JPS6072925A - Organic solvent-soluble photosensitive polyimide - Google Patents
Organic solvent-soluble photosensitive polyimideInfo
- Publication number
- JPS6072925A JPS6072925A JP18352083A JP18352083A JPS6072925A JP S6072925 A JPS6072925 A JP S6072925A JP 18352083 A JP18352083 A JP 18352083A JP 18352083 A JP18352083 A JP 18352083A JP S6072925 A JPS6072925 A JP S6072925A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- aromatic diamine
- photosensitive polyimide
- diamine compound
- organic solvent
- 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
Abstract
Description
【発明の詳細な説明】
本発明は、有機溶媒に対する溶解性が優れた、高分子鎖
中に感光基及び光増感基を含有する高感度の新規な芳香
族ポリイミド、詳しくは、耐熱性、電気的及び機械的性
質に優れ、半導体工業における固体素子への絶縁膜やバ
ンシベーション膜の形成材料、及び半導体の集積回路や
多層プリント配線板などの眉間絶縁材料等として好適な
、有機溶媒可溶性の感光性ポリイミドに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel highly sensitive aromatic polyimide having excellent solubility in organic solvents and containing a photosensitive group and a photosensitizing group in the polymer chain. An organic solvent soluble product with excellent electrical and mechanical properties, suitable as a forming material for insulating films and vansivation films on solid-state devices in the semiconductor industry, and as a glabellar insulating material for semiconductor integrated circuits and multilayer printed wiring boards. Regarding photosensitive polyimide.
半導体工業における固体素子への絶縁膜やバンシベーシ
ョン膜の形成材料、及び半導体集積回路や多層プリント
配線板などの眉間絶縁材料は、耐熱性及び絶縁性に冨む
ことが要請される。斯る観点から、上記のパンシベーシ
ョン膜等を、絶縁性と共に耐熱性の高いポリイミドで形
成することが種々提案されている（特開昭４９−１１５
５４１号公報、特開昭５４−１１６２１６号公報、特開
昭５４−１１６２１１号公報、特開昭５５−−４５７４
７号公報、特開昭５５−４５７４８号公報及び特開昭５
６−４５９１５号公報等参照）。BACKGROUND ART Materials for forming insulating films and vansivation films on solid-state devices in the semiconductor industry, and insulating materials for semiconductor integrated circuits, multilayer printed wiring boards, etc., are required to have high heat resistance and insulation properties. From this point of view, various proposals have been made to form the above-mentioned pansivation film etc. with polyimide, which has high heat resistance as well as insulation properties (Japanese Patent Laid-Open No. 115-1989).
541, JP 54-116216, JP 54-116211, JP 55-4574
No. 7, JP-A-55-45748 and JP-A-Sho. 5
6-45915, etc.).
しかし、一般にこれらのうちポリイミドを用いたものは
、溶媒不溶性で感光基を有しておらず、上述の提案にお
いては、感光基を含有するポリマーは、何れもポリイミ
ド前駆体であるポリアミック酸のカルボン酸をアミド化
、エステル化など変性した形であり、ポリアミック酸を
光硬化時にポリイミドとしたり、光硬化後ポストベーク
してポリイミドとする必要がある。However, in general, those using polyimide are solvent-insoluble and do not have a photosensitive group, and in the above proposal, the polymer containing a photosensitive group is a carboxylic acid of polyamic acid, which is a polyimide precursor. It is a modified form of acid such as amidation or esterification, and it is necessary to convert polyamic acid into polyimide during photo-curing or post-baking after photo-curing to form polyimide.
また、有機溶媒可溶性のポリイミド（感光基を有しない
）に、光硬化性基を有する単量体を混合して光硬化させ
るようにした耐熱性フォトレジスト組成物（特開昭５４
−１０９８２８号公報等参照）もあるが、このような組
成物は、光硬化性が劣り、しかも光硬化後のポリイミド
の耐熱性も充分ではない。また、耐熱性に優れている芳
香族ポリイミドは、一般に溶媒に対する溶解性が劣るの
で、光硬化後未露光部を有機溶媒に溶解させる工程を含
むレリーフパターンの形成には適さない。In addition, a heat-resistant photoresist composition is prepared by mixing a monomer having a photocurable group with an organic solvent-soluble polyimide (which does not have a photosensitive group) and photocuring it (Japanese Patent Laid-Open No. 54
109828, etc.), but such compositions have poor photocurability, and furthermore, the heat resistance of the polyimide after photocuring is not sufficient. Furthermore, aromatic polyimides, which have excellent heat resistance, generally have poor solubility in solvents, and therefore are not suitable for forming relief patterns that include a step of dissolving unexposed areas in an organic solvent after photocuring.
また、テトラカルボン酸二無水物と光架橋性不飽和二重
結合を含むジアミン化合物、例えばジアミノカルコンと
を反応させて、感光性及び耐熱性等に優れたポリイミド
を得ることが提案されている（特開昭５１−１３１２２
’ｉ１号公報参照）。しかし、このようにして得られる
ポリイミドは、感光性に優れているが、有機溶媒に対す
る溶解性が劣るため、溶解に長時間を要し、レリーフパ
ターンを形成する上で実用上の問題がある。It has also been proposed to react tetracarboxylic dianhydride with a diamine compound containing a photocrosslinkable unsaturated double bond, such as diaminochalcone, to obtain a polyimide with excellent photosensitivity and heat resistance ( Japanese Patent Publication No. 51-13122
(See Publication No. i1). However, although the polyimide obtained in this way has excellent photosensitivity, it has poor solubility in organic solvents, so it takes a long time to dissolve, which poses a practical problem in forming relief patterns.
また、上記のような光硬化性のポリマー又は組成物を光
照射により硬化させる場合、それらの有機溶媒溶液に光
重合開始剤や増感剤を添加混合する必要があり、そのた
め有機溶媒溶液塗布後、有機溶媒を蒸発させた時、光重
合開始剤や増感剤がブリードするなどの弊害が生じる。In addition, when photocurable polymers or compositions as described above are cured by light irradiation, it is necessary to add and mix a photopolymerization initiator and sensitizer to the organic solvent solution, so after applying the organic solvent solution However, when the organic solvent is evaporated, problems such as bleeding of the photopolymerization initiator and sensitizer occur.
本発明者等は、上述の現状に鑑み、ｉＩｉ＋熱性、電気
的及び機械的性質に優れたレリーフパターンを光重合開
始剤や増感剤を要することなく容易に形成し得る、感光
性芳香族ポリイミドを提供することを目的として種々検
討した結果、特定の芳香族テトラカルボン酸またはその
二無水物と、２つの特定の芳香族ジアミン化合物との、
共重縮合物からなる芳香族ポリイミドが、優れた感光性
を有し且つ有機溶媒可溶性であり、上記目的を達成し得
ることを知見した。In view of the above-mentioned current situation, the present inventors developed a photosensitive aromatic polyimide that can easily form a relief pattern with excellent thermal, electrical and mechanical properties without the need for a photopolymerization initiator or sensitizer. As a result of various studies aimed at providing
It has been found that an aromatic polyimide made of a copolycondensate has excellent photosensitivity and is soluble in organic solvents, and can achieve the above object.
即ち、本発明は、上記知見に基づきなされたもので、ビ
フェニルテトラカルボン酸成分と、下記一般式（Ｉ）で
表される芳香族ジアミン化合物７０〜９８モル％及び下
記一般式（ＩＩ）で表される芳香族ジアミン化合物３０
〜２モル％との、共重縮合物からなる、有機溶媒可溶性
の感光性ポリイミドを提供するものである。That is, the present invention was made based on the above findings, and consists of a biphenyltetracarboxylic acid component, 70 to 98 mol% of an aromatic diamine compound represented by the following general formula (I), and a biphenyltetracarboxylic acid component represented by the following general formula (II). Aromatic diamine compound 30
The present invention provides an organic solvent-soluble photosensitive polyimide comprising a copolycondensate of ~2 mol %.
