JP2003041004A - Polyimide and laminated material - Google Patents
Polyimide and laminated materialInfo
- Publication number
- JP2003041004A JP2003041004A JP2002150348A JP2002150348A JP2003041004A JP 2003041004 A JP2003041004 A JP 2003041004A JP 2002150348 A JP2002150348 A JP 2002150348A JP 2002150348 A JP2002150348 A JP 2002150348A JP 2003041004 A JP2003041004 A JP 2003041004A
- Authority
- JP
- Japan
- Prior art keywords
- chemical
- same manner
- polyimide
- varnish
- polyimide powder
- 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.)
- Granted
Links
Landscapes
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、ポリイミド及び
このポリイミドを主成分とする樹脂層と基材とからなる
積層体に関し、特に、カルボキシル基を有する二価の有
機基を反応成分として得られるポリイミド及びこのポリ
イミドを主成分とする樹脂層が基材に積層されてなる積
層体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide and a laminate comprising a resin layer containing the polyimide as a main component and a substrate, and in particular, a polyimide obtained by using a divalent organic group having a carboxyl group as a reaction component. Also, the present invention relates to a laminate in which a resin layer containing polyimide as a main component is laminated on a base material.
【０００２】[0002]
【従来の技術】可視光領域において透明性を有するポリ
イミドは種々研究され、その多くは酸二無水物とジアミ
ンを反応させた脂肪族構造のものである。また、ポリマ
ー骨格に脂肪族成分を導入したことによる耐熱性の低下
を避けるために、脂肪族成分を脂肪族環構造（以下「脂
環構造」という）成分に変性したポリイミドも種々研究
されている。Various studies have been made on polyimides having transparency in the visible light region, and most of them have an aliphatic structure obtained by reacting an acid dianhydride with a diamine. In addition, various polyimides obtained by modifying an aliphatic component into an alicyclic structure (hereinafter referred to as “alicyclic structure”) component have been studied in order to avoid a decrease in heat resistance due to the introduction of an aliphatic component into the polymer skeleton. .
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
耐熱性が高く透明性を有するポリイミドは、イミド閉環
後は溶剤に対する溶解性が非常に乏しくなり、沸点の高
い有機極性溶剤又は有機アルカリにのみ可溶性を示し、
ポリイミド樹脂層を剥離する際に用いた溶剤の廃液処理
は環境への負荷が非常に大きい。なお、ここでの沸点の
高い有機極性溶剤及び有機アルカリとしては、Ｎ−メチ
ル−２−ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホル
ムアミド（ＤＭＦ）、ヒドラジン等である。However, the conventional polyimide having high heat resistance and transparency has very poor solubility in a solvent after imide ring closure, and is soluble only in an organic polar solvent or organic alkali having a high boiling point. Indicates
The waste liquid treatment of the solvent used when peeling off the polyimide resin layer has a great impact on the environment. The organic polar solvent and organic alkali having a high boiling point are N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), hydrazine and the like.
【０００４】本発明の目的は、高い耐熱性及び透明性を
有し、しかも環境への負荷の小さい希無機アルカリ水溶
液等の溶剤により樹脂層を剥離することが可能なポリイ
ミド及び積層体を提供することにある。An object of the present invention is to provide a polyimide and a laminate having high heat resistance and transparency, and capable of peeling a resin layer with a solvent such as a dilute inorganic alkaline aqueous solution having a small load on the environment. Especially.
【０００５】[0005]
【課題を解決するための手段】前記目的を達成するた
め、本発明は、ジアミンから選ばれる少なくとも１種の
化合物と酸二無水物から選ばれる少なくとも１種の化合
物を有機溶媒中で反応させてなる生成物であり、前記ジ
アミンの必須成分としてカルボキシル基を一つ以上有す
る脂肪族環構造ジアミンが反応に供せられてなることを
特徴とするポリイミド、及びこのポリイミドを主成分と
する樹脂層が基材上に形成された積層体を提供する。In order to achieve the above object, the present invention comprises reacting at least one compound selected from diamines and at least one compound selected from acid dianhydrides in an organic solvent. Which is a product, wherein a polyimide characterized by being subjected to a reaction with an aliphatic ring structure diamine having one or more carboxyl groups as an essential component of the diamine, and a resin layer containing this polyimide as a main component. A laminate formed on a base material is provided.
【０００６】[0006]
【発明の実施の形態】本発明において、カルボキシル基
を一つ以上有する脂肪族環構造ジアミンとしては、化学
式BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an aliphatic ring structure diamine having one or more carboxyl groups has a chemical formula:
【化３３】 [Chemical 33]
【化３４】 [Chemical 34]
【化３５】 [Chemical 35]
【化３６】 [Chemical 36]
【化３７】
で表わされる化合物をあげることができ、これらは単独
で又は２種以上で使用することができる。[Chemical 37] The compounds represented by can be mentioned, and these can be used alone or in combination of two or more kinds.
【０００７】本発明においては、ジアミン成分としてカ
ルボキシル基を一つ以上有する脂肪族環構造ジアミンの
みの使用であってもよいが、他のジアミン、例えば、化
学式In the present invention, as the diamine component, only an alicyclic diamine having one or more carboxyl groups may be used, but other diamines, for example, chemical formulas
【化３８】 [Chemical 38]
【化３９】 [Chemical Formula 39]
【化４０】 [Chemical 40]
【化４１】 [Chemical 41]
【化４２】 [Chemical 42]
【化４３】 [Chemical 43]
【化４４】 [Chemical 44]
【化４５】 [Chemical formula 45]
【化４６】 [Chemical formula 46]
【化４７】 [Chemical 47]
【化４８】 [Chemical 48]
【化４９】 [Chemical 49]
【化５０】 [Chemical 50]
【化５１】 [Chemical 51]
【化５２】 [Chemical 52]
【化５３】 [Chemical 53]
【化５４】 [Chemical 54]
【化５５】 [Chemical 55]
【化５６】 [Chemical 56]
【化５７】 [Chemical 57]
【化５８】 [Chemical 58]
【化５９】 [Chemical 59]
【化６０】 [Chemical 60]
【化６１】 [Chemical formula 61]
【化６２】 [Chemical formula 62]
【化６３】 [Chemical formula 63]
【化６４】 [Chemical 64]
【化６５】 で表わされる化合物を併用してもよい。[Chemical 65] You may use together the compound represented by.
【０００８】酸二無水物としては、例えば、化学式Examples of the acid dianhydride include those represented by the chemical formula:
【化６６】 [Chemical formula 66]
【化６７】 [Chemical formula 67]
【化６８】 [Chemical 68]
【化６９】 [Chemical 69]
【化７０】 [Chemical 70]
【化７１】 [Chemical 71]
【化７２】
で表わされる化合物をあげることができ、これらは単独
で又は２種以上で使用することができる。[Chemical 72] The compounds represented by can be mentioned, and these can be used alone or in combination of two or more kinds.
【０００９】本発明においては、ジアミン成分として化
学式（１）〜（５）で表わされる化合物で代表されるカ
ルボキシル基を一つ以上有する脂肪族環構造ジアミンを
使用することにより、耐熱性、溶解性及び透明性を兼備
したポリイミドを実現できる。又、カルボキシル基を一
つ以上有する脂肪族環構造ジアミンは、より高い透明性
を実現する上でも有用であり、更に、化学式（６）〜
（１４）で表わされるジアミン成分及び化学式（３
４）、（３５）、（３８）、（４０）で表わされる酸二
無水物成分も高い透明性を実現する上で有用であり、こ
れらの成分を適宜組合わせて反応成分としてなるポリイ
ミドは、より高い透明性の実現を可能とする。In the present invention, heat resistance and solubility are improved by using an aliphatic ring structure diamine having at least one carboxyl group represented by the compounds represented by the chemical formulas (1) to (5) as the diamine component. In addition, a polyimide having transparency can be realized. In addition, the aliphatic ring structure diamine having one or more carboxyl groups is also useful in achieving higher transparency, and further, the chemical formula (6)
The diamine component represented by (14) and the chemical formula (3
The acid dianhydride components represented by 4), (35), (38) and (40) are also useful in achieving high transparency, and the polyimide which is a combination of these components as a reaction component is Enables higher transparency.
【００１０】本発明において、化学式（１）で表わされ
る脂肪族環構造ジアミンの具体例としては、３，５−ジ
アミノシクロヘキサンカルボン酸をあげることができ
る。この化合物は、化学式（１７）で表わされる３，５
−ジアミノ安息香酸を還元することにより製造すること
ができる。３，５−ジアミノ安息香酸を還元する方法と
しては、触媒を用いて接触水素化する方法、化学的還元
剤を用いる方法等がある。In the present invention, 3,5-diaminocyclohexanecarboxylic acid can be mentioned as a specific example of the aliphatic ring structure diamine represented by the chemical formula (1). This compound is represented by the chemical formula (17): 3,5
-It can be produced by reducing diaminobenzoic acid. As a method for reducing 3,5-diaminobenzoic acid, there are a method of catalytic hydrogenation using a catalyst, a method of using a chemical reducing agent, and the like.
