JPS6054666B2 - Heat-resistant photoresist composition and method for producing the same - Google Patents

Heat-resistant photoresist composition and method for producing the same

Info

Publication number
JPS6054666B2
JPS6054666B2 JP13725677A JP13725677A JPS6054666B2 JP S6054666 B2 JPS6054666 B2 JP S6054666B2 JP 13725677 A JP13725677 A JP 13725677A JP 13725677 A JP13725677 A JP 13725677A JP S6054666 B2 JPS6054666 B2 JP S6054666B2
Authority
JP
Japan
Prior art keywords
formulas
tables
mathematical
chemical formulas
chemical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
JP13725677A
Other languages
Japanese (ja)
Other versions
JPS5470820A (en
Inventor
馨 大村
一郎 柴崎
武夫 木村
宗明 木村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP13725677A priority Critical patent/JPS6054666B2/en
Priority to GB7844576A priority patent/GB2008784B/en
Priority to US05/961,534 priority patent/US4180404A/en
Priority to FR7832525A priority patent/FR2409535A1/en
Priority to DE19782849981 priority patent/DE2849981A1/en
Priority to BE191780A priority patent/BE872083A/en
Publication of JPS5470820A publication Critical patent/JPS5470820A/en
Priority to US06/062,800 priority patent/US4310641A/en
Publication of JPS6054666B2 publication Critical patent/JPS6054666B2/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)

Description

【発明の詳細な説明】 （技術分野） 本発明は、絶縁性および耐熱性に優れた新規な″フォト
レジスト組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a novel photoresist composition having excellent insulation properties and heat resistance.

（従来技術とその問題点）今までに各種のフォトレジス
トが開発されているが、これらの多くは感光性というだ
けであり、感光性と絶縁性および耐熱性などの特性を合
わせ持つたものはない。(Prior art and its problems) Various photoresists have been developed so far, but most of them are only photosensitive, and those that have properties such as photosensitivity, insulation, and heat resistance are do not have.

近年、電子産業分野では、半導体回路、ハイブリッド回
路およびプリント回路などにおいては、高密度化の要請
により、多層化の方向に進んでいる。In recent years, in the field of electronic industry, semiconductor circuits, hybrid circuits, printed circuits, and the like have been moving toward multilayering due to demands for higher density.

しかしながら、従来のフォトレジストでは、ｌ絶縁性お
よび耐熱性などの特性が悪く、上記回路に残存させるこ
とは不可能であり、絶縁性および耐熱性が優れた、上記
回路に残存させることの可能なフォトレジストが望まれ
ている。（発明の構成） 本発明者らは、上記特性を持つたフォトレジストを開発
すべく鋭意研究した結果、有機溶媒に可溶性のポリアミ
ドイミドに、シンナメート基を導入する事により、はじ
めて実用特性を有する耐熱性フォトレジストが得られる
事を見い出し、本発ノ明を完成するに到つた。However, conventional photoresists have poor properties such as insulation and heat resistance, and cannot be left in the above circuits. Photoresist is desired. (Structure of the Invention) As a result of intensive research to develop a photoresist with the above-mentioned properties, the present inventors discovered that by introducing a cinnamate group into polyamideimide, which is soluble in organic solvents, they were able to develop a heat-resistant photoresist with practical properties for the first time. The present inventors have discovered that a photoresist with high compatibility can be obtained, and have completed the invention of the present invention.

即ち、本発明は、 （１） 一般式 又は、 又は、 〔ここでＮは し 」 Ｌ５」 ［、」 又は Ｎ″は 又は 一く ）−ｘ−く ）−ｙはＮ又は （Ｒは水素、アルキル基、又はハロゲンを示し、Ｘは−
０−、′＞ＳＯ２、〉ＣＨ２、〉ＣＯｌｌｌ″／Ｃ（Ｃ
Ｈ３）２、又は−Ｓ−を示し、これらは互いに同一であ
つても異なつていても良い。That is, the present invention provides the following formulas: (1) General formula, Represents an alkyl group or halogen, and X is -
0-,'>SO2,>CH2,>COll''/C(C
H3) represents 2 or -S-, which may be the same or different from each other.

