JPH1171104A - Stabilized hydrogen peroxide aqueous solution - Google Patents
Stabilized hydrogen peroxide aqueous solutionInfo
- Publication number
- JPH1171104A JPH1171104A JP15161198A JP15161198A JPH1171104A JP H1171104 A JPH1171104 A JP H1171104A JP 15161198 A JP15161198 A JP 15161198A JP 15161198 A JP15161198 A JP 15161198A JP H1171104 A JPH1171104 A JP H1171104A
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- Prior art keywords
- hydrogen peroxide
- tantalum
- solution
- niobium
- concentration
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、安定化された過酸
化水素水溶液に関し、より詳細には、タンタル，ジルコ
ニウム又はニオブ等の金属元素種を微量添加されてなる
熱安定性に優れた過酸化水素水溶液に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized aqueous hydrogen peroxide solution, and more particularly to a peroxide having excellent thermal stability obtained by adding a small amount of a metal element such as tantalum, zirconium or niobium. It relates to a hydrogen aqueous solution.
【０００２】[0002]
【従来の技術】過酸化水素は、酸化剤として有用な無機
工業薬品であり、繊維、パルプの漂白、殺菌消毒液、有
機合成反応等の多くの分野で幅広く利用され、近年では
電子工業用のウェハー洗浄にも用いられている。これら
の用途に使用されるまでの輸送や保存中に、過酸化水素
の濃度低下を防ぐため、一般に各種の安定剤が添加され
ている。2. Description of the Related Art Hydrogen peroxide is an inorganic industrial chemical useful as an oxidizing agent, and is widely used in many fields such as fiber and pulp bleaching, disinfecting solutions and organic synthesis reactions. It is also used for wafer cleaning. In order to prevent a decrease in the concentration of hydrogen peroxide during transportation and storage before use for these applications, various stabilizers are generally added.
【０００３】過酸化水素水溶液中の過酸化水素濃度を低
下させる原因は、主に過酸化水素水溶液中に含まれてい
る各種の金属不純物によって過酸化水素が触媒的に分解
されるからである。過酸化水素を触媒的に分解させるこ
れらの金属を封鎖（または封止）させて、その分解を防
止させるために、ピロリン酸塩、錫酸塩等の無機酸塩
や、有機キレート剤、有機酸等の有機化合物が添加され
ている。また、過酸化水素の分解やその分解触媒活性を
持つ元素種や化合物および過酸化水素水溶液の安定化方
法についての初歩的知見は、Schumbらの「Hydrogen Per
oxid」、Reinhold出版社、ニューヨーク（１９５５）、
４４７〜５３９頁等に記載されている。[0003] The reason for lowering the concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution is mainly that hydrogen peroxide is catalytically decomposed by various metal impurities contained in the aqueous hydrogen peroxide solution. In order to block (or seal) these metals that catalytically decompose hydrogen peroxide and prevent the decomposition, inorganic salts such as pyrophosphate and stannate, organic chelating agents, and organic acids are used. And other organic compounds. The initial knowledge on the decomposition of hydrogen peroxide, elemental species and compounds having catalytic activity for the decomposition, and a method for stabilizing an aqueous hydrogen peroxide solution is described in Schumb et al.
oxid ", Reinhold Publisher, New York (1955),
It is described on pages 447-539.
