JPH0420540A - Method of etching polyimide film - Google Patents
Method of etching polyimide filmInfo
- Publication number
- JPH0420540A JPH0420540A JP12413990A JP12413990A JPH0420540A JP H0420540 A JPH0420540 A JP H0420540A JP 12413990 A JP12413990 A JP 12413990A JP 12413990 A JP12413990 A JP 12413990A JP H0420540 A JPH0420540 A JP H0420540A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- polyimide film
- quaternary ammonium
- ammonium hydroxide
- urea
- 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
- 238000005530 etching Methods 0.000 title claims abstract description 34
- 229920001721 polyimide Polymers 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- -1 amine compound Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 abstract description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007423 decrease Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract 2
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はポリイミドフィルムの工、チング方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for fabricating and etching polyimide films.
［従来の技術］
従来よりポリイミド樹脂は耐熱性、耐燃性、寸法安定性
、耐薬品性、電気・機械的特性に優れ、多様な用途に用
いられてきている。その−例として、フレキシブルプリ
ント配線板やテープ自動ボンディング用のフィルムキャ
リアがあるが、この用途に用いる場合には、ポリイミド
樹脂をフィルム状として用いて基板を作成し、この基板
のポリイミドフィルムの一部をエツチング加工すること
によりスルーホールを形成する必要かある。[Prior Art] Polyimide resins have been used for a variety of purposes due to their excellent heat resistance, flame resistance, dimensional stability, chemical resistance, and electrical and mechanical properties. Examples include flexible printed wiring boards and film carriers for automatic tape bonding.When used for this purpose, a substrate is created using polyimide resin in the form of a film, and a portion of the polyimide film of this substrate is used. Is it necessary to form through holes by etching?
ところで、従来よりポリイミドフィルムを効率よく、か
つ高精度にエツチングする方法として高濃度アルカリ水
溶液、ヒドラジンを用いる方法か試みられてきているか
、高濃度アルカリ水溶液では、通常の条件では充分なエ
ツチングはできず、極めて苛酷な条件を選択しなければ
ならないばかりか、充分な加工精度は得られないとされ
、またヒドラジンを用いる方法では、エツチングか開始
されるまでのタイムラグが長く、その間にヒドラジンが
ポリイミドフィルム内に浸透し、膨潤を起こし、その結
果、所望の寸法のスルーホールができないとされている
。By the way, attempts have been made to use highly concentrated alkaline aqueous solutions and hydrazine as a method of etching polyimide films efficiently and with high precision. Not only do extremely harsh conditions have to be selected, but it is said that sufficient processing accuracy cannot be obtained.Moreover, in the method using hydrazine, there is a long time lag before etching starts, and during that time, hydrazine is absorbed into the polyimide film. It is said that the metal penetrates into the surface and causes swelling, and as a result, it is impossible to form a through hole of the desired size.
［発明が解決しようとする課題］
このような欠点を解消すべきものとして、ヒドラジンと
エチレンジアミンとの混合溶液を用いる方法が提案され
ている。ヒドラジンとエチレンジアミンとの混合溶液で
は、ポリイミドフィルムの膨潤は起きず、エツチング量
はポリイミドフィルムをエツチング液中に浸せきした時
間に対してほぼ直線的に上昇し、エツチング速度も２４
μｍ／ｆｆ１ｉｎ程度と大きいことが知られている。し
かし、ヒドンジンは吸湿性が強く時間と共に吸湿し、ヒ
ドラジン濃度が低下する。この結果、エツチング速度が
急速に低下し、実用に耐えなくなるため頻繁にエツチン
グ液を更新せざるを得ず、高コストとならざるを得ない
という問題点がある。更に、高濃度のヒドラジンの使用
は白煙の発生をもたらし、これによる作業環境の悪化を
もたらす。さらに、ヒドラジンは毒性が強く、その蒸気
を吸引すると粘膜等に炎症を起こすという問題があり、
多量に取扱う際には実用的ではない。[Problems to be Solved by the Invention] In order to overcome these drawbacks, a method using a mixed solution of hydrazine and ethylenediamine has been proposed. In a mixed solution of hydrazine and ethylenediamine, swelling of the polyimide film does not occur, the amount of etching increases almost linearly with the time that the polyimide film is immersed in the etching solution, and the etching rate also increases by 24%.
It is known that it is as large as about μm/ff1in. However, hydrazine is highly hygroscopic and absorbs moisture over time, resulting in a decrease in hydrazine concentration. As a result, the etching speed rapidly decreases, making it impossible to put it into practical use, and the etching solution must be frequently renewed, resulting in a high cost. Furthermore, the use of high concentrations of hydrazine results in the generation of white smoke, thereby deteriorating the working environment. Furthermore, hydrazine is highly toxic, and inhaling its vapor can cause irritation to mucous membranes.
