JPS6390532A - Photosensitive polyamic acid - Google Patents
Photosensitive polyamic acidInfo
- Publication number
- JPS6390532A JPS6390532A JP23647686A JP23647686A JPS6390532A JP S6390532 A JPS6390532 A JP S6390532A JP 23647686 A JP23647686 A JP 23647686A JP 23647686 A JP23647686 A JP 23647686A JP S6390532 A JPS6390532 A JP S6390532A
- Authority
- JP
- Japan
- Prior art keywords
- polyamic acid
- benzalacetophenone
- compound
- photosensitive
- carboxylic acid
- 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.)
- Pending
Links
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 26
- -1 benzalacetophenone compound Chemical class 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 229920001721 polyimide Polymers 0.000 claims abstract description 4
- 239000009719 polyimide resin Substances 0.000 claims abstract 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 3
- 229920006015 heat resistant resin Polymers 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 150000003949 imides Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical group C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011907 photodimerization Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は感光性を有するポリアミック酸に関する。さら
に詳しくは光によって架橋し得るポリアミック酸で、光
架橋後熱処理を加えることによりイミド化し耐熱性を有
する樹脂を得ることのできるものに関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a photosensitive polyamic acid. More specifically, the present invention relates to a polyamic acid that can be crosslinked by light, and which can be imidized by heat treatment after photocrosslinking to obtain a heat-resistant resin.
従来の技術
感光性ポリアミック酸を製造する方法には、感光剤をポ
リアミック酸溶液に添加する方法（添加法）とポリアミ
ック酸のカルボン酸に感光基を直接導入する方法（直接
導入法）が知られている。Conventional techniques There are two known methods for producing photosensitive polyamic acid: a method in which a photosensitizer is added to a polyamic acid solution (addition method), and a method in which a photosensitive group is directly introduced into the carboxylic acid of polyamic acid (direct introduction method). ing.
添加法で用いられる感光剤としては、芳香族ビスアジド
化合物（特公昭５９−４６３８０号公報）が提案されて
いる。As the photosensitizer used in the addition method, an aromatic bisazide compound (Japanese Patent Publication No. 46380/1983) has been proposed.
直接導入法として用いられる感光基としては、（Ｒ：フ
ルキル、Ｒ１：アルキル、フェニル、アルコキシフェニ
ル、ハロゲンフェニル、Ｒ２：Ｈ。Photosensitive groups used in the direct introduction method include (R: furkyl, R1: alkyl, phenyl, alkoxyphenyl, halogen phenyl, R2: H.
Ｃｌ アルキル、アルキキシ、Ｒ５：炭素環又は複素環
式芳香族残基で環のＣを介して結合される）（特公昭５
５−３０２０７号公報）。Cl alkyl, alkoxy, R5: carbocyclic or heterocyclic aromatic residue bonded via C of the ring) (Japanese Patent Publication No. 5
5-30207).
−ＯＲ’ＯＣ；−Ｃ；＝ＯＨ２（Ｒ： Ｈ，ＯＨ３，Ｒ
’ ：アルキル）（特公昭５Ｂ−４１４２２号公報）、
アミノ基あるいは四級塩を有するアクリル酸エステル特
開昭５４−１４５７９４号公報）などの化合物が知られ
ている。-OR'OC;-C;=OH2(R: H,OH3,R
': alkyl) (Special Publication No. 5B-41422),
Compounds such as acrylic esters having an amino group or a quaternary salt (Japanese Patent Application Laid-open No. 145794/1983) are known.