（但し、上式中、八ｎは芳香族残基を示し、ＸはＨ又は
Ｃ馬を示す、）
１１２ Ｎ −Ｒ１−Ｎ Ｒ２（ＩＩ ）（但し、上式
中、Ｒ１はケトン基を有する有機残基を示す、）
本発明のポリイミドは、感光性を有し、耐熱性を有する
芳香族ポリイミドを使用しているので、画像形成後にイ
ミド化工程が不要であり、従来の非感光性ポリイミドの
ように画像形成用の別のフォトレジスト（光硬化性物質
）を必要とせず、また酸成分がビフェニルテトラカルボ
ン酸、その二無水物などであり、ジアミン成分が前記一
般式（Ｉ）及び（ＩＩ）で表される２種の芳香族ジアミ
ン化合物であって、従来の感光基を有するポリイミドに
比して有機溶媒に対する熔解性に優れているためレリー
フパターンの形成に何等の支障も及ぼさない。(However, in the above formula, 8n represents an aromatic residue, and X represents H or C.) 112 N -R1-N R2 (II) (However, in the above formula, R1 has a ketone group. Since the polyimide of the present invention uses an aromatic polyimide that is photosensitive and has heat resistance, an imidization step is not required after image formation, and it is different from conventional non-photosensitive polyimides. does not require a separate photoresist (photocurable substance) for image formation, and the acid component is biphenyltetracarboxylic acid, its dianhydride, etc., and the diamine component is a compound of the general formula (I) and ( These are two types of aromatic diamine compounds represented by II), which have excellent solubility in organic solvents compared to conventional polyimides having photosensitive groups, and therefore do not pose any hindrance to the formation of relief patterns.
また、本発明のポリイミドは、ジアミン成分と。Moreover, the polyimide of the present invention has a diamine component.
して光増感基を有する前記一般式（ＩＩ）で表される芳
香族ジアミン化合物を使用し、高分子鎖中に光増感基が
導入されているため、光硬化時に光重合開始剤や増感剤
を添加する必要がない。従って、本発明のポリイミドに
よれば、レリーフパターンの形成工程において、光重合
開始剤や増感剤のブレンドの時におこる弊害、ｌｐち、
感光性ポリイミドの有機溶媒溶液を基板に塗布後、有機
溶媒を蒸発させた時、光重合開始剤や増感剤がブリード
するなどの欠点がなく、そのため、光増感基が完全に効
力を発揮し、高感度、高解像度となる。また、低分子の
増感剤を使用しないので、ポリマーの熱重量減少も少な
い。Since the aromatic diamine compound represented by the general formula (II) having a photosensitizing group is used, and the photosensitizing group is introduced into the polymer chain, a photopolymerization initiator or a photopolymerization initiator is used during photocuring. There is no need to add a sensitizer. Therefore, according to the polyimide of the present invention, in the step of forming a relief pattern, there are no problems such as
When an organic solvent solution of photosensitive polyimide is applied to a substrate and the organic solvent is evaporated, there is no problem such as bleeding of the photopolymerization initiator or sensitizer, and therefore the photosensitizing group is fully effective. This results in high sensitivity and high resolution. Furthermore, since a low molecular weight sensitizer is not used, there is little loss of thermal weight of the polymer.
更に、本発明のポリイミドは、感光性ポリアミック酸（
ポリイミド前駆体）のように画像形成後イミド化工程を
必要としないために、工程の簡略化のみならず、素子へ
の熱的影響や収縮による歪や応力を与えることがないな
どの多くの優れた効果がある。Furthermore, the polyimide of the present invention is a photosensitive polyamic acid (
Unlike polyimide precursors, it does not require an imidization process after image formation, so it not only simplifies the process, but also has many advantages such as no distortion or stress due to thermal effects or shrinkage on the device. It has a positive effect.
以下に本発明の感光性ポリイミドについてその製造法と
共に詳述する。The photosensitive polyimide of the present invention will be described in detail below along with its manufacturing method.
前記共重縮合物からなる本発明の感光性ポリイミドの典
型的な構造は、略等モルの酸成分とジアミン成分との共
重縮合物からなり、ジアミン成分中、前記一般式（１）
で表される芳香族ジアミン化合物と前記一般式（ＩＩ）
で表される芳香族ジアミン化合物との割合は前者７０〜
９８モル％に対し後者３０〜２モル％である。A typical structure of the photosensitive polyimide of the present invention comprising the above copolycondensate is a copolycondensate of approximately equimolar amounts of an acid component and a diamine component, and in the diamine component, the general formula (1)
An aromatic diamine compound represented by and the general formula (II)
The ratio with the aromatic diamine compound represented by the former is 70~
The latter is 30-2 mol% compared to 98 mol%.
前記一般式（Ｕ）で表される芳香族ジアミン化合物が全
ジアミン成分に対して２モル％より少ない場合には、得
られるポリイミドは増感性、光硬化開始性などの低下が
あられれるので適当ではなく、また、３０モル％より多
い場合には、得られるポリイミドは前記一般式（１）で
表される芳香族ジアミン単位の減少により、光感度の低
下がおこるので適当ではない。If the amount of the aromatic diamine compound represented by the general formula (U) is less than 2 mol % based on the total diamine components, it is not suitable because the obtained polyimide may have a decrease in sensitization, photocuring initiation, etc. Moreover, if the amount is more than 30 mol %, the resulting polyimide will have a decrease in photosensitivity due to a decrease in aromatic diamine units represented by the above general formula (1), which is not suitable.
そして、本発明の感光性ポリイミドは、次の如き方法で
製造される。The photosensitive polyimide of the present invention is produced by the following method.
即ち、本発明の感光性ポリイミドは、特定の芳香族テト
ラカルボン酸類であるビフェニルテトラカルボン酸、そ
の二無水物などと、前記一般式（■）及び（■）で表さ
れる２つの芳香族ジアミン化合物とを共重縮合してポリ
アミック酸となし、更に該ポリアミック酸を脱水閉環（
イミド化）することにより前記共重縮合物を合成して得
られる。That is, the photosensitive polyimide of the present invention comprises a specific aromatic tetracarboxylic acid such as biphenyltetracarboxylic acid, its dianhydride, and two aromatic diamines represented by the general formulas (■) and (■). A compound is copolycondensed to form a polyamic acid, and the polyamic acid is further dehydrated and ring-closed (
imidization) to synthesize the copolycondensate.
本発明の感光性ポリイミドの製造に用いられる上記ビフ
ェニルテトラカルボン酸成分としては、具体的には３．
３’ 、４．４’ −ビフェニルテトラカルボン酸、ま
たはその二無水物、２，２”。Specifically, the biphenyltetracarboxylic acid component used in the production of the photosensitive polyimide of the present invention is 3.
3',4,4'-biphenyltetracarboxylic acid or its dianhydride, 2,2''.
３．３゛−ビフェニルテトラカルボン酸、またはその二
無水物及び２．３．３°、４゛ −ビフェ二また、前記
一般式（１）で表される芳香族シア従って、前記一般式
（１）で表される芳香族ジアミン化合物としては、具体
的には次のものをあげることができるが、それらに限定
されない。3.3゛-biphenyltetracarboxylic acid, or its dianhydride and 2.3.3゛-biphenyltetracarboxylic acid, and 2.3. ) Specific examples of the aromatic diamine compound represented by formula include, but are not limited to, the following.