【００１１】触媒を用いて接触水素化する方法は、水素
を含む反応容器内において、触媒を含む溶媒下、ジアミ
ノ安息香酸を水素と接触させて還元するものである。こ
の場合、接触水素化をより容易に行うために、ジアミノ
安息香酸を酸又は塩基と反応させてできる塩を用いるこ
とが好ましい。The catalytic hydrogenation method using a catalyst is to reduce diaminobenzoic acid in contact with hydrogen in a reaction vessel containing hydrogen in a solvent containing the catalyst. In this case, in order to carry out the catalytic hydrogenation more easily, it is preferable to use a salt formed by reacting diaminobenzoic acid with an acid or a base.
【００１２】酸又は塩基としては、硫酸、塩酸、硝酸、
臭化水素酸、ヨウ化水素酸、過塩素酸、リン酸、炭酸等
の鉱酸、酢酸等の有機酸、苛性ソーダ、アンモニア、水
素化リチウム等の塩基を挙げることができる。Acids or bases include sulfuric acid, hydrochloric acid, nitric acid,
Mention may be made of mineral acids such as hydrobromic acid, hydroiodic acid, perchloric acid, phosphoric acid and carbonic acid, organic acids such as acetic acid, bases such as caustic soda, ammonia and lithium hydride.
【００１３】触媒としては、接触水素化を促進できるも
のであれば特に限定されず、Ｒｈ／Ａｌ2Ｏ3、Ｒｈ／
Ｃ、Ｒｈ2Ｏ3、Ｒｕ／Ａｌ2Ｏ3、Ｒｕ／Ｃ、ＲｕＯ2、
Ｐｔ／Ａｌ2Ｏ3、Ｐｔ／Ｃ、ＰｔＯ2、Ｐｄ／Ａｌ
2Ｏ3、Ｐｄ／Ｃ、ＰｄＯ等を挙げることができる。The catalyst is not particularly limited as long as it can promote catalytic hydrogenation, and Rh / Al 2 O 3 and Rh /
C, Rh 2 O 3 , Ru / Al 2 O 3 , Ru / C, RuO 2 ,
Pt / Al 2 O 3 , Pt / C, PtO 2 , Pd / Al
2 O 3 , Pd / C, PdO and the like can be mentioned.
【００１４】溶媒としては、反応原料及び目的を溶解で
きるものであれば特に限定されず、塩化メチレンなどの
ハロゲン含有炭化水素溶媒、エーテル、テトラヒドロフ
ラン、ジオキサン、などのエーテル系溶媒、メタノー
ル、エタノール、２−プロパノール、ブタノールなどの
アルコール系溶媒、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ
−メチルピロリドン、ジメチルスルホキシドなどの極性
溶媒等を挙げることができる。The solvent is not particularly limited as long as it can dissolve the reaction raw material and the purpose, and a halogen-containing hydrocarbon solvent such as methylene chloride, an ether solvent such as ether, tetrahydrofuran, dioxane, methanol, ethanol, 2 -Alcohol solvents such as propanol and butanol, N, N-dimethylformamide, N
Examples thereof include polar solvents such as methylpyrrolidone and dimethylsulfoxide.
【００１５】接触水素化する際は、予めジアミノ安息香
酸に溶媒、触媒等を加えて調整後、水素を含む反応容器
内で十分に攪拌することが好ましい。In the catalytic hydrogenation, it is preferable that the solvent, the catalyst and the like are added to diaminobenzoic acid in advance and then the mixture is sufficiently stirred in a reaction vessel containing hydrogen.
【００１６】本発明のポリイミドは、ジアミンと酸二無
水物を有機溶媒に溶解させて直接イミド化することによ
って製造することができ、更にはジアミンと酸二無水物
を有機溶媒中で溶解反応させ、続いてジアミン及び酸二
無水物の少なくとも一方を添加してイミド化することに
よっても製造することができる。ジアミンと酸二無水物
との混合比は、酸二無水物の合計量１モル％に対して、
ジアミンの合計量０．９５〜１．０５モル％とするのが
好ましい。The polyimide of the present invention can be produced by dissolving a diamine and an acid dianhydride in an organic solvent and directly imidizing the same, and further dissolving and reacting the diamine and the acid dianhydride in an organic solvent. Then, it can also be produced by subsequently adding at least one of a diamine and an acid dianhydride and imidizing. The mixing ratio of the diamine and the acid dianhydride is 1 mol% based on the total amount of the acid dianhydride.
The total amount of diamine is preferably 0.95 to 1.05 mol%.
【００１７】有機溶媒としては、Ｎ−メチル−２−ピロ
リドン、ジメチルホルムアミド、ジメチルアセトアミ
ド、スルホラン、アニソール、ジオキソラン、ブチルセ
ルソルブアセテート、ラクトン系等が挙げられ、これら
単独で使用することができるが、２種以上を混合して使
用してもよい。ラクトン系としては、γ−カプロラクト
ン、γ−バレロラクトン、γ−ブチロラクトン、γ−テ
トロン酸、γ−フタリド、γ−フタリド酸、γ−クマリ
ン等が挙げられ、ラクトン系とピリジン、キノリン、Ｎ
−メチルモルフォリン等の塩基化合物との混合物も使用
可能である。Examples of the organic solvent include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, sulfolane, anisole, dioxolane, butylcellosolve acetate and lactone series, which can be used alone. You may mix and use 2 or more types. Examples of the lactone type include γ-caprolactone, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-phthalide acid, and γ-coumarin, and the lactone type and pyridine, quinoline, N
Mixtures with basic compounds such as methylmorpholine can also be used.
【００１８】本発明のポリイミドは、適宜有機溶剤で希
釈してガラス、銅、アルミ、ステンレス等の基材上に塗
布乾燥して樹脂層となし、積層体とすることができる。The polyimide of the present invention can be appropriately diluted with an organic solvent and applied on a substrate such as glass, copper, aluminum or stainless steel and dried to form a resin layer to form a laminate.
【００１９】[0019]
【実施例】以下、本発明の実施例を比較例と共に説明す
る。EXAMPLES Examples of the present invention will be described below together with comparative examples.
【００２０】（実施例１）
［３，５−ジアミノシクロヘキサンカルボン酸の合成］
ジアミノ安息香酸２５ｇ及び２１．５％硫酸７５ｇ、触
媒として５％Ｒｕ／Ａｌ2Ｏ3１．２５ｇを２００ｍｌ攪
拌式オートクレーブに仕込み、水素圧８ＭＰａ、容器内
温度８０℃の条件下で攪拌し、１０時間反応させた。反
応液をろ過、蒸発乾固し、３，５−ジアミノシクロヘキ
サンカルボン酸硫酸塩４１．１ｇを得た。この結晶を水
に溶解し、苛性ソーダを加えてｐＨ＝９．６にした。こ
の液を電気透析装置（商品名「アシライザー」、旭化成
株式会社製）を用いて脱硫酸し、アバポレーションにて
２０％水溶液となるまで濃縮し、３，５−ジアミノシク
ロヘキサンカルボン酸を得た。(Example 1) [Synthesis of 3,5-diaminocyclohexanecarboxylic acid]
25 g of diaminobenzoic acid, 75 g of 21.5% sulfuric acid, and 1.25 g of 5% Ru / Al 2 O 3 as a catalyst were placed in a 200 ml stirring autoclave, and the mixture was stirred under the conditions of hydrogen pressure of 8 MPa and internal temperature of 80 ° C. Reacted for hours. The reaction solution was filtered and evaporated to dryness to obtain 41.1 g of 3,5-diaminocyclohexanecarboxylic acid sulfate. The crystals were dissolved in water and caustic soda was added to adjust the pH to 9.6. This solution was desulfated using an electrodialyzer (trade name “Acilyzer”, manufactured by Asahi Kasei Co., Ltd.) and concentrated by evaporation to a 20% aqueous solution to obtain 3,5-diaminocyclohexanecarboxylic acid. .
