JP3965966B2 - Method for stabilizing quaternary ammonium salt hydrogen peroxide - Google Patents

Description

（式中Ｒ₁は水素原子またはメチル基を表し、置換基Ａは、−ＣＨ₂−、＝ＣＨＯＨ、＝ＣＨ−Ｏ−ＣＯ−Ｒ₂、または−ＣＯ−の２価の基を示す。Ｒ₂は、官能基を有していてもよいアルキル基またはアリール基を表す。）
に示すような化合物を例示することができる。Ｒ₁は、水素原子またはメチル基を示し、置換基Ａは、−ＣＨ₂−、−ＣＨＯＨ−、＝ＣＨ−Ｏ−ＣＯ−Ｒ₂、または−ＣＯ−の２価の基を示す。Ｒ₂としては、官能基を有していてもよいアルキル基またはアリール基を表し、炭素数１〜８が好ましい。
【００１５】
本発明の方法において用いることができるヒンダードアミンの具体例としては、２，２，６，６−テトラメチル−４−ピペリドン、１，２，２，６，６−ペンタメチル−４−ピペリドン、２，２，６，６−テトラメチルピペリジン、１，２，２，６，６−ペンタメチルピペリジン、２，２，６，６−テトラメチル−４−ピペリジノール、１，２，２，６，６−ペンタメチル−４−ピペリジノール、クロトン酸−（２，２，６，６−テトラメチル−４−ピペリデニル）エステル、クロトン酸−（１，２，２，６，６−ペンタメチル−４−ピペリデニル）エステル、コハク酸−ビス（２，２，６，６−テトラメチル−４−ピペリデニル）−エステル、マロン酸−ビス（２，２，６，６−テトラメチル−４−ピペリデニル）−エステル、セバシン酸−ビス（２，２，６，６−テトラメチル−４−ピペリデニル）−エステル等を挙げることができる。
【００１６】
本発明の方法において、ヒンダードアミンの有効添加量は、水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％、さらには０．０１〜１０モル％の範囲で添加することが好ましい。添加量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モル％未満の場合、安定化の効果が見られない場合があり、１０モル％を超えて添加してもヒンダードアミンが溶解しないときがあるため、安定剤を増やした効果が小さい場合がある。
【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（ｐＨ＝１０．７）。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１５１．２ｇ（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０．３ｍｏｌ含有）に、２，２，６，６−テトラメチルピペリジン２．１ｇ（１４．８ｍｍｏｌ）を添加し、攪拌下、室温で３週間保存した。添加前および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０．２％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１５１．０ｇ（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０．３ｍｏｌ含有）に２，２，６，６−テトラメチル−４−ピペリジノール２．３ｇ（１４．８ｍｍｏｌ）を添加し、攪拌下、室温で３週間保存した。添加前および４８時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０．３％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。保存前と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、７０％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が分解していた。
【００２４】
【発明の効果】
本発明安定化方法は、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ものであり、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. Hydrogen peroxide is a compound in which hydrogen peroxide is coordinated to a compound like water in crystallization water. As hydrogen peroxide, hydrogen peroxide of potassium fluoride, rubidium carbonate and urea are known. ing.
[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 by gradually desorbing hydrogen peroxide coordinated at room temperature.
[0004]
As a stabilizer for hydrogen peroxide itself, many compounds such as phosphoric acid, acetanilide and uric acid are known, but hydrogen peroxide of quaternary ammonium salt in which hydrogen peroxide is coordinated to quaternary ammonium salt. No stabilizers are known for.
[0005]
[Problems to be solved by the invention]
As described above, the quaternary ammonium salt hydrogen peroxide, which is a useful compound, gradually decomposes at room temperature, but its stabilization method is not known at all.
[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 studies on a method for stabilizing a hydrogenated product of tetramethylammonium hydroxide, which is a quaternary ammonium salt, the present inventors have found that it can be easily stabilized by adding a hindered amine. It came to complete.
[0008]
That is, the present invention relates to a method for stabilizing a hydrogenated product of a quaternary ammonium salt, which comprises adding a hindered amine to a hydrogenated product of tetramethylammonium hydroxide .
[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 a mixture of the tetramethylammonium hydroxide and hydrogen peroxide, is obtained by mixing at room temperature by adding heat to or, or catalyst.
[0013]
In the method of the present invention, the hindered amine used is an amine having a substituent on both sides of the amino group, and is widely used as a light stabilizer for polymer compounds. As a hindered amine, the following general formula:
[Chemical formula 2]