３．５−ジアミノベンジルアクリレート、３゜５−ジア
ミノベンジルメタクリレート、２．４−ジアミノベンジ
ルアクリレート、２．４−ジアミノベンジルメタクリレ
ートなど。3.5-diaminobenzyl acrylate, 3.5-diaminobenzyl methacrylate, 2.4-diaminobenzyl acrylate, 2.4-diaminobenzyl methacrylate, etc.
また、前記一般式（ＩＩ）で表される芳香族ジアミン化
合物において、Ｒ１で示されるケトン基を有する有機残
基としては、
２
式中、Ａ ｒｔは芳香族環を示し、Ｒ２はメチル基又番
よエチル基を示す）などをあげることができる。In addition, in the aromatic diamine compound represented by the general formula (II), the organic residue having a ketone group represented by R1 is as follows: 2 In the formula, A rt represents an aromatic ring, and R2 represents a methyl group or (representing an ethyl group), etc.
従ゲζ、前記一般式（■）で表される芳香族ジアミン化
合物としては、具体的には次のものをあげることができ
るが、それらに限定されなし）。Examples of the aromatic diamine compound represented by the general formula (■) described above include, but are not limited to, the following.
９．９−ビス（４−アミノフエニＪい一１〇−アンスロ
ン、１．５−ジアミノアントラキノン、１．４−ジアミ
ノアントラキノン、３．３“−ジアミノベンゾフェノン
、４−Ｎ、Ｎ−ジメチルアミノ−３゛、５°−ジアミノ
ベンゾフェノン、１−ジメチルアミノ−４−（３，５−
ジアミノベンゾイル）−ナフタレンなど。9.9-bis(4-aminophenyl-110-anthrone, 1.5-diaminoanthraquinone, 1.4-diaminoanthraquinone, 3.3"-diaminobenzophenone, 4-N,N-dimethylamino-3" , 5°-diaminobenzophenone, 1-dimethylamino-4-(3,5-
diaminobenzoyl)-naphthalene, etc.
本発明の感光性ポリイミドは、ポリイミド０゜５ｇ／Ｎ
−メチル−２−ピロリドン１００＊１の濃度の溶液とし
て３０℃において測定した対数粘度が０．１〜１．５特
に０．２〜１．０の範囲内にあるものが好ましい。The photosensitive polyimide of the present invention is polyimide 0.5 g/N.
-Methyl-2-pyrrolidone It is preferable that the logarithmic viscosity measured at 30° C. as a solution with a concentration of 100*1 is in the range of 0.1 to 1.5, particularly 0.2 to 1.0.
本発明の感光性ポリイミドの製造について更に詳述する
と、前記共重縮合物を合成する際の前記ビフェニルテト
ラカルボン酸成分と前記２種からなる芳香族ジアミン化
合物成分との使用割合は略等モルであり、又、前記一般
式（１）で表される芳香族ジアミン化合物と前記一般式
（ＩＩ）で表される芳香族ジアミン化合物との使用割合
は、前者が７０〜９８モル％で後者が３０〜２モル％で
ある。そして、それらの合成反応は、−比較的低温下に
、先ず重合反応を行わせ、次いでイミド化反応を行わせ
る二段階反応によるのが好ましい。To explain in more detail the production of the photosensitive polyimide of the present invention, when synthesizing the copolycondensate, the ratio of the biphenyltetracarboxylic acid component and the two types of aromatic diamine compound components used is approximately equimolar. Moreover, the usage ratio of the aromatic diamine compound represented by the general formula (1) and the aromatic diamine compound represented by the general formula (II) is 70 to 98 mol% for the former and 30 to 98 mol% for the latter. ~2 mol%. Preferably, these synthetic reactions are carried out by a two-step reaction in which a polymerization reaction is first carried out and then an imidization reaction is carried out at a relatively low temperature.
即ち、先ず、有機溶媒中で１００℃以下、好ましくは８
０℃以下の反応温度で１〜４８時間重合反応を行い、次
いで、この重合反応によって得られるボリアミンク酸溶
液を有機溶媒で希釈した後、１００℃以下、好ましくは
８０℃以下の反応温度で無水酢酸、ピリジン、第３級ア
ミンなどのイミド化剤を加えて０．５〜５時間イミド化
反応を行うのが好ましく、その結果前記共重縮合物が合
成され本発明のポリイミドが得られる。That is, first, the temperature is lower than 100°C, preferably 8°C in an organic solvent.
A polymerization reaction is carried out for 1 to 48 hours at a reaction temperature of 0°C or lower, and then the polyamine chloride solution obtained by this polymerization reaction is diluted with an organic solvent, and then acetic anhydride is added at a reaction temperature of 100°C or lower, preferably 80°C or lower. It is preferable to add an imidizing agent such as pyridine, tertiary amine, etc. and carry out the imidization reaction for 0.5 to 5 hours, and as a result, the above-mentioned copolycondensate is synthesized to obtain the polyimide of the present invention.
上記重合反応及び上記イミド化反応における有機溶媒と
しては、例えばＮ、Ｎ−ジメチルスルホキシド、Ｎ、Ｎ
−ジメチルホルムアミド、Ｎ、 Ｎ−ジエチルホルムア
ミド、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ、Ｎ−ジエチ
ルアセトアミド、Ｎ−メチル−２−ピロリドン、ヘキサ
メチレンホスホアミドなどが用いられる。Examples of the organic solvent in the polymerization reaction and the imidization reaction include N,N-dimethyl sulfoxide, N,N-
-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide, etc. are used.
尚、本発明においては、前記共重縮合物は、前記ビフェ
ニルテトラカルボン酸成分と前記芳香族ジアミン化合物
成分とを有機溶媒中で１００℃以上の高温において一段
階で重合・イミド化反応を行うことによっても合成する
ことができるが、前述の如く、二段階で行うことにより
、安定した生成物を得ることができる。In addition, in the present invention, the copolycondensate is obtained by performing a polymerization/imidization reaction of the biphenyltetracarboxylic acid component and the aromatic diamine compound component in an organic solvent at a high temperature of 100° C. or higher in one step. Although it can also be synthesized in two steps, as described above, a stable product can be obtained by carrying out the synthesis in two steps.
本発明のポリイミドの合成に用いられる前記一般式（１
）で表される芳香族ジアミン化合物は、その合成法には
制限されないが、その好ましい合成法としては、例えば
ジニトロベンジルアルコールと（メタ）アクリル酸クロ
リドとを反応させ、次いで反応物を還元することによっ
て目的とする芳香族ジアミン化合物を合成する方法をあ
げることができる。The general formula (1) used in the synthesis of the polyimide of the present invention
) The method for synthesizing the aromatic diamine compound represented by () is not limited, but a preferred method for synthesizing it is, for example, reacting dinitrobenzyl alcohol and (meth)acrylic acid chloride, and then reducing the reactant. A method for synthesizing the desired aromatic diamine compound can be mentioned.
また、本発明のポリイミドの合成に用いられる前記一般
式（ＩＩ）で表される芳香族ジアミン化合物のうちＲ１
で示される有機残基が
即
であり、その合成法には制限されないが、その好ましい
合成法としては、先ずジニトロ塩化ベンゾイルとアニリ
ンとを反応させてジニトロベンズアニリドを合成し、次
ぎにこれと
２
場合と同じ〕とオキシ塩化リンとを反応させ、得られる
反応物に濃塩酸を加えることによって次いでこれを還元
することによって目的とする芳香族ジアミン化合物を合
成する方法をあげることができる。Furthermore, among the aromatic diamine compounds represented by the general formula (II) used in the synthesis of the polyimide of the present invention, R1
The organic residue represented by is the preferred organic residue, and the method of synthesis thereof is not limited, but a preferred method is to first react dinitrobenzoyl chloride with aniline to synthesize dinitrobenzanilide, and then react this with 2 [same as in the case above] and phosphorus oxychloride, and the resulting reaction product is reduced by adding concentrated hydrochloric acid to synthesize the desired aromatic diamine compound.
