JP3965972B2 - Method for stabilizing quaternary ammonium salt hydrogen peroxide - Google Patents
Method for stabilizing quaternary ammonium salt hydrogen peroxide Download PDFInfo
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- JP3965972B2 JP3965972B2 JP2001341936A JP2001341936A JP3965972B2 JP 3965972 B2 JP3965972 B2 JP 3965972B2 JP 2001341936 A JP2001341936 A JP 2001341936A JP 2001341936 A JP2001341936 A JP 2001341936A JP 3965972 B2 JP3965972 B2 JP 3965972B2
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- Prior art keywords
- hydrogen peroxide
- tetramethylammonium hydroxide
- quaternary ammonium
- ammonium salt
- hydrogenated product
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- 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.)
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Description
【０００１】
【発明の属する技術分野】
本発明は、第四級アンモニウム塩の過酸化水素化物の安定化方法に関する。第四級アンモニウム塩の過酸化水素化物は、フォトレジスト層及びチタン酸化物を剥離する有用な物質である。
【０００２】
【従来の技術】
過酸化水素は、様々な化合物に配位して過酸化水素化物を形成する。過酸化水素化物とは、結晶水における水のように過酸化水素が化合物に配位したものを言う。過酸化水素化物として、フッ化カリウム、炭酸ルビジウム、尿素の過酸化水素化物が知られている。
【０００３】
一方、第四級アンモニウム塩にも過酸化水素が配位し、過酸化水素化物を形成する。第四級アンモニウム塩の過酸化水素化物は、チタン酸化物を水に可溶化する有用な物質であるが、白金などの金属と接触しても分解しない、アミン類と反応しないなど過酸化水素とは化学的性質が全く異なっている。この第四級アンモニウム塩の過酸化水素化物は安定な化合物であるが、室温でも除々に配位した過酸化水素が脱離するなどして分解する。
【０００４】
過酸化水素の安定剤としては、リン酸、サリチル酸、尿酸など多くの安定剤が知られている。しかし、サリチル酸や尿酸を第四級アンモニウム塩の過酸化水素化物に使用すると、第四級アンモニウム塩に配位した過酸化水素化物から過酸化水素が脱離するのを抑制できず、逆に脱離を促進し、分解してしまう。第四級アンモニウム塩の過酸化水素化物の分解は過酸化水素の分解と全く異なるため、第四級アンモニウム塩の過酸化水素化物の安定化方法が求められていた。
【０００５】
【発明が解決しようとする課題】
上述したように、有用な化合物である第四級アンモニウム塩の過酸化水素化物の安定化の方法は全く知られていない。
【０００６】
そのため、本発明の目的は、第四級アンモニウム塩の過酸化水素化物を安定化する方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、第四級アンモニウム塩であるテトラメチルアンモニウムヒドロキシドの過酸化水素化物の安定化方法について鋭意検討した結果、アニリン系化合物を添加する事により容易に安定化できることを見出し、本発明を完成させるに至った。
【０００８】
すなわち、本発明はアニリン系化合物を添加することを特徴とするテトラメチルアンモニウムヒドロキシドの過酸化水素化物の安定化方法である。
【０００９】
以下に本発明をさらに詳細に説明する。
【００１０】
本発明の方法において、テトラメチルアンモニウムヒドロキシドの過酸化水素化物とは、テトラメチルアンモニウムヒドロキシドに対し、結晶水における水のように過酸化水素が配位したものを言う。テトラメチルアンモニウムヒドロキシドの過酸化水素化物は、結晶の形で、空気中、室温で存在することも可能である。
【００１２】
過酸化水素化物はテトラメチルアンモニウムヒドロキシドと過酸化水素を混合し、加熱するか、もしくは触媒を加えて混合することで得られる。
【００１３】
本発明の方法において使用されるアニリン系化合物とは、アニリンおよびアセトアニリドを言う。