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and the substituent A represents a divalent group of —CH ₂ —, ═CHOH, ═CH—O—CO—R ₂ , or —CO—. ₂ represents an alkyl group or an aryl group which may have a functional group.
Examples of such compounds are shown below. R ₁ represents a hydrogen atom or a methyl group, and the substituent A represents a divalent group of —CH ₂ —, —CHOH—, ═CH—O—CO—R ₂ , or —CO—. R ₂ represents an alkyl group or an aryl group which may have a functional group, and preferably has 1 to 8 carbon atoms.
[0015]
Specific examples of hindered amines that can be used in the method of the present invention include 2,2,6,6-tetramethyl-4-piperidone, 1,2,2,6,6-pentamethyl-4-piperidone, 2,2 , 6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol, 1,2,2,6,6-pentamethyl- 4-piperidinol, crotonic acid- (2,2,6,6-tetramethyl-4-piperidenyl) ester, crotonic acid- (1,2,2,6,6-pentamethyl-4-piperidenyl) ester, succinic acid- Bis (2,2,6,6-tetramethyl-4-piperidenyl) -ester, malonic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl) -ester, sebacic acid Bis (2,2,6,6-tetramethyl-4-Piperideniru) - ester, and the like.
[0016]
In the method of the present invention, the effective addition amount of hindered amine can be arbitrarily added by those skilled in the art in consideration of solubility in water and the like, but it is 0 with respect to the hydrogenated product of tetramethylammonium hydroxide. It is preferable to add in the range of 0.001 to 10 mol%, more preferably 0.01 to 10 mol%. If the amount added is less than 0.001 mol% with respect to the tetramethylammonium hydroxide hydrogen peroxide, the stabilizing effect may not be seen. Even if the amount added exceeds 10 mol%, the hindered amine is dissolved. In some cases, the effect of increasing the stabilizer may be small.
[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 packed with a packing material for polar organic solvent gel filtration based on vinyl polymer (made by Tosoh Corporation, trade name “TSKgel α2500”) are connected in series to the packing material, and acetonitrile + 40% is used as the eluent. Water + 0.5% ammonia was used (pH = 10.7). 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
The 2,2,6,6-tetramethyl was added to 151.2 g of a 25% tetramethylammonium hydroxide aqueous solution of hydrogen peroxide prepared in Production Example 1 (containing 0.3 mol of tetramethylammonium hydroxide hydrogen peroxide). Piperidine (2.1 g, 14.8 mmol) was added, and the mixture was stored under stirring at room temperature for 3 weeks. The hydrogenation product of tetramethylammonium hydroxide before and after 3 weeks was analyzed by high performance liquid chromatography (HPLC). As a result, 0.2% of the tetramethylammonium hydroxide hydrogenated product was decomposed. .
[0022]
Example 2
The 2,2,6,6-tetramethyl- 25% tetramethylammonium hydroxide hydrogen peroxide aqueous solution prepared in Production Example 1 was added to 151.0 g (containing 0.3 mol of tetramethylammonium hydroxide hydrogen peroxide). 4-piperidinol 2.3 g (14.8 mmol) was added, and the mixture was stored at room temperature for 3 weeks under stirring. The hydrogenation product of tetramethylammonium hydroxide before and after 48 hours was analyzed by HPLC. As a result, 0.3% of the hydrogenated product 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 before and after storage was analyzed by HPLC, 70% of the tetramethylammonium hydroxide hydrogen peroxide was decomposed.
[0024]
【The invention's effect】
The stabilization method of the present invention suppresses the decomposition of tetramethylammonium hydroxide hydrogen peroxide useful as a resist stripper and a titanium oxide stripper, and its industrial value is high.

Claims (3)

A method of stabilizing a hydrogenated product of tetramethylammonium hydroxide, comprising adding a hindered amine represented by the following general formula having substituents on both sides of an amino group to a hydrogenated product of tetramethylammonium hydroxide. .

(In the formula, R 1 represents a hydrogen atom or a methyl group, and the substituent A represents a divalent group of —CH 2 —, ═CHOH, ═CH—O—CO—R 2, or —CO—. (It represents an alkyl group or an aryl group which may have a functional group.) The hindered amine is 2,2,6,6-tetramethyl-4-piperidone, 1,2,2,6,6-pentamethyl-4-piperidone, 2,2,6,6-tetramethylpiperidine, 1,2,2 , 6,6-pentamethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol, 1,2,2,6,6-pentamethyl-4-piperidinol, crotonic acid- (2,2,6, 6-tetramethyl-4-piperidenyl) ester, crotonic acid- (1,2,2,6,6-pentamethyl-4-piperidenyl) ester, succinic acid-bis (2,2,6,6-tetramethyl-4) -Piperidenyl) -ester, malonic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl) -ester, sebacic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl) - any one or more in a claim 1 quaternary ammonium stabilization method peroxyhydrate salt according selected from the group of esters. One or more of 2,2,6,6-tetramethylpiperidine and 2,2,6,6 monotetramethyl-4-piperidinol is 0.001 to the hydrogenated product of tetramethylammonium hydroxide. The method for stabilizing a hydrogenated product of tetramethyl hydroxide according to claim 1 or 2, wherein 10 to 10 mol% is added.