【００２１】［ポリイミドの合成］
［工程１］攪拌器を取りつけた１０００ｍｌのセパラブ
ル四つ口フラスコに、水分分離トラップを備えた玉付冷
却管を取りつけ、１，２，３，４−シクロペンタンテト
ラカルボン酸二無水物（ＣＰＤＡ、化学式（３４））２
１．０ｇ、３，５−ジアミノシクロヘキサンカルボン酸
（ＤＡＣＣ、化学式（１））１５．８ｇ、γ−カプロラ
クトン１．１ｇ、ピリジン２．０ｇ、Ｎ−メチル−２−
ピロリドン（ＮＭＰ）２００．０ｇ、トルエン４０．０
ｇを加え、常温で窒素雰囲気下で１０分間攪拌した後、
反応槽の内容物を１８０℃に昇温し、攪拌機の回転数を
１８０ｒｐｍに設定して３時間攪拌し、攪拌終了後真空
乾燥を行い反応液（ワニス）を得た。なお留出成分は反
応中に水分分離トラップより適時取り除いた。
［工程２］［工程１］で得たワニスをメタノール中に投
入することによって、生成した沈殿を分離し、粉砕、ろ
過、洗浄および減圧乾燥させる工程を経ることによりポ
リイミド粉末を得た。
［工程３］その後ＮＭＰ２６．０ｇにポリイミド粉末
４．０ｇを溶解してポリイミド溶液を調整した。[Synthesis of Polyimide] [Step 1] A 1,000 ml separable four-necked flask equipped with a stirrer was fitted with a condenser tube with a ball equipped with a water separation trap to prepare 1,2,3,4-cyclopentane tetra. Carboxylic dianhydride (CPDA, chemical formula (34)) 2
1.0 g, 3,5-diaminocyclohexanecarboxylic acid (DACC, chemical formula (1)) 15.8 g, γ-caprolactone 1.1 g, pyridine 2.0 g, N-methyl-2-
Pyrrolidone (NMP) 200.0 g, toluene 40.0
g, and after stirring at room temperature for 10 minutes in a nitrogen atmosphere,
The contents of the reaction tank were heated to 180 ° C., the number of revolutions of the stirrer was set to 180 rpm, and the mixture was stirred for 3 hours. After completion of stirring, vacuum drying was performed to obtain a reaction liquid (varnish). The distillate components were removed from the water separation trap at appropriate times during the reaction. [Step 2] The varnish obtained in [Step 1] was put into methanol to separate the generated precipitate, and the polyimide powder was obtained by the steps of crushing, filtering, washing and drying under reduced pressure. [Step 3] Then, 4.0 g of polyimide powder was dissolved in 26.0 g of NMP to prepare a polyimide solution.
【００２２】（実施例２）
［工程１］実施例１と同様の装置に、ビシクロ（２，
２，２）オクト−７−エン−２，３，５，６−テトラカ
ルボン酸二無水物（ＢＣＤ、化学式（３５））２４．８
ｇ、ＤＡＣＣ１５．８ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、トルエン
４０．０を加え、実施例１の［工程１］と同様にして反
応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。Example 2 [Step 1] A bicyclo (2,
2,2) Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD, chemical formula (35)) 24.8
g, DACC 15.8 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００２３】（実施例３）
［工程１］実施例１と同様の装置に、４，４′−オキシ
ジフタル酸無水物（ＯＤＰＡ、化学式（３８））３１．
０ｇ、ＤＡＣＣ１５．８ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００ｇ、トルエン４
０．０ｇを加え、実施例１の［工程１］と同様にして反
応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Example 3) [Step 1] The same apparatus as in Example 1 was charged with 4,4'-oxydiphthalic anhydride (ODPA, chemical formula (38)) 31.
0 g, DACC 15.8 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200 g, toluene 4
0.0 g was added and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００２４】（実施例４）
［工程１］実施例１と同様の装置に、４，４′−（ヘキ
サフルオロイソプピリデン）フタル酸二無水物（６−Ｆ
ＤＡ、化学式（４０））４４．４ｇ、ＤＡＣＣ１５．８
ｇ、γ−カプロラクトン１．１ｇ、ピリジン２．０ｇ、
ＮＭＰ２００．０ｇ、トルエン４０．０ｇを加え、実施
例１の［工程１］と同様にして反応液（ワニス）を得
た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。Example 4 [Step 1] 4,4 '-(hexafluoroisoppyridene) phthalic acid dianhydride (6-F) was placed in the same apparatus as in Example 1.
DA, chemical formula (40)) 44.4 g, DACC 15.8
g, γ-caprolactone 1.1 g, pyridine 2.0 g,
200.0 g of NMP and 40.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００２５】（実施例５）
［工程１］実施例１と同様の装置に、３，３′，４，
４′−ベンゾフェノンテトラカルボン酸二無水物（ＢＴ
ＤＡ、化学式（３９））３２．２ｇ、ＤＡＣＣ１５．８
ｇ、γ−カプロラクトン１．１ｇ、ピリジン２．０ｇ、
ＮＭＰ２００．０ｇ、トルエン４０．０ｇを加え、実施
例１の［工程１］と同様にして反応液（ワニス）を得
た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Embodiment 5) [Step 1] In the same apparatus as in Embodiment 1, 3, 3 ', 4,
4'-benzophenone tetracarboxylic dianhydride (BT
DA, chemical formula (39)) 32.2 g, DACC 15.8
g, γ-caprolactone 1.1 g, pyridine 2.0 g,
200.0 g of NMP and 40.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００２６】（実施例６）
［工程１］実施例１と同様の装置に、３，３′，４，
４′−ビフェニルテトラカルボン酸二無水物（ＢＰＤ
Ａ、化学式（３７））２９．４ｇ、ＤＡＣＣ１５．８
ｇ、ＮＭＰ２００．０ｇを加え、実施例１の［工程１］
と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Embodiment 6) [Step 1] 3,3 ', 4, in the same apparatus as in Embodiment 1
4'-biphenyltetracarboxylic dianhydride (BPD
A, chemical formula (37)) 29.4 g, DACC 15.8
g, and NMP 200.0 g are added, and [Step 1] of Example 1 is performed.
A reaction solution (varnish) was obtained in the same manner as in. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００２７】（実施例７）
［工程１］実施例１と同様の装置に、ピロメリット酸二
無水物（ＰＭＤＡ、化学式（３６））２１．８ｇ、ＤＡ
ＣＣ１５．８ｇ、ＮＭＰ２００．０ｇを加え、実施例１
の［工程１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。Example 7 [Step 1] 21.8 g of pyromellitic dianhydride (PMDA, chemical formula (36)) and DA were placed in the same apparatus as in Example 1.
CC15.8g, NMP200.0g was added, and Example 1
A reaction solution (varnish) was obtained in the same manner as in [Step 1]. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００２８】（実施例８）
［工程１］実施例１と同様の装置に、６−ＦＤＡ２２．
２ｇ、ＯＰＤＡ１５．５ｇ、ＤＡＣＣ１５．８ｇ、γ−
カプロラクトン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２
００．０ｇ、トルエン４０．０ｇを加え、実施例１の
［工程１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Embodiment 8) [Step 1] A 6-FDA22.
2 g, OPDA 15.5 g, DACC 15.8 g, γ-
Caprolactone 1.1 g, pyridine 2.0 g, NMP2
A reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 1 by adding 00.0 g and toluene 40.0 g. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００２９】（実施例９）
［工程１］実施例１と同様の装置に、ＢＣＤ２４．８
ｇ、ＤＡＣＣ７．８ｇ、３，３′−ジメチル−４，４′
−ジアミノジシクロヘキシルメタン（ＤＭＨＡ、化学式
（１２））１１．９ｇ、γ−カプロラクトン１．１ｇ、
ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、トルエン４
０．０ｇを加え、実施例１の［工程１］と同様にして反
応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Embodiment 9) [Step 1] BCD24.8 was added to the same apparatus as in Embodiment 1.
g, DACC 7.8 g, 3,3′-dimethyl-4,4 ′
-Diaminodicyclohexylmethane (DMHA, chemical formula (12)) 11.9 g, γ-caprolactone 1.1 g,
Pyridine 2.0 g, NMP 200.0 g, toluene 4
0.0 g was added and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００３０】（比較例１）実施例１と同様の装置に、Ｂ
ＰＤＡ２９．４ｇ、１，４−フェニレンジアミン（ｐ−
ＰＤＡ、化学式（５））１０．８ｇ、ＮＭＰ２００．０
ｇを加え、実施例１の［工程１］と同様にして反応液
（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Comparative Example 1) In the same apparatus as in Example 1, B
29.4 g of PDA, 1,4-phenylenediamine (p-
PDA, chemical formula (5)) 10.8 g, NMP200.0
g was added and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００３１】（比較例２）実施例１と同様の装置に、Ｐ
ＭＤＡ２１．８ｇ、４，４′−ジアミノジフェニルエー
テル（ｐ−ＤＡＤＥ、化学式（２７））２０．０ｇ、Ｎ
ＭＰ２００．０ｇを加え、実施例１の［工程１］と同様
にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Comparative Example 2) A device similar to that of Example 1 was prepared by adding P
MDA 21.8 g, 4,4'-diaminodiphenyl ether (p-DADE, chemical formula (27)) 20.0 g, N
MP0.020.0g was added and it carried out similarly to [Process 1] of Example 1, and obtained the reaction liquid (varnish). [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００３２】（比較例３）実施例１と同様の装置に、Ｂ
ＣＤ２４．８ｇ、イソホロンジアミン１７．０ｇ、ｐ−
ＰＤＡ１０．８ｇ、γ−カプロラクトン１．１ｇ、ピリ
ジン２．０ｇ、ＮＭＰ２００．０ｇ、トルエン４０．０
ｇを加え、実施例１の［工程１］と同様にして反応液
（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Comparative Example 3) In the same apparatus as in Example 1,
CD 24.8 g, isophorone diamine 17.0 g, p-
PDA 10.8 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g, toluene 40.0
g was added and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 1. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００３３】（比較例４）実施例１と同様の装置に、Ｏ
ＰＤＡ３１．０ｇ、３，５−ジアミノ安息香酸（ＤＡＢ
ｚ、化学式（１７））１５．２ｇ、γ−カプロラクトン
１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、ト
ルエン４０．０ｇを加え、実施例１の［工程１］と同様
にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１の［工程
２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
の［工程３］と同様に処理してポリイミド溶液を調整し
た。(Comparative Example 4) The same apparatus as in Example 1 was charged with O
PDA 31.0 g, 3,5-diaminobenzoic acid (DAB
z, chemical formula (17) 15.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 g were added, and the reaction solution (varnish) was added in the same manner as in [Step 1] of Example 1. ) Got. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 1 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
A polyimide solution was prepared in the same manner as in [Step 3].
