JPH0670136B2 - Method for producing modified polyimide composition - Google Patents
Method for producing modified polyimide compositionInfo
- Publication number
- JPH0670136B2 JPH0670136B2 JP23907185A JP23907185A JPH0670136B2 JP H0670136 B2 JPH0670136 B2 JP H0670136B2 JP 23907185 A JP23907185 A JP 23907185A JP 23907185 A JP23907185 A JP 23907185A JP H0670136 B2 JPH0670136 B2 JP H0670136B2
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- JP
- Japan
- Prior art keywords
- polyimide
- aromatic
- modified polyimide
- group
- modified
- 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
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- 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
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、可溶性の芳香族ポリイミドを特定のアミン化
合物と反応させて得られた、上記芳香族ポリイミドのイ
ミド環結合が上記アミノ化合物で開環されている変性ポ
リイミドが、有機極性溶媒に均一に溶解している変性ポ
リイミド組成物（ワニス）に関するものであり、本発明
の変性ポリイミド組成物は、種々の無機又は金属材料等
の表面に塗布し、その塗布量を乾燥及び加熱処理するこ
とにより、密着性に優れていると共に光透過性（無色透
明性）に優れた耐熱性及び電気絶縁性の被覆層（薄膜
層）を形成することができ、特に液晶配向膜の形成材料
やインキ材料として好適なものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides an aromatic polyimide having an imide ring bond opened with the amino compound, which is obtained by reacting a soluble aromatic polyimide with a specific amine compound. The modified polyimide that is cyclic is related to a modified polyimide composition (varnish) that is uniformly dissolved in an organic polar solvent, and the modified polyimide composition of the present invention is applied to the surface of various inorganic or metallic materials. Then, the coating amount is dried and heat-treated to form a heat-resistant and electrically-insulating coating layer (thin film layer) having excellent adhesion and light transmission (colorless transparency). In particular, it is suitable as a material for forming a liquid crystal alignment film and an ink material.
ポリイミドは、耐熱性及び電気絶縁性等の優れた性質を
有しており、電気又は電子材料工業等において、液晶配
向膜や電気絶縁性の保護膜（固体素子への絶縁膜、バッ
シベーション膜、半導体集積回路などの層間絶縁膜等）
の形成材料として用いられている。Polyimide has excellent properties such as heat resistance and electrical insulation, and in the electrical or electronic material industry, etc., a liquid crystal alignment film or an electrically insulating protective film (an insulating film to a solid element, a passivation film, Interlayer insulation film for semiconductor integrated circuits, etc.)
It is used as a forming material.
一般的に、ポリイミドは、有機極性溶媒に溶解し難いた
め、ポリイミドの前駆体（ポリアミック酸）の溶液を使
用して、塗布膜を形成し、次いで、該塗布膜を、乾燥と
イミド化のためにかなりの高温で長時間、加熱処理し
て、ポリイミド製の保護膜を形成する必要があり、比較
的低温ではポリイミド製の保護膜を再現性よく形成でき
るものではなかったので、ポリイミド製の保護膜で保護
すべき電気又は電子材料自体を熱的に劣化させてしまう
という問題点がある。In general, since polyimide is difficult to dissolve in an organic polar solvent, a solution of a polyimide precursor (polyamic acid) is used to form a coating film, and then the coating film is dried and imidized. It is necessary to form a protective film made of polyimide by heat treatment at a fairly high temperature for a long time, and it is not possible to form a protective film made of polyimide with good reproducibility at relatively low temperatures. There is a problem that the electric or electronic material itself to be protected by the film is thermally deteriorated.
一方、有機極性溶媒に可溶性のポリイミドもあるが、こ
の種の従来公知のポリイミドは、極めて特殊な溶媒にし
か溶けなかったり、或いは有機極性溶媒に対する溶解性
が劣るため、溶解に長時間を要し且つ均一に溶解しない
等の問題点がある。On the other hand, although there are polyimides soluble in organic polar solvents, conventionally known polyimides of this kind are only soluble in extremely special solvents, or have poor solubility in organic polar solvents, which requires a long time for dissolution. In addition, there is a problem that it does not dissolve uniformly.
また、従来公知のポリイミドにより形成された保護膜
は、ガラスやアルミニウム等の無機又は金属等の基板に
対する密着性が不充分であるという問題点がある。In addition, there is a problem that a conventionally known protective film formed of polyimide has insufficient adhesion to a substrate made of an inorganic material such as glass or aluminum or a metal.
