JP2841426B2 - Soluble polyimide resin - Google Patents
Soluble polyimide resinInfo
- Publication number
- JP2841426B2 JP2841426B2 JP1042798A JP4279889A JP2841426B2 JP 2841426 B2 JP2841426 B2 JP 2841426B2 JP 1042798 A JP1042798 A JP 1042798A JP 4279889 A JP4279889 A JP 4279889A JP 2841426 B2 JP2841426 B2 JP 2841426B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide resin
- diamine
- bis
- solution
- aminophenoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Formation Of Insulating Films (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は電気・電子デバイス、特に半導体装置、液晶
表示装置に用いられるに好適な新規な可溶性ポリイミド
樹脂に関する。The present invention relates to a novel soluble polyimide resin suitable for use in electric / electronic devices, particularly semiconductor devices and liquid crystal display devices.
（ロ）従来の技術 テトラカルボン酸及びその誘導体とジアミンを反応さ
せて得られるポリイミド樹脂は、優れた耐熱性、耐薬品
性を示す為、種々の用途に用いられる。ポリイミド樹脂
の半導体装置への使用に関しては、例えばジャンクショ
ンコート膜、パッシベーション膜、防湿膜、バッファコ
ート膜、α線遮断膜、層間絶縁膜等が公知であり、一部
試みられている。又、ポリイミド樹脂の液晶表示装置へ
の使用に関しては、例えば配向膜等が公知であり既に試
みられている。(B) Conventional technology Polyimide resins obtained by reacting tetracarboxylic acids and their derivatives with diamines are used in various applications because they exhibit excellent heat resistance and chemical resistance. With respect to the use of polyimide resin in semiconductor devices, for example, a junction coat film, a passivation film, a moisture-proof film, a buffer coat film, an α-ray blocking film, an interlayer insulating film, and the like are known and some attempts have been made. As for the use of a polyimide resin in a liquid crystal display device, for example, an alignment film and the like are known and have been tried.
ところで、上記様々な用途においてポリイミド樹脂を
使用する場合、その電気特性が不十分である場合が多
い。By the way, when a polyimide resin is used in the above various uses, its electrical characteristics are often insufficient.
本願発明者はポリイミド樹脂の化学構造と電気特性に
密接な関係が存在することを見出し、既に特願昭63−19
35号において電気特性に優れたポリイミド樹脂を得る手
段を出願した。The present inventor has found that there is a close relationship between the chemical structure and electrical properties of a polyimide resin, and has already filed Japanese Patent Application No. 63-19 / 1988.
No. 35 filed an application for obtaining a polyimide resin with excellent electrical properties.
（ハ）発明が解決しようとする課題 テトラカルボン酸及びその誘導体とジアミンを反応さ
せて得られるポイイミド樹脂は有機溶媒に対する溶解性
が極端に小さく、通常はポリイミド樹脂前駆体（以下、
ポリアミック酸と称す）溶液を合成し、これを半導体装
置、液晶表示装置に塗布し、加熱によりポリアミック酸
をポリイミド樹脂に転化し、且つ脱溶媒する方法が一般
的に採用されている。(C) Problems to be Solved by the Invention A polyimide resin obtained by reacting a tetracarboxylic acid or a derivative thereof with a diamine has extremely low solubility in an organic solvent, and usually a polyimide resin precursor (hereinafter, referred to as a polyimide resin precursor).
Generally, a method of synthesizing a solution (referred to as polyamic acid), applying the solution to a semiconductor device or a liquid crystal display device, converting the polyamic acid to a polyimide resin by heating, and removing the solvent is generally employed.
しかしながら、ポリアミック酸をポリイミド樹脂に転
化するには170℃以上の高温の熱処理が必要であり、高
温にさらされると特性が劣化するような半導体装置、液
晶表示装置に対してはポリイミド樹脂の皮膜を形成する
ことがはなはだ困難であった。However, conversion of polyamic acid to polyimide resin requires heat treatment at a high temperature of 170 ° C. or higher, and a polyimide resin film is required for semiconductor devices and liquid crystal display devices whose characteristics deteriorate when exposed to high temperatures. It was very difficult to form.