而して、本発明の感光性ポリイミドは、レリーフパター
ンの形成材料として使用する場合、有機溶媒に溶解され
た溶液として用いられる。この有機溶媒としては、Ｎ、
Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメチルアセトア
ミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキ
シド、ヘキサメチレンホスホアミドなどをあげることが
でき、感光性ポリイミド′ｆｊ液の好ましい濃度は５〜
３０％である。When the photosensitive polyimide of the present invention is used as a material for forming a relief pattern, it is used as a solution dissolved in an organic solvent. This organic solvent includes N,
N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylene phosphoamide, etc. can be mentioned, and the preferable concentration of the photosensitive polyimide'fj liquid is 5 to 5.
It is 30%.
本発明の感光性ポリイミドは高分子鎮中に光増感基を有
し、増感効果があるので、上記の感光性ポリイミド溶液
には増感剤や光重合開始剤を添加する必要がないが、そ
れらも必要に応じ添加することができ、また、Ｎ、Ｎ−
ジメチルアミノ安息香酸エチルやＮ、Ｎ−ジメチルアミ
ノアントラニル酸メチルなどの増感助剤を添加すること
により更に増感効果を高めることができる。The photosensitive polyimide of the present invention has a photosensitizing group in the polymer base and has a sensitizing effect, so there is no need to add a sensitizer or a photopolymerization initiator to the above photosensitive polyimide solution. , they can also be added as necessary, and N, N-
The sensitizing effect can be further enhanced by adding a sensitizing aid such as ethyl dimethylaminobenzoate or methyl N,N-dimethylaminoanthranilate.
また、上記の感光性ポリイミド溶液に、必要に応じ、エ
チレン性不飽和基を有する光により重合可能な化合物を
添加させることができる。Furthermore, a light-polymerizable compound having an ethylenically unsaturated group can be added to the photosensitive polyimide solution, if necessary.
上記エチレン性不飽和基を有する光により重合可能な化
合物としては、エチレングリコールジ（メタ）アクリレ
ート、プロピレングリコールジ（メタ）アクリレート、
トルメチロールプロパントリ （メタ）アクリレート、
テトラメチロールメタンテトラ（メタ）アクリレート、
Ｎ、Ｎ’ −メチレンビス（メタ）アクリレート、ジエ
チルアミノエチル（メタ）アクリレート、１，３．５−
トリアクリロイルへキサヒドロ−３−）リアジン、トリ
ス（ヒドロキシエチルアクリロイル）イソシアヌレート
などをあげることができる。Examples of the photopolymerizable compound having an ethylenically unsaturated group include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,
tolmethylolpropane tri(meth)acrylate,
tetramethylolmethanetetra(meth)acrylate,
N,N'-methylenebis(meth)acrylate, diethylaminoethyl(meth)acrylate, 1,3.5-
Examples include triacryloylhexahydro-3-)riazine and tris(hydroxyethyl acryloyl)isocyanurate.
本発明の感光性ポリイミドによれば、上記の如く感光性
ポリイミド溶液を調整することＧこより次のようにして
レリーフパターンを形成することカベできる。According to the photosensitive polyimide of the present invention, by preparing the photosensitive polyimide solution as described above, a relief pattern can be formed in the following manner.
即ち、先ず、上記の感光性ポリイミド溶液を基板に塗布
し、これを乾燥して有機溶媒を除去する。That is, first, the above-mentioned photosensitive polyimide solution is applied to a substrate and dried to remove the organic solvent.
基板への塗布は、例えば回転塗布機で行うこと力くでき
る。塗布膜の乾燥は１５０°Ｃ以下、好ましくは１００
℃以下で行う。この際減圧はしてもしなくてもよい。乾
燥後、塗布膜にネガ型のフ第１・マスクチャートを置き
、紫外線、可視光線、電子線、Ｘ線などの活性光線を照
射する。次いで未露光の部分を現像液で洗い流すことに
よりポリイミドのレリーフパターンを得る。上記の現像
液としては、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−
ジメチルアセトアミド、ジメチＪレスル＞トキシＦＸＮ
−メチルー２−ピロリドン、ヘキサメチレン」マスホア
ミドなどの溶剤又は該溶剤とメタノール、エタノールと
の混合系を用いることができる。Coating onto the substrate can be easily carried out using, for example, a rotary coater. The coating film is dried at 150°C or less, preferably at 100°C.
Perform below ℃. At this time, the pressure may or may not be reduced. After drying, a negative first mask chart is placed on the coated film, and active light such as ultraviolet rays, visible light, electron beams, and X-rays is irradiated. The unexposed areas are then washed away with a developer to obtain a polyimide relief pattern. The above developer includes N,N-dimethylformamide, N,N-
Dimethylacetamide, Dimethi J Resul > ToxiFXN
-Methyl-2-pyrrolidone, hexamethylene, masphoamide, or a mixed system of the solvent and methanol or ethanol can be used.
上述の如く、本発明の感光性ポリイミドは、高分子鎖中
に感光基（光重合可能な基）を有し、且つ酸成分がビフ
ェニルテトラカルボン酸、その二無水物などで、ジアミ
ン成分が前記一般式（１）で表される芳香族ジアミン化
合物と前記一般式（■）で表される芳香族ジアミン化合
物である共重縮合物であり、有機溶媒に対する溶解性が
優れており、そのため、光化学的手段によってレリーフ
パターンを容易に形成することができ、且つレリーフパ
ターンを形成する場合、本発明のポリイミドは、優れた
感光性を有し、ポリイミドの耐熱性を保持するために、
従来の非感光性ポリイミドのように、画像形成用の別の
光硬化性物質を特に必要とせず、また、高分子鎖中に光
増感基が導入されているため、光重合開始剤や増感剤を
添加する必要がないので、感光性ポリイミドの有機溶媒
溶液を基板に塗布後、有機溶媒を蒸発さゼた時、光重合
開始剤や増感剤がブリードするなどの欠点がなく、その
ため、光増感基が完全に効力を発揮し、高感度、高解像
度となり、また、低分子の増感剤を使用しないのでポリ
マーの熱重量減少も少なくなり、更に、感光性ポリアミ
ック酸（ポリイミド前駆体）のように画像形成後イミド
化工程を必要としないため、工程の簡略化のみならず、
素子への熱的影響や収縮による歪や応力を与えることが
ないなどの多くの優れた効果がある。しかも、本発明の
感光性ポリイミドにより形成したレリーフパターンは、
耐熱性、電気的及び機械的性質に優れたものであり、半
導体工業における固体素子の絶縁体膜やバソシヘーショ
ン膜として有効であるばかりでなく、ハ・イブリ・ノド
回路やプリント回路の多層配線構造の絶縁膜やソルダー
レジストとして用いることができる。As mentioned above, the photosensitive polyimide of the present invention has a photosensitive group (photopolymerizable group) in the polymer chain, and the acid component is biphenyltetracarboxylic acid, its dianhydride, etc., and the diamine component is the above-mentioned dianhydride. It is a copolycondensate of an aromatic diamine compound represented by the general formula (1) and an aromatic diamine compound represented by the general formula (■), and has excellent solubility in organic solvents, so it is suitable for photochemistry. A relief pattern can be easily formed by manual means, and when forming a relief pattern, the polyimide of the present invention has excellent photosensitivity, and in order to maintain the heat resistance of polyimide,
Unlike conventional non-photosensitive polyimide, there is no need for a separate photocurable substance for image formation, and since a photosensitizing group is introduced into the polymer chain, there is no need for photopolymerization initiators or enhancers. Since there is no need to add a sensitizer, there is no problem such as bleeding of the photopolymerization initiator or sensitizer when the organic solvent is evaporated after applying the photosensitive polyimide organic solvent solution to the substrate. , the photosensitizing group is fully effective, resulting in high sensitivity and high resolution. Also, since no low-molecular sensitizer is used, there is less thermal weight loss of the polymer. Since it does not require an imidization process after image formation as in the case of
It has many excellent effects such as no thermal influence on the element, no strain or stress due to shrinkage, etc. Moreover, the relief pattern formed from the photosensitive polyimide of the present invention is
It has excellent heat resistance, electrical and mechanical properties, and is not only effective as an insulating film and a sorption film for solid-state devices in the semiconductor industry, but also for multilayer wiring structures in hybrid circuits and printed circuits. It can be used as an insulating film or a solder resist.
