JP2001206948A - Solvent-soluble heat-resistant polyimide resin and method of producing the same - Google Patents
Solvent-soluble heat-resistant polyimide resin and method of producing the sameInfo
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- JP2001206948A JP2001206948A JP2000014284A JP2000014284A JP2001206948A JP 2001206948 A JP2001206948 A JP 2001206948A JP 2000014284 A JP2000014284 A JP 2000014284A JP 2000014284 A JP2000014284 A JP 2000014284A JP 2001206948 A JP2001206948 A JP 2001206948A
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- Prior art keywords
- solvent
- polyimide resin
- resistant polyimide
- heat
- soluble
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、自動車等車両部
品、ベアリング周り等の高耐熱のコーティングが必要な
部材、家電製品の部品、半導体装置、ボイラー装置部
品、焼成装置、航空宇宙関連等広く耐熱性を要求される
部材を構成する材料として用いることのできるポリイミ
ドに関し、特に多層プリント基板の絶縁層の材料として
用いることができる溶剤可溶性耐熱性ポリイミド樹脂組
成物、コーティング組成物、該ポリイミド樹脂組成物を
加熱脱炭酸して得られる、成形体、及び成形物の製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wide range of heat-resistant parts such as automobile parts, parts around bearings and the like requiring high heat-resistant coatings, parts of home appliances, semiconductor devices, boiler parts, firing equipment, aerospace-related parts, and the like. Polyimide that can be used as a material for constituting a member requiring properties, in particular, a solvent-soluble heat-resistant polyimide resin composition, a coating composition, and the polyimide resin composition that can be used as a material for an insulating layer of a multilayer printed circuit board And a method for producing a molded article obtained by heat decarboxylation.
【０００２】[0002]
【従来の技術】半導体技術の飛躍的な発展により半導体
パッケージの小型化、多ピン化、ファインピッチ化、電
子部品の極小化などが急速に進み、いわゆる高密度実装
の時代に突入した。それに伴い、プリント配線基板も片
側配線から両面基板へ、さらに多層化、薄型化が進めら
れている（岩田、原園、電子材料，３５（１０），５
３，（１９９６）．）。2. Description of the Related Art With the rapid development of semiconductor technology, the miniaturization of semiconductor packages, the increase in the number of pins, the fine pitch, the miniaturization of electronic components, and the like have rapidly advanced, and the era of so-called high-density mounting has entered. Along with this, printed wiring boards have been further multilayered and thinned from one-sided wiring to double-sided wiring (Iwata, Harazono, Electronic Materials, 35 (10), 5).
3, (1996). ).
【０００３】このような状況により、電子部品における
金属導体層−高分子絶縁層の薄膜化が進んでおり、それ
ぞれ１００μｍ以下の膜厚で用いられることが多い。こ
のように薄膜で配線基板を作製した際、金属導体層−高
分子絶縁層の熱膨張係数の差により、配線基板に反りを
生じてしまう。このような配線基板の反りは、高分子絶
縁層および金属導体層の熱的性質がわかれば、次式によ
り、算出できる（宮明、三木、日東技報，３５（３），
１，（１９９７））。[0003] Under such circumstances, the thickness of the metal conductor layer-polymer insulating layer in the electronic component has been reduced, and each of them is often used in a film thickness of 100 µm or less. When a wiring board is manufactured from such a thin film, the wiring board is warped due to a difference in thermal expansion coefficient between the metal conductor layer and the polymer insulating layer. If the thermal properties of the polymer insulating layer and the metal conductor layer are known, the warpage of the wiring board can be calculated by the following equation (Miyaaki, Miki, Nitto Giho, 35 (3),
1, (1997)).
【０００４】[0004]
【数１】 (Equation 1)
【０００５】Ｅ1 ：金属導体層の弾性率 Ｅ2 ：高分子絶縁層の弾性率 Δα：金属導電層−高分子絶縁層間の熱膨張係数の差 ΔＴ：温度差 ｈ：膜厚 ｉ：配線長E 1 : Elastic modulus of metal conductor layer E 2 : Elastic modulus of polymer insulating layer Δα: Difference in thermal expansion coefficient between metal conductive layer and polymer insulating layer ΔT: Temperature difference h: Film thickness i: Wiring length
【０００６】[0006]
【発明が解決しようとする課題】配線基板の反りを低減
させる方法として、前記式（１）により高分子絶縁層か
らアプローチした場合、次の２種の目標、即ち、 i. 高分子絶縁層の弾性率の低減 ii. 高分子絶縁層と金属導電層の熱膨張率差の低減 のいずれかを達成することが考えられる。As a method for reducing the warpage of the wiring board, when approaching from the polymer insulating layer according to the above-mentioned formula (1), the following two kinds of targets are used: i. Reduction of elastic modulus ii. It is conceivable to achieve either of the following: reduction of difference in thermal expansion coefficient between polymer insulating layer and metal conductive layer.
【０００７】一方、配線作製工程を考えると、高分子絶
縁層を形成するための樹脂組成物が溶媒可溶であること
が作業適性上望ましい。[0007] On the other hand, considering the wiring fabrication process, it is desirable from the viewpoint of workability that the resin composition for forming the polymer insulating layer is soluble in a solvent.
【０００８】上記の配線基板の反りの低減と、作業適正
の向上の両方を同時に満足させることを課題とした場
合、すなわち、 １．用いる樹脂組成物が溶媒可溶で、且つ得られる高分
子絶縁層が低弾性率 ２．用いる樹脂組成物が溶媒可溶で、且つ得られる高分
子絶縁層が低熱膨張率 のいずれかであることが求められる。[0008] When the object is to simultaneously satisfy both the above-mentioned reduction of the warpage of the wiring board and the improvement of workability, that is, 1. The resin composition used is soluble in a solvent, and the obtained polymer insulating layer has a low elastic modulus. It is required that the resin composition to be used is soluble in a solvent and that the resulting polymer insulating layer has any one of low thermal expansion coefficients.
【０００９】通常、高分子材料に低熱膨張性を与える
と、塗膜剛直性が増し、溶媒可溶性が損なわれるという
傾向にある。このような相反する物性を両立した材料と
しては、一般的には、ポリアミック酸型が知られてい
る。ポリアミック酸の形で塗布し、加熱して脱水閉環さ
せポリイミド膜を得るというものである（上田、望月、
高分子加工、４７（１２），１２，（１９９８））。Usually, when a polymer material is imparted with low thermal expansion property, the rigidity of a coating film tends to increase, and the solvent solubility tends to be impaired. A polyamic acid type is generally known as a material having both of these contradictory physical properties. It is applied in the form of polyamic acid, heated and dehydrated for ring closure to obtain a polyimide film (Ueda, Mochizuki,
Polymer processing, 47 (12), 12, (1998)).
【００１０】このポリアミック酸型の問題点として、加
熱時に脱水反応により閉環イミド化するため、塗膜の硬
化収縮が大きく、塗膜にクラック等欠陥が生じ易いとい
う点であり、配線基板等の絶縁樹脂層に用いることには
好ましくない。このような欠点を解消するために、アミ
ック酸型でない、即ち、閉環したポリイミドの状態で溶
媒に溶けかつ低熱膨張率である樹脂組成物の出現が望ま
しい。[0010] The problem of the polyamic acid type is that it undergoes a ring-closing imidization due to a dehydration reaction during heating, so that the curing of the coating film shrinks greatly and defects such as cracks easily occur in the coating film. It is not preferable to use for a resin layer. In order to solve such disadvantages, it is desirable to use a resin composition which is not an amic acid type, that is, a resin composition which is soluble in a solvent and has a low coefficient of thermal expansion in a state of a closed polyimide.
【００１１】このような要望に対し、Ｈａｒｒｉs らは
剛直な骨格のモノマーの側鎖に嵩高い基を導入させ溶媒
可溶性と低熱膨張率を両立した閉環型ポリイミドを得て
いる（Harris.Cheng,Polymer,37(22),(1996)) 。また、
Aummanらは、前記のような特徴を持つ材料として、非常
に嵩高く環状になった新規のモノマーを合成し溶媒可溶
型低熱膨張率閉環型ポリイミドを得ている（Aumman,Tro
fimenko,Polymer forMicroelectronics,Chapt34,(199
4))。これらは、前記２の溶媒可溶でかつ低熱膨張率と
いう樹脂組成物を目指したものである。In response to such demands, Harris et al. Have obtained a ring-closed polyimide having both a solvent solubility and a low coefficient of thermal expansion by introducing a bulky group into the side chain of a monomer having a rigid skeleton (Harris. Cheng, Polymer). , 37 (22), (1996)). Also,
Aumman et al. Have synthesized a novel bulky and cyclic monomer as a material having the above characteristics to obtain a solvent-soluble low thermal expansion ring-closed polyimide (Aumman, Tro
fimenko, Polymer for Microelectronics, Chapter 34, (199
Four)). These aim at the above-mentioned resin composition which is soluble in the solvent and has a low coefficient of thermal expansion.