【０００４】一般に広く使用されている無機系安定剤と
して、リン酸塩、ピロリン酸塩、錫酸塩等に代表される
化合物が挙げられ、価格が安価であることから多量に使
用されている。これらの安定剤の中でリン酸塩は、過酸
化水素による劣化が少ないが、単独では過酸化水素の安
定化効果が小さいことから、多量に添加しなければなら
ない。一方、近年の過酸化水素の主な用途として、電子
工業用のウェハー処理液、食品添加剤、殺菌消毒剤等が
挙げられ、これらの何れの用途においてもその使用量を
削減させることが求められている。また、使用量が多く
なることにより、使用後の蒸発残渣等が増加することと
なり好ましくない。また、金属不純物の封鎖に有効とさ
れるピロリン酸塩は、高温の過酸化水素中においてオル
ト燐酸に分解することから、その封鎖効果がリン酸塩並
に低下するといった欠点を有している。また、錫酸塩に
ついては、アルミニウム製容器に貯蔵するとアルミニウ
ムの過剰な溶出を引き起こし、その溶出アルミニウムに
よって錫酸塩自体が沈殿を起こすために実用上使用でき
ない問題点がある。[0004] Inorganic stabilizers generally widely used include compounds represented by phosphates, pyrophosphates, stannates and the like, and are used in large quantities because of their low cost. Among these stabilizers, phosphates are less likely to be degraded by hydrogen peroxide, but must be added in large amounts because they alone have a small effect of stabilizing hydrogen peroxide. On the other hand, main uses of hydrogen peroxide in recent years include wafer processing solutions for the electronics industry, food additives, disinfectants and the like, and it is required to reduce the amount of use in any of these uses. ing. In addition, an increase in the amount of use is not preferable because evaporation residues and the like after use increase. In addition, pyrophosphate, which is effective for sequestering metal impurities, has a disadvantage that its sequestering effect is reduced to the same level as phosphate since it decomposes into orthophosphoric acid in high-temperature hydrogen peroxide. In addition, stannate has a problem that when stored in an aluminum container, aluminum is excessively eluted and the stannate itself precipitates due to the eluted aluminum, so that it cannot be used practically.
【０００５】さらには、有効とされる有機キレート化合
物は、例えば特公昭５０−３６８３８号公報に、エチレ
ンジアミンテトラメチレン（ホスホン酸）の様なホスホ
ン酸系キレート剤や、エチレンジアミン４酢酸、ニトリ
ロトリ酢酸等が記載されている。しかしながら、これら
のキレート剤の中でエチレンジアミン４酢酸やニトリロ
トリ酢酸は、初期には有効な安定剤であるが、長時間経
過後に、窒素原子を含むこれらの化合物が過酸化水素に
より分解され、安定化能力が低下して、長期間の使用に
は適さない欠点がある。また、ホスホン酸系キレート剤
は、過酸化水素を分解防止させる能力は強いものの、タ
ンクや容器の貯蔵中に容器材質の腐食が激しく、分解活
性を持つ金属不純物の溶出を招くため、硝酸ナトリウ
ム、硝酸アンモニウム等の金属腐食防止剤を多量に併用
することが必要である。従って、前述の様に、蒸発残渣
が増加することとなり、その使用用途が制限されるとい
った問題点がある。更に、これらの有機キレート化合物
は、価格が高価であるため、生産コストの上昇につなが
る点も好ましくない欠点である。Further, effective organic chelating compounds include, for example, Japanese Patent Publication No. 50-36838, phosphonic acid chelating agents such as ethylenediaminetetramethylene (phosphonic acid), ethylenediaminetetraacetic acid, nitrilotriacetic acid and the like. Are listed. However, among these chelating agents, ethylenediaminetetraacetic acid and nitrilotriacetic acid are initially effective stabilizers, but after a long period of time, these compounds containing nitrogen atoms are decomposed by hydrogen peroxide and stabilized. There is a drawback that the performance is reduced and it is not suitable for long-term use. In addition, phosphonic acid-based chelating agents have a strong ability to prevent the decomposition of hydrogen peroxide, but the corrosion of the material of the container during storage of the tank or the container is severe, and the elution of metal impurities having decomposition activity is caused. It is necessary to use a large amount of a metal corrosion inhibitor such as ammonium nitrate. Therefore, as described above, there is a problem that the evaporation residue is increased and its use is restricted. Further, these organic chelate compounds are also disadvantageous in that they are expensive and lead to an increase in production costs.