以下に、本発明の感光性ボリイミ１コの合成しと用いら
れる芳香族ジアミン化合物の合成例、本発明の感光性ポ
リイミドの製造を示す実施例及び本発明の感光性ポリイ
ミドの効果を示す種々の物性試験及びその結果を、比較
例と共に挙げる。Below, examples of synthesis of the aromatic diamine compound used in the synthesis of the photosensitive polyimide of the present invention, examples showing the production of the photosensitive polyimide of the present invention, and various examples showing the effects of the photosensitive polyimide of the present invention are shown. Physical property tests and their results are listed together with comparative examples.
合成例１
３５−ジアミノベンジルアクル− のへ酸第一工程
３．５−ジニトロベンジルアルコール４０ｇをＴＨＦ
４００ｍｌに溶解した溶液に、トリエチルアミン４０．
４ ｇを加え、更にこの溶液に攪拌しながら３〜４℃で
アクリル酸クロリド２０ｇのＴＨＦ２００ｍｌ溶液を４
０分間で滴下して加えた。滴下終了後、更に１時間攪拌
した。その後、この溶液をブフナーロートを用いて濾過
し、濾液をエバポレークで減圧下ＴＨＦを除き、濃縮液
を２，５１の水中に注ぎ込み生成物を析出させ、これを
濾集し、乾燥し、粗ジニトロ化物４６ｇを得た。Synthesis Example 1 35-Diaminobenzyl alcohol First step 3.5-Dinitrobenzyl alcohol 40g was dissolved in THF.
Add 40% triethylamine to the solution dissolved in 400ml.
Add 4 g of acrylic acid chloride to this solution, and add 4 g of a solution of 20 g of acrylic acid chloride in 200 ml of THF at 3 to 4°C while stirring.
It was added dropwise over a period of 0 minutes. After the dropwise addition was completed, the mixture was stirred for an additional hour. Thereafter, this solution was filtered using a Buchner funnel, the THF was removed from the filtrate under reduced pressure using an evaporator, and the concentrated solution was poured into 2.51 m water to precipitate the product. 46 g of compound was obtained.
得られた粗ジニトロ化物をカラムクロマトグラフィー（
カラム６５＋ｗａ＋φ、ワコーゲルＣ−２００３００ｇ
、展開溶媒ベンゼン／酢酸エチル＝１ｖ。The obtained crude dinitrated product was subjected to column chromatography (
Column 65+wa+φ, Wakogel C-200300g
, developing solvent benzene/ethyl acetate = 1v.
／１ｖｏｌ）により精製し、薄黄白色結晶の３．５−ジ
ニトロベンジルアクリレート４２．８ｇ（収率８４％）
を得た。42.8 g (yield: 84%) of 3,5-dinitrobenzyl acrylate as pale yellow-white crystals.
I got it.
第二工程
３５−ジニ ロベンジル 審し− の゛−第一工程で得
られた３、５−ジニトロベンジルアクリレート２０ｇを
酢酸１４０ｇに溶解した溶液を、鉄粉１４０ｇを酢酸７
０ｇ／水７０ｇに懸濁させた溶液に攪拌しながら２０〜
２５℃で少量ずつ加え反応させた。2nd Step 35-Dinirobenzyl Test- 20g of 3,5-dinitrobenzyl acrylate obtained in the first step was dissolved in 140g of acetic acid, and 140g of iron powder was dissolved in 7g of acetic acid.
0 g / 20 ~ while stirring in a solution suspended in 70 g of water.
The mixture was added little by little and reacted at 25°C.
反応後、濾過し、過剰の鉄粉を除去した後、濾液をアン
モニア水で中和し、酢酸エチル２．３２で抽出した。抽
出液を無水硫酸ナトリウムで一夜乾燥した後、酢酸エチ
ル層を２０〜４０ｍ１に濃縮した。得られた濃縮液をカ
ラムクロマトグラフィー（カラム５０ｍ５＋φ、シリカ
ゲル ヮコーゲルＣ−２００１５０ｇ、展開溶媒ベンゼ
ン／酢酸エチ＝３ｖｏｌ／２νｏｌ ）により精製し、
白色結晶の目的物１０．５ｇ （収率６８．９％）を得
た。After the reaction, the mixture was filtered to remove excess iron powder, and the filtrate was neutralized with aqueous ammonia and extracted with 2.3 g of ethyl acetate. After drying the extract over anhydrous sodium sulfate overnight, the ethyl acetate layer was concentrated to 20-40 ml. The obtained concentrate was purified by column chromatography (column 50 m5 + φ, 150 g of silica gel Wokogel C-200, developing solvent benzene/ethyl acetate = 3 vol/2 νol),
10.5 g (yield: 68.9%) of the target product was obtained as white crystals.
元素分析値 （Ｃ１６１１１ｚＮａ Ｏｘとして）ＣＩ
Ｉ Ｎ
実測値（％） ６２．２４ ６．４６ １４．５８計算
値（％） ６５．４９ ６．２９ １４．５Ｔ又、上記
目的物について、赤外吸収スペクトル及びＨ−Ｎ Ｍ
Ｒスペクトルを測定し、目的物であることを確認した。Elemental analysis value (as C16111zNa Ox) CI
I N Actual value (%) 62.24 6.46 14.58 Calculated value (%) 65.49 6.29 14.5T Also, regarding the above target object, infrared absorption spectrum and H-N M
The R spectrum was measured and it was confirmed that it was the desired product.
合成例２
第一工程
３５−ジニ ロベンズアニ曹 ′のＡ
アユ９フフ１ｇに３．５−ジニトロ塩化ベンゾイル２２
．３ ｇを攪拌しながら粉末のまま加えた。Synthesis Example 2 First step 35-dinitrobenzoyl chloride 22 to 1 g of Ayu 9 fufu
．． 3 g was added as a powder while stirring.
５０℃まで発熱があり、黄橙色のペースト状となった。It generated heat up to 50°C and turned into a yellow-orange paste.
更に１０分間攪拌後、反応液を１１の水中に注ぎ込み、
製塩＠（３５％）で酸性にすると白色沈澱を生じた。こ
れを濾過乾燥し、３．５−ジニトロベンズアニリド２３
．５８ｇ（８４，６％）を得た。After further stirring for 10 minutes, the reaction solution was poured into water in Step 11,
When acidified with salt (35%), a white precipitate was formed. This was filtered and dried, and 3,5-dinitrobenzanilide 23
．． 58 g (84.6%) were obtained.
第二工程 ３．５−ジニトロベンズアニリド２３ｇにＮ。Second process 3.23 g of 5-dinitrobenzanilide with N.
Ｎ−ジメチルアニリン６６．３ ｇとオキシ塩化リン３
３、８ ｇを加え１２０〜１３０℃で４時間反応させた
。黒縁色の高粘稠液体の反応物が得られた。66.3 g of N-dimethylaniline and 3 g of phosphorus oxychloride
3.8 g was added and reacted at 120 to 130°C for 4 hours. A highly viscous liquid reaction product with a black border was obtained.