【００１２】しかしながら、前記溶媒可溶型低熱膨張率
閉環型ポリイミドは何れもモノマー合成経路が複雑で収
率が低いため、コスト上の問題がある。However, any of the above-mentioned solvent-soluble, low thermal expansion ring-closed polyimides has a problem in terms of cost because the monomer synthesis route is complicated and the yield is low.
【００１３】次に、ジアミンとして２，２’−disulfob
enzidin(BzDSFA) を用い、酸無水物として１，４，５，
８−tetracarhoxlic dianhydride(NTCDA) を用いて、水
溶性を有するポリイミドを合成する報告がある（Timofe
eva,Khokhlof,Macromol Symp.106,(1996))。この水溶性
ポリイミドは３５０℃７０分加熱することにより脱スル
ホン酸を行ない、フィルムとした場合、非常に低熱膨張
性のフィルムが得られる。しかしながら、脱スルホン酸
基を行った後のフィルムには、水酸基が形成されるため
にフィルムの吸水性が大きく、絶縁信頼性に乏しいフィ
ルムであることが本発明者らにより確認された。Next, 2,2'-disulfob is used as a diamine.
Using enzidin (BzDSFA), 1,4,5
There is a report that a water-soluble polyimide is synthesized using 8-tetracarhoxlic dianhydride (NTCDA) (Timofe
eva, Khokhlof, Macromol Symp. 106, (1996)). This water-soluble polyimide is desulfonated by heating at 350 ° C. for 70 minutes, and when it is made into a film, a very low thermal expansion film is obtained. However, the present inventors confirmed that the film after the desulfonate group had a large water absorption due to the formation of a hydroxyl group and had poor insulation reliability.
【００１４】本発明者らは、スルホン酸基を有するモノ
マーを用いポリイミドを製造した。しかし、スルホン酸
を導入したポリイミドは、クレゾール等のフェノール系
溶媒には良好に溶解するものの、Ｎ−メチル−２−ピロ
リドン（ＮＭＰ）や、ジメチルホルムアミド（ＤＭ
Ｆ）、ジメチルアセトアミド（ＤＭＡｃ）等の汎用的な
有機極性溶媒に対する溶解性が乏しいことを確認した。The present inventors have produced polyimide using a monomer having a sulfonic acid group. However, although the sulfonic acid-introduced polyimide dissolves well in phenol solvents such as cresol, N-methyl-2-pyrrolidone (NMP) and dimethylformamide (DM
F) and poor solubility in general-purpose organic polar solvents such as dimethylacetamide (DMAc).
【００１５】そこで本発明は、溶媒可溶でかつ低熱膨張
率である耐熱性ポリイミド樹脂を提供し、該耐熱性ポリ
イミドを含むコーティング組成物を提供し、該耐熱性ポ
リイミドを用いて溶媒不溶性の成形物を製造する方法を
提供し、また該製造方法により得られた成形物を提供す
ることを目的とする。Accordingly, the present invention provides a heat-resistant polyimide resin which is soluble in a solvent and has a low coefficient of thermal expansion, a coating composition containing the heat-resistant polyimide, and a solvent-insoluble mold using the heat-resistant polyimide. An object of the present invention is to provide a method for producing a product, and to provide a molded product obtained by the production method.
【００１６】[0016]
【課題を解決するための手段】前記した課題を解決する
ために、本発明者らは、スルホン酸基よりも極性の低い
カルボキシル基が、加熱により分解し脱炭酸することに
着目し、剛直な骨格構造を有するポリイミドにカルボキ
シル基を導入することにより、汎用性の有機極性溶媒、
極性溶媒、非極性溶媒に対する溶解性があり、さらに、
ポリイミド樹脂として溶剤溶解性であるが、加熱するこ
とにより脱炭酸して溶剤不溶性となる、低熱膨張率、耐
熱性ポリイミド樹脂組成物を造り出した。Means for Solving the Problems To solve the above-mentioned problems, the present inventors have focused on the fact that a carboxyl group having a lower polarity than a sulfonic acid group is decomposed and decarboxylated by heating. By introducing a carboxyl group into a polyimide having a skeleton structure, a versatile organic polar solvent,
Soluble in polar and non-polar solvents,
A polyimide resin composition having a low coefficient of thermal expansion and having a low coefficient of thermal expansion, which is soluble in a solvent as a polyimide resin but becomes insoluble in a solvent by being decarbonated by heating, was produced.
【００１７】すなわち、本発明の溶媒可溶性耐熱性ポリ
イミド樹脂は、下記一般式（１）That is, the solvent-soluble heat-resistant polyimide resin of the present invention has the following general formula (1)
【００１８】[0018]
【化３】 Embedded image
【００１９】（式中Ｘは四価の有機基、Ｒ1 は二価、三
価又は四価のジアミン又はトリアミン、ｎは３〜８００
の整数を示す。）で表される、骨格中にカルボキシル基
を有するガラス転移温度が２００℃以上の溶媒可溶性耐
熱性ポリイミド樹脂である。Wherein X is a tetravalent organic group, R 1 is a divalent, trivalent or tetravalent diamine or triamine, and n is 3 to 800.
Indicates an integer. ) Is a solvent-soluble polyimide resin having a carboxyl group in the skeleton and having a glass transition temperature of 200 ° C. or higher.
【００２０】前記一般式（１）中のＲ1 で表されるジア
ミン又はトリアミンにおいて、カルボキシル基を有する
三価又は四価のジアミン又はトリアミンの含まれる割合
は、セグメント当たり３〜１００モル％が好ましく、更
に好ましくは１０〜１００モル％、最も好ましくは３５
〜１００モル％有である。In the diamine or triamine represented by R 1 in the general formula (1), the content of the trivalent or tetravalent diamine or triamine having a carboxyl group is preferably 3 to 100 mol% per segment. , More preferably 10 to 100 mol%, most preferably 35
１００100 mol%.
【００２１】なお、側鎖にカルボキシル基を有するポリ
イミドは、既に報告されている（特開平１０−１７１１
１６号公報）。しかし、該公報のポリイミド樹脂に導入
されたカルボキシル基は、ポリイミドに感光性を付与す
るためのものであるが、閉環後のポリイミドが溶媒可溶
性であるかについては何も報告されていない。また、該
公報のポリイミド樹脂は、本発明のような剛直な骨格構
造を有していないため、耐熱性は期待できない。A polyimide having a carboxyl group in the side chain has already been reported (JP-A-10-1711).
No. 16). However, although the carboxyl group introduced into the polyimide resin of the publication is for imparting photosensitivity to the polyimide, nothing is reported as to whether the polyimide after ring closure is solvent-soluble. Further, the polyimide resin disclosed in the publication does not have a rigid skeletal structure as in the present invention, so that heat resistance cannot be expected.
【００２２】本発明の溶媒可溶性耐熱性ポリイミド樹脂
は、１０％熱分解温度が好ましくは２５０℃以上、更に
好ましくは３５０℃以上、最も好ましくは４５０℃以上
であるという耐熱性を有する。また、ガラス転移温度
は、２００℃以上、好ましくは３００℃以上である。The solvent-soluble heat-resistant polyimide resin of the present invention has a heat resistance such that the 10% thermal decomposition temperature is preferably 250 ° C. or higher, more preferably 350 ° C. or higher, and most preferably 450 ° C. or higher. The glass transition temperature is 200 ° C. or higher, preferably 300 ° C. or higher.
【００２３】本発明の溶媒可溶性耐熱性ポリイミド樹脂
は、カルボキシル基を有する成分を含有し、酸価が１０
ｍｍｏｌ／ＫＯＨ以上２００ｍｍｏｌ／ＫＯＨ以下であ
ることが好ましい。酸価が１０ｍｇＫＯＨ／ｇ以下であ
ると、溶媒溶解性が低下し、ポリイミド樹脂が溶媒に溶
けなくなる。The solvent-soluble heat-resistant polyimide resin of the present invention contains a component having a carboxyl group and has an acid value of 10
It is preferable that the concentration be from mmol / KOH to 200 mmol / KOH. If the acid value is 10 mgKOH / g or less, the solubility of the solvent decreases, and the polyimide resin becomes insoluble in the solvent.
【００２４】本発明の溶媒可溶性耐熱性ポリイミド樹脂
を用いて塗膜を形成する場合、塗膜に高度の耐吸水性を
求める目的のためには、酸価が２００ｍｇＫＯＨ／ｇ以
上であると、吸水性が高く、高温高湿下において吸水膨
張して信頼性が低下するという問題を生じる。しかしな
がら、高度の信頼性を必要としなければ室温で放置した
場合でも膨張等を起こすことはないため、特に問題はな
い。In the case of forming a coating film using the solvent-soluble heat-resistant polyimide resin of the present invention, if the acid value is 200 mgKOH / g or more, the water absorbing Therefore, there is a problem that the water absorption and swelling under high temperature and high humidity lowers the reliability. However, if high reliability is not required, expansion or the like does not occur even when left at room temperature, so there is no particular problem.
【００２５】次に、本発明のコーティング組成物は、前
記溶媒可溶性耐熱性ポリイミド樹脂を溶媒に溶解させた
ものである。Next, the coating composition of the present invention is obtained by dissolving the solvent-soluble heat-resistant polyimide resin in a solvent.