【０００６】また、その他の有機化合物についても、例
えば有機ヒドロキシ化合物、ジグリコール酸、芳香族ス
ルホン酸、亜リン酸アシル化物、フェナントロリン、ア
ミノトリアジン、アセトアニリド等の多くが知られてい
る。しかしながら、これらの有機系安定化剤について
は、単独での安定化効果が小さく、また過酸化水素中で
それ自体が酸化されて変化し、効力を失うことから、特
に長期間保存の場合や高濃度の過酸化水素に対しては、
実用上使用できない問題点を有している。As for other organic compounds, for example, many organic hydroxy compounds, diglycolic acid, aromatic sulfonic acid, acylated phosphite, phenanthroline, aminotriazine, acetanilide and the like are known. However, these organic stabilizers alone have a small stabilizing effect, and themselves are oxidized and changed in hydrogen peroxide, losing their efficacy. For a concentration of hydrogen peroxide,
There is a problem that cannot be used practically.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記の様々
な問題点から、対象となる過酸化水素水溶液の過酸化水
素濃度に影響されず、しかも少量の添加量で、持続して
過酸化水素水溶液を安定化させる安定化剤を開発するこ
とを目的としてなされたものであり、その結果、分解損
失が少なく、熱安定性に優れた過酸化水素水溶液を提供
することにある。SUMMARY OF THE INVENTION In view of the above-mentioned various problems, the present invention is not affected by the concentration of hydrogen peroxide in a target aqueous hydrogen peroxide solution, and it is possible to continue the peroxide treatment with a small amount of addition. An object of the present invention is to develop a stabilizer for stabilizing an aqueous hydrogen solution, and as a result, to provide an aqueous hydrogen peroxide solution having a small decomposition loss and excellent thermal stability.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記する
諸問題を解決すべく鋭意研究を行った結果、過酸化水素
に対して金属元素種の中で、タンタル、ジルコニウム又
はニオブ等の元素を有する化合物を過酸化水素水溶液中
に添加させたところ、過酸化水素が分解されず、しかも
過酸化水素の分解が持続して抑止されることを見い出し
て、本発明を完成するに至ったものである。すなわち、
本発明は、タンタル，ジルコニウム及びニオブからなる
群から選ばれた少なくとも一種の金属元素種を含有する
ことを特徴とする安定化された過酸化水素水溶液を提供
するものである。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, among the metal element species, tantalum, zirconium, niobium, and the like, among hydrogen metal species. When a compound having an element was added to an aqueous hydrogen peroxide solution, it was found that hydrogen peroxide was not decomposed, and furthermore, it was found that decomposition of hydrogen peroxide was continuously suppressed, and the present invention was completed. Things. That is,
The present invention provides a stabilized aqueous hydrogen peroxide solution containing at least one kind of metal element selected from the group consisting of tantalum, zirconium and niobium.
【０００９】[0009]
【発明の実施の形態】本発明において、過酸化水素水溶
液を安定化させるために、過酸化水素水溶液に過酸化水
素に対して、単独では過酸化水素を分解させる触媒活性
を持たない元素であるタンタル，ジルコニウム及びニオ
ブからなる群から選ばれた少なくとも一種の金属元素種
を添加することによって、過酸化水素水溶液を持続して
安定化させられ、しかも優れた熱安定性を付与させるこ
とを特徴とするものである。また、これらの三種の金属
元素種において、過酸化水素水溶液を安定化させる作用
効果としては、ジルコニウム元素種よりは、ニオブ元素
種がより好ましく、更に好ましくはタンタル元素種であ
る。また、本発明においては、これらの元素種の何れか
一種のイオンまたはその化合物を過酸化水素水溶液に添
加させることを特徴とするが、必要に応じてこれらの元
素種の二種以上のイオンまたは化合物を添加させてもよ
い。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in order to stabilize an aqueous hydrogen peroxide solution, an aqueous solution of hydrogen peroxide is an element having no catalytic activity to decompose hydrogen peroxide alone against hydrogen peroxide. By adding at least one kind of metal element selected from the group consisting of tantalum, zirconium and niobium, it is possible to stabilize the hydrogen peroxide aqueous solution continuously and to impart excellent thermal stability. Is what you do. In addition, among these three metal element species, the effect of stabilizing the aqueous hydrogen peroxide solution is more preferably a niobium element species, more preferably a tantalum element species, than a zirconium element species. Further, the present invention is characterized in that any one of these element species ions or a compound thereof is added to the aqueous hydrogen peroxide solution, but two or more ions of these element species or Compounds may be added.
