| JP2785394B2 (en) * | 1989-11-24 | 1998-08-13 | 宇部興産株式会社 | Thermoplastic aromatic polyimide |
| JPH08225645A (en) * | 1995-12-18 | 1996-09-03 | Nitto Denko Corp | Colorless clear polyimide molding and production thereof |
| WO2001034678A1 (en) * | 1999-11-10 | 2001-05-17 | Kaneka Corporation | Soluble polyimide and composition comprising the same, bonding sheet, adhesive laminated film for covering accelerator beam tube, and adhesive laminated film for covering conductor wire for accelerator quench heater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49120993A (en) * | 1973-03-23 | 1974-11-19 | ||
| JPS5176977A (en) * | 1974-12-27 | 1976-07-03 | Hitachi Ltd | HANDOTAISOSHINOHYOMENANTEI KASHORIHOHO |
| JPS5230319A (en) * | 1975-09-04 | 1977-03-08 | Nippon Hoso Kyokai <Nhk> | Compensation circuit of digital type gamma |
| JPS5876425A (en) * | 1981-10-30 | 1983-05-09 | Hitachi Chem Co Ltd | Preparation of polymer containing imide ring |
| JPS59191012A (en) * | 1983-04-13 | 1984-10-30 | Sharp Corp | Liquid crystal display element |
-
1984
- 1984-12-14 JP JP26297684A patent/JPS61141731A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49120993A (en) * | 1973-03-23 | 1974-11-19 | ||
| JPS5176977A (en) * | 1974-12-27 | 1976-07-03 | Hitachi Ltd | HANDOTAISOSHINOHYOMENANTEI KASHORIHOHO |
| JPS5230319A (en) * | 1975-09-04 | 1977-03-08 | Nippon Hoso Kyokai <Nhk> | Compensation circuit of digital type gamma |
| JPS5876425A (en) * | 1981-10-30 | 1983-05-09 | Hitachi Chem Co Ltd | Preparation of polymer containing imide ring |
| JPS59191012A (en) * | 1983-04-13 | 1984-10-30 | Sharp Corp | Liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61141731A (en) | 1986-06-28 |
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