更に、従来公知のポリイミドは、光透過性（無色透明
性）が悪く、一般に黄色に着色しており、着色を嫌う用
途には使用できず、用途が限定されるという問題点があ
る。Further, conventionally known polyimides have poor light transmittance (colorless transparency) and are generally colored in yellow, so that they cannot be used in applications where coloring is disliked, and there is a problem that the applications are limited.
本発明者等は、上述の問題点が解消されたポリイミドを
提供すべく鋭意研究した結果、可溶性の芳香族ポリイミ
ドを、特定のアミン化合物と反応させて得られた、上記
芳香族ポリイミドのイミド環結合が上記アミン化合物で
開環されている変性ポリイミドが、有機極性溶媒に対す
る溶解性に極めて優れており、且つ無機又は金属等の基
板に対する密着性に優れていると共に光透過性（無色透
明性）に優れた耐熱性及び電気絶縁性の被覆層（薄膜
層）を形成することができることを知見した。The present inventors, as a result of intensive research to provide a polyimide in which the above problems have been solved, a soluble aromatic polyimide, obtained by reacting with a specific amine compound, the imide ring of the aromatic polyimide The modified polyimide in which the bond is ring-opened with the above amine compound is extremely excellent in solubility in an organic polar solvent, and is also excellent in adhesion to a substrate such as an inorganic or metallic material, and is also light transmissive (colorless transparency). It was found that a coating layer (thin film layer) having excellent heat resistance and electric insulation can be formed.
本発明は、上記知見に基づきなされたもので、芳香族テ
トラカルボン酸成分と芳香族ジアミン成分とを重合及び
イミド化して得られた可溶性芳香族ポリイミドを、一般
式R1−NH−R2（但し、R1は炭素数１〜６のアルキル基で
あり、R2は水酸基、及びカルボキシル基からなる群から
選ばれた極性基を有する炭素数１〜６の炭化水素基又は
炭素数６〜13の芳香族炭化水素基である）で示される極
性基含有アミン化合物と反応させ、該反応で上記可溶性
芳香族ポリイミドのイミド環結合の少なくとも５％以上
開環させて変性ポリイミドとし、上記変性ポリイミドを
有機極性溶媒に１〜50重量％の濃度で均一に溶解させて
製造することを特徴とする変性ポリイミド組成物の製法
を提供するものである。The present invention was made based on the above findings, a soluble aromatic polyimide obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and an aromatic diamine component, a general formula R 1 -NH-R 2 ( However, R 1 is an alkyl group having 1 to 6 carbon atoms, R 2 is a hydrocarbon group having 1 to 6 carbon atoms or a carbon group having 6 to 13 carbon atoms, which has a polar group selected from the group consisting of a hydroxyl group and a carboxyl group. Of the aromatic hydrocarbon group of), and at least 5% or more of the imide ring bond of the soluble aromatic polyimide is opened in the reaction to give a modified polyimide. Disclosed is a method for producing a modified polyimide composition, which is produced by uniformly dissolving it in an organic polar solvent at a concentration of 1 to 50% by weight.
以下に本発明の変性ポリイミド組成物の製法について詳
述する。The method for producing the modified polyimide composition of the present invention is described in detail below.
本発明の組成物を構成する変性ポリイミドの製造に用い
られる可溶性芳香族ポリイミドは、例えば、芳香族テト
ラカルボン酸成分と芳香族ジアミン成分とを、略等モ
ル、有機極性溶媒中で、かなり高温（好ましくは約100
〜300℃の温度、特に好ましくは120〜250℃の温度）に
加熱して、一段で重合及びイミド化することによって製
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100℃以下の温度、特に2
0〜70℃の温度で重合して芳香族ポリアミック酸（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
ック酸を適当な条件でイミド化して製造される。The soluble aromatic polyimide used in the production of the modified polyimide constituting the composition of the present invention is, for example, an aromatic tetracarboxylic acid component and an aromatic diamine component, approximately equimolar, in an organic polar solvent, at a considerably high temperature ( Preferably about 100
~ 300 ℃, particularly preferably 120 ~ 250 ℃), by heating and polymerizing and imidizing in one step, or the above two components, approximately equimolar, organic polar solvent. , Preferably at temperatures below about 100 ° C., especially 2
It is produced by polymerizing at a temperature of 0 to 70 ° C. to produce an aromatic polyamic acid (a precursor of aromatic polyimide), and imidizing the aromatic polyamic acid under appropriate conditions.