）を示し、Ｙ″は水素又は一℃０−ＣＨ−ＣＨ−ーーー
ー＜′″ ）を示し、ｍは０又は正の整数、ｎは正の整
数を示す。), Y″ represents hydrogen or 1°C0-CH-CH-<''), m represents 0 or a positive integer, and n represents a positive integer.

〕で表わされるポリマーと、芳香族炭化水素、芳香族ア
ミノ化合物、芳香族ニトロ化合物、フェノール性化合物
、芳香族ケトン類、キノン類、アントロン類の中から選
ばれた一種以上の増感剤となる事を特徴とする耐熱性フ
ォトレジスト組成物、および（２） 一般式 又は、 〔ここでＮは ［Ｊ し、ｌ］ し、５，』 又は Ｎ″は一＼２７− ーく Ｈ ）一、又は 一 又は、 し、ｘは−０−、〉ＳＯ２、＞ＣＨ２、〕ＣＯ、 只
一 ゝ〉Ｃ（ＣＨ３）２、又は−ｓ−し、これらは
互いに同一であつても異なつマ２θも良い。] and one or more sensitizers selected from aromatic hydrocarbons, aromatic amino compounds, aromatic nitro compounds, phenolic compounds, aromatic ketones, quinones, and anthrones. a heat-resistant photoresist composition characterized by or 1 or , x is -0-, 〉SO2, ＞CH2, 〕CO, only ゝゝゝ〉C(CH3)2, or -s-, and these may be the same or different Ma 2θ good.

）を示し、Ｙ″は水素又は一℃０−ＣＨ＝ＣＨ−イ″
）を示し、ｍはＯ）の整数、ｎは正の整数を示す。), Y″ is hydrogen or 1°C0-CH=CH-i″
), m is an integer of O), and n is a positive integer.

〕て表わさ第１５機溶媒に可溶性のポリアミドイミドと
、シシイルクロライドを、副生するハロゲン化水潟和す
るに充分な量の第三級アミンの存在下１Ｚ機極性溶媒中
て反応させる事を特徴とする而フォトレジストの製造法
を提供するものでＪθ 通常のポリアミドイミドは、有
機溶媒に文不溶である為に、シンナメート基の導入お」
ーテイングが不可能であり、またポリアミトド合成の途
中の段階の有機溶媒に可溶なポ１，ド酸は、シンナメー
ト基の導入は一応可能マ５が、反応のコントロールがむ
づかしく、ま１アミド酸はアミド結合に隣接してカルボ
キシが存在しているために、加水分解を受け易く液とし
て長時間保存しておくと、加水分解σに重合体の分子量
が著しく低下するというクＯ有しており、更にポリアミ
ド酸をポリアミトドに転化させるのに、コーティング後
高温交必要である。このような欠点を除いた本？は、有
機溶媒に可溶なポリアミドイミドを月事により、容易に
シンナメート基を導入すイ出来、また得られたフォトレ
ジストは安定で、かつコーティング可能で、溶剤を除去
するだけで熱安定性および電気特性の良好なフォトレジ
スト膜を得る事が可能となる。] Reacting polyamideimide soluble in the 15th solvent and cisyl chloride in a 1Z polar solvent in the presence of a sufficient amount of tertiary amine to lag by-produced halogenated water. It provides a method for producing photoresists with the following characteristics: Jθ Since ordinary polyamideimide is insoluble in organic solvents, it is necessary to introduce cinnamate groups.
In addition, it is possible to introduce a cinnamate group into a polyamide acid, which is impossible to react with, and which is soluble in an organic solvent during the intermediate stage of polyamide synthesis.However, it is difficult to control the reaction, and Since acids have a carboxy group adjacent to the amide bond, they are easily hydrolyzed and if stored as a liquid for a long time, the molecular weight of the polymer will drop significantly due to hydrolysis. Furthermore, high temperature exchange is required after coating to further convert the polyamic acid to polyamic acid. A book without these flaws? The cinnamate group can be easily introduced into polyamideimide which is soluble in organic solvents, and the resulting photoresist is stable and can be coated.Simply removing the solvent improves thermal stability and It becomes possible to obtain a photoresist film with good electrical properties.