この反応物を濃塩酸２００ｍ１の１．５１水溶液に攪拌
しながら加えると発熱があり、初めタール状であったが
、攪拌するとしだいに緑色粉末となった。When this reaction product was added to a 1.51 aqueous solution of 200 ml of concentrated hydrochloric acid with stirring, it generated heat and was tar-like at first, but gradually turned into a green powder as it was stirred.
これを４０〜５０℃で１時間攪拌し、−夜装置した後濾
過した。濾集物を５％の塩酸水溶液２００１中に入れ５
０〜６０℃で１時間で洗い濾過し、濾集物を更に濃塩酸
１５０ｍ１に加え４０〜５０℃で熔解し、不溶分を濾別
し、濾液を冷却後水酸化ナトリウム８０ｇの１：Ｓｔ水
溶液を氷冷した溶液中に注ぎ込むと、黄緑色の沈澱物１
１．４ｇ（４５゜８％）を得た。This was stirred at 40-50°C for 1 hour, heated overnight, and then filtered. Place the filtered material in 5% hydrochloric acid aqueous solution 2001.5
Wash and filter at 0 to 60°C for 1 hour, add the filtered material to 150 ml of concentrated hydrochloric acid and melt at 40 to 50°C, remove insoluble matter by filtration, cool the filtrate, and add 1:St aqueous solution of 80 g of sodium hydroxide. When poured into an ice-cold solution, a yellow-green precipitate 1
1.4 g (45°8%) was obtained.
この沈澱物の精製はカラムクロマトグラフィーにより行
った。即ち、５０−φＸ ５００ｍｌのクロマド管にワ
コーゲル（Ｃ−２００） ２００ ｇを充填し、ベンゼ
ンを展開溶媒として分離し、黄橙色の針状結晶の４−Ｎ
、Ｎ−ジメチルアミノ−３゛、５′−ジニトロベンゾフ
ェノン９．５ｇを得た。Purification of this precipitate was performed by column chromatography. That is, 200 g of Wakogel (C-200) was filled in a 50-φX 500 ml chromad tube, separated using benzene as a developing solvent, and yellow-orange needle-like crystals of 4-N
, N-dimethylamino-3',5'-dinitrobenzophenone (9.5 g) was obtained.
第三工程
第二工程で得られた４−Ｎ、Ｎ−ジメチルアミノ−３′
、５°−ジニトロベンゾフェノン９．５ｇを塩化第１ス
ズ４３．９ｇ、濃塩酸１２０＋＋１及び酢酸３６＋＋１
からなる溶液中に攪拌しながら室温で粉末のまま３０〜
４０分間で加え反応させた。Third step 4-N,N-dimethylamino-3' obtained in the second step
, 9.5 g of 5°-dinitrobenzophenone was mixed with 43.9 g of stannous chloride, concentrated hydrochloric acid 120++1 and acetic acid 36++1
As a powder at room temperature with stirring into a solution consisting of
It was added and reacted for 40 minutes.
更に、９０℃で３時間反応を続りた後、室温に戻し、反
応液を２３％のアンモニア水２００ｍ１の１．５１水溶
液を水冷した溶液中に注ぎ込むと白色懸濁液となった。After continuing the reaction at 90° C. for 3 hours, the temperature was returned to room temperature, and the reaction solution was poured into a water-cooled solution of 200 ml of 23% ammonia water to form a white suspension.
この白色懸濁液を酢酸エチルで抽出し、酢酸エチル層を
無水硫酸ナトリウムで乾燥し、酢酸エチルをエバポレー
タで除去し、微黄色の鱗片状結晶の目的物７．３ｇ（還
元収率９４．４％）を得た。This white suspension was extracted with ethyl acetate, the ethyl acetate layer was dried over anhydrous sodium sulfate, and the ethyl acetate was removed using an evaporator. %) was obtained.
融点 １６４〜１６５℃
元素分析値 （Ｃ，５ＨｎＮ、０として）ＨＮ
実測値（％）７０．９０ ６．７２ １６．５８組算値
（％） ７０．５６ ６．７１ １６．４６又、上記目
的物について、赤外吸収スペクトル及びＨ−ＮＭＲスペ
クトルを測定し、目的物であることを確認した。Melting point 164-165°C Elemental analysis value (C,5HnN, as 0) HN Actual value (%) 70.90 6.72 16.58 Combined value (%) 70.56 6.71 16.46 Also, for the above purpose The infrared absorption spectrum and H-NMR spectrum of the substance were measured, and it was confirmed that it was the desired substance.
実施例Ｉ
Ｎ−メチル−２−ピロリドン（ＮＭＰ）９．３ｍｌに２
．３，３°、４°−ビフェニルテトラカルボン酸二無水
物１．４０６ｇと３，５−ジアミノベンツルアクリレ−
１−０，７３４ｇと４−Ｎ、Ｎ−ジメチルアミノ−３’
、５’−ジアミノベンゾフェノン０．２４４ｇを加え
、３０℃で２４時間攪拌して反応させボリアミンク酸を
得た。Example I 9.3 ml of N-methyl-2-pyrrolidone (NMP)
．． 1.406 g of 3,3°,4°-biphenyltetracarboxylic dianhydride and 3,5-diaminobenzyl acrylate
1-0,734g and 4-N,N-dimethylamino-3'
, 0.244 g of 5'-diaminobenzophenone was added, and the mixture was stirred and reacted at 30° C. for 24 hours to obtain polyamine chloride.
次に、このボリアミンク酸にＮＭＰ３４．９ｍｌを加え
希釈したのち、無水酢酸９．７５ ｇ、ピリジン３．７
３ｇ、ベンゼン６．８１及びＮＭＰ５．８ｓ＋１を加え
、５０℃で２時間反応させポリイミド化物を得た。Next, 34.9 ml of NMP was added to this polyamic acid to dilute it, and then 9.75 g of acetic anhydride and 3.7 g of pyridine were added.
3 g of benzene, 6.81 g of benzene, and 5.8 s+1 of NMP were added, and the mixture was reacted at 50° C. for 2 hours to obtain a polyimide.
このポリイミド化物溶液中にメタノールを滴下して加え
、ポリイミドを析出させ濾別して、黄色のポリイミド粉
末（本発明のポリイミド）を得た。Methanol was added dropwise to this polyimide solution to precipitate polyimide, which was filtered off to obtain yellow polyimide powder (polyimide of the present invention).
実施例２
ＮＭＰ９．８ｍｌに２．３．３’ 、４’−ビフェニル
テトラカルボン酸二無水物１．４１４ｇと３，５−ジア
ミノベンジルアクリレート０．７３８ｇと９．９−ビス
（４−アミノフェニル）−１Ｏ−アンスロン０．３６２
ｇを加え、３０℃で２４時間攪拌して反応させポリア
ミック酸を得た。Example 2 1.414 g of 2.3.3',4'-biphenyltetracarboxylic dianhydride, 0.738 g of 3,5-diaminobenzyl acrylate, and 9.9-bis(4-aminophenyl) in 9.8 ml of NMP. -1O-Anthrone 0.362
g was added thereto, and the mixture was stirred and reacted at 30° C. for 24 hours to obtain a polyamic acid.
次に、このポリアミック酸にＮＭＰ３６．８ｍｌを加え
希釈したのち、無水酢酸９．８０ｇ、ピリジン３．７４
ｇ、ベンゼン７、Ｌｌ及びＮＭＰ６．１＋＊１を加え、
５０℃で２時間反応させポリイミド化物を得た。Next, 36.8 ml of NMP was added to this polyamic acid to dilute it, and then 9.80 g of acetic anhydride and 3.74 g of pyridine were added.
g, add benzene 7, Ll and NMP6.1+*1,
The reaction was carried out at 50°C for 2 hours to obtain a polyimide.