前記芳香族テトラカルボン酸成分としては、例えば、2,
3,3′,4′−ビフェニルテトラカルボン酸又はその酸二
無水物、3,3′,4,4′−ビフェニルテトラカルボン酸又
はその酸二無水物、2,2′,3′,3′−ビフェニルテトラ
カルボン酸又はその酸二無水物、2,3,3′,4′−ベンゾ
フェノンテトラカルボン酸又はその酸二無水物、3,3′,
4,4′−ベンゾフェノンテトラカルボン酸又はその酸二
無水物、ピロメリット酸又はその酸二無水物等が挙げら
れ、上記芳香族テトラカルボン酸のエステル化物、塩等
でも良いが、ビフェニルテトラカルボン酸二無水物、特
に2,3,3′,4′−ビフェニルテトラカルボン酸二無水物
が好ましい。The aromatic tetracarboxylic acid component, for example, 2,
3,3 ', 4'-biphenyltetracarboxylic acid or its acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid or its acid dianhydride, 2,2 ', 3', 3 ' -Biphenyltetracarboxylic acid or its acid dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid or its acid dianhydride, 3,3',
4,4'-benzophenone tetracarboxylic acid or its acid dianhydride, pyromellitic acid or its acid dianhydride, and the like, esterified products of the above aromatic tetracarboxylic acids, salts and the like, but biphenyl tetracarboxylic acid Dianhydrides, especially 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, are preferred.
前記芳香族ジアミン成分としては、例えば、ビス（４−
アミノフェノキシフェニル）スルホン、2,2−ジ（４−
アミノフェノキシフェニル）プロパン、4,4′−ジ（４
−アミノフェノキシ）ビフェニル、1,4−ジ（４−アミ
ノフェノキシ）ベンゼン、アニシジン、トリジン、9,10
−ビス（４−アミノフェニル）アントラセン、9,9−ビ
ス（４−アミノフェニル）フルオレン等の芳香族環を多
数有する多環芳香族ジアミンが好ましいものとして挙げ
られるが、この他、下記の感光基を有する芳香族ジアミ
ン化合物等を用いることもできる。Examples of the aromatic diamine component include bis (4-
Aminophenoxyphenyl) sulfone, 2,2-di (4-
Aminophenoxyphenyl) propane, 4,4'-di (4
-Aminophenoxy) biphenyl, 1,4-di (4-aminophenoxy) benzene, anisidine, tolidine, 9,10
A polycyclic aromatic diamine having a large number of aromatic rings such as -bis (4-aminophenyl) anthracene and 9,9-bis (4-aminophenyl) fluorene can be mentioned as preferable ones. It is also possible to use an aromatic diamine compound having
3,5−ジアミン安息香酸エチルアクリル酸エステル、2,4
−ジアミン安息香酸エチルアクリル酸エステル、3,5−
ジアミノ安息香酸エチルメタクリル酸エステル、2,4−
ジアミノ安息香酸エチルメタクリル酸エステル、3,5−
ジアミノ安息香酸グリシジルアクリレートエステル、2,
4−ジアミノ安息香酸グリシジルアクリレートエステ
ル、3,5−ジアミノ安息香酸グリシジルメタクリレート
エステル、2,4−ジアミノ安息香酸グリシジルメタクリ
レートエステル、3,5−ジアミノ安息香酸ケイ皮エステ
ル、2,4−ジアミノ安息香酸ケイ皮エステル等の安息香
酸エステル類;3,5−ジアミノベンジルアクリレート、3,
5−ジアミノベンジルメタクリレート等のベンジルアク
リレート類;4−アクリルアミド−3,4′−ジアミノジフ
ェニルエーテル、２−アクリルアミド−3,4′−ジアミ
ノジフェニルエーテル、４−シンナムアミド−3,4′−
ジアミノジフェニルエーテル、3,4′−ジアクリルアミ
ド−３′,4−ジアミノジフェニルエーテル、3,4′−ジ
シンナムアミド−３′,4−ジアミノジフェニルエーテ
ル、４−メチル−２′−（２−メタクリロイルオキシカ
ルボニル）−3,4′−ジアミノジフェニルエーテル、４
−メチル−２′−（２−アクリロイルオキシカルボニ
ル）−3,4′−ジアミノジフェニルエーテル等のジフェ
ニルエーテル類；及び4,4′−ジアミノカルコン、3,3′
−ジアミノカルコン、3,4′−ジアミノカルコン、３′,
4−ジアミノカルコン、４′−メチル−３′,4−ジアミ
ノカルコン、４′−メトキシ−３′,4−ジアミノカルコ
ン、３′−メチル−3,5−ジアミノカルコン等のカルコ
ン類。3,5-diamine benzoic acid ethyl acrylate, 2,4
-Diamine benzoic acid ethyl acrylate, 3,5-
Diaminobenzoic acid ethyl methacrylic acid ester, 2,4-
Diaminobenzoic acid ethyl methacrylic acid ester, 3,5-
Diaminobenzoic acid glycidyl acrylate ester, 2,
4-diaminobenzoic acid glycidyl acrylate ester, 3,5-diaminobenzoic acid glycidyl methacrylate ester, 2,4-diaminobenzoic acid glycidyl methacrylate ester, 3,5-diaminobenzoic acid cinnamate ester, 2,4-diaminobenzoic acid silica Benzoic acid esters such as skin esters; 3,5-diaminobenzyl acrylate, 3,