本発明に用いられる一般式 又は、 〔ここでＮは ］″ 「 ５？、／ ？、７」 ？、７」］ 又は Ｎ″は一＼ λ− ζヌニーλ廖ヌーー７−、又は 廖く−ニ）−０−〈−ー）− さ″はＮ又は（Ｒは水素
、アルキル基、又はハロゲンを示し、Ｘは−０−、〉Ｓ
Ｏ２、〉ＣＨ２、〉ＣＯｌ？頗−５ゝ〉Ｃ（ＣＨ３）２
、又は−ｓ−を示し、これらは互いに同一であつても異
なつていても良い。The general formula used in the present invention or [Here, N is ]""5?, / ?, 7"? , 7''] or N'' is 1\λ- , X is -0-, 〉S
O2, 〉CH2, 〉COl? Chest-5ゝ〉C(CH3)2
, or -s-, which may be the same or different.

）を示し、ｍは０又は正の整数、ｎは正の整数を示す。
〕で表わされる有機溶媒に可溶性のポリアミドイミドの
製造法としては、一般式 （ここでＲは水素、アルキル基、又はハロゲンを示し、
Ｘは−０−、′：ニーＳＯ，、′：ニーＣＨ２、〉ＣＯ
ｌ一下７゛＞Ｃ（ＣＨ．）２、又は−ｓ−を示し、これ
らは互いに同一であつても異なつていても良い。), m is 0 or a positive integer, and n is a positive integer.
] As a method for producing organic solvent-soluble polyamideimide represented by the general formula (where R represents hydrogen, an alkyl group, or a halogen,
X is -0-,': Knee SO,,': Knee CH2,〉CO
1-7゛>C(CH.)2, or -s-, which may be the same or different.

）で表わされる芳香族ジアミンとトリメリト酸クロライ
ドを反応させる方法、一般式又は、（ここでＲは水素、
アルキル基、又はハロゲンを示し、Ｘは−０−、＞ＳＯ
２、〉ＣＨ２、＞ＣＯｌ上− ゛〉Ｃ（Ｃ？）・、又は
−ｓ−を示し、これらは互いに同一であつも異なつてい
ても良い。) A method of reacting an aromatic diamine represented by
Indicates an alkyl group or halogen, X is -0-, >SO
2.〉CH2, >COL - ゛〉C(C?)• or -s-, which may be the same or different from each other.

）で表わされるビスイミドカルボン酸と３・３″−ジイ
ソシアナートジフェニルを反応させる方法、一般式０＝
Ｃ＝Ｎ−んザーＮ＝Ｃ＝０（ここでＮ″はベーンー、一
＼−バー〉一 又は？〈−ンー０−（−７，〉一 （
Ｒは水素、アルキル基、又はハロゲンを示し、Ｘは−０
−、）（ＣＨ３）２、又は−Ｓ−を示し、これらは互い
に同一であつても異なつていても良い。) A method of reacting bisimidocarboxylic acid represented by
C=N-zer N=C=0 (here N'' is vane, 1\-bar>1 or?〈-n-0-(-7,〉1)
R represents hydrogen, an alkyl group, or a halogen, and X is -0
-, )(CH3)2, or -S-, which may be the same or different from each other.

）で表わされるジイソシアナートと式のビスイミドカル
ボン酸を反応させる方法などがある。) and a method of reacting a bisimidecarboxylic acid of the formula.