発明が解決しようとする問題点
芳香族ビスアジド化合物を感光剤として添加する方法や
ポリアミック酸のカルボン酸に感光基を直接導入する方
法において、ポリアミック酸をイミド化するため高温で
加熱すると以下の問題が発生していた。すなわち、ポリ
アミック酸が脱水縮合時に体積収縮を起こすが、感光性
を付与する念めに添加した感光剤や導入した感光基の分
子も高温加熱時に分解蒸発し、生成するポリイミド膜の
残膜率（初期膜厚に対して加熱処理後に残存する膜厚の
割合）が低下していた。この残膜率を向上させるには、
感光成分の導入割合を低下させる必要がある。この低下
が過度であると感光性樹脂としての性能が低下する。Problems to be Solved by the Invention In the method of adding an aromatic bisazide compound as a photosensitizer or the method of directly introducing a photosensitive group into the carboxylic acid of polyamic acid, heating at high temperature to imidize polyamic acid causes the following problems. It was occurring. In other words, polyamic acid undergoes volumetric shrinkage during dehydration condensation, but the photosensitizer added to impart photosensitivity and the molecules of the photosensitive group introduced also decompose and evaporate during high-temperature heating, resulting in an increase in the residual film rate of the resulting polyimide film ( The ratio of the film thickness remaining after heat treatment to the initial film thickness was decreasing. To improve this residual film rate,
It is necessary to reduce the introduction ratio of photosensitive components. If this decrease is excessive, the performance as a photosensitive resin will deteriorate.
問題点を解決するための手段
ポリアミック酸中に含まれるカルボン酸にベンザルアセ
トフェノン系化合物がエステル結合した構成とする。Means for Solving the Problems The polyamic acid has a structure in which a benzalacetophenone compound is ester bonded to a carboxylic acid contained in the polyamic acid.
作用
ベンザルアセトフェノン系化合物の光二量化反応がポリ
アミック酸の光架橋反応に対して効率的に作用するため
、感光基濃度を低下させることができ、その結果、生成
するポリイミド膜の残膜率を著しく改善できるものと考
えられる。Effect The photodimerization reaction of the benzalacetophenone compound acts efficiently on the photocrosslinking reaction of polyamic acid, so the concentration of photosensitive groups can be lowered, and as a result, the residual film rate of the polyimide film produced can be significantly reduced. This is considered to be something that can be improved.
実施例
具体的には、次のようなベンザルアセトフェノン系化合
物を用いる。Examples Specifically, the following benzalacetophenone compound is used.
アルキル、アルコキシ、水酸基）
これら化合物を以下に示すようにポリアミック酸中に含
まれるカルボン酸の少くなくとも一つに、エステル結合
を介して結合する。alkyl, alkoxy, hydroxyl group) These compounds are bonded to at least one of the carboxylic acids contained in the polyamic acid via an ester bond as shown below.
この感光性ポリアミック酸に光を照射するとベンザルア
セトフェノン部が三量化し、現像液に対して不溶化する
。ベンザルアセトフェノン化合物の含有量はポリアミッ
ク酸中のカルボン酸１ｏＯ分子に対して２〜１０分子が
適当である。少ないと感光性を示めさず、多くなると残
膜率が低下する。When this photosensitive polyamic acid is irradiated with light, the benzalacetophenone moiety is trimerized and becomes insoluble in the developer. The content of the benzalacetophenone compound is suitably 2 to 10 molecules per 100 molecules of carboxylic acid in the polyamic acid. If it is too low, photosensitivity will not be exhibited, and when it is too high, the remaining film rate will decrease.
以下、本発明を実施例で説明する。The present invention will be explained below with reference to Examples.
実施例１
ポリアミック酸として、芳香族ジカルボン酸とジアミン
からなるＤｕｐＯｎｔ社製ＰＩ−２５２５感光基成分と
しては、ベンザルアセトフェノン系を用いた。ポリアミ
ック酸のＮメチル−２ピロリドン１０％溶液１００Ｉに
対して感光基成分を０．５９を混合し、１１０°Ｃに加
熱し脱水反応を行なっ次。溶媒成分を除去し、生成した
樹脂の赤外吸収スペクトルを測定すると、エステル結合
の吸収が観測された。したがって、エステル結合の介し
て、感光基が結合していることが確認された。Example 1 As a polyamic acid, PI-2525 manufactured by DupOnt, which consists of an aromatic dicarboxylic acid and a diamine, was used.As a photosensitive group component, benzalacetophenone was used. 0.59 of a photosensitive group component was mixed with 100 I of a 10% N-methyl-2-pyrrolidone solution of polyamic acid, and the mixture was heated to 110°C to perform a dehydration reaction. When the solvent component was removed and the infrared absorption spectrum of the resulting resin was measured, absorption of ester bonds was observed. Therefore, it was confirmed that the photosensitive group was bonded via an ester bond.