Benzyl acrylates such as 5-diaminobenzyl methacrylate; 4-acrylamido-3,4'-diaminodiphenyl ether, 2-acrylamido-3,4'-diaminodiphenyl ether, 4-cinnamamide-3,4'-
Diaminodiphenyl ether, 3,4'-diacrylamide-3 ', 4-diaminodiphenyl ether, 3,4'-dicinnamamide-3', 4-diaminodiphenyl ether, 4-methyl-2 '-(2-methacryloyloxycarbonyl) -3 , 4'-diaminodiphenyl ether, 4
Diphenyl ethers such as -methyl-2 '-(2-acryloyloxycarbonyl) -3,4'-diaminodiphenyl ether; and 4,4'-diaminochalcone, 3,3'
-Diaminochalcone, 3,4'-diaminochalcone, 3 ',
Chalcones such as 4-diaminochalcone, 4'-methyl-3 ', 4-diaminochalcone, 4'-methoxy-3', 4-diaminochalcone, 3'-methyl-3,5-diaminochalcone.
前記芳香族ジアミン成分として前記多環芳香族ジアミン
と前記感光基を有する芳香族ジアミン化合物とを併用し
て得られたポリイミドを用いると、クラック性能が良好
となる。When a polyimide obtained by using the polycyclic aromatic diamine and the aromatic diamine compound having the photosensitive group in combination is used as the aromatic diamine component, good crack performance is obtained.
また、前記芳香族テトラカルボン酸成分と前記芳香族ジ
アミン成分との重合に使用される有機極性溶媒として
は、例えば、ジメチルスルホキシド、ジエチルスルホキ
シド等のスルホキシド系溶媒、N,N−ジメチルホルムア
ミド、N,N−ジエチルホルムアミド等のホルムアミド系
溶媒、N,N−ジメチルアセトアミド、N,N−ジエチルアセ
トアミド等のアセトアミド系溶媒、Ｎ−メチル−２−ピ
ロリドン、Ｎ−ビニル−２−ピロリドン等のピロリドン
系溶媒、ヘキサメチレンスルホキシド、γ−ブチロラキ
トン等、或いは、フェノール、ｏ−,m−又はｐ−クレゾ
ール、キシレノール、ハロゲン化フェノール（パラクロ
ルフェノール、オルトクロルフェノール、パラブロムフ
ェノール等）、カテコール等のフェノール系溶媒等を挙
げることができる。The organic polar solvent used in the polymerization of the aromatic tetracarboxylic acid component and the aromatic diamine component, for example, dimethyl sulfoxide, sulfoxide solvent such as diethyl sulfoxide, N, N-dimethylformamide, N, Formamide solvents such as N-diethylformamide, N, N-dimethylacetamide, acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, Hexamethylene sulfoxide, γ-butyrolakiton, etc., or phenolic solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenols (parachlorophenol, orthochlorophenol, parabromphenol, etc.), catechol, etc. Can be mentioned.
本発明の組成物を構成する変性ポリイミドの製造に用い
られる可溶性芳香族ポリイミドは、高分子量のポリマー
であり、例えば、濃度;0.5g/100ml溶媒（Ｎ−メチル−
２−ピロリドン）である溶液で、30℃の測定温度で測定
した対数粘度（ポリマーの重合度の程度を示す）が、0.
1〜2.0であること、特に0.3〜1.5程度であることが好ま
しい。The soluble aromatic polyimide used in the production of the modified polyimide constituting the composition of the present invention is a high molecular weight polymer, for example, concentration: 0.5 g / 100 ml solvent (N-methyl-
2-pyrrolidone), the logarithmic viscosity (indicating the degree of polymerization of the polymer) measured at a measurement temperature of 30 ° C. is 0.
It is preferably 1 to 2.0, and more preferably about 0.3 to 1.5.
また、本発明の組成物を構成する変性ポリイミドの製造
に用いられる前記一般式R1−NH−R2で示される極性基含
有アミン化合物としては、エタノールアミン、Ｎ−メチ
ルエタノールアミン、グリシン、ｐ−アミノ安息香酸等
を挙げることができる。Further, as the polar group-containing amine compound represented by the general formula R 1 —NH—R 2 used for the production of the modified polyimide constituting the composition of the present invention, ethanolamine, N-methylethanolamine, glycine, p -Aminobenzoic acid and the like can be mentioned.
