JPS6120946A - Composition for peeling photoresist - Google Patents
Composition for peeling photoresistInfo
- Publication number
- JPS6120946A JPS6120946A JP14140284A JP14140284A JPS6120946A JP S6120946 A JPS6120946 A JP S6120946A JP 14140284 A JP14140284 A JP 14140284A JP 14140284 A JP14140284 A JP 14140284A JP S6120946 A JPS6120946 A JP S6120946A
- Authority
- JP
- Japan
- Prior art keywords
- peeling
- ch2cl2
- compsn
- photoresist
- epoxides
- 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
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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Detergent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
゛本発明は、安定性が改良・されたフォトレジスト剥離
用組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoresist stripping composition with improved stability.
各種部品を搭載し、接続する配線を絶縁体上に配線図形
で作成したプリント配線板は、片面１両面、又は多層配
線板等各種の形体が知られている。プリント配線板のパ
ターン作成には、パターン密度が高い場合、スクリーン
印刷法よりもフォトレジストを用いた写真法が好ましい
とされている。フォトレジストは露光→現像→エツチン
グ等の工程を経て最終的にはすべて剥離することが必要
である。このようなフォトレジストの剥離剤には持分、
昭５２−４５２４１号公報に記載された塩化メチレン及
びメタノールの混合物が知られている。フォトレジスト
剥離剤に要求される性能は、レジストの剥離能力が高い
ことの他プリント配線板に用いる各種材料、特に金属材
料に対して影響を与えないこと等が挙げられる。Printed wiring boards on which various parts are mounted and connecting wiring formed in the form of wiring diagrams on an insulator are known in various forms such as single-sided, double-sided, and multilayer wiring boards. When creating patterns for printed wiring boards, when the pattern density is high, a photographic method using a photoresist is said to be preferable to a screen printing method. The photoresist must undergo steps such as exposure, development, etching, and finally be stripped off. Such photoresist strippers include equity,
A mixture of methylene chloride and methanol described in Japanese Patent No. 52-45241 is known. The performance required of a photoresist stripping agent includes not only high resist stripping ability but also no influence on various materials used in printed wiring boards, especially metal materials.
本発明は、プリント配線板材質への影響が少なく安定性
の高いフォトレジスト剥離剤を新規に提供するものであ
り、塩化メチレン及びアルコール類を必須成分として含
むフォトレジスト剥離剤に、エポキサイド類及び／又は
アミン類を配合したことを特徴とするフートレジスト剥
離用組成物に関するものである。The present invention provides a new highly stable photoresist stripper that has little effect on printed wiring board materials, and includes epoxides and/or a photoresist stripper that contains methylene chloride and alcohols as essential components. Alternatively, the present invention relates to a footresist stripping composition characterized in that it contains an amine.
本発明におけるフォトレジスト剥離用組成物中の塩化メ
チレン及びアルコール類の配合割合は合計で９０ｗｔ％
以上、好ましくは９５ｗｔ％以上が適当である。これ以
下であると充分なフォトレジストの剥離能力が得られな
い、塩化メチレンとアルコール類の配合比は１両者の共
沸組成となる配合比付近を選択することが好ましいが、
実質的に不燃性とする必要があり、引火性のアルコール
類は引火点のない塩化メチレンに対し少量とすることも
重要である。例えば、塩化メチレンとメタノールでは約
１３：ｌ、塩化メチレンとインプロパツールでは約１２
＝１の配合比において共沸組成を形成し、実質的に不燃
性で問題はないが、エタノールでは９５ｗｔ％以上必要
であ、す、むしろ共沸組成は好ましくない。共沸組成あ
るいはその付近での使用は、蒸留再生使用時に、組成比
変動が大きくならず、剥離性能を一定に保てる利点があ
る。通常は塩化メチレンとアルコール類の配合比を７＝
１〜２５：ｌとすればよい。その他のアルコール類の好
適例には、ｎ−プロピルアルコール、ｎ−ブチルアルコ
ール、イソブチルアルコール、第２ブチルアルコール、
第３ブチルアルコール等の低級アルコール類がある。こ
れらのアルコール類は、本発明の目的を阻害しない限り
、２種以上混合使用することもできる。The total blending ratio of methylene chloride and alcohol in the photoresist stripping composition of the present invention is 90 wt%.