上記有機溶媒に可溶性のポリアミドイミドとシンナモイ
ルクロライドとの反応は、シンナモイルクロライドをポ
リアミドイミドの重合単位置モルに対して０．００１〜
１０モル使用される。シンナメート基の導入率は、０．
１〜１００％、すなわちｍ／ｎ＝０〜１０００が用いら
れ、特にｍ／ｎ＝０〜１００が好ましい範囲である。ま
たシンナメート基は末端に導入されてもよい。また上記
反応に使用される三級アミンとしては、トリメチルアミ
ン、トリエチルアミン、トリプロルピルアミン、トリブ
チルアミン、トリ第二級プロピルアミン、アリルジエチ
ルアミン、ジメチルーｎ−ブチルアミン、ジエチルイソ
プロピルアミン、ベンジルジメチルアミン、ジオクチル
ベンジルアミン、ジオクチルクロロベンジルアミン、ジ
メチルシクロヘキシルアミン、ジメチルフェネチルアミ
ン、ベンジルメチルエチルアミン、（クロロフェネチル
）ブロモベンジルアミン、１−ジメチルアミノー２ーフ
ェニルプロパン、１−ジメチルーアミノー４ーペンタン
等のごとき脂肪族第三級アミン、ピリジン、キヌクリジ
ンのごときピリジン類、Ｎ−アルキルピロール、Ｎ−ア
ルキルピロリジン、Ｎ−アルキルピペリジン、キノリン
、イソキノリン、Ｎ−アルキルテトラヒドロキノリン、
Ｎ−アルキルテトラヒドロイソキノリン、Ｎ−アルキル
モルフオリン等の環状アミン、Ｎ，Ｎ−ジメチルアニリ
ン、メチルジフェニルアミン等がある。その使用量は副
生するハロゲン化水素を中和するに充分な量であること
が好ましい。反応は、有機極性溶媒、例えば、Ｎ，Ｎ−
ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド
、Ｎ−メチルピロリドン、ジメチルスルホキシド、ヘキ
サメチルホスホアミド中で行われ、ベンゼン、トルエン
、キシレン、ジオキサン、クレゾール等の通常の溶媒を
共存させても良く、１５０℃以下の温度で１〜２峙間行
われる。In the reaction between polyamideimide soluble in the above organic solvent and cinnamoyl chloride, the amount of cinnamoyl chloride is 0.001 to 0.001 to
10 moles are used. The introduction rate of cinnamate group is 0.
1 to 100%, that is, m/n=0 to 1000, is used, and m/n=0 to 100 is particularly preferred. A cinnamate group may also be introduced at the end. The tertiary amines used in the above reaction include trimethylamine, triethylamine, triprolpylamine, tributylamine, tri-secondary propylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, benzyldimethylamine, and dioctylbenzylamine. , dioctylchlorobenzylamine, dimethylcyclohexylamine, dimethylphenethylamine, benzylmethylethylamine, (chlorophenethyl)bromobenzylamine, 1-dimethylamino-2-phenylpropane, 1-dimethyl-amino-4-pentane, etc. amines, pyridine, pyridines such as quinuclidine, N-alkylpyrrole, N-alkylpyrrolidine, N-alkylpiperidine, quinoline, isoquinoline, N-alkyltetrahydroquinoline,
Examples include cyclic amines such as N-alkyltetrahydroisoquinoline and N-alkylmorpholine, N,N-dimethylaniline, and methyldiphenylamine. It is preferable that the amount used is sufficient to neutralize by-produced hydrogen halide. The reaction is carried out in an organic polar solvent, e.g.
It is carried out in dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphoamide, and a common solvent such as benzene, toluene, xylene, dioxane, cresol, etc. may be coexisting, and the temperature is 150°C. It is carried out for 1 to 2 hours at the following temperature.