本発明は、溶媒を蒸発させるのみでポリイミド樹脂の
皮膜を形成することのできるシクロブタンテトラカルボ
ン酸又はその二無水物若しくは前記テトラカルボン酸の
ジカルボン酸ジ酸ハロゲン化物を用いた可溶性ポリイミ
ド樹脂を提供することにある。The present invention provides a soluble polyimide resin using cyclobutanetetracarboxylic acid or a dianhydride thereof or a dicarboxylic acid diacid halide of the tetracarboxylic acid capable of forming a polyimide resin film only by evaporating a solvent. It is in.
（ニ）課題を解決するための手段 本願発明者は、上記問題点を解決すべく鋭意努力検討
した結果、シクロブタンテトラカルボン酸及びその誘導
体と特定のジアミンを用いたポリイミド樹脂が意外にも
耐熱性に優れ、且つ溶媒可溶性を示すことを見出し、本
発明を完成するに至った。(D) Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, a polyimide resin using cyclobutanetetracarboxylic acid and its derivative and a specific diamine is unexpectedly heat resistant. The present invention was found to be excellent in solvent solubility and showed solvent solubility, and completed the present invention.
即ち、本発明は、シクロブタンテトラカルボン酸又は
その二無水物若しくは前記テトラカルボン酸のジカルボ
ン酸ジ酸ハロゲン化物とジアミンを反応させ得られるポ
リイミド樹脂において、ジアミンが、一般式［Ｉ］及び
／又は一般式［II］で示されるジアミンで、得られるポ
リイミド樹脂が極性溶媒に可溶であることを特徴とする
可溶性ポリイミド樹脂に関するものである。That is, the present invention provides a polyimide resin obtained by reacting a diamine with cyclobutanetetracarboxylic acid or a dianhydride thereof or a dicarboxylic acid diacid halide of the tetracarboxylic acid, wherein the diamine is represented by the general formula [I] and / or The present invention relates to a soluble polyimide resin which is a diamine represented by the formula [II] and wherein the obtained polyimide resin is soluble in a polar solvent.
（R1、R2、R3、R4は炭素数１から４のアルキル基であ
り、おのおの同じであっても異なっていてもよい。） （Ｘは２値の有機基であり、 を示す。） 本発明の可溶性ポリイミド樹脂を得るために使用され
るジアミンの具体例としては、4,4′−メチレン−ビス
−（2,6−ジエチルアニリン）（以下、MDEAと略記す
る）、4,4′−メチレン−ビス−（２−イソプロピル−
６−メチルアニリン）（以下、MIMAと略記する）、4,
4′−メチレン−ビス−（2,6−ジイソプロピルアニリ
ン）（以下、MDIAと略記する）、ビス〔４−（３−アミ
ノフェノキシ）フェニル〕スルホン、2,2−ビス〔４−
（３−アミノフェノキシ）フェニル〕プロパン、2,2−
ビス〔４−（３−アミノフェノキシ）フェニル〕ヘキサ
フロロプロパン等の芳香族ジアミンが挙げられる。 (R 1 , R 2 , R 3 , and R 4 are alkyl groups having 1 to 4 carbon atoms, which may be the same or different.) (X is a binary organic group, Is shown. Specific examples of the diamine used to obtain the soluble polyimide resin of the present invention include 4,4′-methylene-bis- (2,6-diethylaniline) (hereinafter abbreviated as MDEA), 4,4 '-Methylene-bis- (2-isopropyl-
6-methylaniline) (hereinafter abbreviated as MIMA), 4,
4'-methylene-bis- (2,6-diisopropylaniline) (hereinafter abbreviated as MDIA), bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4-
(3-aminophenoxy) phenyl] propane, 2,2-
And aromatic diamines such as bis [4- (3-aminophenoxy) phenyl] hexafluoropropane.