【００１０】本発明において、これらの元素種の使用時
の形態としては、上記するようにイオンや、水酸化物、
酸化物等の酸素化合物や、硫酸塩、硝酸塩、硼酸塩、リ
ン酸塩、炭酸塩等の無機化合物及び酢酸塩、蓚酸塩、ク
エン酸等の有機化合物が挙げられ、これらの全てが過酸
化水素水溶液を安定化させるに優れた効果を呈するもの
である。In the present invention, these elements may be used in the form of ions, hydroxides,
Oxygen compounds such as oxides; inorganic compounds such as sulfates, nitrates, borates, phosphates, and carbonates; and organic compounds such as acetates, oxalates, and citric acid, all of which are hydrogen peroxide. It exhibits an excellent effect in stabilizing the aqueous solution.
【００１１】そこで、本発明における安定化剤のタンタ
ル元素種は、過酸化水素水溶液中に添加後、均一に混合
されるイオン、水溶性化合物又は酸性水溶液であれば特
に限定することなく適宜選択して使用されるものであ
る。本発明においては、例えば、フッ化タンタル、オク
タフルオロタンタル酸ナトリウム等が好適な例として挙
げられる。特に、タンタル金属元素種の化合物は、水や
過酸化水素に対し難溶性である化合物が多いことから、
上記する塩化タンタル／硫酸の例のように、硝酸又は硫
酸等の過酸化水素を分解させない無機酸等に溶解し、適
当な濃度に調整したものを添加しても良い。Accordingly, the tantalum element species of the stabilizer in the present invention is appropriately selected without particular limitation as long as it is an ion, a water-soluble compound or an acidic aqueous solution which is uniformly mixed after being added to the aqueous hydrogen peroxide solution. Is used. In the present invention, for example, preferable examples include tantalum fluoride and sodium octafluorotantalate. In particular, since many compounds of the tantalum metal element type are hardly soluble in water and hydrogen peroxide,
As in the example of tantalum chloride / sulfuric acid described above, a solution prepared by dissolving in a non-decomposing inorganic acid such as nitric acid or sulfuric acid and adjusting the concentration to an appropriate concentration may be added.
【００１２】本発明において、過酸化水素水溶液中に添
加させるタンタル元素濃度は、０．０１〜５０重量ｐｐ
ｍ、好ましくは０．０５〜５０重量ｐｐｍ、より好まし
くは０．７〜２０重量ｐｐｍ、特に好ましくは１〜１０
重量ｐｐｍの範囲である。この添加量が上記の下限値未
満では、十分な安定性が得られなく、また上限値を超え
るとむしろ安定性が低下するばかり、不経済であり、し
かも蒸発残渣を増す要因となることから好ましくない。
なお、実用上の過酸化水素水溶液中には、過酸化水素を
触媒的に分解させる不純物の金属種が共存している。そ
のため、上記の添加量は、一般的には、これらの不純物
濃度に影響されて変動するものである。In the present invention, the concentration of the tantalum element added to the aqueous hydrogen peroxide solution is 0.01 to 50 wt.
m, preferably 0.05 to 50 ppm by weight, more preferably 0.7 to 20 ppm by weight, particularly preferably 1 to 10 ppm by weight.
It is in the range of ppm by weight. When the amount is less than the above lower limit, sufficient stability cannot be obtained, and when the amount exceeds the upper limit, the stability is rather deteriorated. Absent.
It should be noted that a metal species of an impurity that catalytically decomposes hydrogen peroxide coexists in a practical aqueous hydrogen peroxide solution. Therefore, the above-mentioned amount of addition generally varies depending on the concentration of these impurities.
【００１３】また、本発明におけるニオブ元素は、上記
のタンタルと同様に、過酸化水素水溶液中に添加後、均
一に混合されるイオン、水溶性化合物又は酸性水溶液で
あれば特に限定されるものでない。本発明では、例え
ば、酸化ニオブ／硫酸、炭化ニオブ／硝酸、シュウ酸水
素ニオブ／シュウ酸、ヘプタフルオロニオブ酸カリウ
ム、ヘプタフルオロオキソニオブ酸カリウム・水和物等
が好適な例として挙げられる。また、タンタル種と同様
に水や過酸化水素に対し難溶性である、例えば、酸化ニ
オブ／硫酸のように、それらを、硝酸又は硫酸等の過酸
化水素を分解しない無機酸等に溶解し、適当な濃度に調
整したものを添加しても良い。The niobium element in the present invention is not particularly limited as long as it is an ion, a water-soluble compound or an acidic aqueous solution which is uniformly mixed after being added to an aqueous hydrogen peroxide solution, similarly to the above-mentioned tantalum. . In the present invention, preferred examples include niobium oxide / sulfuric acid, niobium carbide / nitric acid, niobium hydrogen oxalate / oxalic acid, potassium heptafluoroniobate, potassium heptafluorooxoniobate hydrate, and the like. Also, like tantalum species, it is hardly soluble in water or hydrogen peroxide, for example, dissolve them in an inorganic acid such as niobium oxide / sulfuric acid which does not decompose hydrogen peroxide such as nitric acid or sulfuric acid, Those adjusted to an appropriate concentration may be added.