【００２６】次に、本発明の耐熱性ポリイミド成形物の
製造方法は、前記溶媒可溶性耐熱性ポリイミド樹脂を成
型し、１３０℃〜５００℃の温度で加熱処理をすること
により、脱カルボキシル化させて溶媒不溶とする方法で
ある。Next, in the method for producing a heat-resistant polyimide molded article of the present invention, the above-mentioned solvent-soluble heat-resistant polyimide resin is molded and subjected to a heat treatment at a temperature of 130 ° C. to 500 ° C. to be decarboxylated. This is a method of making the solvent insoluble.
【００２７】さらに具体化した本発明の耐熱性ポリイミ
ド樹脂成形物の製造方法は、溶媒可溶性耐熱性ポリイミ
ド樹脂を含有するコーティング組成物を、基材にコーテ
ィングし、乾燥させることを特徴とし、さらに乾燥した
ものを１３０℃〜５００℃の温度で加熱処理することに
より溶媒不溶性にすることもできる。脱カルボキシル化
を起こすためには、好ましくは、前記ポリイミド樹脂成
形物の加熱処理温度が４００℃〜５００℃において、３
分〜１２０分である。The method for producing a heat-resistant polyimide resin molded article of the present invention, which is further embodied, is characterized in that a coating composition containing a solvent-soluble heat-resistant polyimide resin is coated on a substrate and dried. The resulting mixture can be made insoluble in a solvent by heat-treating it at a temperature of 130 ° C to 500 ° C. In order to cause decarboxylation, preferably, the heat treatment temperature of the polyimide resin molded product is 3 to 400 ° C. to 500 ° C.
Minutes to 120 minutes.
【００２８】ポリイミド 前記一般式（１）のポリイミドのＲ1 成分としてのジア
ミン又はトリアミンには、好ましくは次の一般式（２）
で示される構成単位が使用できるが、本発明はこれに限
定されない。The diamine or triamine of the R 1 component of the polyimide of the polyimide Formula (1) is preferably the following general formula (2)
Can be used, but the present invention is not limited to this.
【００２９】[0029]
【化４】 Embedded image
【００３０】一般式（２）で示される化合物の好ましい
具体例には、カルボキシル基を有する三価又は四価のジ
アミン又はトリアミンと、これ以外のジアミン又はトリ
アミンがある。Preferred specific examples of the compound represented by the general formula (2) include a trivalent or tetravalent diamine or triamine having a carboxyl group and other diamines or triamines.
【００３１】カルボキシル基を有する三価又は四価のジ
アミン又はトリアミンの具体例には、３，５−ジアミノ
安息香酸、３，３’−ジカルボキシ−４，４’−ジアミ
ノフェニルメタン、及び２，２’−ベンジジンジカルボ
ン酸から選ばれた１種以上が挙げられる。Specific examples of the trivalent or tetravalent diamine or triamine having a carboxyl group include 3,5-diaminobenzoic acid, 3,3′-dicarboxy-4,4′-diaminophenylmethane, One or more kinds selected from 2′-benzidine dicarboxylic acid are exemplified.
【００３２】前記以外のジアミン又はトリアミンには、
４，４’−ジアミノフェニルエーテル、４，４’−ジア
ミノフェニルスルホン、４，４’−ジアミノフェニルメ
タン、及び２，２’−トリフルオロメチルベンジジンか
ら選ばれた１種又は２種以上のジアミン又はトリアミン
の混合物が好ましい。さらに、本発明で使用できる前記
以外のジアミン又はトリアミンには、２，４（又は、
２，５−）ジアミノトルエン、１，４ベンゼンジアミ
ン、１，３ベンゼンジアミン、６−メチル１，３−ベン
ゼンジアミン、４，４’−ジアミノ−３，３’−ジメチ
ル−１，１’−ビフェニル、４，４’−ジアミノ−３，
３’−ジメトキシ−１，１’−ビフェニル、４，４’−
メチレンビス（ベンゼンアミン）、４，４’−オキシビ
ス（ベンゼンアミン）、３，４’−オキシビス（ベンゼ
ンアミン）、３，３’−カルボキニル（ベンゼンアミ
ン）、４，４’−チオビス（ベンゼンアミン）、４，
４’−スルホニル（ベンゼンアミン）、３，３’−スル
ホニル（ベンゼンアミン）、１−メチルエチリジン４，
４’−ビス（ベンゼンアミン）、３，３’−ジクロロ−
４，４’−ジアミノビフェニル、３，３’−ジニトロ−
４，４’−ジアミノビフェニル、３，３’−ジアミノベ
ンゾフェノン、１，５−ジアミノナフタレン、１−トリ
フルオロメチル２，２，２−トリフルオロエチリジン
４，４’−ビス（ベンゼンアミン）、１，１，１，３，
３，３−ヘキサフルオロ−２−ビス−４（４−アミノフ
ェニル）プロパン、４，４’−ジアミノベンズアニリ
ド、２，６−ジアミノピリジン、４，４’−ジアミノ−
３，３’，５，５’−テトラメチルビフェニル、２，２
ビス〔４（４−アミノフェノキシ）フェニル〕プロパ
ン、ビス〔４（３−アミノフェノキシ）フェニル〕スル
ホン、ビス〔４（４−アミノフェノキシ）フェニル〕ス
ルホン、ビス〔４（４−アミノフェノキシ）フェニル〕
エチル、１，４−ビス（４−アミノフェノキシ）ベンゼ
ン、１，３ビス（３−アミノフェノキシ）ベンゼン、
９，９−ビス（４−アミノフェニル）フルオレン、ベン
ジジン−３，３−ジカルボン酸、４，４−（または、
３，４’−、３，３’−、２，４’−）ジアミノ−ビフ
ェニルエーテル、ジアミノシラン化合物、等を挙げるこ
とができる。しかしながら、本発明はこれらの化合物に
限定されない。Other diamines or triamines include:
One or more diamines selected from 4,4′-diaminophenyl ether, 4,4′-diaminophenylsulfone, 4,4′-diaminophenylmethane, and 2,2′-trifluoromethylbenzidine; Mixtures of triamines are preferred. Further, other diamines or triamines that can be used in the present invention include 2,4 (or
2,5-) diaminotoluene, 1,4 benzenediamine, 1,3 benzenediamine, 6-methyl-1,3-benzenediamine, 4,4′-diamino-3,3′-dimethyl-1,1′-biphenyl , 4,4'-diamino-3,
3'-dimethoxy-1,1'-biphenyl, 4,4'-
Methylene bis (benzeneamine), 4,4′-oxybis (benzeneamine), 3,4′-oxybis (benzeneamine), 3,3′-carboxynyl (benzeneamine), 4,4′-thiobis (benzeneamine), 4,
4'-sulfonyl (benzeneamine), 3,3'-sulfonyl (benzeneamine), 1-methylethylidine 4,
4'-bis (benzeneamine), 3,3'-dichloro-
4,4'-diaminobiphenyl, 3,3'-dinitro-
4,4′-diaminobiphenyl, 3,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1-trifluoromethyl 2,2,2-trifluoroethylidine 4,4′-bis (benzeneamine), , 1,1,3,
3,3-hexafluoro-2-bis-4 (4-aminophenyl) propane, 4,4′-diaminobenzanilide, 2,6-diaminopyridine, 4,4′-diamino-
3,3 ′, 5,5′-tetramethylbiphenyl, 2,2
Bis [4 (4-aminophenoxy) phenyl] propane, bis [4 (3-aminophenoxy) phenyl] sulfone, bis [4 (4-aminophenoxy) phenyl] sulfone, bis [4 (4-aminophenoxy) phenyl]
Ethyl, 1,4-bis (4-aminophenoxy) benzene, 1,3bis (3-aminophenoxy) benzene,
9,9-bis (4-aminophenyl) fluorene, benzidine-3,3-dicarboxylic acid, 4,4- (or
3,4′-, 3,3′-, 2,4′-) diamino-biphenyl ether, diaminosilane compounds, and the like. However, the invention is not limited to these compounds.
【００３３】これらは単独でも二種以上混合したポリイ
ミド組成物とすることもできる。また、カルボキシル基
を有するジアミン及び／又は酸無水物と組み合わせても
良い。これらの組み合わせを選ぶ際、これらの組み合わ
せが溶媒可溶となる組成を選ぶ必要がある。These can be used alone or as a mixture of two or more. Moreover, you may combine with the diamine and / or acid anhydride which have a carboxyl group. When selecting these combinations, it is necessary to select a composition in which these combinations are soluble in a solvent.
【００３４】本発明の溶媒可溶性耐熱性ポリイミド樹脂
は、前記ジアミン又はトリアミンと反応させるもう一方
の構成成分として、酸二無水物を用いる。このような酸
二無水物の好ましい具体例には、ピロメリット酸二無水
物、１，４，５，８−ナフタレンテトラカルボン酸二無
水物、及び３，３’，４，４’−ビフタル酸二無水物等
のテトラカルボン酸二無水物が用いられる。The solvent-soluble heat-resistant polyimide resin of the present invention uses an acid dianhydride as another component to be reacted with the diamine or triamine. Preferred specific examples of such an acid dianhydride include pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride and 3,3 ′, 4,4′-biphthalic acid A tetracarboxylic dianhydride such as dianhydride is used.