而して、本発明の組成物を構成する変性ポリイミドは、
前記可溶性芳香族ポリイミドを前記極性基含有アミン化
合物と反応させ、前記可溶性芳香族ポリイミドのイミド
環結合の少なくとも５％以上、好ましくは10〜60％程度
を前記極性基含有アミン化合物で開環させることによっ
て得られる。Thus, the modified polyimide constituting the composition of the present invention,
Reacting the soluble aromatic polyimide with the polar group-containing amine compound to open at least 5%, preferably about 10 to 60%, of the imide ring bond of the soluble aromatic polyimide with the polar group-containing amine compound. Obtained by
イミド環結合の開環の割合（イミド環結合100個当たり
の開環させた個数：以下反応率と言うこともある）が５
％未満であると、ポリイミドの変性が不充分で、本発明
の目的とする変性ポリイミド組成物は得られない。The rate of ring opening of the imide ring bond (the number of rings opened per 100 imide ring bonds: sometimes referred to as the reaction rate hereinafter) is 5
If it is less than%, the modification of the polyimide is insufficient and the modified polyimide composition aimed at by the present invention cannot be obtained.
前記可溶性芳香族ポリイミドと前記極性基含有アミン化
合物との反応は、例えば、可溶性芳香族ポリイミドを反
応溶媒に溶解し、これに極性基含有アミン化合物を添加
し、通常、反応温度10〜100℃、反応時間0.5〜50時間の
条件下に行われる。The reaction between the soluble aromatic polyimide and the polar group-containing amine compound, for example, the soluble aromatic polyimide is dissolved in a reaction solvent, the polar group-containing amine compound is added thereto, usually, the reaction temperature 10 ~ 100 ℃, The reaction time is 0.5 to 50 hours.
反応溶媒溶液中の可溶性芳香族ポリイミドの濃度は、３
〜50重量％程度とするのが好ましい。The concentration of soluble aromatic polyimide in the reaction solvent solution is 3
It is preferably about 50% by weight.
また、極性基含有アミン化合物の使用量は、可溶性芳香
族ポリイミドのイミド環結合に対して略等モルとするの
が好ましい。The amount of the polar group-containing amine compound used is preferably approximately equimolar to the imide ring bond of the soluble aromatic polyimide.
変性ポリイミドにおけるイミド環結合の開環の割合（反
応率）は、上記の反応条件を適宜調整することにより規
制することができる。The ring-opening ratio (reaction rate) of the imide ring bond in the modified polyimide can be regulated by appropriately adjusting the above reaction conditions.
前記可溶性芳香族ポリイミドと前記極性基含有アミン化
合物との反応に使用される反応溶媒としては、例えば、
Ｎ−メチルピロリドン、Ｎ−ビニルピロリドン、N,N−
ジメチルホルムアミド、N,N−ジメチルアセトアミド、
ジメチルスルホキシド、ｐ−クレゾール、ｐ−クロロフ
ェノール等が挙げられる。The reaction solvent used in the reaction of the soluble aromatic polyimide and the polar group-containing amine compound, for example,
N-methylpyrrolidone, N-vinylpyrrolidone, N, N-
Dimethylformamide, N, N-dimethylacetamide,
Dimethyl sulfoxide, p-cresol, p-chlorophenol and the like can be mentioned.
而して、本発明の変性ポリイミド組成物（ワニス）は、
前述の如くして得られる変性ポリイミドを有機極性溶媒
に、１〜50重量％、好ましくは２〜30重量％の濃度で均
一に溶解させることによって得られる。Thus, the modified polyimide composition (varnish) of the present invention is
It can be obtained by uniformly dissolving the modified polyimide obtained as described above in an organic polar solvent at a concentration of 1 to 50% by weight, preferably 2 to 30% by weight.
上記有機極性溶媒としては、前述の変性ポリイミドの製
造で使用された反応溶媒と同様の有機極性溶媒等を挙げ
ることができる。Examples of the organic polar solvent include the same organic polar solvents as the reaction solvent used in the production of the modified polyimide described above.
本発明の変性ポリイミド組成物は、25℃での回転粘度が
0.1〜5000ポイズ、特に0.2〜2000ポイズ程度にすること
が好ましい。The modified polyimide composition of the present invention has a rotational viscosity at 25 ° C.
It is preferably 0.1 to 5000 poise, particularly 0.2 to 2000 poise.