It is not practical when handling large quantities.
本発明の目的は上記従来技術の問題点を解消し、より実
用的で、コストの低下を可能とするエツチング方法の提
供にある。SUMMARY OF THE INVENTION An object of the present invention is to provide an etching method that solves the problems of the prior art, is more practical, and allows for lower costs.
［課題を解決するための手段］
すなわち、上記課題を解決する本発明のエツチング方法
は２〜３５重量％の水酸化第四アンモニウムと８〜２３
重量％のアミン化合物と １５重量％以上の尿素とを含
み、かつ、その液温が３０〜゛７０℃の溶液をエツチン
グ液として用いるものである。[Means for Solving the Problems] That is, the etching method of the present invention for solving the above problems uses 2 to 35% by weight of quaternary ammonium hydroxide and 8 to 23% by weight of quaternary ammonium hydroxide.
A solution containing 15% by weight or more of an amine compound and 15% by weight or more of urea and having a temperature of 30 to 70°C is used as the etching solution.
本発明で用いうる水酸化第四アンモニウムとは、水酸化
テトラメチルアンモニウム、水酸化テトラエチルアンモ
ニウム等であり、アミン化合物とは、エチレンジアミン
、キシレンジアミン、トリメチレンジアミン、メチレン
ジアミン、プロピレンジアミン、テトラメチレンジアミ
ン、へ牛すメチレンジアミン、ペンタメチレンジアミン
等である。Quaternary ammonium hydroxide that can be used in the present invention includes tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and amine compounds include ethylenediamine, xylenediamine, trimethylenediamine, methylenediamine, propylenediamine, and tetramethylenediamine. , hexamethylenediamine, pentamethylenediamine, etc.
［作用］
本発明において、エツチング液中の水酸化第四アンモニ
ウム濃度を低くすると工・ソチング能力が極端に低下す
る。しかし、高すぎるとエツチング能力は大きくなるも
のの、寸法安定性が悪化する。[Function] In the present invention, when the concentration of quaternary ammonium hydroxide in the etching solution is lowered, the etching/soching ability is extremely reduced. However, if it is too high, the etching ability will increase, but the dimensional stability will deteriorate.
−このため、エツチング液中の水酸化第四アンモニウム
の濃度は２〜３５重量％（以下％と示す。）とすること
が必要である。また、エツチング液中のアミン化合物の
量が少ないと工、２チング能力が低下して実用的でなく
なり、多すぎるとエツチング能力は高くなるものの寸法
精度が悪化する。このため、アミン化合物の濃度は８〜
２３％とすることが必要である。尿素はエツチング能力
を太き（する作用よりもスルーホールの形状を良好にす
る作用が大きい。この作用を充分発揮させるためにはそ
の濃度は１５％以上とすることが必要である。- Therefore, it is necessary that the concentration of quaternary ammonium hydroxide in the etching solution be 2 to 35% by weight (hereinafter referred to as %). Furthermore, if the amount of the amine compound in the etching solution is too small, the etching ability will be reduced, making it impractical; if it is too large, the etching ability will be high, but the dimensional accuracy will be deteriorated. Therefore, the concentration of the amine compound is 8~
It is necessary to set it to 23%. Urea has a greater effect on improving the shape of the through-hole than increasing the etching ability. In order to fully exhibit this effect, its concentration must be 15% or more.
エツチング温度は高ければ高いほどエツチング速度が上
昇するが、反面寸法精度が低下する。このため、良好な
エツチング速度と寸法精度とを得るためにはエツチング
温度を３０〜７０℃にする必要がある。The higher the etching temperature is, the higher the etching rate will be, but on the other hand, the dimensional accuracy will be lower. Therefore, in order to obtain good etching speed and dimensional accuracy, it is necessary to set the etching temperature to 30 to 70°C.
本発明者は、本発明の方法で生じているエツチング機構
は、水酸化第四アンモニウム及び尿素の加水分解によっ
て生じたアンモニアによりイミド環の分断と低分子化が
起こり、次いでアミン化合物によりアミド化が起こり、
次いで溶解するものと推定している。The present inventor believes that the etching mechanism that occurs in the method of the present invention is that the imide ring is fragmented and reduced in molecular weight by ammonia generated by the hydrolysis of quaternary ammonium hydroxide and urea, and then amidation occurs by the amine compound. happened,
It is estimated that it will then dissolve.