【００１４】
アニリンのベンゼン骨格上の水素原子の代わりに結合可能な置換基としては、例えば、アルキル基、アミノ基、ニトロ基、ヒドロキシ基、アルコキシ基、カルボキシル基（水素原子の代わりにアルキル基が結合している場合を含む）等をあげることができる。また、アニリンの窒素原子と結合している水素原子の代わりに結合可能な置換基としては、例えば、アルキル基、フェニル基、アセチル基等をあげることができる。
【００１６】
本発明の方法において、アニリン系化合物の添加量は、テトラメチルアンモニウムヒドロキシドの過酸化水素化物及び／又はその溶液への溶解性等を考慮して当業者が任意に添加することができるが、テトラメチルアンモニウムヒドロキシドの過酸化水素化物に対して０．００１〜１０モル％が好ましく、０．０１〜１０モル％が更に好ましい。この範囲で添加することにより、添加したアニリン系化合物が反応系内で十分溶解してテトラメチルアンモニウムヒドロキシドの過酸化水素化物を安定化することができる。
【００１７】
【実施例】
本発明を以下の実施例により更に詳細に説明するが、本発明はこれらに限定されるものではない。
【００１８】
製造例（テトラメチルアンモニウムヒドロキシドの過酸化水素化物の製造）
５９０ｇの１５％テトラメチルアンモニウムヒドロキシド（０．９７ｍｏｌ）を８０℃に加熱し、これに３５％過酸化水素水１５０ｇ（１．５４ｍｏｌ）を滴下した。過剰の過酸化水素の分解による発泡がなくなるまで加熱し、その後、減圧下、水を留去し、テトラメチルアンモニウムヒドロキシドの過酸化水素化物を得た。
【００１９】
このテトラメチルアンモニウムヒドロキシドの過酸化水素化物に水を加え、２５％水溶液にした。
【００２０】
分析方法
充填剤にビニルポリマーを基剤とした極性有機溶媒系ゲルろ過用充填剤（東ソー(株)製、商品名「ＴＳＫｇｅｌα２５００」）を充填したカラムを２本直列に接続し、溶離液にアセトニトリル＋４０％水＋０．５％アンモニアを用いた。この溶離液を流速０．８ｍｌ／ｍｉｎで流しながら試料を２０μｌ注入し、ＲＩおよびＵＶ検出器を用いて分析を行った。なお、分析方法は、特願２００１−３３６１４０号に記載の方法に従った。
【００２１】
実施例１
製造例１で製造した２５％テトラメチルアンモニウムヒドロキシドの過酸化水素化物水溶液６８．９ｇ（テトラメチルアンモニウムヒドロキシドの過酸化水素化物０．１４ｍｏｌ含有）にアニリン０．７ｇ（７．０ｍｍｏｌ）を添加し、攪拌下、室温で３週間保存した。３週間後のテトラメチルアンモニウムヒドロキシドの過酸化水素化物を高速液体クロマトグラフィー（ＨＰＬＣ）により分析したところ、テトラメチルアンモニウムヒドロキシドの過酸化水素化物の０．５％が分解していた。
【００２２】
実施例２
製造例１で製造した２５％テトラメチルアンモニウムヒドロキシドの過酸化水素化物水溶液８０．１ｇ（テトラメチルアンモニウムヒドロキシドの過酸化水素化物０．１６ｍｏｌ含有）にアセトアニリド１．０ｇ（７．８ｍｍｏｌ）を添加し、攪拌下、室温で３週間保存した。３週間後のテトラメチルアンモニウムヒドロキシドの過酸化水素化物をＨＰＬＣにより分析したところ、テトラメチルアンモニウムヒドロキシドの過酸化水素化物の２％が分解していた。
【００２３】
比較例１
製造例１で製造した２５％テトラメチルアンモニウムヒドロキシドの過酸化水素化物を攪拌下、室温で２週間保存した。２週間保存後のテトラメチルアンモニウムヒドロキシドの過酸化水素化物水溶液をＨＰＬＣで分析したところ、テトラメチルアンモニウムヒドロキシドの過酸化水素化物の７０％が分解していた。
【００２４】
比較例２
製造例1で製造した２５％テトラメチルアンモニウムヒドロキシドの過酸化水素化物１４７．５ｇ（テトラメチルアンモニウムヒドロキシドの過酸化水素化物０．２９ｍｏｌ含有）に尿酸２．４ｇ（１４．４ｍｍｏｌ）を添加し、攪拌下１週間放置した。１週間後のテトラメチルアンモニウムヒドロキシドの過酸化水素化物をＨＰＬＣにより分析したところ、テトラメチルアンモニウムヒドロキシドの過酸化水素化物の６５％が分解していた。
【００２５】
【発明の効果】
本発明の安定化方法は、レジスト剥離剤、チタン酸化物剥離剤として有用なテトラメチルアンモニウムヒドロキシドの過酸化水素化物の分解を抑制する方法であり、その工業的価値は高い。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for stabilizing a hydrogenated product of a quaternary ammonium salt. Quaternary ammonium salt hydrogen peroxide is a useful material for stripping the photoresist layer and titanium oxide.