本発明の変性ポリイミド組成物は、例えば、被覆すべき
対象物（回路基板、光センサー等）の表面に、常温又は
加温下、回転塗布機又は印刷機等を使用する適当な方法
で、均一な厚さに塗布し、該組成物の塗布膜を形成し、
次いで、その塗布膜を約100℃以上、特に120〜450℃の
温度で乾燥させることによって、変性ポリイミドの固化
膜を製造することができる。The modified polyimide composition of the present invention is, for example, uniformly applied to the surface of an object to be coated (circuit board, optical sensor, etc.) at room temperature or under heating by a suitable method using a spin coater or a printer. To form a coating film of the composition,
Then, the coated film is dried at a temperature of about 100 ° C. or higher, particularly 120 to 450 ° C., whereby a solidified film of modified polyimide can be produced.
以下に本発明の実施例を挙げて本発明を更に詳細に説明
する。Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention.
実施例１ ・可溶性芳香族ポリイミドの合成 下記第１表に示すスケールによりそれぞれ次のようにし
て、下記第１表に示す対数粘度を有する可溶性芳香族ポ
リイミド粉末を得た。Example 1-Synthesis of Soluble Aromatic Polyimide A soluble aromatic polyimide powder having a logarithmic viscosity shown in Table 1 below was obtained in the following manner on the scale shown in Table 1 below.
セパラブルフラスコ（撹拌棒、窒素導入口、及び水分定
量受器付）に2,3,3′,4′−ビフェニルテトラカルボン
酸二無水物（ａ−BPDA）及びビス（４−アミノフェノキ
シフェニル）スルホン（BAPS）を加え、これに１時間窒
素を流し、反応系内の空気を置換する。次いで、これに
Ｎ−メチル−２−ピロリドン（NMP）を加え、直ちにフ
ラスコを190℃のオイルバス中に浸し、窒素を流しなが
ら撹拌する。生成する水を過剰のNMPと共に水分定量受
器でとる。８時間反応を行わせ、芳香族ポリイミドを生
成させる。次いで、反応液を冷却後、反応液にNMPを加
え希釈する。然る後、ミキサーにメタノール１を入
れ、反応液を、ミキサーで激しく撹拌されているメタノ
ール中に少しずつ加えて、生成している芳香族ポリイミ
ドを析出させ、これを濾過する。濾過後、得られた芳香
族ポリイミドをメタノール400mlの入ったミキサー中で
洗浄する。この洗浄を２回繰り返した後、芳香族ポリイ
ミドを減圧乾燥して、可溶性芳香族ポリイミド粉末を得
る。In a separable flask (with a stir bar, nitrogen inlet, and water content receiver) 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA) and bis (4-aminophenoxyphenyl) Sulfone (BAPS) is added, and nitrogen is flown into this for 1 hour to replace the air in the reaction system. Then, N-methyl-2-pyrrolidone (NMP) is added thereto, and the flask is immediately immersed in an oil bath at 190 ° C. and stirred while flowing nitrogen. The water produced is taken up in a water content receiver with excess NMP. The reaction is carried out for 8 hours to produce an aromatic polyimide. Then, after cooling the reaction solution, NMP is added to the reaction solution to dilute it. Then, methanol 1 is put into the mixer, and the reaction solution is gradually added to methanol which is vigorously stirred by the mixer to precipitate the aromatic polyimide produced, and this is filtered. After filtration, the aromatic polyimide obtained is washed in a mixer containing 400 ml of methanol. After repeating this washing twice, the aromatic polyimide is dried under reduced pressure to obtain a soluble aromatic polyimide powder.
・変性ポリイミドの合成 前述のようにして得られた可溶性芳香族ポリイミド粉末
を、下記第２表に示す反応条件下に、Ｎ−メチルエタノ
ールアミンと反応させて、変性ポリイミドを得た。尚、
生成した変性ポリイミドの析出は、前記の可溶性芳香族
ポリイミドの析出と同様にして行い、変性ポリイミドは
粉状のポリマーとして得た。 -Synthesis of modified polyimide The soluble aromatic polyimide powder obtained as described above was reacted with N-methylethanolamine under the reaction conditions shown in Table 2 below to obtain a modified polyimide. still,
The modified polyimide thus produced was deposited in the same manner as the soluble aromatic polyimide, and the modified polyimide was obtained as a powdery polymer.
また、この合成反応における、反応時間とイミド環結合
の開環の割合（反応率）との関係を下記第２表に示す。Table 2 below shows the relationship between the reaction time and the ring-opening ratio (reaction rate) of the imide ring bond in this synthetic reaction.