シンナメート基を導入したポリアミドイミド溶液は、そ
のままでもある特定の用途に使用することが可能である
が、水、メタノール、アセトン、トルエン、シクロヘキ
サン等のポリマーを溶解しない溶剤中に沈殿させて分離
取得して、不純物を取り除いた後、ジメチルアセトアミ
ド等の極性溶媒中に再び溶解して使用するのが好ましい
。A polyamideimide solution with cinnamate groups introduced can be used as is for certain specific purposes, but it can be separated and obtained by precipitating it in a solvent that does not dissolve the polymer, such as water, methanol, acetone, toluene, or cyclohexane. After removing impurities, it is preferable to dissolve it again in a polar solvent such as dimethylacetamide and use it.

上記シンナメート基を導入したポリアミドイミドは、単
独でも感光性を有するが、増感剤を添加して使用するの
が実用的に好ましい。添加量はポリマーに対して０．０
１〜５０重量％特に０．１〜１濾量％が好ましい範囲で
ある。本発明に使用される増感剤としては、ナフタリン
、アントラセン、フェナントレン、クリセンなどの芳香
族炭化水素：ニトロベンゼン、Ｐージニトロベンゼン、
１，３，５−トリニトロベンゼン、Ｐ−ニトロジフェニ
ル、ｍ−ニトロアニリｊン、Ｐ−ニトロアニリン、２，
４ージニトロアニリン、ピクラミド、２−クロロー４−
ニトロアニリン、２，６−ジクロロー４−ニトロアニリ
ン、Ｐ−ニトロフェノール、２，４ージニトロフェノー
ル、２，４，６−トリニトロフェノールなどの・芳香族
アミノ化合物、芳香族ニトロ化合物、フェノール性化合
物；ベンズアルデヒド、９−アントラアルデヒド、アセ
トフェノン、ベンゾフェノン、ジベンザルアセトン、ベ
ンジル、Ｐ，Ｐ′−ジアノベゾフエノン、Ｐ，Ｐ５−ジ
メチルアミノペンａゾフエノン、Ｐ，Ｐ′−テトラメチ
ルジアミノベンゾフェノンなどの芳香族ケトン類；１，
２−ナフトキノン、１，４−ナフトキノン、アントラキ
ノン、１，２−ベンズアントラキノンなどのキノン類；
アントロン、１，９−ベンズアントロン、６ーフェニル
ー１，９−ベンズアントロン、２−ケトー３−アザー１
，９−ベンズアントロン、３−メチルー１，３ージアザ
ー１，９−ベンズアントロンなどのアントロン類などが
あり、これらは単独或いは混合して用いても良く、更に
第三成分を添加しても良い。Although the polyamideimide into which a cinnamate group has been introduced has photosensitivity even when used alone, it is practically preferable to use it with the addition of a sensitizer. Addition amount is 0.0 to polymer
The preferred range is 1 to 50% by weight, particularly 0.1 to 1% by weight. Sensitizers used in the present invention include aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, and chrysene; nitrobenzene, P-dinitrobenzene;
1,3,5-trinitrobenzene, P-nitrodiphenyl, m-nitroaniline, P-nitroaniline, 2,
4-dinitroaniline, picramide, 2-chloro4-
Aromatic amino compounds, aromatic nitro compounds, phenolic compounds such as nitroaniline, 2,6-dichloro-4-nitroaniline, P-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol ; benzaldehyde, 9-anthraldehyde, acetophenone, benzophenone, dibenzalacetone, benzyl, P,P'-dianobezophenone, P,P5-dimethylaminopenazophenone, P,P'-tetramethyldiaminobenzophenone, etc. Aromatic ketones; 1,
Quinones such as 2-naphthoquinone, 1,4-naphthoquinone, anthraquinone, 1,2-benzanthraquinone;
Anthrone, 1,9-benzanthrone, 6-phenyl-1,9-benzanthrone, 2-keto 3-other 1
, 9-benzanthrone, 3-methyl-1,3-diaza-1,9-benzanthrone, etc., and these may be used alone or in combination, and a third component may be added.