【００３５】本発明の溶媒可溶性耐熱性ポリイミド樹脂
に用いられる酸二無水物では前記以外の具体的には、
３，４，３’，４’ビフェニルテトラカルボン酸二無水
物、３，４，３’，４’ベンゾフェノンテトラカルボン
酸二無水物、２，３，３’，４’ビフェニルエーテルテ
トラカルボン酸二無水物、３，４，３’，４’ビフェニ
ルスルホンテトラカルボン酸二無水物、ビス（ジカルボ
キシルフェニル）プロパン二無水物、4,4'-[2,2,2-トリ
フルオロ-1-(トリフルオロメチル) エチリデン]ビス(1,
2- ベンゼンジカルボン酸二無水物) （６ＦＤＡ）、ビ
ストリフルオロメチル化ピロメリット酸、ビス（ジカル
ボキシルフェニル）スルホン二無水物、ビス（ジカルボ
キシルフェニル）エーテル二無水物、チオフェンテトラ
カルボン酸二無水物、ピロメリット酸二無水物、１，
２，５，６ナフタレンテトラカルボン酸二無水物、２、
３、５、６−ピリジンテトラカルボン酸二無水物、等の
芳香族酸二無水物、１，２，３，４−ブタンテトラカル
ボン酸二無水物、シクロペンタンテトラカルボン酸二無
水物、ビシクロオクテンテトラカルボン酸、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、５（２，５−ジオキソテト
ラヒドロフリル）３−メチル−３シクロヘキセン−１，
２−ジカルボン酸無水物、等の脂肪族酸二無水物を挙げ
ることができる。In the acid dianhydride used in the solvent-soluble heat-resistant polyimide resin of the present invention, specifically, other than the above,
3,4,3 ', 4'biphenyltetracarboxylic dianhydride, 3,4,3', 4'benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'biphenylethertetracarboxylic dianhydride Product, 3,4,3 ', 4'biphenylsulfonetetracarboxylic dianhydride, bis (dicarboxylphenyl) propane dianhydride, 4,4'-[2,2,2-trifluoro-1- (tri Fluoromethyl) ethylidene] bis (1,
2-benzenedicarboxylic dianhydride) (6FDA), bistrifluoromethylated pyromellitic acid, bis (dicarboxylphenyl) sulfone dianhydride, bis (dicarboxylphenyl) ether dianhydride, thiophenetetracarboxylic dianhydride , Pyromellitic dianhydride, 1,
2,5,6 naphthalenetetracarboxylic dianhydride, 2,
Aromatic acid dianhydrides such as 3,5,6-pyridinetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, bicyclooctene Tetracarboxylic acid, bicyclo (2,2,2) -oct-7-ene-2,3,5,6-
Tetracarboxylic dianhydride, 5 (2,5-dioxotetrahydrofuryl) 3-methyl-3-cyclohexene-1,
Examples thereof include aliphatic dianhydrides such as 2-dicarboxylic anhydride.
【００３６】しかしながら、本発明はこれらの化合物に
限定されない。これらは単独、又は二種以上の組み合わ
せで使用される。また、スルホン酸基を有するジアミン
及び／又は酸無水物と組み合わせて用いても良い。ポリ
イミドにする場合、これらの組み合わせの中から溶媒可
溶となる組成を選ぶ必要がある。However, the present invention is not limited to these compounds. These are used alone or in combination of two or more. Further, it may be used in combination with a diamine having a sulfonic acid group and / or an acid anhydride. In the case of using polyimide, it is necessary to select a solvent-soluble composition from these combinations.
【００３７】本発明の酸無水物には、カルボキシル基を
含ませてもよい。このようなカルボキシル基を有する酸
無水物は、下記の一般式（３）で表される化合物が好ま
しく使用できるが、これらに限定されない。The acid anhydride of the present invention may contain a carboxyl group. As the acid anhydride having such a carboxyl group, a compound represented by the following general formula (3) can be preferably used, but is not limited thereto.
【００３８】[0038]
【化５】 Embedded image
【００３９】骨格中にカルボキシル基を有するポリイミ
ドを得る方法は、前記した原料に示したように、原料と
して、カルボキシル基を有するジアミン、及び／又はカ
ルボキシル基を有する酸二無水物を用いる方法、また
は、保護基を導入し潜在的にカルボキシル基になり得る
ような置換基を有するジアミン及び／又は保護基を導入
し、潜在的にカルボキシル基になり得るような置換基を
有する酸二無水物を用い、前駆体を形成後、脱保護しカ
ルボキシル基とする方法などが挙げられるが特に限定さ
れない。また後者の場合、イミド化後に脱保護を行なっ
ても良い。As a method for obtaining a polyimide having a carboxyl group in the skeleton, a method using a diamine having a carboxyl group and / or an acid dianhydride having a carboxyl group as a raw material, as shown in the above-mentioned raw materials, or Using a diamine having a substituent capable of introducing a protecting group and potentially becoming a carboxyl group and / or an acid dianhydride having a substituent capable of introducing a protecting group and potentially forming a carboxyl group. And a method of forming a precursor and then deprotecting it to form a carboxyl group, but the method is not particularly limited. In the latter case, deprotection may be performed after imidization.
【００４０】本発明のポリイミド樹脂は、主にｍ−クレ
ゾール、ｏ−クレゾール、ｐ−クレゾール、フェノー
ル、ＮＭＰ、ＤＭＦ、ＤＭＡｃ、γ−ブチロラクトン、
ＤＭＳＯ、スルホラン等の有機極性溶媒に可溶性である
が、ポリイミドの組成によっては水アセトン、ＴＨＦに
も可溶となる。The polyimide resin of the present invention is mainly composed of m-cresol, o-cresol, p-cresol, phenol, NMP, DMF, DMAc, γ-butyrolactone,
It is soluble in organic polar solvents such as DMSO and sulfolane, but also soluble in water acetone and THF depending on the composition of the polyimide.
【００４１】さらに本発明のポリイミド樹脂は前記した
ように耐熱温度が高いので、特に、多層基板等の電子材
料に用いる場合には、耐熱性という観点から好ましい。Further, since the polyimide resin of the present invention has a high heat resistance temperature as described above, it is preferable from the viewpoint of heat resistance especially when it is used for an electronic material such as a multilayer substrate.
【００４２】また本発明のポリイミド樹脂のイミド化率
は好ましくは８５％以上、より好ましくは９０％以上、
特に好ましくは９５％以上が好ましい。イミド化率が８
５％以下では、ポリイミド溶液の保存安定性が低下す
る。The imidation ratio of the polyimide resin of the present invention is preferably at least 85%, more preferably at least 90%,
Particularly preferably, it is 95% or more. Imidation rate is 8
If it is less than 5%, the storage stability of the polyimide solution will decrease.
【００４３】本発明のポリイミド樹脂の重量平均分子量
は８０００〜１００００００が好ましい。特に好ましく
は２００００〜８００００である。分子量が８０００以
下であると、均一な塗膜を得難く、１００００００以上
では高濃度の溶液が得られずプロセス適性が悪い。The weight average molecular weight of the polyimide resin of the present invention is preferably 8,000 to 1,000,000. Particularly preferably, it is 20,000 to 80,000. When the molecular weight is 8,000 or less, it is difficult to obtain a uniform coating film, and when the molecular weight is 1,000,000 or more, a high-concentration solution cannot be obtained and process suitability is poor.
【００４４】本発明において分子量測定は東ソー（株）
製高速ＧＰＣ装置を用いた。用いたカラムは東ソー
（株）製ＴＳＫｇｅｌ αＭ（商品名）であり、溶媒は
ＮＭＰ１リットルに対し、バッファとして＋５０ｍｍｏ
ｌ リン酸＋５０ｍｍｏｌ ＬｉＢｒを溶解させたもの
を用い、流速０．５ｃｃ／ｍｉｎで測定を行なったもの
である。In the present invention, the molecular weight is measured by Tosoh Corporation.
A high-speed GPC device was used. The column used was TSKgel αM (trade name) manufactured by Tosoh Corporation. The solvent was +50 mmol as a buffer per 1 liter of NMP.