【００１４】本発明において、過酸化水素水溶液中に含
有させるニオブ元素の添加濃度は、タンタル元素と同様
に、過酸化水素水溶液中の分解触媒活性を持つ金属不純
物濃度に依存するため一概に特定できないが、実際に使
用する上で、過酸化水素水溶液中のニオブ元素濃度とし
て、０．０１〜５０重量ｐｐｍ、好ましくは０．１０〜
３０重量ｐｐｍ、より好ましくは０．３〜２０重量ｐｐ
ｍ、特に好ましくは０．７〜３重量ｐｐｍの範囲であ
る。また、この添加量もタンタル種と同様に、下限値未
満では、十分な安定性が得られなく、また上限値を超え
るとむしろ安定性が低下するばかりでなく、不経済であ
り、しかも蒸発残渣を増す要因となることから好ましく
ない。In the present invention, the addition concentration of the niobium element contained in the aqueous hydrogen peroxide solution cannot be specified unconditionally because it depends on the concentration of metal impurities having a decomposition catalytic activity in the aqueous hydrogen peroxide solution, like the tantalum element. However, in actual use, the concentration of the niobium element in the aqueous hydrogen peroxide solution is 0.01 to 50 ppm by weight, preferably 0.10 to 50 ppm.
30 weight ppm, more preferably 0.3 to 20 weight pp
m, particularly preferably in the range of 0.7 to 3 ppm by weight. Also, as with the tantalum species, if the amount is less than the lower limit, sufficient stability cannot be obtained, and if the amount exceeds the upper limit, not only the stability is lowered, but also uneconomical It is not preferable because it becomes a factor of increasing
【００１５】さらにはまた、本発明におけるジルコニウ
ム元素種は、上記するタンタルおよびニオブ元素種と同
様に、過酸化水素水溶液中に添加後、均一に混合できる
イオン、水溶性化合物又は酸性水溶液であれば特に限定
されるものではなく、本発明では、例えば、硝酸ジルコ
ニル・五水和物、二硝酸酸化ジルコニウム二水和物、硫
酸ジルコニウム・四水和物、炭酸ジルコニウムアンモニ
ウム、ヘキサフルオロジルコニウム酸ナトリウム等が好
適な例として挙げられる。また水酸化ジルコニルや酸化
ジルコニル、また酢酸ジルコニウム等の酢酸塩、蓚酸ジ
ルコニウム等の蓚酸塩等の水や過酸化水素に対し難溶性
である化合物は、同様にこれらを硝酸又は硫酸等の過酸
化水素を分解しない無機酸等に溶解させて使用される。Further, the zirconium element species in the present invention, like the tantalum and niobium element species described above, may be any ion, water-soluble compound or acidic aqueous solution which can be uniformly mixed after being added to an aqueous hydrogen peroxide solution. Although not particularly limited, in the present invention, for example, zirconyl nitrate pentahydrate, zirconium oxide dinitrate dihydrate, zirconium sulfate tetrahydrate, ammonium zirconium carbonate, sodium hexafluorozirconate, etc. A preferred example is given. Compounds which are hardly soluble in water or hydrogen peroxide such as zirconyl hydroxide, zirconyl oxide, or acetate such as zirconium acetate, or oxalate such as zirconium oxalate may be similarly treated with hydrogen peroxide such as nitric acid or sulfuric acid. Is used by dissolving it in an inorganic acid that does not decompose it.