【００３４】実施例１〜９及び比較例１〜４のポリイミ
ド溶液をガラス板上に塗布乾燥して積層体を製造し、希
無機アルカリ水溶液への溶解性及び光透過率を測定し、
その結果を表１に示した。The polyimide solutions of Examples 1 to 9 and Comparative Examples 1 to 4 were applied onto a glass plate and dried to produce a laminate, and the solubility in a dilute inorganic alkaline aqueous solution and the light transmittance were measured.
The results are shown in Table 1.
【００３５】希無機アルカリ水溶液への溶解性評価：ガ
ラス基板上にポリイミド樹脂組成物溶液をスピンコート
法により塗布した後、乾燥して樹脂層を厚さ３μmに形
成することにより溶解試験用サンプルを作成した。次
に、この溶解試験用サンプルを１％水酸化ナトリウム水
溶液、及び１％水酸化カリウム水溶液に投入し、樹脂層
の溶解性を評価し、樹脂層が溶解した場合を○、不溶の
場合を×とした。Evaluation of Solubility in Dilute Inorganic Alkaline Aqueous Solution: A polyimide resin composition solution was applied on a glass substrate by a spin coating method, and then dried to form a resin layer having a thickness of 3 μm to obtain a dissolution test sample. Created. Next, this dissolution test sample was put into a 1% aqueous sodium hydroxide solution and a 1% aqueous potassium hydroxide solution, and the solubility of the resin layer was evaluated. And
【００３６】光透過率の測定：ガラス基板上にポリイミ
ド樹脂組成物溶液をスピンコート法により塗布した後、
乾燥し、樹脂層を厚さ２５μmに形成することにより光
透過率評価用サンプルを作成した。この光透過率評価用
サンプルとリファレンス用の樹脂層を全く設けていない
ガラス基板により、ＵＶ−可視分光光度計を用いて、３
８０ｎｍでの光透過率を測定し、樹脂層の光透過率が５
０％以上を○、３０〜５０％を△、３０％以下を×とし
た。Measurement of light transmittance: After coating a polyimide resin composition solution on a glass substrate by spin coating,
A sample for light transmittance evaluation was prepared by drying and forming a resin layer with a thickness of 25 μm. By using this UV transmittance-visible spectrophotometer, the sample for light transmittance evaluation and the glass substrate on which no resin layer for reference is provided are used.
The light transmittance at 80 nm was measured, and the light transmittance of the resin layer was 5
0% or more was ◯, 30 to 50% was Δ, and 30% or less was X.
【００３７】[0037]
【表１】 [Table 1]
【００３８】（実施例１０）
［工程１］攪拌器を取りつけた１０００ｍｌのセパラブ
ル四つ口フラスコに、水分分離トラップを備えた玉付冷
却管を取りつけ、ＣＰＤＡ２１．０ｇ、４，６−ジアミ
ノ−１，３−シクロヘキサンジカルボン酸（１，３−Ｄ
ＡＣＤ、化学式（２））２０．２ｇ、γ−カプロラクト
ン１．１ｇ、ピリジン２．０ｇ、Ｎ−メチル−２−ピロ
リドン（ＮＭＰ）２００．０ｇ、トルエン４０．０ｇを
加え、常温で窒素雰囲気下で１０分間攪拌した後、反応
槽の内容物を１８０℃に昇温し、攪拌機の回転数を１８
０ｒｐｍに設定して３時間攪拌し、攪拌終了後真空乾燥
を行い反応液（ワニス）を得た。なお留出成分は反応中
に水分分離トラップより適時取り除いた。
［工程２］［工程１］で得たワニスをメタノール中に投
入することによって、生成した沈殿を分離し、粉砕、ろ
過、洗浄および減圧乾燥させる工程を経ることによりポ
リイミド粉末を得た。
［工程３］その後ＮＭＰ２６．０ｇにポリイミド粉末
４．０ｇを溶解してポリイミド溶液を調整した。(Example 10) [Step 1] A 1000 ml separable four-necked flask equipped with a stirrer was fitted with a condenser tube with a ball equipped with a water separation trap, and 21.0 g of CPDA, 4,6-diamino-1. , 3-Cyclohexanedicarboxylic acid (1,3-D
ACD, chemical formula (2)) 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, N-methyl-2-pyrrolidone (NMP) 200.0 g, toluene 40.0 g were added, and at room temperature under a nitrogen atmosphere. After stirring for 10 minutes, the content in the reaction vessel was heated to 180 ° C and the rotation speed of the stirrer was set to 18
The reaction liquid (varnish) was obtained by setting the speed to 0 rpm and stirring for 3 hours, and after completion of stirring, vacuum drying was performed. The distillate components were removed from the water separation trap at appropriate times during the reaction. [Step 2] The varnish obtained in [Step 1] was put into methanol to separate the generated precipitate, and the polyimide powder was obtained by the steps of crushing, filtering, washing and drying under reduced pressure. [Step 3] Then, 4.0 g of polyimide powder was dissolved in 26.0 g of NMP to prepare a polyimide solution.
【００３９】（実施例１１）
［工程１］実施例１０と同様の装置に、ＢＣＤ２４．８
ｇ、１，３−ＤＡＣＤ２０．２ｇ、γ−カプロラクトン
１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、ト
ルエン４０．０を加え、実施例１０の［工程１］と同様
にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１０の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
０の［工程３］と同様に処理してポリイミド溶液を調整
した。(Embodiment 11) [Step 1] A device similar to that of Embodiment 10 was used, and BCD 24.8 was used.
g, 1,3-DACD 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g, toluene 40.0 were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 10. Got [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 10 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 0, a polyimide solution was prepared.
【００４０】（実施例１２）
［工程１］実施例１０と同様の装置に、ＯＤＰＡ３１．
０ｇ、１，３−ＤＡＣＤ２０．２ｇ、γ−カプロラクト
ン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００ｇ、トル
エン４０．０ｇを加え、実施例１０の［工程１］と同様
にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１０の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
０の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 12) [Step 1] ODPA31.
0 g, 1,3-DACD 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200 g, and toluene 40.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 10. It was [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 10 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 0, a polyimide solution was prepared.
【００４１】（実施例１３）
［工程１］実施例１０と同様の装置に、６−ＦＤＡ４
４．４ｇ、１，３−ＤＡＣＤ２０．２ｇ、γ−カプロラ
クトン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０
ｇ、トルエン４０．０ｇを加え、実施例１０の［工程
１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１０の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
０の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 13) [Step 1] 6-FDA4 was added to the same apparatus as in Example 10.
4.4 g, 1,3-DACD 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP200.0
g and toluene 40.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 10. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 10 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 0, a polyimide solution was prepared.
【００４２】（実施例１４）
［工程１］実施例１０と同様の装置に、ＢＴＤＡ３２．
２ｇ、１，３−ＤＡＣＤ２０．２ｇ、γ−カプロラクト
ン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、
トルエン４０．０ｇを加え、実施例１０の［工程１］と
同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１０の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
０の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 14) [Step 1] BTDA 32.
2 g, 1,3-DACD 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g,
40.0 g of toluene was added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 10. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 10 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 0, a polyimide solution was prepared.
【００４３】（実施例１５）
［工程１］実施例１０と同様の装置に、ＢＰＤＡ２９．
４ｇ、１，３−ＤＡＣＤ２０．２ｇ、ＮＭＰ２００．０
ｇを加え、実施例１０の［工程１］と同様にして反応液
（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１０の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
０の［工程３］と同様に処理してポリイミド溶液を調整
した。(Embodiment 15) [Step 1] BPDA 29.
4g, 1,3-DACD20.2g, NMP200.0
g was added and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 10. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 10 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 0, a polyimide solution was prepared.