本組成物は実質的に溶解する前記重合溶媒などの適当な
溶媒を用い、溶液の粘度は所望の被膜の厚さに合わせて
調節することができ、この溶液は噴霧または浸漬法或い
はローラーなどにより塗布される。The viscosity of the solution can be adjusted according to the desired thickness of the coating by using a suitable solvent such as the above-mentioned polymerization solvent in which the composition is substantially dissolved. applied.

本発明の画像形成プロセスの１例を次に示す。An example of the image forming process of the present invention is shown below.

本発明にかかる組成物を基板上に塗布し、実質的に粘性
のない状態に乾燥して、シンナメート基の光２量化を生
じさせる為には、例えば水銀ランプなどの紫外線で所定
のパターンに露光される。露光時間は適宜選定されるが
、長い露光時間は一般的に有害ではない。紫外線などに
よる露光後、前記重合溶媒或いは前記重合溶媒と前記沈
殿溶媒との混合溶媒またはアルカリ水溶液などの適当な
溶剤を用いて非露光部を洗い出す。また場合によつては
、洗い出し後加熱処理を施しても良い。以下に本発明の
態様を一層明確にするために、実施例を挙げて説明する
が、本発明は実施例によりその範囲を制限されるもので
はない。（実施例）ｍ−フェニレンジアミン２．５Ｖ（
０．０２３モル）とピリジン２ｍ１とをジメチルアセト
アミド３５ｍ１に乾燥した窒素を通じながら溶解し、氷
水で５℃に冷却して、トリメリト酸無水物の４一酸クロ
ライド４．３ｑ（０．０２０モル）を加えた。The composition according to the present invention is applied onto a substrate, dried to a substantially non-viscous state, and exposed in a predetermined pattern to ultraviolet light from, for example, a mercury lamp, in order to cause photodimerization of the cinnamate group. be done. Exposure times are chosen accordingly, but longer exposure times are generally not harmful. After exposure to ultraviolet light or the like, the unexposed areas are washed out using a suitable solvent such as the polymerization solvent, a mixed solvent of the polymerization solvent and the precipitation solvent, or an aqueous alkaline solution. Further, depending on the case, heat treatment may be performed after washing. EXAMPLES In order to further clarify aspects of the present invention, examples will be given and explained below, but the scope of the present invention is not limited by the examples. (Example) m-phenylenediamine 2.5V (
0.023 mol) and 2 ml of pyridine were dissolved in 35 ml of dimethylacetamide while blowing dry nitrogen, cooled to 5°C with ice water, and 4.3 q (0.020 mol) of 4-monoacid chloride of trimellitic anhydride was dissolved. added.