その他目的に応じ本発明を阻害しない程度に他の脂肪
族ジアミン、芳香族ジアミンを混合して使用してもよ
い。Other aliphatic diamines and aromatic diamines may be mixed and used to the extent that the present invention is not hindered, depending on other purposes.
そのようなジアミンの具体例としては、4,4′−ジア
ミノ−3,3′−ジメチルジシクロヘキシルメタン、4,4′
−ジアミノジフェニルエーテル、4,4′−ジアミノジフ
ェニルメタン、1,4−ビス（４−アミノフェノキシ）ベ
ンゼン、1,3−ビス（４−アミノフェノキシ）ベンゼ
ン、ビス〔４−（４−アミノフェノキシ）フェニル〕ス
ルホン、2,2−ビス〔４−（４−アミノフェノキシ）フ
ェニル〕プロパン、2,2−ビス〔４−（４−アミノフェ
ノキシ）フェニル〕ヘキサフロロプロパン等があげられ
る。Specific examples of such diamines include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] Sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like.
本発明の可溶性ポリイミド樹脂を得るための重合方法
には特に限定はないが、Ｎ−メチルピロリドン（以下、
NMPと略記する）、ジメチルアセトアミド（以下、DMAc
と略記する）等の極性溶媒中で、テトラカルボン酸及び
その誘導体とジアミンとの反応からポリアミック酸を合
成し、脱水閉環する方法が好ましい。The polymerization method for obtaining the soluble polyimide resin of the present invention is not particularly limited, but N-methylpyrrolidone (hereinafter, referred to as N-methylpyrrolidone)
NMP), dimethylacetamide (hereinafter, DMAc
In a polar solvent (e.g., abbreviated as), a method of synthesizing a polyamic acid from a reaction of a tetracarboxylic acid or a derivative thereof with a diamine and subjecting the resultant to a dehydration ring closure is preferable.
テトラカルボン酸及びその誘導体とジアミンの反応温
度は−20〜150℃の任意の温度を選択することができる
が、特に−５〜100℃の範囲が好ましい。The reaction temperature of the tetracarboxylic acid and its derivative with the diamine can be selected from any temperature in the range of -20 to 150C, but is particularly preferably in the range of -5 to 100C.
更に、ポリアミック酸をポリイミド樹脂に転化するに
は、ポリアミック酸を溶液状態のまま150〜250℃で１〜
10時間加熱すればよい。Further, in order to convert the polyamic acid to a polyimide resin, the polyamic acid is kept in a solution state at 150 to 250 ° C. for 1 to 1 hour.
Heat for 10 hours.
脱水閉環反応で生成した水を取り除くためトルエン等
を添加し共沸脱水することも可能である。In order to remove water generated by the dehydration ring closure reaction, it is also possible to perform azeotropic dehydration by adding toluene or the like.
このようにして得られたポリイミド樹脂溶液は、その
まま実用に供することも可能であるし、一度メタノール
等に投入しポリイミド樹脂を回収し、再びNMP、DMAc等
の極性溶媒に溶解してもよい。The polyimide resin solution thus obtained can be used for practical use as it is, or may be once poured into methanol or the like to recover the polyimide resin, and then dissolved again in a polar solvent such as NMP or DMAc.
ポリアミック酸をポリイミド樹脂に転化するために、
公知の脱水閉環触媒を使用して化学的に閉環する方法も
ある。To convert polyamic acid to polyimide resin,
There is also a method of chemically closing a ring using a known dehydration ring closing catalyst.
この場合も上記加熱による方法と同様に脱水閉環の終
了したポリイミド樹脂溶液をそのまま実用に供すること
も可能であるし、一度メタノールに投入しポリイミド樹
脂を回収し再びNMP、DMAc等の極性溶媒に溶解してもよ
い。In this case, it is also possible to use the polyimide resin solution after dehydration and ring closure as it is in the same manner as the above-mentioned heating method, or to put it in methanol once to recover the polyimide resin and dissolve it again in a polar solvent such as NMP or DMAc. May be.