このポリイミド化物溶液中にメタノールを滴下して加え
、ポリイミドを析出させ濾別して、黄色のポリイミド粉
末（本発明のポリイミド）を得た。Methanol was added dropwise to this polyimide solution to precipitate polyimide, which was filtered off to obtain yellow polyimide powder (polyimide of the present invention).
物性試験
、上記実施例１及び２で得たポリイミドについて下記（
１）〜（６）の物性試験を行い下表に示す結果を得た。Physical property test The following (
The physical property tests 1) to (6) were conducted and the results shown in the table below were obtained.
（１）ポリイミドの粘度
ポリイミド０．５ｇ／ＮＭＰ１００ｍ１の濃度のポリイ
ミド溶液を３０℃で対数粘度を測定した。(1) Viscosity of polyimide The logarithmic viscosity of a polyimide solution having a concentration of 0.5 g of polyimide/100 ml of NMP was measured at 30°C.
（２）ポリイミドの成膜性
厚さ約ｌθμのポリイミドフィルムをガラス板上に作成
し、これを水に浸して剥離し、１８０゛に折り曲げ、ク
ラックのない場合をＯ、クラックありを△、Ｍ膜時にク
ランクの生じるものを×とした。(2) Film forming properties of polyimide A polyimide film with a thickness of about lθμ was created on a glass plate, immersed in water, peeled off, and bent to 180°. O for no cracks, △, M for cracks. Those in which cranking occurred during film formation were marked as ×.
（３）ポリイミドの−ＮＭＰに対する溶解性常温におい
てＮＭＰに対するポリイミドの溶解度（ｗｔ％）を測定
した。(3) Solubility of polyimide in -NMP The solubility (wt%) of polyimide in NMP was measured at room temperature.
（４）ポリイミドフィルムの溶解性
ポリイミドのＮＭＰ １０％溶液から作成した厚さ約ｌ
Ｏμのポリイミドフィルムを室温でＮＭＰ中に浸漬し攪
拌し、該フィルムが熔解するまでの時間で溶解性を測定
した。(4) Solubility of polyimide film Made from a 10% NMP solution of polyimide, approximately 1 thick
A polyimide film of Oμ was immersed in NMP at room temperature and stirred, and the solubility was measured by measuring the time until the film melted.
（５）熱分解開始温度
理学電気側型差動熱天秤ＴＧ−ＤＳＣにより、重量減の
開始温度を測定した。(5) Thermal Decomposition Start Temperature The start temperature of weight loss was measured using an electric side type differential thermobalance TG-DSC.
（６）光硬化特性 ポリイミドのＮＭＰＩＯ％溶液に２ ｐｈｒのＮ。(6) Photocuring properties 2 phr N in NMPIO% solution of polyimide.
Ｎ−ジメチルアミノアントラニル酸メチルを添加して調
製した感光性ポリイミド溶液をガラス板上に回転塗布機
（２０００〜５０００ｒｐｍ ）を用いて塗布し、圧力
１〜２ ｍｍ１１ｇの減圧下、５０℃で５時間乾燥して
数μの厚さく下表参照）の薄膜を作成し、この薄膜につ
い′ζ下記の光感度及び解像力の試験に供した。A photosensitive polyimide solution prepared by adding methyl N-dimethylaminoanthranilate was applied onto a glass plate using a spin coater (2000-5000 rpm), and the mixture was heated at 50°C for 5 hours under a reduced pressure of 1-2 mm and 11 g. After drying, a thin film having a thickness of several μm (see the table below) was prepared, and this thin film was subjected to the photosensitivity and resolution tests described below.
■光感度
上記薄膜を、超高圧水銀灯（ジェットライト２ｋＷ）を
用いて、照度７．２ｍＷ ／ｃｊ （３５０ｍμ）で照
射して光硬化させ、光硬化する迄の光照射量（Ｊ １０
Ｊ）を測定した。■Photosensitivity The above thin film is photocured by irradiating it with an ultra-high pressure mercury lamp (jet light 2kW) at an illuminance of 7.2mW/cj (350mμ), and the amount of light irradiation (J 10
J) was measured.
■解像力
上記薄膜についてテストチャートとして凸版印刷■製ネ
ガ型テストチャート（トラパンテストチャートＮ、最小
線中０．９８±０．２５μ）を用いてレリーフパターン
を形成し、パターンの良否を判定した。(2) Resolution Regarding the above thin film, a relief pattern was formed using a negative type test chart manufactured by Toppan Printing (Trapan Test Chart N, 0.98±0.25μ in the minimum line) as a test chart, and the quality of the pattern was determined.
比較例Ｉ
ＮＭＰ１２．Ｏｍｌにピロメリット酸二無水物１．４６
ｇと３．５−ジアミノ安息香酸エチルメタクリル酸エス
テル０．９２ ｇと４，４”−ジアミノジフェニルエー
テル０．７０ ｇを加え、３０’Ｃで２４時間ｆｌ！拌
して反応させポリアミック酸を得た。このポリアミック
酸の対数粘度は０．４３であった。Comparative Example I NMP12. Pyromellitic dianhydride 1.46 in Oml
g, 3.5-diaminobenzoic acid ethyl methacrylate 0.92 g, and 4,4''-diaminodiphenyl ether 0.70 g were added, and the mixture was stirred at 30'C for 24 hours to react to obtain polyamic acid. The logarithmic viscosity of this polyamic acid was 0.43.
次に、このポリアミック酸溶液にＮＭＰ４５．０＃ｌｌ
を加え希釈したのち、無水酢酸１４．２８ ｇ、ピリジ
ン５．４６ｇ、ベンゼン８．８１及びＮ Ｍ Ｐ ７．
５ＩＩｌｌを加え、５０℃で反応させたところ、２０分
後に黄色のポリイミド粉末が析出した。そのままさらに
１２０分間反応させた。Next, add NMP45.0#ll to this polyamic acid solution.
After dilution by adding 14.28 g of acetic anhydride, 5.46 g of pyridine, 8.81 g of benzene and 7.
When 5IIll was added and reacted at 50°C, yellow polyimide powder was precipitated 20 minutes later. The reaction was continued for an additional 120 minutes.
析出した黄色のポリイミド粉末を濾別後、このポリイミ
ド粉末１０ｍｇをＮＭＰｌｏｍｌに溶解しようとしたと
ころ溶解しなかった。After filtering off the precipitated yellow polyimide powder, an attempt was made to dissolve 10 mg of this polyimide powder in NMploml, but it did not dissolve.
従って、このポリイミドでの光感度、解像力は測定不能
であった。Therefore, it was impossible to measure the photosensitivity and resolution of this polyimide.