1 Phosphoric acid +50 mmol LiBr was dissolved therein, and the measurement was performed at a flow rate of 0.5 cc / min.
【００４５】種々のモノマーを用い、合成を行なう場合
に、反応液のモノマー濃度が約１０％程度の時はゲル化
の進行するものも見受けられる。しかし、イミド化反応
しやすい１，４，５，８−ナフタレンテトラカルボン酸
二無水物を用いると高濃度の反応溶液でもゲル化の進行
が生じないことが判明している。また、ゲル化の起こり
易いモノマーを用いても、充分に前駆体への重合反応を
低温で行なった後、反応液の濃度を希薄にし無水酢酸等
の触媒を用いる化学的イミド化法でイミド化を行なうこ
とでもゲル化が防げる。In the case of performing synthesis using various monomers, when the monomer concentration of the reaction solution is about 10%, some gelation is observed. However, it has been found that the use of 1,4,5,8-naphthalenetetracarboxylic dianhydride, which easily undergoes an imidization reaction, does not cause gelation to proceed even in a highly concentrated reaction solution. In addition, even if a monomer that easily undergoes gelation is used, the polymerization reaction to the precursor is sufficiently performed at a low temperature, then the concentration of the reaction solution is diluted, and imidization is performed by a chemical imidization method using a catalyst such as acetic anhydride. Gelling can also be prevented by performing
【００４６】[0046]
【実施例】試薬の調製３，３’，４，４’−ビフェニル
テトラカルボキシリックジアンハイドライド（略語：Ｂ
ＰＤＡ）、ナフタレン−１，４，５，８−テトラカルボ
キシリックジアンハイドライド（略語：ＮＴＣＤＡ）、
４，４’−ジアミノジフェニルメタン（略語：ＤＡＤＰ
Ｍ）は東京化成のものをそのまま用いた。３，３’−ジ
カルボキシ−４，４’−ジアミノフェニルメタン（略
語：ＭＢＡＡ）は和歌山精化のものをそのまま用いた。EXAMPLES Preparation of reagents 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (abbreviation: B
PDA), naphthalene-1,4,5,8-tetracarboxylic dianhydride (abbreviation: NTCDA),
4,4'-diaminodiphenylmethane (abbreviation: DADP
M) was directly used by Tokyo Chemical Industry. 3,3′-Dicarboxy-4,4′-diaminophenylmethane (abbreviation: MBAA) was used directly from Wakayama Seika.
【００４７】〔実施例１〕ｏ−クレゾール中で以下のよ
うな一段階でポリイミドＡの合成を行なった。ｏ−クレ
ゾール１００ｇ中に分子内にカルボキシル基を有するＭ
ＢＡＡ１９ｍｍｏｌを入れ、室温で４０分撹拌した。Ｍ
ＢＡＡのクレゾールに対する溶解性が低く、この状態で
は若干不溶物が残るため、トリエチルアミンを０．００
５１ｍｏｌ添加し、設定温度７０℃（内温６０〜７０
℃）で撹拌して均一な溶液にした。その後、５０℃に液
温を下げ、触媒として安息香酸を０．０１４ｍｏｌ添加
した。その後、酸無水物ＮＴＣＤＡ１９ｍｍｏｌを添加
し、内温５０℃のままで１．５時間撹拌を行ない均一な
溶液を得た。その後、設定温度を２１０℃、内温１８０
℃に上昇させ、３時間内温１８０℃で撹拌を行ない、イ
ミド化反応を行なった。Example 1 Polyimide A was synthesized in one step as follows in o-cresol. M having a carboxyl group in the molecule in 100 g of o-cresol
19 mmol of BAA was added and stirred at room temperature for 40 minutes. M
BAA has low solubility in cresol, and in this state, some insoluble matter remains.
Add 51 mol, set temperature 70 ° C (internal temperature 60-70)
C.) to a homogeneous solution. Thereafter, the liquid temperature was lowered to 50 ° C., and 0.014 mol of benzoic acid was added as a catalyst. Thereafter, 19 mmol of acid anhydride NTCDA was added, and the mixture was stirred for 1.5 hours while keeping the internal temperature at 50 ° C. to obtain a uniform solution. After that, the set temperature is set to 210 ° C.
C., and the mixture was stirred at an internal temperature of 180.degree. C. for 3 hours to carry out an imidization reaction.
【００４８】反応終了後、はじめにメタノール６００ｍ
ｌ／濃塩酸３０ｍｌ、その後、メタノール５００ｍｌを
投入し再沈殿を行なった。その後、メタノール５００ｍ
ｌ中で撹拌洗浄を２回行なった。その後、７０℃の温風
乾燥を１２時間行ない、収量８．８ｇの白桃色粉末を
得、ポリイミドＡとした。After completion of the reaction, first, 600 m
1/30 ml of concentrated hydrochloric acid and then 500 ml of methanol were added to perform reprecipitation. Then, 500m of methanol
The washing with stirring was performed twice in 1 l. Thereafter, hot air drying at 70 ° C. was performed for 12 hours to obtain 8.8 g of a white pink powder in a yield of polyimide A.
【００４９】〔実施例２〕ｏ−クレゾール中で以下のよ
うな一段階でポリイミドＢの合成を行なった。ｏ−クレ
ゾール１００ｇ中に分子内にカルボキシル基を有するＭ
ＢＡＡ１９ｍｍｏｌを入れ、室温で４０分間撹拌した。
ＭＢＡＡのクレゾールに対する溶解性が低く、この状態
では若干不溶物が残るため、トリエチルアミンを０．０
０５１ｍｏｌ添加し、設定温度７０℃（内温６０〜７０
℃）で撹拌して均一な溶液にした。その後、５０℃に液
温を下げ、触媒として安息香酸を０．０１４ｍｏｌ添加
した。その後、酸無水物ＢＰＤＡ１９ｍｍｏｌを添加
し、内温５０℃のままで１．５時間撹拌を行ない均一な
溶液を得た。その後、設定温度を２１０℃、内温１８０
℃に上昇させ、１時間内温１８０℃で撹拌を行なったと
ころゲル化した。このゲルを、ポリイミドＢとした。Example 2 Polyimide B was synthesized in one step as follows in o-cresol. M having a carboxyl group in the molecule in 100 g of o-cresol
BAA (19 mmol) was added, and the mixture was stirred at room temperature for 40 minutes.
MBAA has low solubility in cresol, and in this state, some insoluble matter remains.
051 mol, and set temperature 70 ° C (internal temperature 60-70)
C.) to a homogeneous solution. Thereafter, the liquid temperature was lowered to 50 ° C., and 0.014 mol of benzoic acid was added as a catalyst. Thereafter, 19 mmol of acid anhydride BPDA was added, and the mixture was stirred for 1.5 hours while keeping the internal temperature at 50 ° C. to obtain a uniform solution. After that, the set temperature is set to 210 ° C.
The solution was heated to 180 ° C. and stirred at an internal temperature of 180 ° C. for 1 hour. This gel was designated as polyimide B.
【００５０】〔比較例１〕ｏ−クレゾール中で以下のよ
うな一段階でポリイミドＣの合成を行なった。ｏ−クレ
ゾール１００ｇ中に分子内にカルボキシル基を有しない
ＤＡＤＰＭ１９ｍｍｏｌを入れ、５０℃で３０分間撹拌
し、均一な溶液にした。その後、５０℃に液温を下げ、
触媒として安息香酸を２００ｍｇ添加した。その後、Ｂ
ＰＤＡを１９ｍｍｏｌ添加し、そのまま９０分撹拌を行
ない均一な溶液とした。共沸溶媒としてトルエン５０ｍ
ｌを加えた後、液温を１８０℃に上げ、１．５時間撹拌
を行なったところ、白色沈殿が析出し反応溶媒の粘度が
急激に減少した。この粉末を、メタノールで洗浄したも
のをポリイミドＣとした。Comparative Example 1 Polyimide C was synthesized in o-cresol in one step as follows. 19 mmol of DADPM having no carboxyl group in the molecule was added to 100 g of o-cresol, and the mixture was stirred at 50 ° C. for 30 minutes to form a uniform solution. After that, lower the liquid temperature to 50 ° C,
200 mg of benzoic acid was added as a catalyst. Then, B
19 mmol of PDA was added, and the mixture was stirred for 90 minutes to form a uniform solution. 50m of toluene as azeotropic solvent
After adding 1, the liquid temperature was raised to 180 ° C. and the mixture was stirred for 1.5 hours. As a result, a white precipitate was deposited and the viscosity of the reaction solvent was rapidly reduced. This powder was washed with methanol to obtain polyimide C.
【００５１】〔実施例３〕溶媒溶解性評価 各ポリイミドを３０ｃｃサンプル管瓶に採取、ＮＭＰ、
ｍ−クレゾール、イオン交換水で２０倍、２００倍希釈
し、ホットプレート付き電磁スターラーで８０℃設定で
撹拌した。目視で不溶物を確認した。ポリイミドＢはゲ
ルのため評価しなかった。その結果を下記の表１に示
す。ポリイミドＣに用いたジアミン（ＤＡＤＰＭ）は、
ポリイミドＡに用いたジアミンよりカルボキシル基を取
り除いた構造と同一である。また、酸無水物が異なるも
のの一般にポリイミドＡに用いられている酸無水物より
ポリイミドＣに用いられている酸無水物の方が溶解性が
高いため、カルボキシル基導入による溶解性向上の効果
が発現されている。ポリイミドＡは、ｍ−クレゾールよ
りもＮＭＰの方が溶解性が良好であり、ＮＭＰに対して
溶解性を向上させる成分としてカルボキシル基の導入が
効果的であると判断できる。Example 3 Solvent Solubility Evaluation Each polyimide was collected in a 30 cc sample tube bottle, and NMP,
The mixture was diluted 20-fold and 200-fold with m-cresol and ion-exchanged water, and stirred at 80 ° C. with an electromagnetic stirrer equipped with a hot plate. Insoluble matter was visually confirmed. Polyimide B was not evaluated because it was a gel. The results are shown in Table 1 below. The diamine (DADPM) used for Polyimide C is
The structure is the same as the structure obtained by removing the carboxyl group from the diamine used for polyimide A. In addition, although the acid anhydride is different, the acid anhydride used for polyimide C has higher solubility than the acid anhydride generally used for polyimide A, so that the effect of improving the solubility by introducing a carboxyl group is exhibited. Have been. In polyimide A, NMP has better solubility than m-cresol, and it can be judged that the introduction of a carboxyl group is more effective as a component for improving the solubility in NMP.
