JPH0415233A - Etching of polyimide film - Google Patents
Etching of polyimide filmInfo
- Publication number
- JPH0415233A JPH0415233A JP11772190A JP11772190A JPH0415233A JP H0415233 A JPH0415233 A JP H0415233A JP 11772190 A JP11772190 A JP 11772190A JP 11772190 A JP11772190 A JP 11772190A JP H0415233 A JPH0415233 A JP H0415233A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- polyimide film
- urea
- present
- alkali
- 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 42
- 229920001721 polyimide Polymers 0.000 title claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 7
- -1 amine compound Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 3
- 230000007423 decrease Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture 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
- 206010061218 Inflammation Diseases 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 231100001231 less toxic Toxicity 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
- 235000011118 potassium hydroxide Nutrition 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
- 238000009331 sowing Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
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・ソチング方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for processing and sowing 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がある。[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. Through-holes must be formed 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が試みられてきているが
、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、エツチングが開始
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, methods using highly concentrated alkaline aqueous solutions and hydrazine have been attempted as methods for etching polyimide films efficiently and with high precision, but with highly concentrated alkaline aqueous solutions, sufficient etching cannot be achieved under normal conditions. However, in the method using hydrazine, there is a long time lag before etching starts, and during that time the hydrazine is exposed to the polyimide film. It is said that the metal penetrates into the inside of the hole and causes swelling, resulting in the inability 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
μｍｎ ７ｍ ｉｎ程度と大きいことが知られている。[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 to be as large as about 7 min.
しかし、ヒドラ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。However, hydrazine is highly hygroscopic and absorbs moisture over time.
Hydrazine concentration decreases. 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 inhalation of its vapor causes inflammation of mucous membranes, making it impractical to handle in 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.
し課題を解決するための手段］
本発明者は、種々検討した結果、特定の組成の溶液を用
いれば、実用上支障のないエツチング速度が得られ、か
つコストの低下を可能とすることを見出し本発明に至っ
た。[Means for Solving the Problems] As a result of various studies, the present inventor found that by using a solution with a specific composition, it is possible to obtain an etching rate that does not pose any practical problem and also to reduce costs. This led to the present invention.
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２．２〜１６重量％のアルカリと １４〜２２重量％
のアミン化合物と１４重量％以上の尿素とを含み、液温
５０〜７０℃の水溶液をエツチング液として用いるもの
である。That is, the etching method of the present invention that solves the above problems uses 2.2 to 16% by weight of alkali and 14 to 22% by weight.
An aqueous solution containing an amine compound of 14% by weight or more and urea of 14% by weight or more and having a liquid temperature of 50 to 70°C is used as an etching liquid.
本発明で用いうるアルカリは、苛性ソーダと苛性カリ等
のアルカリ金属水酸化物であり、アミン化合物は、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、ヘキサメチレンジアミン、ペンタメチ
レンジアミン等である。The alkalis that can be used in the present invention are alkali metal hydroxides such as caustic soda and caustic potash, and the amine compounds include ethylenediamine, xylene diamine, trimethylene diamine, methylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine, and pentamethylene diamine. diamines, etc.
［作用コ
本発明において、エツチング液中のアルカリ濃度を低く
するとエツチング能力が極端に低下し、高くするとエツ
チング時に使用しうるレジストがなくなる。このため、
エツチング液中のアルカリ濃度は２．２〜１６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濃度が低いとエツチング能
力が低下して実用的でなくなり、高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１４〜２２％とすることが必要で
ある。尿素の量か少ないと得られるスルーホールの形状
を良好にできないが、あるＩ以上加えても、形状はそれ
以上良好にならない。[Operations] In the present invention, when the alkali concentration in the etching solution is low, the etching ability is extremely reduced, and when it is high, there is no resist that can be used during etching. For this reason,
The alkali concentration in the etching solution is 2.2 to 16% by weight (
Hereinafter, it is indicated as %. ). Furthermore, if the concentration of the amine compound in the etching solution is too low, the etching ability will be reduced, making it impractical; if it is too high, the etching ability will be high, but the dimensional accuracy will be deteriorated. For this reason,
It is necessary that the concentration of the amine compound be 14-22%. If the amount of urea is too small, the shape of the resulting through-hole cannot be made good, but even if more than a certain amount I is added, the shape cannot be made any better.
このため、尿素濃度は１４％以上とすることが必要であ
る。なお、本発明のエツチング液組成では、尿素の溶解
度は約４０％が上限である。For this reason, it is necessary that the urea concentration be 14% or more. In the etching solution composition of the present invention, the upper limit of the solubility of urea is about 40%.
以下、実施例と図とを用いて本発明をさらに説明する。Hereinafter, the present invention will be further explained using examples and figures.
（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・デュポン社性）を３０１１１１１１角に裁断し
、４．８％のＮａＯＨと １９．３％のエチレンジアミ
ン所定量の尿素を含む溶液をエツチング液とし、この液
を所定温度に維持しつつ前記ポリイミドフィルムを浸せ
きし、エツチング速度を測定した。この結果より求めた
加えた尿素濃度と温度とエツチング速度との関係を第１
図に示した。第１図において、Ａはエツチング温度は７
０”Ｃ１Ｂは６０℃、Ｃは５０℃での結果であり、△、
口、○はそれぞれ形状が良好な物となったことを示し、
ム、閣、・はそれぞれ不良となった物を示す。(Example) A polyimide film with a thickness of 50 μm (trade name: Kapton Toshi, DuPont) was cut into 30111111 squares and etched with a solution containing 4.8% NaOH and 19.3% ethylenediamine in a predetermined amount of urea. The polyimide film was immersed in this solution while maintaining it at a predetermined temperature, and the etching rate was measured. The relationship between the added urea concentration, temperature, and etching rate obtained from this result is
Shown in the figure. In Figure 1, A is an etching temperature of 7.