【００１６】また、過酸化水素水溶液中に含有させるジ
ルコニウム元素の添加濃度は、タンタル、ニオブ元素と
同様に、過酸化水素水溶液中の分解触媒活性を持つ金属
不純物濃度に依存するため一概に特定できないが、実際
に使用する上で、過酸化水素水溶液中のニオブ元素濃度
として、０．０１〜５０重量ｐｐｍ、好ましくは０．０
５〜２０重量ｐｐｍ、より好ましくは０．３〜１０重量
ｐｐｍ、特に好ましくは０．７〜３重量ｐｐｍの範囲に
ある。また、この添加量もタンタルまたはニオブ種と同
様に、下限値未満では、十分な安定性が得られなく、ま
た上限値を超えるとむしろ安定性が低下するばかりでな
く、不経済であり、しかも蒸発残渣を増す要因となるこ
とから好ましくない。Further, the addition concentration of the zirconium element contained in the aqueous hydrogen peroxide solution cannot be specified unconditionally because it depends on the concentration of metal impurities having a catalytic activity for decomposition in the aqueous hydrogen peroxide solution, similarly to the tantalum and niobium elements. However, in actual use, the concentration of niobium in the aqueous hydrogen peroxide solution is 0.01 to 50 ppm by weight, preferably 0.0
It is in the range of 5 to 20 ppm by weight, more preferably 0.3 to 10 ppm by weight, particularly preferably 0.7 to 3 ppm by weight. Also, as with the tantalum or niobium species, if the amount is less than the lower limit, sufficient stability cannot be obtained, and if the amount exceeds the upper limit, not only the stability is lowered, but also uneconomical, and It is not preferable because it causes an increase in evaporation residue.
【００１７】そこで、これらのタンタル、ニオブ又はジ
ルコニウム元素種の添加方法は、水溶性のものであれば
液体、固体を直接添加しても良く、予め水又は過酸化水
素、過酸化水素を分解しない硝酸、硫酸等の無機酸に溶
解したマスターバッチを調整し添加する方法でも良い。
また、他の安定剤や安定助剤などと共に添加してもよ
い。更に、水や過酸化水素に対し余り溶解度の高くない
化合物の場合、前述のように過酸化水素を分解しない無
機酸又は有機酸等に溶解し、適当な濃度に調整したもの
を添加する方法もよい。Therefore, as a method for adding these tantalum, niobium or zirconium element species, a liquid or solid may be directly added as long as it is water-soluble, and water or hydrogen peroxide or hydrogen peroxide is not decomposed in advance. A method of adjusting and adding a master batch dissolved in an inorganic acid such as nitric acid or sulfuric acid may be used.
Further, it may be added together with other stabilizers and stabilizing assistants. Furthermore, in the case of a compound having a very low solubility in water or hydrogen peroxide, a method of dissolving the compound in an inorganic acid or an organic acid which does not decompose hydrogen peroxide as described above and adding a solution adjusted to an appropriate concentration may also be used. Good.
【００１８】また、本発明で使用される過酸化水素水溶
液の濃度は、通常、市販されている過酸化水素濃度が１
〜９０重量％の範囲にあることから、特にこの濃度に限
定されるものでは無いが、好ましくは２０〜７０重量％
の範囲の過酸化水素水溶液に対してタンタル、ニオブ又
はジルコニウム元素種のイオンまたは化合物を添加させ
ることにより、過酸化水素水溶液を安定化させることが
可能である。The concentration of the aqueous hydrogen peroxide solution used in the present invention is usually 1% of the commercially available concentration of hydrogen peroxide.
Although it is not particularly limited to this concentration since it is in the range of 90 to 90% by weight, it is preferably 20 to 70% by weight.
By adding ions or compounds of the elemental species of tantalum, niobium or zirconium to the aqueous solution of hydrogen peroxide in the range described above, it is possible to stabilize the aqueous solution of hydrogen peroxide.