As mentioned above, preferably 95 wt% or more is appropriate. If it is less than this, sufficient photoresist stripping ability cannot be obtained.The blending ratio of methylene chloride and alcohol is preferably selected to be around a blending ratio that provides an azeotropic composition of both.
It is necessary to make it substantially non-flammable, and it is also important to use a small amount of flammable alcohols compared to methylene chloride, which has no flash point. For example, methylene chloride and methanol are about 13:l, and methylene chloride and impropatool are about 12:1.
At a blending ratio of 1, an azeotropic composition is formed, which is substantially nonflammable and poses no problem; however, in the case of ethanol, 95 wt % or more is required, and an azeotropic composition is rather undesirable. Use at or near an azeotropic composition has the advantage that the composition ratio does not fluctuate greatly during distillation regeneration and that the stripping performance can be kept constant. Usually, the mixing ratio of methylene chloride and alcohol is 7=
The ratio may be 1 to 25:l. Suitable examples of other alcohols include n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol,
There are lower alcohols such as tertiary butyl alcohol. Two or more of these alcohols may be used in combination as long as they do not impede the object of the present invention.
プリント配線板の絶縁部は、エポキシ樹脂やフェノール
樹脂と紙やガラスＨ＆維等との複合材から形成されてい
る。又、配線板の表面メッキには、スズー鉛メッキ、銅
メッキ、あるいは二・ブチルを下地とした金メッキ等が
用いられている。フォトレジスト剥離剤は、これらのプ
リント配線板を構成する各種材質に悪影響を与えず、又
剥離材自身も、特に金属等の影響により分解しないこと
が求められる。しかしながら、フォトレジスト剥離剤の
主要部を構成する塩化メチレンは、剥離力も優れ、不燃
性で、毒性も低いという特性を有するものの、金属、油
、酸素、光又は水分の共存下に蒸留再使用する際には１
分解する傾向が強く、その安定化は是非とも必要である
。一方、プリント配線板の材質に対する影響は、塩化メ
チレン自身ではなく、塩化メチレンが分解して生成する
酸によるものが大きく、この点からも塩化メチレンを含
む剥離剤の安定化は重要である。The insulating portion of the printed wiring board is made of a composite material of epoxy resin or phenol resin, paper, glass H&fiber, or the like. Furthermore, tin-lead plating, copper plating, gold plating with di-butyl as a base, etc. are used for surface plating of wiring boards. The photoresist stripping agent is required not to have an adverse effect on the various materials constituting these printed wiring boards, and the stripping agent itself is also required not to decompose, especially due to the influence of metals and the like. However, although methylene chloride, which constitutes the main component of photoresist strippers, has excellent stripping power, is nonflammable, and has low toxicity, it cannot be distilled and reused in the presence of metals, oil, oxygen, light, or moisture. Occasionally 1
It has a strong tendency to decompose, and its stabilization is absolutely necessary. On the other hand, the influence on the material of printed wiring boards is largely due to the acid generated by decomposition of methylene chloride, rather than the methylene chloride itself, and from this point of view as well, stabilization of stripping agents containing methylene chloride is important.
本発明における剥離剤は、エポキサイド類及び／又はア
ミン類を配合することにより、前述の安定化を良く達成
することができる。エポキサイド類としては分子内に少
なくとも１つの隣あり、具体的にはプロピレンオキサイ
ド、 １．２−ブチレンオキサイド、２．３−ブチレン
オキサイド、エピクロルヒドリン、スチレンオキサイド
、ブチルグリシジルエーテル、フェニルグリシ、ジルエ
ーテル、グリシドール等が好ましい。The above-mentioned stabilization can be well achieved by incorporating epoxides and/or amines into the release agent of the present invention. Epoxides have at least one neighbor in the molecule, and specifically include propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, styrene oxide, butyl glycidyl ether, phenylglycide, dyl ether, and glycidol. etc. are preferred.