ただちに発熱反応がおこり、溶液の温度は３５℃まで上
昇した。室温でさらに１時間攪拌を続けた後、無水酢酸
１０ｍ１とピリジン４ｍ１との混合物を加え、５０℃で
２時間攪拌した。このようにして得られた有機溶媒に可
溶性のポリアミドイミド溶液に、シンナモイルクロライ
ド３．８ｙとピリジン２ｍｔを加えて、５０℃で４時間
反応させて後、メタノール２５０ｍｔと氷５００ｍｔと
の混合溶媒中に注ぎ、シンナメート基を導入したポリア
ミドイミドを沈殿させ、次いでメタノール洗浄した後乾
燥して、定量的に生成物を得た。得られた生成物のシン
ナメート基の導入率は、５％であつた。上記シンナメー
ト基の導入されたポリアミドイミド０．５ｙ＜１５Ｐ，
Ｐ″−テトラメチルジアミノベンゾフェノン０．０１ｙ
をジメチルアセトアミドに溶解して、ガラス基板に塗布
乾燥した後、３Ｋ．Ｗ．の水銀ランプを用いて、所定の
パターンを５分間露光した。An exothermic reaction immediately occurred and the temperature of the solution rose to 35°C. After continuing stirring at room temperature for an additional hour, a mixture of 10 ml of acetic anhydride and 4 ml of pyridine was added, followed by stirring at 50° C. for 2 hours. To the thus obtained organic solvent-soluble polyamideimide solution, 3.8y of cinnamoyl chloride and 2mt of pyridine were added, and after reacting at 50°C for 4 hours, the mixture was dissolved in a mixed solvent of 250mt of methanol and 500mt of ice. The cinnamate group-introduced polyamideimide was precipitated, washed with methanol, and dried to obtain a quantitative product. The introduction rate of cinnamate groups in the obtained product was 5%. The above-mentioned cinnamate group-introduced polyamideimide 0.5y<15P,
P″-tetramethyldiaminobenzophenone 0.01y
was dissolved in dimethylacetamide, applied to a glass substrate, dried, and then coated with 3K. W. A predetermined pattern was exposed for 5 minutes using a mercury lamp.

Claims (1)

【特許請求の範囲】 １ 一般式 ▲数式、化学式、表等があります▼、 又は、 ▲数式、化学式、表等があります▼ 又は、 ▲数式、化学式、表等があります▼ 〔ここでＡｒは▲数式、化学式、表等があります▼、▲
数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、又は、▲数式、化
学式、表等があります▼、 Ａｒ′は▲数式、化学式、表等があります▼、▲数式、
化学式、表等があります▼又は▲数式、化学式、表等が
あります▼、Ａｒ″はＡｒ又はＡｒ′ （Ｒは水素、アルキル基、又はハロゲンを示し、Ｘは−
Ｏ−、▲数式、化学式、表等があります▼、▲数式、化
学式、表等があります▼、▲数式、化学式、表等があり
ます▼、▲数式、化学式、表等があります▼、▲数式、
化学式、表等があります▼、又は−Ｓ−を示し、これら
は互いに同一であつても異なつていても良い。 ）を示し、Ｙ′は水素又は▲数式、化学式、表等があり
ます▼を示し、ｍは０又は正の整数、ｎは正の整数を示
す。 〕で表わされるポリマーと、芳香族炭化水素、芳香族ア
ミノ化合物、芳香族ニトロ化合物、フェノール性化合物
、芳香族ケトン類、キノン類、アントロン類の中から選
ばれた一種以上の増感剤とからなる事を特徴とする耐熱
性フォトレジスト組成物。 ２ 一般式 ▲数式、化学式、表等があります▼ 又は、 ▲数式、化学式、表等があります▼ 又は、 ▲数式、化学式、表等があります▼ 〔ここでＡｒは▲数式、化学式、表等があります▼、▲
数式、化学式、表等があります▼ ▲数式、化学式、表等があります▼、又は▲数式、化学
式、表等があります▼、 Ａｒ′は▲数式、化学式、表等があります▼、▲数式、
化学式、表等があります▼、又は▲数式、化学式、表等
があります▼、Ａｒ″はＡｒ又はＡｒ′ （Ｒは水素、アルキル基、又はハロゲンを示し、Ｘは−
Ｏ−、▲数式、化学式、表等があります▼、▲数式、化
学式、表等があります▼、▲数式、化学式、表等があり
ます▼、▲数式、化学式、表等があります▼、▲数式、
化学式、表等があります▼、又は−Ｓ−を示し、これら
は互いに同一であつても異なつていても良い。 ）を示し、ｍは０または正の整数、ｎは正の整数を示す
。〕で表わされる有機溶媒に可溶性のポリアミドイミド
と、シンナモイルクロライドを、副生するハロゲン化水
素を中和するに充分な量の第三級アミンの存在下に、有
機極性溶媒中で反応させる事を特徴とする耐熱性フォト
レジストの製造法。[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Here, Ar is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Ar′ is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formula ,
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Ar'' is Ar or Ar' (R represents hydrogen, alkyl group, or halogen, and X is -
O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ or -S-, which may be the same or different. ), Y' represents hydrogen or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, m represents 0 or a positive integer, and n represents a positive integer. ] and one or more sensitizers selected from aromatic hydrocarbons, aromatic amino compounds, aromatic nitro compounds, phenolic compounds, aromatic ketones, quinones, and anthrones. A heat-resistant photoresist composition characterized by: 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Here, Ar stands for ▲ Mathematical formulas, chemical formulas, tables, etc. There is▼、▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Ar' is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Ar'' is Ar or Ar' (R represents hydrogen, an alkyl group, or a halogen, and X is -
O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ or -S-, which may be the same or different. ), m is 0 or a positive integer, and n is a positive integer. ] Reacting polyamideimide soluble in an organic solvent and cinnamoyl chloride in an organic polar solvent in the presence of a sufficient amount of tertiary amine to neutralize by-produced hydrogen halide. A method for producing a heat-resistant photoresist characterized by:
JP13725677A 1977-11-17 1977-11-17 Heat-resistant photoresist composition and method for producing the same Expired JPS6054666B2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP13725677A JPS6054666B2 (en) 1977-11-17 1977-11-17 Heat-resistant photoresist composition and method for producing the same
GB7844576A GB2008784B (en) 1977-11-17 1978-11-15 Heat resistant photoresist composition and process for preparing the same
US05/961,534 US4180404A (en) 1977-11-17 1978-11-16 Heat resistant photoresist composition and process for preparing the same
FR7832525A FR2409535A1 (en) 1977-11-17 1978-11-17 HEAT-RESISTANT "PHOTORESIST" COMPOSITION AND METHOD FOR PREPARING THE SAME
DE19782849981 DE2849981A1 (en) 1977-11-17 1978-11-17 HEAT-RESISTANT PHOTORESIS MATERIAL AND METHOD FOR MANUFACTURING IT
BE191780A BE872083A (en) 1977-11-17 1978-11-17 HEAT-RESISTANT "PHOTORESIST" COMPOSITION AND METHOD FOR PREPARING THE SAME
US06/062,800 US4310641A (en) 1977-11-17 1979-08-01 Heat resistant photoresist composition and process for preparing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP13725677A JPS6054666B2 (en) 1977-11-17 1977-11-17 Heat-resistant photoresist composition and method for producing the same