なお、本発明の実施において、用いるエツチングレジス
トは耐薬品性の面よりビスアジド系環化天然ゴムや環化
ブタジェンゴム等のゴム系レジストとすることが望まし
く。レジストの厚さは、形成した膜中にピンホールを生
じさせないようにするために２μｍ以上とすることが必
要であり、パターン寸法精度を低下させないようにする
ために１０μｍ以下とすることが好ましい。In the practice of the present invention, the etching resist used is preferably a rubber-based resist such as bisazide-based cyclized natural rubber or cyclized butadiene rubber from the viewpoint of chemical resistance. The thickness of the resist needs to be 2 μm or more to prevent pinholes from forming in the formed film, and preferably 10 μm or less to avoid deteriorating pattern dimensional accuracy.
［実施例］
厚さ ５０μｍのポリイミドフィルム（商品名 カプト
ン 東し・デニボン社製）の全面に、ビスアジド系環化
天然ゴムをベースとしたフォトレジスト（商品名ＦＳＲ
富士薬品工業社製）をホワイラーで塗布した後、７０℃
で３０分間乾燥し、５〜７μｍの厚さのレジスト膜を形
成した。次いで片面に所定のマスクを設け、両面に１１
０ ｍｊの紫外線を照射してレジストを感光させた。そ
の後現像し、１３０℃で３０分間ポストベークを行ない
部分的にポリイミドフィルムの露出面を持つパターンを
形成した。次いで、１０．２％の水酸化テトラメチルア
ンモニウムと２０．４％のエチレンジアミンと ２８．
６％の尿素とを含む溶液を５０℃に加温し、前記ポリイ
ミドフィルムをこのエツチング液に浸せきしてエツチン
グを行なった。その結果、得られた孔の寸法はマスクと
ほぼ同一であり、スルーホールの形状も良好であった。[Example] A photoresist (product name: FSR) based on bisazide-based cyclized natural rubber was applied to the entire surface of a 50 μm thick polyimide film (product name: Kapton, manufactured by Toshi Denibon Co., Ltd.).
After applying Fuji Pharmaceutical Co., Ltd.) with a whiter, the temperature was 70°C.
The resist film was dried for 30 minutes to form a resist film with a thickness of 5 to 7 μm. Next, a prescribed mask is provided on one side, and 11
The resist was exposed to ultraviolet light of 0 mj. Thereafter, it was developed and post-baked at 130° C. for 30 minutes to form a pattern having a partially exposed surface of the polyimide film. Then 10.2% tetramethylammonium hydroxide and 20.4% ethylenediamine 28.
A solution containing 6% urea was heated to 50° C., and the polyimide film was immersed in this etching solution for etching. As a result, the dimensions of the holes obtained were almost the same as those of the mask, and the shape of the through holes was also good.
［発明の効果］
本発明の方法によれば、ヒドラジンを含まないので従来
のエツチング液よりも毒性が低く、かつ吸湿によるエツ
チング速度の低下がなく、コストが安くなり、実操業で
容易に使用できるようになるばかりか寸法制度の良い孔
を形成できる。[Effects of the Invention] According to the method of the present invention, since it does not contain hydrazine, it is less toxic than conventional etching solutions, does not reduce the etching rate due to moisture absorption, is inexpensive, and can be easily used in actual operations. Not only this, but also holes with good dimensional accuracy can be formed.
Claims (1)
量％のアミン化合物と１５重量％以上の尿素とを含み、
かつ、その液温が３０〜７０℃の溶液をエッチング液と
して用いることを特徴とするポリイミドフィルムのエッ
チング方法。Containing 2 to 35% by weight of quaternary ammonium hydroxide, 8 to 23% by weight of an amine compound, and 15% by weight or more of urea,
A method for etching a polyimide film, characterized in that a solution having a liquid temperature of 30 to 70°C is used as an etching liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12413990A JPH0420540A (en) | 1990-05-16 | 1990-05-16 | Method of etching polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12413990A JPH0420540A (en) | 1990-05-16 | 1990-05-16 | Method of etching polyimide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0420540A true JPH0420540A (en) | 1992-01-24 |
Family
ID=14877890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12413990A Pending JPH0420540A (en) | 1990-05-16 | 1990-05-16 | Method of etching polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0420540A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2718454A1 (en) * | 1994-04-11 | 1995-10-13 | Samsung Electronics Co Ltd | Method for treating a polyimide surface. |
-
1990
- 1990-05-16 JP JP12413990A patent/JPH0420540A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2718454A1 (en) * | 1994-04-11 | 1995-10-13 | Samsung Electronics Co Ltd | Method for treating a polyimide surface. |
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