【００５２】[0052]
【表１】 [Table 1]
【００５３】〔実施例４〕脱カルボン酸基反応の追跡 図１は、ポリイミドＡの熱重量分析を行った結果を縦軸
に重量％、横軸に温度（℃）をとったグラフである。図
１によれば、４２０℃を過ぎた辺りから急激な重量減少
があり、丁度８０％の重量に落ちた周辺で重量減少の程
度が収まっているのがわかる。この結果は、加熱により
脱炭酸反応が起こると仮定した場合に、二酸化炭素が発
生したとした時の理論量と近い値である。Example 4 Tracking of Decarboxylation Group Reaction FIG. 1 is a graph showing the results of thermogravimetric analysis of polyimide A, in which the vertical axis represents weight% and the horizontal axis represents temperature (° C.). According to FIG. 1, it can be seen that there is a sharp decrease in weight around 420 ° C., and the extent of the decrease in weight is reduced around the point where the weight has just dropped to 80%. This result is a value close to the theoretical amount when carbon dioxide is generated assuming that a decarboxylation reaction occurs by heating.
【００５４】図２は、ポリイミドＡを４００℃に保持し
た場合と、４５０℃に保持した場合における各重量変化
を示したグラフである。図２によれば、ポリイミドＡを
４００℃で加熱を続けた場合より、４５０℃で加熱を続
けた場合の方が重量減少が収まるのが早くなっているこ
とがわかる。以上の結果より、ポリイミドＡについての
熱処理条件は４５０℃の方が好ましいことがわかる。FIG. 2 is a graph showing weight changes when the polyimide A is kept at 400 ° C. and when it is kept at 450 ° C. According to FIG. 2, it can be seen that the weight loss stops faster when heating the polyimide A at 450 ° C. than when heating it at 400 ° C. From the above results, it is understood that the heat treatment condition for polyimide A is preferably 450 ° C.
【００５５】〔実施例５〕ＩＲスペクトルによる分析 シリコンウエハ上にポリイミドＡの１μｍの塗膜を形成
した。該ポリイミドＡの塗膜に対して４５０℃、１５分
の熱処理を与えた。該熱処理の前後でＩＲスペクトルを
日本分光社製ＦＩ／ＩＲ−６１０（商品名）により測定
した。その結果を図３に示す。Example 5 Analysis by IR Spectrum A 1 μm film of polyimide A was formed on a silicon wafer. The polyimide A coating film was subjected to a heat treatment at 450 ° C. for 15 minutes. Before and after the heat treatment, IR spectra were measured by FI / IR-610 (trade name) manufactured by JASCO Corporation. The result is shown in FIG.
【００５６】図３によれば、１７３０ｃｍ-1付近のピー
クがベーク後に減少しているのがわかる。ｎ−メチル−
２−ピロリトンに対する溶解試験を行ったところ、ポリ
イミドＡの塗膜は加熱処理前に溶解していたが、加熱処
理後には溶解しなくなっていた。図３のＩＲスペクトル
の結果より、４５０℃の加熱処理の過程で塗膜に何らか
の変化が起こったものと考えられる。ポリイミドＡの塗
膜に耐溶媒性が発現されたのはそのためではないかと考
えられる。FIG. 3 shows that the peak around 1730 cm -1 decreases after baking. n-methyl-
When a dissolution test was performed on 2-pyrroliton, the coating film of polyimide A was dissolved before the heat treatment, but was not dissolved after the heat treatment. From the result of the IR spectrum of FIG. 3, it is considered that some change occurred in the coating film during the heat treatment at 450 ° C. It is considered that the solvent resistance was developed in the polyimide A coating film.
【００５７】さらに、ポリイミドＡの室温から３５０℃
までの昇温の過程をＩＲスペクトルで追跡した。その結
果を図４に昇温スペクトルとして示す。図４によれば、
ピークに全く変化がなく、ＴＧＡの結果よりも明らかな
ように少なくとも３５０℃までは分解などが起こってい
ないので、ポリイミドＡは安定な物質であるといえる。Further, from the room temperature of the polyimide A to 350 ° C.
The process of heating up to was monitored by IR spectrum. The result is shown in FIG. 4 as a heating spectrum. According to FIG.
Since there is no change in the peak and no decomposition or the like has occurred at least up to 350 ° C. as is clear from the TGA result, it can be said that polyimide A is a stable substance.
【００５８】〔実施例６〕熱物性評価 ポリイミドＡの１０％ＮＭＰ溶液を１０ｃｍ×１０ｃｍ
の膜厚１２μｍの銅箔上にコーティングし、１２０℃３
０分間オーブンにて乾燥した。その後、４５０℃１５分
間窒素雰囲気下において熱硬化を行い、１０μｍ膜厚の
コーティング被膜を得た。その後、液温５０℃、４５ボ
ーメ塩化第二鉄中において銅箔のエッチングを行い、ポ
リイミドフィルムを得た。該ポリイミドフィルムを長さ
約２ｃｍ、幅５ｍｍに切り出し、Ｒｉｇａｋｕ社製Ther
moPlusII TMA8310（商品名）を用いて熱膨張係数の測定
を行った。測定条件は荷重１０ｇ、温度範囲室温〜３５
０℃、昇温速度１０℃／ｍｉｎで行った。膨張係数は１
００℃から軟化点温度までの平均をとった。また、同様
にして得たフィルムをレオメトリックサイエンス社製Ｒ
ＳＡ−２を用い、室温〜４００℃まで昇温速度５℃／ｍ
ｉｎで動的粘弾性試験を行った。また、その際にＴａｎ
δのピークをガラス転移点Ｔｇとした。その結果を下記
の表２に示す。Example 6 Evaluation of Thermophysical Properties A 10% NMP solution of polyimide A was applied to 10 cm × 10 cm.
Is coated on a copper foil having a thickness of 12 μm at 120 ° C.
It was dried in an oven for 0 minutes. Thereafter, thermosetting was performed in a nitrogen atmosphere at 450 ° C. for 15 minutes to obtain a coating film having a thickness of 10 μm. Thereafter, the copper foil was etched at a liquid temperature of 50 ° C. and in 45 Baume ferric chloride to obtain a polyimide film. The polyimide film was cut into a length of about 2 cm and a width of 5 mm, and was manufactured by Rigaku Ther.
The coefficient of thermal expansion was measured using moPlusII TMA8310 (trade name). The measurement conditions were a load of 10 g and a temperature range of room temperature to 35.
The test was performed at 0 ° C. at a rate of temperature increase of 10 ° C./min. Expansion coefficient is 1
The average from 00 ° C to the softening point temperature was taken. In addition, a film obtained in the same manner was manufactured by Rheometric Science Co., Ltd.
Using SA-2, heating rate from room temperature to 400 ° C 5 ° C / m
The dynamic viscoelasticity test was performed in. At that time, Tan
The peak of δ was defined as the glass transition point Tg. The results are shown in Table 2 below.
【００５９】[0059]
【表２】 [Table 2]
【００６０】表２から分かるように、本発明のポリイミ
ド樹脂は４００℃以上のＴｇを示す耐熱性が非常に良好
であり、しかも低熱膨張率である。As can be seen from Table 2, the polyimide resin of the present invention has a very good heat resistance showing a Tg of 400 ° C. or higher and has a low coefficient of thermal expansion.
【００６１】〔実施例７〕吸水性評価 熱膨張係数測定と同様な方法で、１０×１０ｃｍ、膜厚
１０〜２０μｍのポリイミドＡのフィルムを調製した。
リファレンスとして、Ｋａｐｔｏｎ １００Ｈフィルム
（東レ・デュポン社製、商品名）を用いた。前記各フィ
ルムについてドライボックスで湿度を変化させ重量変化
を測定し、吸湿性の湿度依存性を調べた。その結果を図
５に示す。図５のグラフによれば、市販のポリイミドフ
ィルムよりもポリイミドＡフィルムの方が吸湿性が大き
いことがわかる。これは、４５０℃１５分の加熱処理条
件では脱炭酸が完全に進行していないためではないかと
考えられる。これは、溶解性を損なわない範囲でカルボ
キシル基の導入量を少なくすることで解決できると思わ
れる。その際の導入量の下限はポリイミド骨格の構造に
よる。Example 7 Evaluation of Water Absorption A film of polyimide A having a size of 10 × 10 cm and a film thickness of 10 to 20 μm was prepared in the same manner as in the measurement of the coefficient of thermal expansion.