【００４４】（実施例１６）
［工程１］実施例１０と同様の装置に、ＯＤＰＡ１５．
５ｇ、ピロメリット酸二無水物（ＰＭＤＡ、化学式（３
６））１０．９ｇ、ＤＭＨＭ１１．９ｇ、１，３−ＤＡ
ＣＤ２０．２ｇ、ＮＭＰ２００．０ｇを加え、実施例１
０の［工程１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１０の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
０の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 16) [Step 1] ODPA15.
5 g, pyromellitic dianhydride (PMDA, chemical formula (3
6)) 10.9 g, DMHM 11.9 g, 1,3-DA
Example 2 was added with 20.2 g of CD and 200.0 g of NMP.
A reaction solution (varnish) was obtained in the same manner as in [Step 1] of 0. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 10 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 0, a polyimide solution was prepared.
【００４５】（実施例１７）
［工程１］実施例１０と同様の装置に、６−ＦＤＡ２
２．２ｇ、ＯＰＤＡ１５．５ｇ、１，３−ＤＡＣＤ２
０．２ｇ、γ−カプロラクトン１．１ｇ、ピリジン２．
０ｇ、ＮＭＰ２００．０ｇ、トルエン４０．０ｇを加
え、実施例１０の［工程１］と同様にして反応液（ワニ
ス）を得た。
［工程２］［工程１］で得たワニスを実施例１０の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
０の［工程３］と同様に処理してポリイミド溶液を調整
した。(Embodiment 17) [Step 1] The same apparatus as in Embodiment 10 was charged with 6-FDA2.
2.2g, OPDA15.5g, 1,3-DACD2
0.2 g, γ-caprolactone 1.1 g, pyridine 2.
0 g, 200.0 g of NMP, and 40.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 10. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 10 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 0, a polyimide solution was prepared.
【００４６】（実施例１８）
［工程１］実施例１０と同様の装置に、ＢＣＤ２４．８
ｇ、１，３−ＤＡＣＤ１０．１ｇ、３，３′−ジメチル
−４，４′−ジアミノジシクロヘキシルメタン１１．９
ｇ、γ−カプロラクトン１．１ｇ、ピリジン２．０ｇ、
ＮＭＰ２００．０ｇ、トルエン４０．０ｇを加え、実施
例１０の［工程１］と同様にして反応液（ワニス）を得
た。
［工程２］［工程１］で得たワニスを実施例１０の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
０の［工程３］と同様に処理してポリイミド溶液を調整
した。(Embodiment 18) [Step 1] A device similar to that of Embodiment 10 is charged with BCD 24.8.
g, 1,3-DACD 10.1 g, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane 11.9
g, γ-caprolactone 1.1 g, pyridine 2.0 g,
200.0 g of NMP and 40.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 10. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 10 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 0, a polyimide solution was prepared.
【００４７】実施例１０〜１８のポリイミド樹脂組成物
をガラス板上に塗布乾燥して積層体を製造し、希無機ア
ルカリ水溶液への溶解性及び光透過率を測定し、その結
果を表２に示した。The polyimide resin compositions of Examples 10 to 18 were coated on a glass plate and dried to produce a laminate, and the solubility and light transmittance in a dilute inorganic alkaline aqueous solution were measured. The results are shown in Table 2. Indicated.
【００４８】[0048]
【表２】 [Table 2]
【００４９】（実施例１９）
［工程１］攪拌器を取りつけた１０００ｍｌのセパラブ
ル四つ口フラスコに、水分分離トラップを備えた玉付冷
却管を取りつけ、ＣＰＤＡ２１．０ｇ、２，５−ジアミ
ノ−１，４−シクロヘキサンジカルボン酸（１，４−Ｄ
ＡＣＤ、化学式（３））２０．２ｇ、γ−カプロラクト
ン１．１ｇ、ピリジン２．０ｇ、Ｎ−メチル−２−ピロ
リドン（ＮＭＰ）２００．０ｇ、トルエン４０．０ｇを
加え、常温で窒素雰囲気下で１０分間攪拌した後、反応
槽の内容物を１８０℃に昇温し、攪拌機の回転数を１８
０ｒｐｍに設定して３時間攪拌し、攪拌終了後真空乾燥
を行い反応液（ワニス）を得た。なお留出成分は反応中
に水分分離トラップより適時取り除いた。
［工程２］［工程１］で得たワニスをメタノール中に投
入することによって、生成した沈殿を分離し、粉砕、ろ
過、洗浄および減圧乾燥させる工程を経ることによりポ
リイミド粉末を得た。
［工程３］その後ＮＭＰ２６．０ｇにポリイミド粉末
４．０ｇを溶解してポリイミド溶液を調整した。Example 19 [Step 1] A 1000 ml separable four-necked flask equipped with a stirrer was fitted with a condenser tube with a ball equipped with a water separation trap, and CPDA 21.0 g, 2,5-diamino-1. , 4-Cyclohexanedicarboxylic acid (1,4-D
ACD, chemical formula (3)) 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, N-methyl-2-pyrrolidone (NMP) 200.0 g, and toluene 40.0 g were added, and at room temperature under a nitrogen atmosphere. After stirring for 10 minutes, the content in the reaction vessel was heated to 180 ° C and the rotation speed of the stirrer was set to 18
The reaction liquid (varnish) was obtained by setting the speed to 0 rpm and stirring for 3 hours, and after completion of stirring, vacuum drying was performed. The distillate components were removed from the water separation trap at appropriate times during the reaction. [Step 2] The varnish obtained in [Step 1] was put into methanol to separate the generated precipitate, and the polyimide powder was obtained by the steps of crushing, filtering, washing and drying under reduced pressure. [Step 3] Then, 4.0 g of polyimide powder was dissolved in 26.0 g of NMP to prepare a polyimide solution.
【００５０】（実施例２０）
［工程１］実施例１９と同様の装置に、ＢＣＤ２４．８
ｇ、１，４−ＤＡＣＤ２０．２ｇ、γ−カプロラクトン
１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、ト
ルエン４０．０を加え、実施例１９の［工程１］と同様
にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１９の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
９の［工程３］と同様に処理してポリイミド溶液を調整
した。(Embodiment 20) [Step 1] BCD24.8 was added to the same apparatus as in Embodiment 19.
g, 1,4-DACD 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g, toluene 40.0 were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 19. Got [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 19 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 9 above, a polyimide solution was prepared.
【００５１】（実施例２１）
［工程１］実施例１９と同様の装置に、ＯＤＰＡ３１．
０ｇ、１，４−ＤＡＣＤ２０．２ｇ、γ−カプロラクト
ン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００ｇ、トル
エン４０．０ｇを加え、実施例１９の［工程１］と同様
にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１９の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
９の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 21) [Step 1] ODPA31.
0 g, 1,4-DACD 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200 g, and toluene 40.0 g were added, and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 19. It was [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 19 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 9 above, a polyimide solution was prepared.
【００５２】（実施例２２）
［工程１］実施例１９と同様の装置に、６−ＦＤＡ４
４．４ｇ、１，４−ＤＡＣＤ２０．２ｇ、γ−カプロラ
クトン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０
ｇ、トルエン４０．０ｇを加え、実施例１９の［工程
１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１９の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
９の［工程３］と同様に処理してポリイミド溶液を調整
した。(Embodiment 22) [Step 1] 6-FDA4 was added to the same apparatus as in Embodiment 19.
4.4 g, 1,4-DACD 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP200.0
g and toluene 40.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 19. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 19 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 9 above, a polyimide solution was prepared.
【００５３】（実施例２３）
［工程１］実施例１９と同様の装置に、ＢＴＤＡ３２．
２ｇ、１，３−ＤＡＣＤ２０．２ｇ、γ−カプロラクト
ン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、
トルエン４０．０ｇを加え、実施例１９の［工程１］と
同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１９の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
９の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 23) [Step 1] BTDA 32.
2 g, 1,3-DACD 20.2 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g,
40.0 g of toluene was added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 19. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 19 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 9 above, a polyimide solution was prepared.
【００５４】（実施例２４）
［工程１］実施例１９と同様の装置に、ＢＰＤＡ２９．
４ｇ、１，４−ＤＡＣＤ２０．２ｇ、ＮＭＰ２００．０
ｇを加え、実施例１９の［工程１］と同様にして反応液
（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１９の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
９の［工程３］と同様に処理してポリイミド溶液を調整
した。Example 24 [Step 1] BPDA29.
4g, 1,4-DACD20.2g, NMP200.0
g was added and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 19. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 19 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 9 above, a polyimide solution was prepared.
【００５５】（実施例２５）
［工程１］実施例１９と同様の装置に、ＰＭＤＡ２１．
８ｇ、１，４−ＤＡＣＤ２０．２ｇ、ＮＭＰ２００．０
ｇを加え、実施例１９の［工程１］と同様にして反応液
（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例１９の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
９の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 25) [Step 1] PMDA21.