特に好ましいエポキサイド類はエピクロルヒドリンやプ
ロピレンオキサイドである。エポキサイド類の配合量は
特に限定されるものではないが、剥離剤中に０．０２〜
３ ｗｔ％、好ましくは０．０５〜０．８ ｗｔ％の少
量で充分な安定化効果がある。Particularly preferred epoxides are epichlorohydrin and propylene oxide. The amount of epoxides added is not particularly limited, but is 0.02~
A small amount of 3 wt%, preferably 0.05 to 0.8 wt%, has a sufficient stabilizing effect.
アミン類としては、ジイソプロピルアミン。Diisopropylamine is an amine.
シクロヘキシルアミン、ジアリルアミン、トメチルヘン
シルアミン、 Ｎ、Ｎ−ジメチルベンジルアミン、Ｎ−
アルキルモルホリン等が好適でアリ、特に好ましいもの
は、ジイソプロピルアミン。Cyclohexylamine, diallylamine, tomethylhensylamine, N,N-dimethylbenzylamine, N-
Preferred are alkylmorpholines, and particularly preferred is diisopropylamine.
ジアリルアミン、Ｎ−メチルベンジルアミンである。ア
ミン類の配合量はエポキサイド類と同様、特に限定され
るものではなく、剥離剤中に０．００１〜０．１ ｗｔ
％、好ましくは０．０１〜０．０１３ｗｔ％の極微量配
合すればよく、これ以上配合しても不経済となるだけで
、効果に大きな差はない。diallylamine and N-methylbenzylamine. Similar to epoxides, the amount of amines blended is not particularly limited, and may be 0.001 to 0.1 wt in the release agent.
%, preferably 0.01 to 0.013 wt%, and even if more than this is added, it will only become uneconomical and there will be no significant difference in effect.
本発明における剥離剤にはその他の溶剤を配合してもよ
く、例えば塩化メチレン及びアルコール類に、１，２−
ジクロルエタンを０４２〜７ｗｔ％、好ましくは０．５
〜５ｗｔ％配合することにより、剥離性能がさらに向上
し、剥離スピードを上げることができる。１．２−ジク
ロルエタンは、メタノールやイソプロパツールと同程度
の引火点を有するものの、塩化メチレンに対する配合量
はこれらのアルコールよりも少量の添加で効果があり、
１．２−ジクロルエタンの添加によっても、実質的に不
燃性とすることができる。The stripping agent of the present invention may contain other solvents, such as methylene chloride and alcohols, 1,2-
042 to 7 wt% dichloroethane, preferably 0.5
By incorporating ~5wt%, the peeling performance can be further improved and the peeling speed can be increased. Although 1.2-dichloroethane has a flash point similar to that of methanol and isopropanol, it is effective when added in a smaller amount to methylene chloride than these alcohols.
Addition of 1,2-dichloroethane can also make it substantially nonflammable.
本発明の剥離用組成物により剥離し得るフォトレジスト
としては、何ら限定されず、ポジ型又はネカ型の光露光
用レジスト、遠紫外露光用レジスト、Ｘ線又は電子線用
レジストを挙げることができる。光露光用レジストの材
質ニハフェノール及びタレゾールノボラック樹脂をベー
スにしたキノンジアジド系、シス−１，４−ポリイソプ
レンを主成分とする環化ゴム系、ポリけい皮酸系等があ
り、遠紫外用レジストにはポリメチルメタアクリレート
、ポリメチルイソプロペニルケトン等があり、電子線、
Ｘ線しジストｊこはポリメタクリル酸メチル、メタクリ
ル酸グリシジル−アクリル酸エチル共重合体、メタクリ
ル酸メチル−メタクリル酸共重合体等が知られているが
、本発明の剥離用組成物はいずれにも有効である。The photoresist that can be peeled off with the stripping composition of the present invention is not limited in any way, and examples thereof include positive type or negative type light exposure resists, deep ultraviolet exposure resists, and X-ray or electron beam resists. . Resist materials for light exposure include quinone diazide based on Nihaphenol and Talezol novolac resins, cyclized rubber based on cis-1,4-polyisoprene, polycinnamic acid, etc. For deep ultraviolet use. Resists include polymethyl methacrylate, polymethyl isopropenyl ketone, etc.