[0002]
[Prior art]
Hydrogen peroxide coordinates to various compounds to form hydrogen peroxide. The hydrogen peroxide is a compound in which hydrogen peroxide is coordinated to a compound like water in crystal water. Known hydrogen peroxides include potassium fluoride, rubidium carbonate, and urea.
[0003]
On the other hand, hydrogen peroxide is coordinated to the quaternary ammonium salt to form a hydrogen peroxide. Quaternary ammonium salt hydrogen peroxide is a useful substance that solubilizes titanium oxide in water. However, it does not decompose even when it comes into contact with metals such as platinum, and does not react with amines. Are completely different in chemical properties. This hydrogenated product of the quaternary ammonium salt is a stable compound, but decomposes at room temperature, for example, by gradually desorbing the coordinated hydrogen peroxide.
[0004]
As stabilizers for hydrogen peroxide, many stabilizers such as phosphoric acid, salicylic acid, and uric acid are known. However, if salicylic acid or uric acid is used as a quaternary ammonium salt hydrogen peroxide, it cannot be prevented from desorbing from the hydrogen peroxide coordinated to the quaternary ammonium salt. It promotes separation and decomposes. Since the decomposition of the quaternary ammonium salt hydrogenated product is completely different from the decomposition of hydrogen peroxide, a method for stabilizing the quaternary ammonium salt hydrogenated product has been demanded.
[0005]
[Problems to be solved by the invention]
As described above, there is no known method for stabilizing a hydrogenated product of a quaternary ammonium salt, which is a useful compound.
[0006]
Therefore, an object of the present invention is to provide a method for stabilizing a hydrogenated product of a quaternary ammonium salt.
[0007]
[Means for Solving the Problems]
As a result of intensive investigations on the method for stabilizing the hydrogenated product of tetramethylammonium hydroxide, which is a quaternary ammonium salt, the present inventors have found that it can be easily stabilized by adding an aniline compound. The invention has been completed.
[0008]
That is, the present invention is a method for stabilizing a hydrogenated product of tetramethylammonium hydroxide , characterized by adding an aniline compound.
[0009]
The present invention is described in further detail below.
[0010]
In the method of the present invention, the tetramethylammonium hydroxide peroxyhydrate, to tetramethylammonium hydroxide, refers to hydrogen peroxide as the water in the crystal water is coordinated. Tetramethylammonium hydroxide hydrogen peroxide may be present in the form of crystals in air at room temperature.
[0012]
Peroxide hydride mixing tetramethylammonium hydroxide and hydrogen peroxide, it is obtained by adding and mixing the heated either, or catalyst.
[0013]
The aniline-based compound used in the method of the present invention refers to aniline and acetanilide .
[0014]
Examples of substituents that can be bonded instead of hydrogen atoms on the benzene skeleton of aniline include, for example, alkyl groups, amino groups, nitro groups, hydroxy groups, alkoxy groups, carboxyl groups (in which And the like). In addition, examples of the substituent that can be bonded instead of the hydrogen atom bonded to the nitrogen atom of aniline include an alkyl group, a phenyl group, and an acetyl group.
[0016]
In the method of the present invention, the addition amount of the aniline compound can be arbitrarily added by those skilled in the art in consideration of the hydrogen peroxide of tetramethylammonium hydroxide and / or its solubility in a solution, 0.001-10 mol% is preferable with respect to the hydrogenated product of tetramethylammonium hydroxide , and 0.01-10 mol% is still more preferable. By adding in this range, the added aniline compound can be sufficiently dissolved in the reaction system, and the hydrogenated product of tetramethylammonium hydroxide can be stabilized.