8g, 1,4-DACD20.2g, NMP200.0
g was added and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 19. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 19 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 9 above, a polyimide solution was prepared.
【００５６】（実施例２６）
［工程１］実施例１９と同様の装置に、６−ＦＤＡ２
２．２ｇ、ＯＰＤＡ１５．５ｇ、１，４−ＤＡＣＤ２
０．２ｇ、γ−カプロラクトン１．１ｇ、ピリジン２．
０ｇ、ＮＭＰ２００．０ｇ、トルエン４０．０ｇを加
え、実施例１９の［工程１］と同様にして反応液（ワニ
ス）を得た。
［工程２］［工程１］で得たワニスを実施例１９の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
９の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 26) [Step 1] 6-FDA2 was added to the same apparatus as in Example 19.
2.2g, OPDA 15.5g, 1,4-DACD2
0.2 g, γ-caprolactone 1.1 g, pyridine 2.
0 g, NMP 200.0 g, and toluene 40.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 19. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 19 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 9 above, a polyimide solution was prepared.
【００５７】（実施例２７）
［工程１］実施例１９と同様の装置に、ＢＣＤ２４．８
ｇ、１，４−ＤＡＣＤ１０．１ｇ、ＤＭＨＭ１１．９
ｇ、γ−カプロラクトン１．１ｇ、ピリジン２．０ｇ、
ＮＭＰ２００．０ｇ、トルエン４０．０ｇを加え、実施
例１９の［工程１］と同様にして反応液（ワニス）を得
た。
［工程２］［工程１］で得たワニスを実施例１９の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例１
９の［工程３］と同様に処理してポリイミド溶液を調整
した。(Embodiment 27) [Step 1] BCD24.8 was added to the same apparatus as in Embodiment 19.
g, 1,4-DACD 10.1 g, DMHM 11.9
g, γ-caprolactone 1.1 g, pyridine 2.0 g,
200.0 g of NMP and 40.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 19. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 19 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 1
In the same manner as in [Step 3] of 9 above, a polyimide solution was prepared.
【００５８】実施例１９〜２７のポリイミド溶液をガラ
ス板上に塗布乾燥して積層体を製造し、希無機アルカリ
水溶液への溶解性及び光透過率を測定し、その結果を表
３に示した。The polyimide solutions of Examples 19 to 27 were applied on a glass plate and dried to produce a laminate, and the solubility in the dilute inorganic alkaline aqueous solution and the light transmittance were measured. The results are shown in Table 3. .
【００５９】[0059]
【表３】 [Table 3]
【００６０】（実施例２８）
［工程１］攪拌器を取りつけた１０００ｍｌのセパラブ
ル四つ口フラスコに、水分分離トラップを備えた玉付冷
却管を取りつけ、ＣＰＤＡ２１．０ｇ、３，５−ジアミ
ノ−２，６−ジヒドロキシルシクロヘキサンカルボン酸
（ＤＤＣＣ、化学式（４））１９．０ｇ、γ−カプロラ
クトン１．１ｇ、ピリジン２．０ｇ、Ｎ−メチル−２−
ピロリドン（ＮＭＰ）２００．０ｇ、トルエン４０．０
ｇを加え、常温で窒素雰囲気下で１０分間攪拌した後、
反応槽の内容物を１８０℃に昇温し、攪拌機の回転数を
１８０ｒｐｍに設定して３時間攪拌し、攪拌終了後真空
乾燥を行い反応液（ワニス）を得た。なお留出成分は反
応中に水分分離トラップより適時取り除いた。
［工程２］［工程１］で得たワニスをメタノール中に投
入することによって、生成した沈殿を分離し、粉砕、ろ
過、洗浄および減圧乾燥させる工程を経ることによりポ
リイミド粉末を得た。
［工程３］その後ＮＭＰ２６．０ｇにポリイミド粉末
４．０ｇを溶解してポリイミド溶液を調整した。(Example 28) [Step 1] A 1000 ml separable four-necked flask equipped with a stirrer was fitted with a condenser tube with a ball equipped with a water separation trap, and CPDA 21.0 g, 3,5-diamino-2. , 6-Dihydroxylcyclohexanecarboxylic acid (DDCC, chemical formula (4)) 19.0 g, γ-caprolactone 1.1 g, pyridine 2.0 g, N-methyl-2-
Pyrrolidone (NMP) 200.0 g, toluene 40.0
g, and after stirring at room temperature for 10 minutes in a nitrogen atmosphere,
The contents of the reaction tank were heated to 180 ° C., the number of revolutions of the stirrer was set to 180 rpm, and the mixture was stirred for 3 hours. After completion of stirring, vacuum drying was performed to obtain a reaction liquid (varnish). The distillate components were removed from the water separation trap at appropriate times during the reaction. [Step 2] The varnish obtained in [Step 1] was put into methanol to separate the generated precipitate, and the polyimide powder was obtained by the steps of crushing, filtering, washing and drying under reduced pressure. [Step 3] Then, 4.0 g of polyimide powder was dissolved in 26.0 g of NMP to prepare a polyimide solution.
【００６１】（実施例２９）
［工程１］実施例２８と同様の装置に、ＢＣＤ２４．８
ｇ、ＤＤＣＣ１９．０ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、トルエン
４０．０を加え、実施例２８の［工程１］と同様にして
反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例２８の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例２
８の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 29) [Step 1] BCD24.8 was added to the same apparatus as in Example 28.
g, DDCC 19.0 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 28. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 28 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 2
A polyimide solution was prepared in the same manner as in [Step 3] of 8.
【００６２】（実施例３０）
［工程１］実施例２８と同様の装置に、ＯＤＰＡ３１．
０ｇ、ＤＤＣＣ１９．０ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００ｇ、トルエン４
０．０ｇを加え、実施例２８の［工程１］と同様にして
反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例２８の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例２
８の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 30) [Step 1] ODPA31.
0 g, DDCC 19.0 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200 g, toluene 4
0.0 g was added, and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 28. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 28 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 2
A polyimide solution was prepared in the same manner as in [Step 3] of 8.
【００６３】（実施例３１）
［工程１］実施例２８と同様の装置に、６−ＦＤＡ４
４．４ｇ、ＤＤＣＣ１９．０ｇ、γ−カプロラクトン
１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、ト
ルエン４０．０ｇを加え、実施例２８の［工程１］と同
様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例２８の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例２
８の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 31) [Step 1] 6-FDA4 was added to the same apparatus as in Example 28.
4.4 g, DDCC 19.0 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 28. It was [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 28 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 2
A polyimide solution was prepared in the same manner as in [Step 3] of 8.
【００６４】（実施例３２）
［工程１］実施例２８と同様の装置に、ＢＴＤＡ３２．
２ｇ、ＤＤＣＣ１９．０ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、トルエン
４０．０ｇを加え、実施例２８の［工程１］と同様にし
て反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例２８の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例２
８の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 32) [Step 1] BTDA32.
2 g, DDCC 19.0 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 28. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 28 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 2
A polyimide solution was prepared in the same manner as in [Step 3] of 8.
【００６５】（実施例３３）
［工程１］実施例２８と同様の装置に、ＢＰＤＡ２９．
４ｇ、ＤＤＣＣ１９．０ｇ、ＮＭＰ２００．０ｇを加
え、実施例２８の［工程１］と同様にして反応液（ワニ
ス）を得た。
［工程２］［工程１］で得たワニスを実施例２８の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例２
８の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 33) [Step 1] BPDA 29.
4 g, DDCC 19.0 g, and NMP 200.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 28. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 28 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 2
A polyimide solution was prepared in the same manner as in [Step 3] of 8.
【００６６】（実施例３４）
［工程１］実施例２８と同様の装置に、ＰＭＤＡ２１．
８ｇ、ＤＤＣＣ１９．０ｇ、ＮＭＰ２００．０ｇを加
え、実施例２８の［工程１］と同様にして反応液（ワニ
ス）を得た。
［工程２］［工程１］で得たワニスを実施例２８の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例２
８の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 34) [Step 1] PMDA21.
8 g, DDCC 19.0 g, and NMP 200.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 28. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 28 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 2
A polyimide solution was prepared in the same manner as in [Step 3] of 8.
【００６７】（実施例３５）
［工程１］実施例２８と同様の装置に、６−ＦＤＡ２
２．２ｇ、ＯＰＤＡ１５．５ｇ、ＤＤＣＣ１９．０ｇ、
γ−カプロラクトン１．１ｇ、ピリジン２．０ｇ、ＮＭ
Ｐ２００．０ｇ、トルエン４０．０ｇを加え、実施例２
８の［工程１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例２８の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例２
８の［工程３］と同様に処理してポリイミド溶液を調整
した。Example 35 [Step 1] 6-FDA2 was added to the same apparatus as in Example 28.