For X-ray stripping, polymethyl methacrylate, glycidyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-methacrylic acid copolymer, etc. are known, but the stripping composition of the present invention can be used with any of them. is also valid.
本発明の剥離用組成物は、特にプリント配線板製造時の
フォトレジスト剥離に適しているが、その他のフォトレ
ジスト応用分野例えば、半導体、リードフレーム、ＴＶ
用ラシャドウマスクの電子部品分野をはしめ、金属、セ
ラミ・ンク、カラス等の蝕刻分野における剥離剤として
も極めて効果的である。The stripping composition of the present invention is particularly suitable for stripping photoresists during the production of printed wiring boards, but is also suitable for other photoresist application fields such as semiconductors, lead frames, and TVs.
It is extremely effective as a remover in the field of electronic parts for ray shadow masks, and also in the field of etching of metals, ceramic ink, glass, etc.
以下、本発明の実施例についてさらに具体的に説明する
。Examples of the present invention will be described in more detail below.
実施例１［安定性能］
鉄片、水分、酸素を共存させ、光照射下に加熱還流を７
日間行ない、鉄片の状態及び安定性能評価前後の液のｐ
Ｈを測定することにより、本発明の剥離剤の安定性能を
評価した。結果を第１表に−示す。Example 1 [Stability performance] Iron pieces, moisture, and oxygen were allowed to coexist, and heated under reflux under light irradiation for 7
The condition of the iron piece and the p of the liquid before and after stability performance evaluation were conducted for several days.
The stability performance of the release agent of the present invention was evaluated by measuring H. The results are shown in Table 1.
Claims (1)
ォトレジスト剥離剤に、エポキサイド類及び／又はアミ
ン類を配合したことを特徴とするフォトレジスト剥離用
組成物。1. A photoresist stripping composition comprising a photoresist stripping agent containing methylene chloride and alcohol as essential components, and epoxides and/or amines added thereto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14140284A JPS6120946A (en) | 1984-07-10 | 1984-07-10 | Composition for peeling photoresist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14140284A JPS6120946A (en) | 1984-07-10 | 1984-07-10 | Composition for peeling photoresist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6120946A true JPS6120946A (en) | 1986-01-29 |
| JPH0374828B2 JPH0374828B2 (en) | 1991-11-28 |
Family
ID=15291166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14140284A Granted JPS6120946A (en) | 1984-07-10 | 1984-07-10 | Composition for peeling photoresist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6120946A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330848A (en) * | 1986-07-21 | 1988-02-09 | エルフ アトケム ソシエテ アノニム | Composition mainly composed of methylene chloride and removal of photoresist film applying the same |
| JPH01158444A (en) * | 1987-03-11 | 1989-06-21 | Tokyo Ohka Kogyo Co Ltd | Photoresist remover |
| US5399202A (en) * | 1991-12-19 | 1995-03-21 | Hitachi, Ltd. | Resist-peeling liquid and process for peeling a resist using the same |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4913103A (en) * | 1972-04-07 | 1974-02-05 | ||
| JPS49116012A (en) * | 1973-02-23 | 1974-11-06 | ||
| JPS49135905A (en) * | 1973-05-16 | 1974-12-27 | ||
| JPS49135904A (en) * | 1973-05-16 | 1974-12-27 | ||