[0017]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[0018]
Production example (production of hydrogenated product of tetramethylammonium hydroxide )
590 g of 15% tetramethylammonium hydroxide (0.97 mol) was heated to 80 ° C., and 150 g (1.54 mol) of 35% aqueous hydrogen peroxide was added dropwise thereto. The mixture was heated until foaming due to decomposition of excess hydrogen peroxide disappeared, and then water was distilled off under reduced pressure to obtain a hydrogenated product of tetramethylammonium hydroxide.
[0019]
Water was added to the hydrogenated product of tetramethylammonium hydroxide to make a 25% aqueous solution.
[0020]
Analysis method Two columns filled with a packing material for polar organic solvent gel filtration (trade name “TSKgel α2500” manufactured by Tosoh Corporation) based on vinyl polymer as a packing material are connected in series, and acetonitrile is used as an eluent. + 40% water + 0.5% ammonia was used. 20 μl of sample was injected while flowing this eluent at a flow rate of 0.8 ml / min, and analysis was performed using RI and UV detectors. The analysis method followed the method described in Japanese Patent Application No. 2001-336140.
[0021]
Example 1
0.7 g (7.0 mmol) of aniline was added to 68.9 g of the 25% tetramethylammonium hydroxide hydrogen peroxide aqueous solution prepared in Production Example 1 (containing 0.14 mol of tetramethylammonium hydroxide hydrogen peroxide). And stored for 3 weeks at room temperature under stirring. When hydrogen peroxide of tetramethylammonium hydroxide after 3 weeks was analyzed by high performance liquid chromatography (HPLC), 0.5% of the hydrogenated product of tetramethylammonium hydroxide was decomposed.
[0022]
Example 2
Addition of 1.0 g (7.8 mmol) of acetanilide to 80.1 g of 25% tetramethylammonium hydroxide hydrogen peroxide aqueous solution (containing 0.16 mol of tetramethylammonium hydroxide hydrogen peroxide) prepared in Production Example 1 And stored for 3 weeks at room temperature under stirring. The hydrogen peroxide of tetramethylammonium hydroxide after 3 weeks was analyzed by HPLC. As a result, 2% of the hydrogen peroxide of tetramethylammonium hydroxide was decomposed.
[0023]
Comparative Example 1
The hydrogenated product of 25% tetramethylammonium hydroxide produced in Production Example 1 was stored for 2 weeks at room temperature under stirring. When the aqueous solution of tetramethylammonium hydroxide hydrogen peroxide after storage for 2 weeks was analyzed by HPLC, 70% of the tetramethylammonium hydroxide hydrogen peroxide was decomposed.
[0024]
Comparative Example 2
2.4 g (14.4 mmol) of uric acid was added to 147.5 g of the hydrogenated product of 25% tetramethylammonium hydroxide produced in Production Example 1 (containing 0.29 mol of the hydrogenated product of tetramethylammonium hydroxide). The mixture was allowed to stand for 1 week under stirring. One week later, the hydrogenated product of tetramethylammonium hydroxide was analyzed by HPLC. As a result, 65% of the hydrogenated product of tetramethylammonium hydroxide was decomposed.
[0025]
【The invention's effect】
The stabilization method of the present invention is a method for suppressing the decomposition of tetramethylammonium hydroxide hydrogen peroxide, which is useful as a resist stripper and a titanium oxide stripper, and has high industrial value.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001341936A JP3965972B2 (en) | 2001-11-07 | 2001-11-07 | Method for stabilizing quaternary ammonium salt hydrogen peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001341936A JP3965972B2 (en) | 2001-11-07 | 2001-11-07 | Method for stabilizing quaternary ammonium salt hydrogen peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003146949A JP2003146949A (en) | 2003-05-21 |
| JP3965972B2 true JP3965972B2 (en) | 2007-08-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001341936A Expired - Fee Related JP3965972B2 (en) | 2001-11-07 | 2001-11-07 | Method for stabilizing quaternary ammonium salt hydrogen peroxide |
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| Country | Link |
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| JP (1) | JP3965972B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007039595A (en) * | 2005-08-05 | 2007-02-15 | Kao Corp | Liquid bleaching detergent composition |
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| JP2003146949A (en) | 2003-05-21 |
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