2.2g, OPDA 15.5g, DDCC 19.0g,
γ-caprolactone 1.1 g, pyridine 2.0 g, NM
P200.0g and toluene 40.0g were added, and Example 2
A reaction solution (varnish) was obtained in the same manner as in [Step 1] of 8. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 28 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 2
A polyimide solution was prepared in the same manner as in [Step 3] of 8.
【００６８】（実施例３６）
［工程１］実施例２８と同様の装置に、ＢＣＤ２４．８
ｇ、ＤＤＣＣ９．５ｇ、ＤＭＨＭ１１．９ｇ、γ−カプ
ロラクトン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２０
０．０ｇ、トルエン４０．０ｇを加え、実施例２８の
［工程１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例２８の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例２
８の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 36) [Step 1] BCD24.8 was added to the same apparatus as in Example 28.
g, DDCC 9.5 g, DMHM 11.9 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP20.
0.0 g and 40.0 g of toluene were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 28. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 28 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 2
A polyimide solution was prepared in the same manner as in [Step 3] of 8.
【００６９】実施例２８〜３６のポリイミド溶液をガラ
ス板上に塗布乾燥して積層体を製造し、希無機アルカリ
水溶液への溶解性及び光透過率を測定し、その結果を表
４に示した。The polyimide solutions of Examples 28 to 36 were applied on a glass plate and dried to produce a laminate, and the solubility in the dilute inorganic alkaline aqueous solution and the light transmittance were measured. The results are shown in Table 4. .
【００７０】[0070]
【表４】 [Table 4]
【００７１】（実施例３７）
［工程１］攪拌器を取りつけた１０００ｍｌのセパラブ
ル四つ口フラスコに、水分分離トラップを備えた玉付冷
却管を取りつけ、ＣＰＤＡ２１．０ｇ、４，４′−ジア
ミノジシクロヘキシルメタン−３，３′−ジカルボン酸
（ＤＡＤＣ、化学式（５））２９．８ｇ、γ−カプロラ
クトン１．１ｇ、ピリジン２．０ｇ、Ｎ−メチル−２−
ピロリドン（ＮＭＰ）２００．０ｇ、トルエン４０．０
ｇを加え、常温で窒素雰囲気下で１０分間攪拌した後、
反応槽の内容物を１８０℃に昇温し、攪拌機の回転数を
１８０ｒｐｍに設定して３時間攪拌し、攪拌終了後真空
乾燥を行い反応液（ワニス）を得た。なお留出成分は反
応中に水分分離トラップより適時取り除いた。
［工程２］［工程１］で得たワニスをメタノール中に投
入することによって、生成した沈殿を分離し、粉砕、ろ
過、洗浄および減圧乾燥させる工程を経ることによりポ
リイミド粉末を得た。
［工程３］その後ＮＭＰ２６．０ｇにポリイミド粉末
４．０ｇを溶解してポリイミド溶液を調整した。(Example 37) [Step 1] A 1000 ml separable four-necked flask equipped with a stirrer was equipped with a condenser tube with a ball equipped with a water separation trap, and CPDA 21.0 g, 4,4'-diaminodicyclohexyl was installed. Methane-3,3'-dicarboxylic acid (DADC, chemical formula (5)) 29.8 g, γ-caprolactone 1.1 g, pyridine 2.0 g, N-methyl-2-
Pyrrolidone (NMP) 200.0 g, toluene 40.0
g, and after stirring at room temperature for 10 minutes in a nitrogen atmosphere,
The contents of the reaction tank were heated to 180 ° C., the number of revolutions of the stirrer was set to 180 rpm, and the mixture was stirred for 3 hours. After completion of stirring, vacuum drying was performed to obtain a reaction liquid (varnish). The distillate components were removed from the water separation trap at appropriate times during the reaction. [Step 2] The varnish obtained in [Step 1] was put into methanol to separate the generated precipitate, and the polyimide powder was obtained by the steps of crushing, filtering, washing and drying under reduced pressure. [Step 3] Then, 4.0 g of polyimide powder was dissolved in 26.0 g of NMP to prepare a polyimide solution.
【００７２】（実施例３８）
［工程１］実施例３７と同様の装置に、ＢＣＤ２４．８
ｇ、ＤＡＤＣ２９．８ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、トルエン
４０．０を加え、実施例３７の［工程１］と同様にして
反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例３７の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例３
７の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 38) [Step 1] BCD24.8 was added to the same apparatus as in Example 37.
g, DADC 29.8 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 37. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 37 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 3
A polyimide solution was prepared in the same manner as in [Step 3] of 7.
【００７３】（実施例３９）
［工程１］実施例３７と同様の装置に、ＯＤＰＡ３１．
０ｇ、ＤＡＤＣ２９．８ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００ｇ、トルエン４
０．０ｇを加え、実施例３７の［工程１］と同様にして
反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例３７の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例３
７の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 39) [Step 1] ODPA31.
0 g, DADC 29.8 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200 g, toluene 4
0.0 g was added, and a reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 37. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 37 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 3
A polyimide solution was prepared in the same manner as in [Step 3] of 7.
【００７４】（実施例４０）
［工程１］実施例３７と同様の装置に、６−ＦＤＡ４
４．４ｇ、ＤＡＤＣ２９．８ｇ、γ−カプロラクトン
１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、ト
ルエン４０．０ｇを加え、実施例３７の［工程１］と同
様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例３７の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例３
７の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 40) [Step 1] 6-FDA4 was added to the same apparatus as in Example 37.
4.4 g, DADC 29.8 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 37. It was [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 37 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 3
A polyimide solution was prepared in the same manner as in [Step 3] of 7.
【００７５】（実施例４１）
［工程１］実施例３７と同様の装置に、ＢＴＤＡ３２．
２ｇ、ＤＡＤＣ２９．８ｇ、γ−カプロラクトン１．１
ｇ、ピリジン２．０ｇ、ＮＭＰ２００．０ｇ、トルエン
４０．０ｇを加え、実施例３７の［工程１］と同様にし
て反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例３７の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例３
７の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 41) [Step 1] BTDA 32.
2 g, DADC 29.8 g, γ-caprolactone 1.1
g, pyridine 2.0 g, NMP 200.0 g, and toluene 40.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 37. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 37 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 3
A polyimide solution was prepared in the same manner as in [Step 3] of 7.
【００７６】（実施例４２）
［工程１］実施例３７と同様の装置に、ＢＰＤＡ２９．
４ｇ、ＤＡＤＣ２９．８ｇ、ＮＭＰ２００．０ｇを加
え、実施例３７の［工程１］と同様にして反応液（ワニ
ス）を得た。
［工程２］［工程１］で得たワニスを実施例３７の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例３
７の［工程３］と同様に処理してポリイミド溶液を調整
した。Example 42 [Step 1] BPDA29.
4 g, DADC 29.8 g, and NMP 200.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 37. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 37 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 3
A polyimide solution was prepared in the same manner as in [Step 3] of 7.
【００７７】（実施例４３）
［工程１］実施例３７と同様の装置に、ＰＭＤＡ２１．
８ｇ、ＤＡＤＣ２９．８ｇ、ＮＭＰ２００．０ｇを加
え、実施例３７の［工程１］と同様にして反応液（ワニ
ス）を得た。
［工程２］［工程１］で得たワニスを実施例３７の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例３
７の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 43) [Step 1] PMDA21.
8 g, DADC 29.8 g, and NMP 200.0 g were added, and a reaction liquid (varnish) was obtained in the same manner as in [Step 1] of Example 37. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 37 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 3
A polyimide solution was prepared in the same manner as in [Step 3] of 7.
【００７８】（実施例４４）
［工程１］実施例３７と同様の装置に、６−ＦＤＡ２
２．２ｇ、ＯＰＤＡ１５．５ｇ、ＤＡＤＣ２９．８ｇ、
γ−カプロラクトン１．１ｇ、ピリジン２．０ｇ、ＮＭ
Ｐ２００．０ｇ、トルエン４０．０ｇを加え、実施例３
７の［工程１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例３７の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例３
７の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 44) [Step 1] 6-FDA2 was added to the same apparatus as in Example 37.
2.2g, OPDA 15.5g, DADC 29.8g,
γ-caprolactone 1.1 g, pyridine 2.0 g, NM
P200.0g and toluene 40.0g were added, and Example 3
A reaction solution (varnish) was obtained in the same manner as in [Step 1] of 7. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 37 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 3
A polyimide solution was prepared in the same manner as in [Step 3] of 7.
【００７９】（実施例４５）
［工程１］実施例３７と同様の装置に、ＢＣＤ２４．８
ｇ、ＤＡＤＣ１４．９ｇ、ＤＭＨＭ１１．９ｇ、γ−カ
プロラクトン１．１ｇ、ピリジン２．０ｇ、ＮＭＰ２０
０．０ｇ、トルエン４０．０ｇを加え、実施例３７の
［工程１］と同様にして反応液（ワニス）を得た。
［工程２］［工程１］で得たワニスを実施例３７の［工
程２］と同様に処理してポリイミド粉末を得た。
［工程３］［工程２］で得たポリイミド粉末を実施例３
７の［工程３］と同様に処理してポリイミド溶液を調整
した。(Example 45) [Step 1] BCD24.8 was added to the same apparatus as in Example 37.
g, DADC 14.9 g, DMHM 11.9 g, γ-caprolactone 1.1 g, pyridine 2.0 g, NMP20.