【００１９】本発明において、タンタル、ニオブ又はジ
ルコニウム元素の化合物の中で、水や過酸化水素に対し
難溶性の化合物を溶解するために使用される無機酸又は
有機酸は、過酸化水素を分解しない硝酸、硫酸、弗酸、
塩酸等の無機酸、安息香酸、クエン酸、蓚酸、サリチル
酸、酢酸等の有機酸から、何れか一種または二種以上を
適宜組み合わせて使用することができる。また、これら
の酸の使用量は、対象となる化合物に依存するため、一
概に特定されないが、特に過剰な使用は過酸化水素の安
定性を悪化させることから、適宜に適正量を定めればよ
い。また、本発明においては、過酸化水素を分解させな
い硝酸、硫酸、弗酸、塩酸等の無機酸を、金属表面処理
等の使用用途等に応じて過酸化水素水溶液中に任意量を
添加することも差しつかえない。In the present invention, among the compounds of the elemental tantalum, niobium or zirconium, the inorganic or organic acid used for dissolving the compound which is hardly soluble in water or hydrogen peroxide decomposes hydrogen peroxide. Not nitric acid, sulfuric acid, hydrofluoric acid,
Any one or a combination of two or more of inorganic acids such as hydrochloric acid and organic acids such as benzoic acid, citric acid, oxalic acid, salicylic acid, and acetic acid can be used. In addition, the amount of these acids used is dependent on the target compound, and thus is not specified unconditionally. However, in particular, excessive use deteriorates the stability of hydrogen peroxide. Good. In the present invention, an arbitrary amount of an inorganic acid such as nitric acid, sulfuric acid, hydrofluoric acid, or hydrochloric acid that does not decompose hydrogen peroxide is added to the aqueous hydrogen peroxide solution according to the intended use such as metal surface treatment. I don't mind.
【００２０】さらには、必要に応じて硼酸塩等のｐＨ調
整剤、塩化ナトリウム等の等張化剤ならびに珪酸ナトリ
ウム、珪酸マグネシウム等の安定化助剤等を単独又は組
み合わせて過酸化水素水溶液中に添加してもよい。以上
から、本発明による安定化過酸化水素水溶液には、従来
から使用されている各種の公知の過酸化水素安定化剤を
併用することなく、過酸化水素水溶液を安定化させるこ
とが可能である。Further, if necessary, a pH adjuster such as borate, a tonicity agent such as sodium chloride and a stabilizing aid such as sodium silicate and magnesium silicate are used alone or in combination in an aqueous hydrogen peroxide solution. It may be added. From the above, it is possible to stabilize the aqueous hydrogen peroxide solution in the stabilized aqueous hydrogen peroxide solution according to the present invention without using any of various conventionally known hydrogen peroxide stabilizers. .
【００２１】[0021]
【実施例】以下に本発明の効果を実施例及び比較例によ
り具体的に説明するが、本発明はこれら実施例に限定さ
れるものではない。 実施例１ 市販の３１．２重量％過酸化水素水溶液（三菱ガス化
学、関東化学、試薬電子工業用グレード）に、タンタ
ル、ニオブ、ジルコニウム（関東化学（株）社製原子吸
光分析用１，０００ｐｐｍ標準原液使用）をそれぞれ
０．０５重量ｐｐｍ〜５０重量ｐｐｍ、過酸化水素に対
して分解触媒活性を持つ鉄及びクロム（関東化学（株）
社製原子吸光分析用試薬１，０００ｐｐｍ標準原液使
用）を各々１重量ｐｐｂ添加した過酸化水素水溶液を調
製し、その安定度を、ＪＩＳ Ｋ−１４６３（１９７
１），５．５章に定める工業用過酸化水素の安定度測定
法に基づいて求めた。本方法は、所定の試料を硬質メス
フラスコ中に入れ、沸騰水浴中で標線が水浴の水面下に
没する様に保ちながら５時間加熱し、試験前後の過酸化
水素濃度を１／１０Ｎ過マンガン酸カリウム溶液を用い
た滴定（ＪＩＳ Ｋ−１４６３、５．２．４章）により
求め、以下に示した式により５時間後の過酸化水素残存
率を過酸化水素水溶液の安定度とするものである。安定
度試験の結果を第１表に示した。 安定度 Ｈ＝Ｊ’／Ｊ×１００ Ｈ ：安定度（％） Ｊ’：５時間加熱後の過酸化水素濃度（％） Ｊ ：試験前の過酸化水素濃度（％）EXAMPLES The effects of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 Tantalum, niobium, and zirconium (1,000 ppm for atomic absorption spectrometry manufactured by Kanto Chemical Co., Ltd.) were added to a commercially available 31.2% by weight aqueous hydrogen peroxide solution (grade of Mitsubishi Gas Chemical, Kanto Chemical, reagent electronics industry). Iron and chromium (Kanto Chemical Co., Ltd.) having a decomposition catalyst activity for hydrogen peroxide of 0.05 wt ppm to 50 wt ppm, respectively.