0"C1B is the result at 60℃, C is the result at 50℃, △,
The mouth and ○ indicate that the shape is good,
Mu, Kaku, and . each indicate defective items.
本発明者は、種々の実用化のための条件を検討し、その
結果、エツチング速度は、寸法精度を優先させる場合に
は、１μｍ ／ ｍｉｎ以上であれば良いことを見出し
たが、この条件を満足させるためには、第１図より尿素
濃度を１４％以上とし、エツチング温度を５０℃以上と
しなければならないことがわかる。エツチング温度が高
ければ高いほどエツチング速度は速くなるが、エツチン
グ溶液がアルカリ性であるため、７０”Ｃ以下とする法
が作業環境上好ましい。The present inventor investigated various conditions for practical use and found that when giving priority to dimensional accuracy, the etching speed should be 1 μm/min or more. In order to satisfy the requirements, it can be seen from FIG. 1 that the urea concentration must be 14% or higher and the etching temperature must be 50° C. or higher. The higher the etching temperature, the faster the etching rate, but since the etching solution is alkaline, it is preferable to set the etching temperature to 70''C or less in view of the working environment.
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、アルカリと尿素との反応により生じたアンモニアに
よりイミド環が分断され、低分子化が起こり、次いでア
ミンによりアミド化が起こり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 by ammonia generated by the reaction between an alkali and urea, resulting in lower molecular weight, and then amidation occurs with the amine and dissolves. It is estimated that
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１０μ−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 must 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. .
［実施例コ
厚さ ５０μｍのポリイミドフィルム（商品名カプトン
東し・デュポン社製）の表面上に、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°
Ｃで３０分間乾燥し、５〜７μ真の厚さのレジスト膜を
形成した。次いで、所定のマスクを通して１１０ 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°Ｃ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、１３．３％のＮａＯＨと１７．７％のとエ
チレンジアミンと２４．６％の尿素を含む本発明のエツ
チング液を５０°Ｃに加温、保持し、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。この結果、マスク寸法とほぼ同じ寸法の孔を形
成できた。[Example] A photoresist (product name: FSR) based on bisazide-based cyclized natural rubber was applied on the surface of a polyimide film (product name: Kapton, manufactured by DuPont) with a thickness of 50 μm.
After applying Fuji Pharmaceutical Co., Ltd.) with a whirler, 70°
C for 30 minutes to form a resist film with a true thickness of 5 to 7 μm. Then, through a predetermined mask, 110 mj
The resist was exposed to ultraviolet light. 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. Next, the etching solution of the present invention containing 13.3% NaOH, 17.7% ethylenediamine, and 24.6% urea was heated and maintained at 50°C, and the polyimide film was immersed in this etching solution. Then I did the etching. As a result, holes with approximately the same dimensions as the mask dimensions could be formed.
［発明の効果コ
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
チング速度の低下かなく、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。[Effects of the Invention] The method of the present invention does not contain hydrazine, so it is less toxic than conventional etching solutions, does not reduce the etching rate due to moisture absorption, is less expensive, and can be easily used in actual operations. It becomes like this.
第１図は本発明の実施の１例を示したものである。 特許出願人 住友金属鉱山株式会社 FIG. 1 shows an example of implementation of the present invention. Patent applicant: Sumitomo Metal Mining Co., Ltd.
Claims (1)
アミン化合物と１４重量％以上の尿素とを含み、液温５
０〜７０℃の水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。Contains 2.2 to 16% by weight of alkali, 14 to 22% by weight of amine compound, and 14% by weight or more of urea, and has a liquid temperature of 5%.
A method for etching a polyimide film, characterized in that an aqueous solution at 0 to 70°C is used as an etching solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11772190A JPH0415233A (en) | 1990-05-09 | 1990-05-09 | Etching of polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11772190A JPH0415233A (en) | 1990-05-09 | 1990-05-09 | Etching of polyimide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0415233A true JPH0415233A (en) | 1992-01-20 |
Family
ID=14718649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11772190A Pending JPH0415233A (en) | 1990-05-09 | 1990-05-09 | Etching of polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0415233A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6783921B2 (en) | 2001-06-28 | 2004-08-31 | Sumitomo Electric Industries, Ltd. | Method for etching laminated assembly including polyimide layer |
| US9909063B2 (en) | 2010-11-03 | 2018-03-06 | 3M Innovative Properties Company | Polymer etchant and method of using same |
-
1990
- 1990-05-09 JP JP11772190A patent/JPH0415233A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6783921B2 (en) | 2001-06-28 | 2004-08-31 | Sumitomo Electric Industries, Ltd. | Method for etching laminated assembly including polyimide layer |
| US9909063B2 (en) | 2010-11-03 | 2018-03-06 | 3M Innovative Properties Company | Polymer etchant and method of using same |
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