A reaction solution (varnish) was obtained in the same manner as in [Step 1] of Example 37 by adding 0.0 g and toluene 40.0 g. [Step 2] The varnish obtained in [Step 1] was treated in the same manner as in [Step 2] of Example 37 to obtain a polyimide powder. [Step 3] The polyimide powder obtained in [Step 2] was used in Example 3
A polyimide solution was prepared in the same manner as in [Step 3] of 7.
【００８０】実施例３７〜４５のポリイミド溶液をガラ
ス板上に塗布乾燥して積層体を製造し、希無機アルカリ
水溶液への溶解性及び光透過率を測定し、その結果を表
５に示した。The polyimide solutions of Examples 37 to 45 were applied onto a glass plate and dried to produce a laminate, and the solubility in a dilute inorganic alkaline aqueous solution and the light transmittance were measured. The results are shown in Table 5. .
【００８１】[0081]
【表５】 [Table 5]
【００８２】[0082]
【発明の効果】本発明によれば、高い耐熱性を有し、且
つ高い透明性を有するポリイミド樹脂を主成分とした樹
脂層を基板上に形成することが可能となる。又、この樹
脂層は希無機アルカリ水溶液により不要部分を簡単に溶
解剥離できることから、既存の設備をそのまま転用で
き、且つ剥離液による環境への負荷を低く抑えることが
できる。According to the present invention, it is possible to form a resin layer having a high heat resistance and a high transparency as a main component of a polyimide resin on a substrate. In addition, since this resin layer can easily dissolve and peel off unnecessary parts with a dilute inorganic alkaline aqueous solution, existing equipment can be used as it is, and the load on the environment caused by the peeling liquid can be suppressed to a low level.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 本田 祐樹 茨城県日立市日高町５丁目１番１号 日立 電線株式会社総合技術研究所内 (72)発明者 安藤 好幸 茨城県日立市日高町５丁目１番１号 日立 電線株式会社総合技術研究所内 (72)発明者 浅野 健次 茨城県日立市日高町５丁目１番１号 日立 電線株式会社総合技術研究所内 (72)発明者 伊藤 雄三 茨城県日立市日高町５丁目１番１号 日立 電線株式会社総合技術研究所内 Ｆターム(参考） 4F100 AH03B AK49B AK49K AL06B AT00A BA02 JB01 JB08 JJ03 JN01 4J043 PA02 PA04 PA15 QB15 QB26 RA35 SA06 SA62 SA71 SB01 SB02 TA22 TB01 TB02 UA032 UA041 UA081 UA082 UA132 UA381 UA521 UA761 UB011 UB062 UB122 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yuki Honda Hitachi, 1-1 Hidaka-cho, Hitachi City, Ibaraki Prefecture Electric Cable Co., Ltd. (72) Inventor Yoshiyuki Ando Hitachi, 1-1 Hidaka-cho, Hitachi City, Ibaraki Prefecture Electric Cable Co., Ltd. (72) Inventor Kenji Asano Hitachi, 1-1 Hidaka-cho, Hitachi City, Ibaraki Prefecture Electric Cable Co., Ltd. (72) Inventor Yuzo Ito Hitachi, 1-1 Hidaka-cho, Hitachi City, Ibaraki Prefecture Electric Cable Co., Ltd. F-term (reference) 4F100 AH03B AK49B AK49K AL06B AT00A BA02 JB01 JB08 JJ03 JN01 4J043 PA02 PA04 PA15 QB15 QB26 RA35 SA06 SA62 SA71 SB01 SB02 TA22 TB01 TB02 UA032 UA041 UA081 UA082 UA132 UA381 UA521 UA761 UB011 UB062 UB122
Claims (5)
合物と酸二無水物から選ばれる少なくとも１種の化合物
を有機溶媒中で反応させてなる生成物であり、前記ジア
ミンの必須成分としてカルボキシル基を一つ以上有する
脂肪族環構造ジアミンが反応に供せられてなることを特
徴とするポリイミド。1. A product obtained by reacting at least one compound selected from diamines and at least one compound selected from acid dianhydrides in an organic solvent, wherein a carboxyl group is contained as an essential component of the diamine. A polyimide, characterized in that it comprises one or more diamines having an alicyclic structure and is subjected to a reaction.
構造ジアミンは、化学式 【化１】 【化２】 【化３】 【化４】 及び 【化５】 で表わされる化合物から選ばれる少なくとも１種である
請求項１記載のポリイミド。2. An aliphatic ring structure diamine having one or more carboxyl groups is represented by the chemical formula: [Chemical 2] [Chemical 3] [Chemical 4] And [Chemical 5] The polyimide according to claim 1, which is at least one selected from compounds represented by:
二無水物として 【化１１】 【化１２】 【化１３】 及び 【化１４】 で表わされる化合物から選ばれる少なくとも１種が反応
に供せられてなる請求項１記載のポリイミド。3. A diamine having the chemical formula: [Chemical 7] [Chemical 8] [Chemical 9] And [Chemical 10] At least one selected from the compounds represented by [Chemical 12] [Chemical 13] And [Chemical 14] The polyimide according to claim 1, wherein at least one selected from the compounds represented by the following is subjected to the reaction.
学式 【化２０】 【化２１】 【化２２】 【化２３】 【化２４】 【化２５】 【化２６】 【化２７】 及び 【化２８】 で表わされる化合物から選ばれる少なくとも１種が、酸
二無水物として 【化２９】 【化３０】 【化３１】 及び 【化３２】 で表わされる化合物から選ばれる少なくとも１種が反応
に供せられてなる請求項１記載のポリイミド。4. A diamine having the chemical formula: [Chemical 16] [Chemical 17] [Chemical 18] And [Chemical 19] And at least one compound selected from compounds represented by the following chemical formula: [Chemical 21] [Chemical formula 22] [Chemical formula 23] [Chemical formula 24] [Chemical 25] [Chemical formula 26] [Chemical 27] And [Chemical 28] At least one selected from the compounds represented by [Chemical 30] [Chemical 31] And [Chemical 32] The polyimide according to claim 1, wherein at least one selected from the compounds represented by the following is subjected to the reaction.
ポリイミドを含有する樹脂層が基材に積層されてなるこ
とを特徴とする積層体。5. A laminate comprising a resin layer containing the polyimide according to any one of claims 1 to 4 laminated on a base material.
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| JP2002150348A JP3912183B2 (en) | 2001-05-25 | 2002-05-24 | Polyimide and laminate |
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|---|---|---|---|
| JP2001-156433 | 2001-05-25 | ||
| JP2001156433 | 2001-05-25 | ||
| JP2002150348A JP3912183B2 (en) | 2001-05-25 | 2002-05-24 | Polyimide and laminate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003055846A1 (en) * | 2001-12-27 | 2003-07-10 | Mitsui Chemicals, Inc. | Diaminodicarboxylic acids and intermediates thereof |
| US7022855B2 (en) | 2001-04-12 | 2006-04-04 | Meiji Seika Kaisha, Ltd. | Halogen-substituted quinoline derivatives and ectoparasite control agent |
| JP2011137063A (en) * | 2009-12-28 | 2011-07-14 | Toray Ind Inc | Polyimide resin aqueous solution, polyimide-based resin aqueous solution, polyazole resin aqueous solution |
| CN111072964A (en) * | 2019-12-31 | 2020-04-28 | 阜阳欣奕华材料科技有限公司 | Polyimide precursor composition and preparation method and application thereof |
-
2002
- 2002-05-24 JP JP2002150348A patent/JP3912183B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7022855B2 (en) | 2001-04-12 | 2006-04-04 | Meiji Seika Kaisha, Ltd. | Halogen-substituted quinoline derivatives and ectoparasite control agent |
| WO2003055846A1 (en) * | 2001-12-27 | 2003-07-10 | Mitsui Chemicals, Inc. | Diaminodicarboxylic acids and intermediates thereof |
| JP2011137063A (en) * | 2009-12-28 | 2011-07-14 | Toray Ind Inc | Polyimide resin aqueous solution, polyimide-based resin aqueous solution, polyazole resin aqueous solution |
| CN111072964A (en) * | 2019-12-31 | 2020-04-28 | 阜阳欣奕华材料科技有限公司 | Polyimide precursor composition and preparation method and application thereof |
| CN111072964B (en) * | 2019-12-31 | 2022-07-12 | 北京欣奕华科技有限公司 | Polyimide precursor composition and preparation method and application thereof |
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