本発明のテトラカルボン酸及びその誘導体とジアミン
から得られるポリイミド樹脂溶液は、スピンコート法若
しくは印刷法で半導体装置、液晶表示装置に塗布し溶媒
を加熱蒸発させるのみでポリイミド樹脂皮膜を形成する
ことができる。The polyimide resin solution obtained from the tetracarboxylic acid and the derivative thereof and the diamine of the present invention can be applied to a semiconductor device or a liquid crystal display device by spin coating or printing to form a polyimide resin film simply by heating and evaporating the solvent. it can.
（ホ）発明の効果 本発明の可溶性ポリイミドは有機溶媒に可溶なため、
溶媒を蒸発させることのみで耐熱性に優れたポリイミド
樹脂皮膜を形成できる。(E) Effect of the Invention Since the soluble polyimide of the present invention is soluble in an organic solvent,
A polyimide resin film having excellent heat resistance can be formed only by evaporating the solvent.
それ故電気・電子デバイス、特に高温にさらされると
特性が劣化するような半導体装置、液晶表示装置に使用
するにあたり有用である。Therefore, it is useful for use in electric / electronic devices, especially semiconductor devices and liquid crystal display devices whose characteristics deteriorate when exposed to high temperatures.
（ヘ）実施例 以下に実施例を挙げ、更に詳しく説明するが本発明は
これらに限定されるものではない。(F) Examples Examples will be described below in more detail, but the present invention is not limited thereto.
実施例−１ MDEA 12.42g、シクロブタンテトラカルボン酸二無水
物7.74gをNMP 115g中、室温で４時間反応させポリアミ
ック酸溶液を調製した。Example 1 MDEA (12.42 g) and cyclobutanetetracarboxylic dianhydride (7.74 g) were reacted in 115 g of NMP at room temperature for 4 hours to prepare a polyamic acid solution.
得られたポリアミック酸溶液は固形分14.9重量％で粘
度は163cpsであった。The resulting polyamic acid solution had a solid content of 14.9% by weight and a viscosity of 163 cps.
この溶液をNMPにより固形分10.0重量％に希釈後180℃
で３時間加熱し脱水閉環反応を行った。加熱終了後の溶
液は均一透明であり、沈殿は全く見られなかった。After diluting this solution with NMP to a solid content of 10.0% by weight,
For 3 hours to carry out a dehydration ring closure reaction. After the completion of the heating, the solution was uniformly transparent and no precipitate was observed.
この溶液をキャストし、100℃で1.5時間真空乾燥し得
られたフィルムの赤外吸収スペクトルを測定した。This solution was cast and dried under vacuum at 100 ° C. for 1.5 hours, and the infrared absorption spectrum of the obtained film was measured.
赤外吸収スペクトルを図−１に示す。 Fig. 1 shows the infrared absorption spectrum.
1776cm-1、811cm-1にイミド基のピークが明瞭に存在
することが分かる。It can be seen that the peak of the imide group clearly exists at 1776 cm -1 and 811 cm -1 .
又、空気中での５％重量減温度は360℃であった。 The 5% weight loss temperature in air was 360 ° C.
実施例−２ ジアミンとしてMIMAを用いた他は実施例−１と同様に
操作しポリイミド樹脂溶液を得た。Example 2 A polyimide resin solution was obtained in the same manner as in Example 1, except that MIMA was used as the diamine.
結果を表−１に示す。 The results are shown in Table 1.
実施例−３ ジアミンとしてMDIAを用いた他は実施例−１と同様に
操作しポリイミド樹脂溶液を得た。Example 3 A polyimide resin solution was obtained in the same manner as in Example 1, except that MDIA was used as the diamine.