・本発明の変性ポリイミド組成物の調製 前述のようにして得られたポリイミド粉末〔イミド環結
合の開環の割合（反応率）:36％〕をNMPに、12重量％の
濃度で均一に溶解し、本発明の変性ポリイミド組成物
（ワニス）を得た。 -Preparation of modified polyimide composition of the present invention The polyimide powder obtained as described above [ratio of ring opening of imide ring bond (reaction rate): 36%] is uniformly dissolved in NMP at a concentration of 12% by weight. Then, the modified polyimide composition (varnish) of the present invention was obtained.
・密着性及び耐熱性試験 本発明の変性ポリイミド組成物について、各種基板に対
する密着性及び耐熱性を次のようにして測定した。-Adhesion and heat resistance test The modified polyimide composition of the present invention was measured for adhesion and heat resistance to various substrates as follows.
前述の如くして調製した12重量％濃度の本発明の変性ポ
リイミド組成物を、スピンコート（2000rpm）により基
板の上に塗布し、200℃で30分間乾燥して、0.5μｍ厚の
芳香族ポリイミド製の塗膜を作成し、この塗膜の基板に
対する密着性をクロスカットテープ剥離により調べた。
その結果を下記第３表に示す。尚、下記第３表におい
て、密着性の試験結果は、試験後基板に密着している塗
膜の面積パーセントで示してある。The modified polyimide composition of the present invention having a concentration of 12% by weight prepared as described above is applied onto a substrate by spin coating (2000 rpm), dried at 200 ° C. for 30 minutes, and then a 0.5 μm thick aromatic polyimide is applied. A coating film was prepared, and the adhesion of the coating film to the substrate was examined by peeling the cross-cut tape.
The results are shown in Table 3 below. In Table 3 below, the results of the adhesion test are shown by the area percentage of the coating film adhered to the substrate after the test.
〔耐熱性〕 前述の如くして調製した12重量％濃度の本発明の変性ポ
リイミド組成物より作成した５μｍ厚のフイルムを200
℃で30分間乾燥後、TGAにより、減量開始温度及び５％
減量温度を測定した。その結果は次の通りであった。 [Heat Resistance] A film having a thickness of 5 .mu.m prepared from the modified polyimide composition of the present invention having a concentration of 12% by weight prepared as described above is used as 200
After drying for 30 minutes at ℃, by TGA, weight loss start temperature and 5%
The weight loss temperature was measured. The results were as follows.
減量開始温度 240℃ ５％減量温度 375℃ また、12重量％濃度の本発明の変性ポリイミド組成物よ
り作成した12μｍ厚のフイルムを200℃で30分間乾燥
後、TMAを測定した。その結果は、5.2×10-5（／℃）の
膨張係数であった。Weight loss starting temperature 240 ° C. 5% Weight loss temperature 375 ° C. A 12 μm thick film prepared from the modified polyimide composition of the present invention having a concentration of 12% by weight was dried at 200 ° C. for 30 minutes, and then TMA was measured. The result was an expansion coefficient of 5.2 × 10 −5 (/ ° C.).
実施例２ 下記第４表に示す芳香族テトラカルボン酸成分及び芳香
族ジアミン成分を用い、実施例１と同様にしてそれぞれ
下記第４表に示す対数粘度を有する可溶性芳香族ポリイ
ミド粉末を得た。これらの可溶性芳香族パリイミド粉末
を、実施例１と同様の反応条件下に、下記第４表に示す
極性基含有アミン化合物と反応させて、それぞれ下記第
４表に示すイミド環結合の開環の割合（反応率）を有す
る変性ポリイミド粉末を得た。Example 2 Soluble aromatic polyimide powders having logarithmic viscosities shown in Table 4 below were obtained in the same manner as in Example 1 using the aromatic tetracarboxylic acid component and aromatic diamine component shown in Table 4 below. These soluble aromatic pariimide powders were reacted with the polar group-containing amine compounds shown in Table 4 below under the same reaction conditions as in Example 1 to give ring-opening of the imide ring bond shown in Table 4 below. A modified polyimide powder having a ratio (reaction rate) was obtained.
これらの変性ポリイミド粉末をNMPに12重量％の濃度で
それぞれ均一に溶解し、本発明の変性ポリイミド組成物
（ワニス）をそれぞれ得た。Each of these modified polyimide powders was uniformly dissolved in NMP at a concentration of 12% by weight to obtain a modified polyimide composition (varnish) of the present invention.
得られた本発明の変性ポリイミド組成物について、各種
蒸着基板に対する密着性をJIS D0202に準じてそれぞれ
測定した。その結果を下記第４表に示す。With respect to the obtained modified polyimide composition of the present invention, the adhesion to various vapor deposition substrates was measured according to JIS D0202. The results are shown in Table 4 below.