特許出願人 宇 部 興 産 株式会社 代理人 弁理士 羽 鳥 修patent applicant Ube Kosan Co., Ltd. Agent Patent attorney Osamu Hatori
Claims (1)
で表される芳香族ジアミン化合物７０〜９８モル％及び
下記一般式（ＩＩ）で表される芳香族ジアミン化合物３
０〜２モル％との、共重縮合物からなる、有機溶媒可溶
性の感光性ポリイミド。 （但し、上式中、Ａｒｌは芳香族残基を示し、ＸはＨ又
はＣＨ３を示す。） １１２ Ｎ −Ｒｓ −Ｎ Ｈｚ （ＩＩ ）（但し、
上式中、Ｒ１はケトン基を有する有機残基を示す。）[Claims] A biphenyltetracarboxylic acid component and the following general formula (1)
70 to 98 mol% of aromatic diamine compound represented by and aromatic diamine compound 3 represented by the following general formula (II)
An organic solvent-soluble photosensitive polyimide consisting of a copolycondensate of 0 to 2 mol%. (However, in the above formula, Arl represents an aromatic residue, and X represents H or CH3.) 112 N -Rs -N Hz (II) (However,
In the above formula, R1 represents an organic residue having a ketone group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18352083A JPS6072925A (en) | 1983-09-30 | 1983-09-30 | Organic solvent-soluble photosensitive polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18352083A JPS6072925A (en) | 1983-09-30 | 1983-09-30 | Organic solvent-soluble photosensitive polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6072925A true JPS6072925A (en) | 1985-04-25 |
| JPH0225378B2 JPH0225378B2 (en) | 1990-06-01 |
Family
ID=16137281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18352083A Granted JPS6072925A (en) | 1983-09-30 | 1983-09-30 | Organic solvent-soluble photosensitive polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6072925A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4765137A (en) * | 1986-03-07 | 1988-08-23 | Yamaha Hatsudoki Kabushiki Kaisha | Exhaust gas control means for engine |
| JPH0243221A (en) * | 1988-06-10 | 1990-02-13 | Occidental Chem Corp | New soluble polyimide siloxane and its manufacture and use |
| US4909033A (en) * | 1985-11-26 | 1990-03-20 | Yamaha Hatsudoki Kabushiki Kaisha | High performance exhaust system for internal combustion engine |
| JPH02163741A (en) * | 1988-12-16 | 1990-06-25 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using same |
| JPH0359034A (en) * | 1989-07-27 | 1991-03-14 | Hitachi Chem Co Ltd | Production of polyimide resin |
| US5665523A (en) * | 1994-03-29 | 1997-09-09 | Nitto Denko Corporation | Heat-resistant negative photoresist composition, photosensitive substrate, and process for forming negative pattern |
| US5674461A (en) * | 1993-12-09 | 1997-10-07 | Honda Giken Kogyo Kabushiki Kaisha | Exhaust device |
| US5851736A (en) * | 1991-03-05 | 1998-12-22 | Nitto Denko Corporation | Heat-resistant photoresist composition, photosensitive substrate, and process for forming heat-resistant positive or negative pattern |
| US6001534A (en) * | 1997-03-31 | 1999-12-14 | Shin-Etsu Chemical Co., Ltd. | Photosensitive resin composition |
| US6436593B1 (en) | 1999-09-28 | 2002-08-20 | Hitachi Chemical Dupont Microsystems Ltd. | Positive photosensitive resin composition, process for producing pattern and electronic parts |
| US7435525B2 (en) | 2004-05-07 | 2008-10-14 | Hitachi Chemical Dupont Microsystems Ltd. | Positive photosensitive resin composition, method for forming pattern, and electronic part |
| US7638254B2 (en) | 2004-05-07 | 2009-12-29 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, method for forming pattern, and electronic part |
| US20110200939A1 (en) * | 2009-08-28 | 2011-08-18 | Lg Chem, Ltd. | Polyamic acid, polyimide, photosensitive resin composition comprising the same and dry film manufactured by the same |
| WO2011105576A1 (en) * | 2010-02-26 | 2011-09-01 | 日産化学工業株式会社 | Diamine compound, liquid crystal aligning agent and liquid crystal display element |
| US8298747B2 (en) | 2007-03-12 | 2012-10-30 | Hitachi Chemical Dupont Microsystems, Ltd. | Photosensitive resin composition, process for producing patterned hardened film with use thereof and electronic part |
| US8420291B2 (en) | 2007-10-29 | 2013-04-16 | Hitachi Chemical Dupont Microsystems, Ltd. | Positive photosensitive resin composition, method for forming pattern, electronic component |
| US8758977B2 (en) | 2005-09-22 | 2014-06-24 | Hitachi Chemical Dupont Microsystems, Ltd. | Negative-type photosensitive resin composition, pattern forming method and electronic parts |
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-
1983
- 1983-09-30 JP JP18352083A patent/JPS6072925A/en active Granted
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4909033A (en) * | 1985-11-26 | 1990-03-20 | Yamaha Hatsudoki Kabushiki Kaisha | High performance exhaust system for internal combustion engine |
| US4765137A (en) * | 1986-03-07 | 1988-08-23 | Yamaha Hatsudoki Kabushiki Kaisha | Exhaust gas control means for engine |
| JPH0243221A (en) * | 1988-06-10 | 1990-02-13 | Occidental Chem Corp | New soluble polyimide siloxane and its manufacture and use |
| JPH02163741A (en) * | 1988-12-16 | 1990-06-25 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using same |
| JPH0359034A (en) * | 1989-07-27 | 1991-03-14 | Hitachi Chem Co Ltd | Production of polyimide resin |
| US5851736A (en) * | 1991-03-05 | 1998-12-22 | Nitto Denko Corporation | Heat-resistant photoresist composition, photosensitive substrate, and process for forming heat-resistant positive or negative pattern |
| US5674461A (en) * | 1993-12-09 | 1997-10-07 | Honda Giken Kogyo Kabushiki Kaisha | Exhaust device |
| US5665523A (en) * | 1994-03-29 | 1997-09-09 | Nitto Denko Corporation | Heat-resistant negative photoresist composition, photosensitive substrate, and process for forming negative pattern |
| US6001534A (en) * | 1997-03-31 | 1999-12-14 | Shin-Etsu Chemical Co., Ltd. | Photosensitive resin composition |
| US6436593B1 (en) | 1999-09-28 | 2002-08-20 | Hitachi Chemical Dupont Microsystems Ltd. | Positive photosensitive resin composition, process for producing pattern and electronic parts |
| US7435525B2 (en) | 2004-05-07 | 2008-10-14 | Hitachi Chemical Dupont Microsystems Ltd. | Positive photosensitive resin composition, method for forming pattern, and electronic part |
| US7638254B2 (en) | 2004-05-07 | 2009-12-29 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive resin composition, method for forming pattern, and electronic part |
| EP2469337A1 (en) | 2004-05-07 | 2012-06-27 | Hitachi Chemical DuPont MicroSystems Ltd. | Positive photosensitive resin composition, method for forming pattern, and electronic component |
| US8758977B2 (en) | 2005-09-22 | 2014-06-24 | Hitachi Chemical Dupont Microsystems, Ltd. | Negative-type photosensitive resin composition, pattern forming method and electronic parts |
| US8871422B2 (en) | 2005-09-22 | 2014-10-28 | Hitachi Chemical Dupont Microsystems Ltd. | Negative-type photosensitive resin composition, pattern forming method and electronic parts |
| US8298747B2 (en) | 2007-03-12 | 2012-10-30 | Hitachi Chemical Dupont Microsystems, Ltd. | Photosensitive resin composition, process for producing patterned hardened film with use thereof and electronic part |
| US8420291B2 (en) | 2007-10-29 | 2013-04-16 | Hitachi Chemical Dupont Microsystems, Ltd. | Positive photosensitive resin composition, method for forming pattern, electronic component |
| US20110200939A1 (en) * | 2009-08-28 | 2011-08-18 | Lg Chem, Ltd. | Polyamic acid, polyimide, photosensitive resin composition comprising the same and dry film manufactured by the same |
| WO2011105576A1 (en) * | 2010-02-26 | 2011-09-01 | 日産化学工業株式会社 | Diamine compound, liquid crystal aligning agent and liquid crystal display element |
| JP5783166B2 (en) * | 2010-02-26 | 2015-09-24 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal display element and diamine compound |
| JP2018081225A (en) * | 2016-11-17 | 2018-05-24 | Jsr株式会社 | Liquid crystal alignment agent, method for manufacturing liquid crystal device, liquid crystal alignment film, liquid crystal device, and polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0225378B2 (en) | 1990-06-01 |
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