As a reference, Kapton 100H film (trade name, manufactured by Dupont Toray) was used. The humidity of each of the films was changed in a dry box to measure the change in weight, and the humidity dependency of the moisture absorption was examined. The result is shown in FIG. According to the graph of FIG. 5, it can be seen that the polyimide A film has higher hygroscopicity than the commercially available polyimide film. This is probably because decarboxylation did not completely proceed under the heat treatment conditions of 450 ° C. for 15 minutes. It seems that this can be solved by reducing the amount of carboxyl groups introduced as long as the solubility is not impaired. The lower limit of the amount introduced at that time depends on the structure of the polyimide skeleton.
【００６２】[0062]
【発明の効果】本発明は、本来溶媒不溶性である剛直な
骨格構造を有するポリイミドに対して、カルボキシル基
を導入することにより、汎用性の有機極性溶媒に対する
溶解性があり、さらに、加熱することにより脱炭酸して
溶剤不溶性となる、低熱膨張率、耐熱性ポリイミド樹脂
組成物である。According to the present invention, a polyimide having a rigid skeleton structure, which is originally insoluble in a solvent, has a solubility in a general-purpose organic polar solvent by introducing a carboxyl group. Is a heat-resistant polyimide resin composition having a low coefficient of thermal expansion and becoming solvent-insoluble due to decarboxylation.
【００６３】本発明の溶媒可溶性耐熱性ポリイミド樹脂
は、１０％熱分解温度が好ましくは２５０℃以上、更に
好ましくは３５０℃以上、最も好ましくは４５０℃以上
であるという耐熱性を有する。さらに高温の熱処理を加
えることにより耐溶媒性を付与することができる。The solvent-soluble heat-resistant polyimide resin of the present invention has a heat resistance such that the 10% thermal decomposition temperature is preferably 250 ° C. or higher, more preferably 350 ° C. or higher, and most preferably 450 ° C. or higher. Further, by applying a high-temperature heat treatment, solvent resistance can be imparted.
【図１】ポリイミドＡの熱重量分析を行った結果を縦軸
に重量％、横軸に温度（℃）をとったグラフである。FIG. 1 is a graph showing the results of thermogravimetric analysis of polyimide A, in which the vertical axis represents weight% and the horizontal axis represents temperature (° C.).
【図２】ポリイミドＡを４００℃に保持した場合と、４
５０℃に保持した場合における各重量変化を示したグラ
フである。FIG. 2 shows a case where polyimide A is kept at 400 ° C.
It is the graph which showed each weight change at the time of keeping at 50 degreeC.
【図３】シリコンウエハ上に形成したポリイミドＡの１
μｍの塗膜に対して、４５０℃、１５分の熱処理を与え
た際の、熱処理の前後のＩＲスペクトルを示す図であ
る。FIG. 3 shows polyimide A formed on a silicon wafer.
It is a figure which shows the IR spectrum before and after the heat processing at the time of giving a heat processing of 450 degreeC and 15 minutes with respect to a coating film of micrometers.
【図４】ポリイミドＡの室温から３５０℃までの昇温の
過程のＩＲスペクトルを示す図である。FIG. 4 is a diagram showing an IR spectrum of polyimide A in the process of raising the temperature from room temperature to 350 ° C.
【図５】ポリイミドＡフィルムと比較のフィルムについ
てドライボックスで湿度を変化させ重量変化を測定し、
吸湿性の湿度依存性を調べた結果を示すグラフである。FIG. 5 is a graph showing a comparison between a polyimide A film and a comparative film, a change in humidity in a dry box, and a change in weight.
It is a graph which shows the result of having investigated the humidity dependency of the hygroscopicity.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F071 AA60 AF05 AF45 AG28 AH12 AH13 BA02 4J002 CM041 GH00 GN00 GQ00 GQ01 HA05 4J038 DJ021 GA06 HA156 JA33 JA63 JA70 JB13 JB27 JC11 JC13 LA02 MA07 MA09 MA10 MA12 MA13 MA14 NA11 NA13 NA21 PA19 PB06 PB07 PB09 PC02 4J043 PA02 PA04 PA19 QB26 QB31 QB36 RA35 SA03 SA06 SA07 SA43 SA44 SA52 SA54 SA62 SB01 SB02 SB03 TA22 TB01 TB02 UA121 UA122 UA131 UA132 UA141 UA151 UA251 UA261 UA262 UA361 UB011 UB021 UB061 UB121 UB131 UB151 UB241 UB281 UB301 UB311 VA011 VA021 VA041 VA051 VA061 VA071 VA081 VA091 YA08 YA13 YB02 YB08 ZA12 ZA23 ZB03 ZB47 ZB50 ZB51 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA60 AF05 AF45 AG28 AH12 AH13 BA02 4J002 CM041 GH00 GN00 GQ00 GQ01 HA05 4J038 DJ021 GA06 HA156 JA33 JA63 JA70 JB13 JB27 JC11 JC13 LA02 MA07 MA09 MA10 MA11 NA13 NA14 PB07 PB09 PC02 4J043 PA02 PA04 PA19 QB26 QB31 QB36 RA35 SA03 SA06 SA07 SA43 SA44 SA52 SA54 SA62 SB01 SB02 SB03 TA22 TB01 TB02 UA121 UA122 UA131 UA132 UA141 UA151 VA UA251 UA261 UA262 UA361 UB011 01 UB021 UB011 UB011 UB011 VA071 VA081 VA091 YA08 YA13 YB02 YB08 ZA12 ZA23 ZB03 ZB47 ZB50 ZB51
Claims (23)
ジアミン又はトリアミン、ｎは３〜８００の整数を示
す。）で表される、骨格中にカルボキシル基を有するガ
ラス転移温度が２００℃以上の溶媒可溶性耐熱性ポリイ
ミド樹脂。[Claim 1] The following general formula (1) (Wherein X is a tetravalent organic group, R 1 is a divalent, trivalent or tetravalent diamine or triamine, and n represents an integer of 3 to 800), and has a carboxyl group in the skeleton. A solvent-soluble heat-resistant polyimide resin having a glass transition temperature of 200 ° C. or higher.
アミン又はトリアミンにおいて、カルボキシル基を有す
る三価又は四価のジアミン又はトリアミンの含まれる割
合は、セグメント当たり３〜１００モル％である請求項
１記載の溶媒可溶性耐熱性ポリイミド樹脂。2. In the diamine or triamine represented by R 1 in the general formula (1), the content of the trivalent or tetravalent diamine or triamine having a carboxyl group is 3 to 100 mol% per segment. The solvent-soluble heat-resistant polyimide resin according to claim 1, which is:
アミン又はトリアミンにおいて、カルボキシル基を有す
る三価又は四価のジアミン又はトリアミンの含まれる割
合は、セグメント当たりの３５〜１００モル％である請
求項１記載の溶媒可溶性耐熱性ポリイミド樹脂。3. In the diamine or triamine represented by R 1 in the general formula (1), the content of the trivalent or tetravalent diamine or triamine having a carboxyl group is 35 to 100 mol per segment. % Of the solvent-soluble heat-resistant polyimide resin according to claim 1.
価又は四価のジアミン又はトリアミンは、下記一般式
（２） 【化２】 で表されることを特徴とする請求項１、２又は３記載の
溶媒可溶性耐熱性ポリイミド樹脂。4. The trivalent or tetravalent diamine or triamine represented by R 1 in the general formula (1) is represented by the following general formula (2): The solvent-soluble heat-resistant polyimide resin according to claim 1, wherein the polyimide resin is represented by:
価のジアミン又はトリアミンは、３，５−ジアミノ安息
香酸、３，３’−ジカルボキシ−４，４’−ジアミノフ
ェニルメタン、及び２，２’−ベンジジンジカルボン酸
から選ばれた１種以上である請求項１乃至４の何れか１
項記載の溶媒可溶性耐熱性ポリイミド樹脂。5. The trivalent or tetravalent diamine or triamine having a carboxyl group is 3,5-diaminobenzoic acid, 3,3′-dicarboxy-4,4′-diaminophenylmethane, and 2,2 5. The method according to claim 1, which is at least one selected from '-benzidine dicarboxylic acid.
The solvent-soluble heat-resistant polyimide resin according to the above item.
価のジアミン又はトリアミン以外の、ジアミン又はトリ
アミンは、４，４’−ジアミノフェニルエーテル、４，
４’−ジアミノフェニルスルホン、４，４’−ジアミノ
フェニルメタン、及び２，２’−トリフルオロメチルベ
ンジジンから選ばれた１種又は２種以上の混合物である
請求項１乃至５の何れか１項記載の溶媒可溶性耐熱性ポ
リイミド樹脂。6. A diamine or triamine other than the trivalent or tetravalent diamine or triamine having a carboxyl group is 4,4′-diaminophenyl ether,
6. One or a mixture of two or more kinds selected from 4'-diaminophenylsulfone, 4,4'-diaminophenylmethane, and 2,2'-trifluoromethylbenzidine. The solvent-soluble heat-resistant polyimide resin described in the above.