結果を表−１に示す。 The results are shown in Table 1.
実施例−４ ビス〔４−（３−アミノフェノキシ）フェニル〕スル
ホン17.3g、シクロブタンテトラカルボン酸二無水物7.8
4gをNMP 142g中室温で４時間反応させポリアミック酸
溶液を調製した。Example-4 bis [4- (3-aminophenoxy) phenyl] sulfone 17.3 g, cyclobutanetetracarboxylic dianhydride 7.8
4 g was reacted in 142 g of NMP at room temperature for 4 hours to prepare a polyamic acid solution.
得られたポリアミック酸溶液は固形分15.0重量％で粘
度は13.4poiseであった。The resulting polyamic acid solution had a solid content of 15.0% by weight and a viscosity of 13.4 poise.
この溶液55.6gを取り、NMPを28.2g添加し固形分10.0
重量％に希釈した。Take 55.6 g of this solution, add 28.2 g of NMP and solid content 10.0
Diluted to weight%.
更にピリジン6.3g無水酢酸13.7gを添加し50℃で３時
間反応させた。Further, 6.3 g of pyridine and 13.7 g of acetic anhydride were added and reacted at 50 ° C. for 3 hours.
その後このポリイミド樹脂溶液をメタノール中に投入
しポリイミド樹脂を回収し、真空乾燥を行った。得られ
たポリイミド樹脂を固形分10.0重量％となるようにNMP
に溶解させた。Thereafter, the polyimide resin solution was put into methanol, and the polyimide resin was recovered, followed by vacuum drying. NMP so that the obtained polyimide resin has a solid content of 10.0% by weight.
Was dissolved.
溶液は均一透明であり、不溶分は全く存在しなかっ
た。The solution was homogeneous and transparent, with no insolubles present.
このポリイミド樹脂溶液をキャストし、100℃で1.5時
間真空乾燥し得られたフィルムの赤外吸収スペクトルを
測定した。This polyimide resin solution was cast and vacuum dried at 100 ° C. for 1.5 hours, and the infrared absorption spectrum of the obtained film was measured.
赤外吸収スペクトルを図−２に示す。 Fig. 2 shows the infrared absorption spectrum.
1778cm-1にイミド基のピークが明瞭に存在することが
分かる。It can be seen that the peak of the imide group is clearly present at 1778 cm -1 .
又、空気中での５％重量減は438℃であった。 The 5% weight loss in air was 438 ° C.
実施例−５ ジアミンとして、ビス−〔４−（３−アミノフェノキ
シ）フェニル〕スルホン、MDEAを等モル用いた他は実施
例４と同様に操作しポリイミド樹脂溶液を得た。Example-5 A polyimide resin solution was obtained in the same manner as in Example 4, except that bis- [4- (3-aminophenoxy) phenyl] sulfone and MDEA were used in equimolar amounts as the diamine.
結果を表−２に示す。 Table 2 shows the results.
実施例−６ ジアミンとして、MDEA、2,2−ビス〔４−（４−アミ
ノフェノキシ）フェニル〕ヘキサフロロプロパンを等モ
ル用いた他は実施例−４と同様に操作しポリイミド樹脂
溶液を得た。Example -6 A polyimide resin solution was obtained in the same manner as in Example 4, except that MDEA and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane were used in equimolar amounts as the diamine. .
結果を表−２に示す。 Table 2 shows the results.
実施例−７ ジアミンとしてビス〔４−（３−アミノフェノキシ）
フェニル〕スルホン、2,2−ビス〔４−（４−アミノフ
ェノキシ）フェニル〕ヘキサフロロプロパンを等モル用
いた他は実施例−４と同様に操作しポリイミド樹脂溶液
を得た。Example-7 Bis [4- (3-aminophenoxy) as a diamine
Phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane were used in the same manner as in Example 4 except that equimolar amounts were used to obtain a polyimide resin solution.