| JPS49135903A (en) * | 1973-05-16 | 1974-12-27 | ||
| JPS5217003A (en) * | 1975-07-30 | 1977-02-08 | Hitachi Maxell Ltd | Magnetic recording tape |
| JPS5217002A (en) * | 1975-07-30 | 1977-02-08 | Toshiba Corp | Manufaceuring method of pick-up cantilever |
| JPS5245241A (en) * | 1975-10-08 | 1977-04-09 | Hitachi Metals Ltd | Wide-band concentrated constant type circulator |
| JPS5545636A (en) * | 1978-09-28 | 1980-03-31 | Toagosei Chem Ind Co Ltd | Stabilization of methylene chloride |
| JPS5597479A (en) * | 1978-12-01 | 1980-07-24 | Dow Chemical Europ | Stabilized methylene chloride composition for steam rendering |
| JPS5637212A (en) * | 1979-08-29 | 1981-04-10 | Kyoritsu Yuki Kogyo Kenkyusho:Kk | Activated carbon dehydrating method |
| JPS56113715A (en) * | 1980-02-12 | 1981-09-07 | Shin Etsu Chem Co Ltd | Methylene chloride composition |
| JPS56131530A (en) * | 1980-08-05 | 1981-10-15 | Tokuyama Soda Co Ltd | Stabilizing method of methylene chloride |
| JPS59487A (en) * | 1982-06-23 | 1984-01-05 | 東洋エクステリア株式会社 | Extensible gate door |
-
1984
- 1984-07-10 JP JP14140284A patent/JPS6120946A/en active Granted
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4913103A (en) * | 1972-04-07 | 1974-02-05 | ||
| JPS49116012A (en) * | 1973-02-23 | 1974-11-06 | ||
| JPS49135905A (en) * | 1973-05-16 | 1974-12-27 | ||
| JPS49135904A (en) * | 1973-05-16 | 1974-12-27 | ||
| JPS49135903A (en) * | 1973-05-16 | 1974-12-27 | ||
| JPS5217003A (en) * | 1975-07-30 | 1977-02-08 | Hitachi Maxell Ltd | Magnetic recording tape |
| JPS5217002A (en) * | 1975-07-30 | 1977-02-08 | Toshiba Corp | Manufaceuring method of pick-up cantilever |
| JPS5245241A (en) * | 1975-10-08 | 1977-04-09 | Hitachi Metals Ltd | Wide-band concentrated constant type circulator |
| JPS5545636A (en) * | 1978-09-28 | 1980-03-31 | Toagosei Chem Ind Co Ltd | Stabilization of methylene chloride |
| JPS5597479A (en) * | 1978-12-01 | 1980-07-24 | Dow Chemical Europ | Stabilized methylene chloride composition for steam rendering |
| JPS5637212A (en) * | 1979-08-29 | 1981-04-10 | Kyoritsu Yuki Kogyo Kenkyusho:Kk | Activated carbon dehydrating method |
| JPS56113715A (en) * | 1980-02-12 | 1981-09-07 | Shin Etsu Chem Co Ltd | Methylene chloride composition |
| JPS56131530A (en) * | 1980-08-05 | 1981-10-15 | Tokuyama Soda Co Ltd | Stabilizing method of methylene chloride |
| JPS59487A (en) * | 1982-06-23 | 1984-01-05 | 東洋エクステリア株式会社 | Extensible gate door |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330848A (en) * | 1986-07-21 | 1988-02-09 | エルフ アトケム ソシエテ アノニム | Composition mainly composed of methylene chloride and removal of photoresist film applying the same |
| JPH0449939B2 (en) * | 1986-07-21 | 1992-08-12 | Atochem | |
| JPH01158444A (en) * | 1987-03-11 | 1989-06-21 | Tokyo Ohka Kogyo Co Ltd | Photoresist remover |
| US5399202A (en) * | 1991-12-19 | 1995-03-21 | Hitachi, Ltd. | Resist-peeling liquid and process for peeling a resist using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0374828B2 (en) | 1991-11-28 |
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