の有機基は、有機酸二無水物である請求項１乃至６の何
れか１項記載の溶媒可溶性耐熱性ポリイミド樹脂。7. The solvent-soluble heat-resistant polyimide resin according to claim 1, wherein the tetravalent organic group represented by X in the general formula (1) is an organic acid dianhydride. .
二無水物、１，４，５，８−ナフタレンテトラカルボン
酸二無水物、及び３，３’，４，４’−ビフタル酸二無
水物から選ばれた１種又は２種以上の混合物である請求
項７記載の溶媒可溶性耐熱性ポリイミド樹脂。8. The organic acid dianhydride includes pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphthalic dianhydride. The solvent-soluble heat-resistant polyimide resin according to claim 7, which is one kind or a mixture of two or more kinds selected from anhydrides.
ｍｍｏｌ／ＫＯＨ以下である請求項１乃至８の何れか１
項記載の溶媒可溶性耐熱性ポリイミド樹脂。9. An acid value of not less than 10 mmol / KOH and not more than 200
9. The method according to claim 1, wherein the amount is not more than mmol / KOH.
The solvent-soluble heat-resistant polyimide resin according to the above item.
る請求項１乃至９の何れか１項記載の溶媒可溶性耐熱性
ポリイミド樹脂。10. The solvent-soluble heat-resistant polyimide resin according to claim 1, having a 10% thermal decomposition temperature of 250 ° C. or higher.
る請求項１乃至９の何れか１項記載の溶媒可溶性耐熱性
ポリイミド樹脂。11. The solvent-soluble heat-resistant polyimide resin according to claim 1, which has a 10% thermal decomposition temperature of 350 ° C. or higher.
る請求項１乃至９の何れか１項記載の溶媒可溶性耐熱性
ポリイミド樹脂。12. The solvent-soluble heat-resistant polyimide resin according to claim 1, which has a 10% thermal decomposition temperature of 450 ° C. or more.
１乃至１２の何れか１項記載の溶媒可溶性耐熱性ポリイ
ミド樹脂。13. The solvent-soluble heat-resistant polyimide resin according to claim 1, which has an imidization ratio of 85% or more.
０００である請求項１乃至１３の何れか１項記載の溶媒
可溶性耐熱性ポリイミド樹脂。14. A weight average molecular weight of 8,000 to 1,000.
14. The solvent-soluble heat-resistant polyimide resin according to any one of claims 1 to 13, wherein
請求項１乃至１４の何れか１項記載の溶媒可溶性耐熱性
ポリイミド樹脂。15. The solvent-soluble heat-resistant polyimide resin according to claim 1, which has a glass transition temperature of 300 ° C. or higher.
溶媒可溶性耐熱性ポリイミド樹脂を溶媒に溶解及び／又
は分散させてなるコーティング組成物。16. A coating composition obtained by dissolving and / or dispersing the solvent-soluble heat-resistant polyimide resin according to any one of claims 1 to 15 in a solvent.
溶媒可溶性耐熱性ポリイミド樹脂を成型し、１３０℃〜
５００℃の温度で加熱処理をすることを特徴とする耐熱
性ポリイミド樹脂成形物の製造方法。17. The solvent-soluble heat-resistant polyimide resin according to claim 1, which is molded at 130 ° C.
A method for producing a heat-resistant polyimide resin molded product, wherein a heat treatment is performed at a temperature of 500 ° C.
を基材にコーティングし、乾燥させることを特徴とする
耐熱性ポリイミド樹脂成形物の製造方法。18. A method for producing a heat-resistant polyimide resin molded product, comprising coating a substrate with the coating composition according to claim 16 and drying the substrate.
を基材にコーティングし、乾燥させ、１３０℃〜５００
℃の温度で加熱処理することにより溶媒不溶性にするこ
とを特徴とする耐熱性ポリイミド樹脂成形物の製造方
法。19. A substrate coated with the coating composition according to claim 16, dried, and heated to a temperature of 130 ° C. to 500 ° C.
A method for producing a heat-resistant polyimide resin molded product, wherein the resin is made insoluble by heat treatment at a temperature of ° C.
温度が４００℃〜５００℃において、３分〜１２０分で
ある請求項１７、１８又は１９記載の耐熱性ポリイミド
樹脂成形物の製造方法。20. The method for producing a heat-resistant polyimide resin molded product according to claim 17, 18 or 19, wherein the heat treatment temperature of the polyimide resin molded product is 3 minutes to 120 minutes at 400 ° C. to 500 ° C.
の製造方法により得られた耐熱性ポリイミド樹脂成形
物。21. A heat-resistant polyimide resin molded product obtained by the method according to claim 17, 18, 19, or 20.
解させることが可能な溶媒が、極性溶媒及び非極性溶媒
から選ばれたことを特徴とする請求項１乃至１５の何れ
か１項記載の溶媒可溶性耐熱性ポリイミド樹脂。22. The solvent-soluble solvent according to claim 1, wherein the solvent capable of dissolving the solvent-soluble heat-resistant polyimide resin is selected from a polar solvent and a non-polar solvent. Heat resistant polyimide resin.
解させることが可能な溶媒が、ｍ−クレゾール、ｏ−ク
レゾール、ｐ−クレゾール、フェノール、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、γ−ブチロラクトン、ＤＭＳＯ、スルホラ
ン、水、アセトン、ＴＨＦから選ばれる請求項１乃至１
５の何れか１項記載の溶媒可溶性耐熱性ポリイミド樹
脂。23. A solvent capable of dissolving a solvent-soluble heat-resistant polyimide resin is m-cresol, o-cresol, p-cresol, phenol, N-methyl-
2. A compound selected from 2-pyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, DMSO, sulfolane, water, acetone, and THF.
6. The solvent-soluble heat-resistant polyimide resin according to any one of 5.
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|---|---|---|---|
| JP2000014284A JP4705216B2 (en) | 2000-01-24 | 2000-01-24 | Solvent-soluble heat-resistant polyimide resin and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000014284A JP4705216B2 (en) | 2000-01-24 | 2000-01-24 | Solvent-soluble heat-resistant polyimide resin and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
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| JP4705216B2 JP4705216B2 (en) | 2011-06-22 |
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|---|---|---|---|
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016056480A1 (en) * | 2014-10-10 | 2016-04-14 | 東レ株式会社 | Polyimide solution, heat-resistant non-woven fabric, and method for manufacturing same |
| CN108774143A (en) * | 2018-07-31 | 2018-11-09 | 湖南工业大学 | A kind of Triamine monomer and its preparation method and application centered on naphthalene structure |
| CN115948054A (en) * | 2023-01-09 | 2023-04-11 | 常州大学 | Green water-soluble polyimide high-strength film and preparation method thereof |
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|---|---|---|---|---|
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| JPS62100530A (en) * | 1985-10-25 | 1987-05-11 | Ube Ind Ltd | Soluble aromatic polyimide composition |
| JPH028221A (en) * | 1987-09-25 | 1990-01-11 | Centre Etud De Materiaux Org Pour Technol Avancees | Polyimide composition etchable in basic medium |
| JPH09104839A (en) * | 1995-10-12 | 1997-04-22 | Dainippon Toryo Co Ltd | Polyimide composition for electrodeposition and coating film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49106599A (en) * | 1973-02-08 | 1974-10-09 | ||
| JPS62100530A (en) * | 1985-10-25 | 1987-05-11 | Ube Ind Ltd | Soluble aromatic polyimide composition |
| JPH028221A (en) * | 1987-09-25 | 1990-01-11 | Centre Etud De Materiaux Org Pour Technol Avancees | Polyimide composition etchable in basic medium |
| JPH09104839A (en) * | 1995-10-12 | 1997-04-22 | Dainippon Toryo Co Ltd | Polyimide composition for electrodeposition and coating film |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016056480A1 (en) * | 2014-10-10 | 2016-04-14 | 東レ株式会社 | Polyimide solution, heat-resistant non-woven fabric, and method for manufacturing same |
| CN106795285A (en) * | 2014-10-10 | 2017-05-31 | 东丽株式会社 | Polyimide solution, heat-resistant non-woven fabric and its manufacture method |
| KR20170067749A (en) * | 2014-10-10 | 2017-06-16 | 도레이 카부시키가이샤 | Polyimide solution, heat-resistant non-woven fabric, and method for manufacturing same |
| US10669377B2 (en) | 2014-10-10 | 2020-06-02 | Toray Industries, Inc. | Polyimide solution, heat-resistant non-woven fabric, and method for manufacturing same |
| CN106795285B (en) * | 2014-10-10 | 2020-06-05 | 东丽株式会社 | Polyimide solution, heat-resistant nonwoven fabric, and method for producing same |
| KR102339152B1 (en) | 2014-10-10 | 2021-12-15 | 도레이 카부시키가이샤 | Heat-resistant non-woven fabric and method for manufacturing same |
| CN108774143A (en) * | 2018-07-31 | 2018-11-09 | 湖南工业大学 | A kind of Triamine monomer and its preparation method and application centered on naphthalene structure |
| CN115948054A (en) * | 2023-01-09 | 2023-04-11 | 常州大学 | Green water-soluble polyimide high-strength film and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP4705216B2 (en) | 2011-06-22 |
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