結果を表−２に示す。 Table 2 shows the results.
比較例 １ ジアミンとして2,2−ビス〔４−（４−アミノフェノ
キシ）フェニル〕ヘキサフロロプロパンを用いた他は実
施例−１と同様に操作を行ったが、180℃での加熱によ
る脱水閉環反応の途中で沈澱が生成した。Comparative Example 1 The same operation as in Example 1 was carried out except that 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane was used as the diamine, but dehydration and ring closure by heating at 180 ° C. A precipitate formed during the course of the reaction.
この沈澱物の５％重量減温度は空気中で454℃であっ
た。The 5% weight loss temperature of the precipitate was 454 ° C in air.
比較例 ２ ジアミンとして1,4−ビス（４−アミノフェノキシ）
ベンゼンを用いた他は実施例−１と同様に操作を行った
が、180℃での加熱による脱水閉環反応の途中で沈澱が
生成した。Comparative Example 2 1,4-bis (4-aminophenoxy) as a diamine
The same operation as in Example 1 was performed except that benzene was used, but a precipitate was formed during the dehydration ring closure reaction by heating at 180 ° C.
図−１は実施例−１で得られたポリイミド樹脂の赤外吸
収スペクトルを示す。 図−２は実施例−４で得られたポリイミド樹脂の赤外吸
収スペクトルを示す。FIG. 1 shows an infrared absorption spectrum of the polyimide resin obtained in Example-1. FIG. 2 shows an infrared absorption spectrum of the polyimide resin obtained in Example-4.
Claims (1)
無水物若しくは前記テトラカルボン酸のジカルボン酸ジ
酸ハロゲン化物とジアミンを反応させることにより得ら
れるポリイミド樹脂において、ジアミンが、一般式
［Ｉ］及び／又は一般式［II］で示されるジアミンで、
得られるポリイミド樹脂が極性溶媒に可溶であることを
特徴とする可溶性ポリイミド樹脂。 （R1、R2、R3、R4は炭素数１から４のアルキル基であ
り、おのおの同じであっても異なっていてもよい。） （Ｘは２価の有機基であり、 を示す。）1. A polyimide resin obtained by reacting cyclobutanetetracarboxylic acid or a dianhydride thereof or a dicarboxylic acid diacid halide of the tetracarboxylic acid with a diamine, wherein the diamine is represented by the general formula [I] and / or A diamine represented by the general formula [II],
A soluble polyimide resin, wherein the obtained polyimide resin is soluble in a polar solvent. (R 1 , R 2 , R 3 , and R 4 are alkyl groups having 1 to 4 carbon atoms, which may be the same or different.) (X is a divalent organic group, Is shown. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1042798A JP2841426B2 (en) | 1989-02-22 | 1989-02-22 | Soluble polyimide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1042798A JP2841426B2 (en) | 1989-02-22 | 1989-02-22 | Soluble polyimide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02219827A JPH02219827A (en) | 1990-09-03 |
| JP2841426B2 true JP2841426B2 (en) | 1998-12-24 |
Family
ID=12645986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1042798A Expired - Lifetime JP2841426B2 (en) | 1989-02-22 | 1989-02-22 | Soluble polyimide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2841426B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015110684A (en) * | 2012-03-22 | 2015-06-18 | 日産化学工業株式会社 | Polyamic acid and polyimide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS606726A (en) * | 1983-06-25 | 1985-01-14 | Nissan Chem Ind Ltd | Novel polyimide resin and its production |
| JPS6147932A (en) * | 1984-08-15 | 1986-03-08 | Nissan Chem Ind Ltd | Liquid crystal display element |
| JPH0648338B2 (en) * | 1987-04-16 | 1994-06-22 | 日産化学工業株式会社 | Alignment treatment agent for liquid crystal display devices |
-
1989
- 1989-02-22 JP JP1042798A patent/JP2841426B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02219827A (en) | 1990-09-03 |
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