〔発明の効果〕 本発明の変性ポリイミド組成物は、可溶性の芳香族ポリ
イミドを特定のアミン化合物により変性した、有機極性
溶媒に対する溶解性に優れた耐熱性の変性ポリイミド
が、有機極溶媒に均一に溶解しているもので、種々の無
機又は金属材料等の表面に塗布して、その塗布層を乾燥
及び加熱処理することにより、密着性に優れていると共
に光透過性（無色透明性）に優れた耐熱性及び電気絶縁
性の被覆層（薄膜層）を形成することができ、また、水
分により白化することがなく、透明で均一な厚みの膜を
形成することができ、特に液晶配向膜の形成材料として
好適なものであり、その他インキ材料の用途等にも用い
られる。 [Effects of the Invention] The modified polyimide composition of the present invention is a soluble aromatic polyimide modified with a specific amine compound, which is a heat-resistant modified polyimide having excellent solubility in an organic polar solvent, which is uniformly mixed in an organic polar solvent. It is dissolved, and by applying it to the surface of various inorganic or metallic materials, etc., and drying and heating the applied layer, it has excellent adhesion and excellent light transmission (colorless transparency). A heat-resistant and electrically insulating coating layer (thin film layer) can be formed, and a transparent and uniform film can be formed without being whitened by moisture. It is suitable as a forming material and is also used for other purposes such as ink materials.
Claims (1)
ミン成分とを重合及びイミド化して得られた可溶性芳香
族ポリイミドを、一般式R1−NH−R2（但し、R1は炭素数
１〜６のアルキル基であり、R2は水酸基、及びカルボキ
シル基からなる群から選ばれた極性基を有する炭素数１
〜６の炭化水素基又は炭素数６〜13の芳香族炭化水素基
である）で示される極性基含有アミン化合物と反応さ
せ、該反応で上記可溶性芳香族ポリイミドのイミド環結
合の少なくとも５％以上開環させて変性ポリイミドと
し、 上記変性ポリイミドを有機極性溶媒に１〜50重量％の濃
度で均一に溶解させて製造することを特徴とする変性ポ
リイミド組成物の製法。1. A soluble aromatic polyimide obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component and an aromatic diamine component to obtain a soluble aromatic polyimide represented by the general formula R 1 —NH—R 2 (where R 1 is a carbon number 1 To 6 alkyl groups, R 2 has a polar group selected from the group consisting of a hydroxyl group and a carboxyl group, and has 1 carbon atom
To a hydrocarbon group of 6 to 6 or an aromatic hydrocarbon group of 6 to 13 carbon atoms), and at least 5% or more of the imide ring bond of the soluble aromatic polyimide in the reaction. A method for producing a modified polyimide composition, which comprises ring-opening to obtain a modified polyimide, and uniformly dissolving the modified polyimide in an organic polar solvent at a concentration of 1 to 50% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23907185A JPH0670136B2 (en) | 1985-10-25 | 1985-10-25 | Method for producing modified polyimide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23907185A JPH0670136B2 (en) | 1985-10-25 | 1985-10-25 | Method for producing modified polyimide composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62100529A JPS62100529A (en) | 1987-05-11 |
| JPH0670136B2 true JPH0670136B2 (en) | 1994-09-07 |
Family
ID=17039416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23907185A Expired - Fee Related JPH0670136B2 (en) | 1985-10-25 | 1985-10-25 | Method for producing modified polyimide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0670136B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9556311B2 (en) | 2012-07-19 | 2017-01-31 | Samsung Electronics Co., Ltd. | Polyimide precursor composition, article prepared by using same, and display device including the article |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2010095601A1 (en) | 2009-02-19 | 2012-08-23 | 日本バルカー工業株式会社 | Functional molded body and method for producing the same |
| US8518525B2 (en) * | 2010-12-09 | 2013-08-27 | E I Du Pont De Nemours And Company | Polyimide nanoweb with amidized surface and method for preparing |
| JP2016040356A (en) * | 2014-08-13 | 2016-03-24 | ソルピー工業株式会社 | Polyimide composition, method for producing polyimide molding, and method for producing polyimide film |
| CN112812301A (en) * | 2021-01-04 | 2021-05-18 | 株洲时代新材料科技股份有限公司 | Preparation of soluble polyimide, black soluble polyimide composite glue solution prepared from soluble polyimide, preparation and application of black soluble polyimide composite glue solution |
-
1985
- 1985-10-25 JP JP23907185A patent/JPH0670136B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9556311B2 (en) | 2012-07-19 | 2017-01-31 | Samsung Electronics Co., Ltd. | Polyimide precursor composition, article prepared by using same, and display device including the article |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62100529A (en) | 1987-05-11 |
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