Publications (2)

Publication Number Publication Date
JPS5470820A JPS5470820A (en) 1979-06-07
JPS6054666B2 true JPS6054666B2 (en) 1985-11-30

Family

ID=15194402

Family Applications (1)

Application Number Title Priority Date Filing Date
JP13725677A Expired JPS6054666B2 (en) 1977-11-17 1977-11-17 Heat-resistant photoresist composition and method for producing the same

Country Status (2)

Country Link
JP (1) JPS6054666B2 (en)
BE (1) BE872083A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02162170A (en) * 1988-12-15 1990-06-21 Daihatsu Motor Co Ltd Car body rear structure for automobile

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0224680B1 (en) * 1985-12-05 1992-01-15 International Business Machines Corporation Diazoquinone sensitized polyamic acid based photoresist compositions having reduced dissolution rates in alkaline developers
JPH0646302B2 (en) * 1987-06-22 1994-06-15 株式会社日立製作所 Heat-resistant photosensitive polymer composition
JP2006342335A (en) * 2005-05-11 2006-12-21 Hitachi Chem Co Ltd Polyamide-imide and resin composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02162170A (en) * 1988-12-15 1990-06-21 Daihatsu Motor Co Ltd Car body rear structure for automobile

Also Published As

Publication number Publication date
BE872083A (en) 1979-05-17
JPS5470820A (en) 1979-06-07

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