実施例２
ガラス基板に、ＰＩ２５２６を塗布し、ステップ加熱を
行ないイミド化反応を行ない残膜率を測定すると、６０
％であった。次に、実施例１の方法で感光基を付与した
Ｐ Ｉ ２５２５を基板に塗布し、溶媒を乾燥除去後、
紫外光を露光し、ステップ加熱を行ないイミド化を行な
った。ＰＩ−２６２６を基準として、残膜率を測定する
と、９６チであった。感光基部での減少割合は６チであ
ることがわかった。Example 2 PI2526 was applied to a glass substrate, step heating was performed to perform an imidization reaction, and the remaining film rate was measured.
%Met. Next, P I 2525 to which a photosensitive group was added by the method of Example 1 was applied to the substrate, and after drying and removing the solvent,
Imidization was performed by exposing to ultraviolet light and performing step heating. When the residual film rate was measured using PI-2626 as a standard, it was 96. It was found that the reduction rate at the photosensitive base was 6 cm.
発明の効果
本発明のベンザルアセトフェノン系化合物は、ポリアミ
ック酸の感光性能に著しく有効に作用し、残膜率を著し
く改善しうるものである。Effects of the Invention The benzalacetophenone compound of the present invention has an extremely effective effect on the photosensitivity of polyamic acid, and can significantly improve the residual film rate.
Claims (1)
きるポリアミック酸において、ポリアミック酸中に含ま
れるカルボン酸のすくなくとも一つに、一般式 ▲数式、化学式、表等があります▼あるいは ▲数式、化学式、表等があります▼ （式中Ｒ＝水素、アルキル、アルコキシ、水酸基）であ
らわされるベンザルアセトフェノン系化合物がエステル
結合したことを特徴とする感光性ポリアミック酸。[Claims] In a polyamic acid that can be heat-treated to obtain a polyimide resin, at least one of the carboxylic acids contained in the polyamic acid has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ Alternatively, there are ▲mathematical formulas, chemical formulas, tables, etc.▼ Photosensitive polyamic acid characterized by an ester bond of a benzalacetophenone compound represented by (in the formula, R = hydrogen, alkyl, alkoxy, hydroxyl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23647686A JPS6390532A (en) | 1986-10-03 | 1986-10-03 | Photosensitive polyamic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23647686A JPS6390532A (en) | 1986-10-03 | 1986-10-03 | Photosensitive polyamic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6390532A true JPS6390532A (en) | 1988-04-21 |
Family
ID=17001303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23647686A Pending JPS6390532A (en) | 1986-10-03 | 1986-10-03 | Photosensitive polyamic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6390532A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02154263A (en) * | 1988-12-06 | 1990-06-13 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using this photosensitive resin composition |
| CN105418921A (en) * | 2015-12-01 | 2016-03-23 | 吉林大学 | Cross-linkable polyimide with high sulfonation degree as well as preparation method and application thereof in proton exchange membranes |
-
1986
- 1986-10-03 JP JP23647686A patent/JPS6390532A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02154263A (en) * | 1988-12-06 | 1990-06-13 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element using this photosensitive resin composition |
| CN105418921A (en) * | 2015-12-01 | 2016-03-23 | 吉林大学 | Cross-linkable polyimide with high sulfonation degree as well as preparation method and application thereof in proton exchange membranes |
| CN105418921B (en) * | 2015-12-01 | 2017-06-16 | 吉林大学 | A kind of highly sulfonated crosslinkable polyimide, preparation method and its application in terms of PEM |
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