An aqueous solution of hydrogen peroxide was prepared by adding 1 wt.% Ppb of each of the reagents for atomic absorption spectrometry (manufactured by Co., Ltd., 1,000 ppm standard stock solution).
1), determined based on the method for measuring the stability of industrial hydrogen peroxide specified in Chapter 5.5. In this method, a predetermined sample is placed in a hard volumetric flask, and heated in a boiling water bath for 5 hours while keeping the marked line submerged under the surface of the water bath to reduce the concentration of hydrogen peroxide before and after the test to 1 / 10N. It is determined by titration using a potassium manganate solution (JIS K-1463, Chapter 5.2.4), and the residual ratio of hydrogen peroxide after 5 hours is defined as the stability of the aqueous hydrogen peroxide solution according to the following equation. It is. Table 1 shows the results of the stability test. Stability H = J ′ / J × 100 H: Stability (%) J ′: Hydrogen peroxide concentration (%) after heating for 5 hours J: Hydrogen peroxide concentration (%) before test
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】表から明らかなように、三種の安定化剤種
のなかで、タンタル金属種がより優れていることが判
る。 比較例１ 実施例１で用いた市販の過酸化水素水溶液に、過酸化水
素に対して分解触媒活性を持つ鉄及びクロム（関東化学
（株）社製原子吸光分析用試薬１，０００ｐｐｍ標準原
液使用）を各々１重量ｐｐｂとなるように添加した過酸
化水素水溶液を調製し、安定化効果を示す元素種を添加
せずに実施例１と同様の方法で安定度試験を実施した。
その結果、安定度は９６．５％であった。As can be seen from the table, of the three stabilizer species, the tantalum metal species is better. Comparative Example 1 The commercially available aqueous hydrogen peroxide solution used in Example 1 was mixed with iron and chromium having a catalytic activity for decomposing hydrogen peroxide (using a 1,000 ppm standard undiluted solution for atomic absorption analysis manufactured by Kanto Chemical Co., Ltd.). ) Was added so as to be 1 wt. Ppb each, and a stability test was carried out in the same manner as in Example 1 without adding an elemental species exhibiting a stabilizing effect.
As a result, the stability was 96.5%.
【００２５】比較例２ 実施例１で用いた市販の過酸化水素水溶液に、過酸化水
素に対して分解触媒活性を持つ鉄及びクロム（関東化学
（株）社製原子吸光分析用試薬１，０００ｐｐｍ標準原
液使用）を各々１重量ｐｐｂとなるように添加した過酸
化水素水溶液を調製し、更に従来から使用されている過
酸化水素安定化剤であるピロリン酸水素ナトリウムを１
重量ｐｐｍ添加し、実施例１と同様の方法で安定度試験
を実施した。その結果、安定度は９７．４％であった。Comparative Example 2 The commercially available aqueous hydrogen peroxide solution used in Example 1 was mixed with iron and chromium having a catalytic activity for decomposing hydrogen peroxide (1,000 ppm of a reagent for atomic absorption analysis manufactured by Kanto Chemical Co., Ltd.). An aqueous solution of hydrogen peroxide was prepared by adding 1% by weight of ppb to each solution, and sodium hydrogen pyrophosphate, a conventionally used hydrogen peroxide stabilizer, was added to 1% by weight of ppb.
A stability test was performed in the same manner as in Example 1 by adding ppm by weight. As a result, the stability was 97.4%.
【００２６】比較例３ 実施例１で用いた市販の過酸化水素水溶液に、過酸化水
素に対して分解触媒活性を持つ鉄及びクロム（関東化学
（株）社製原子吸光分析用試薬１，０００ｐｐｍ標準原
液使用）を各々１重量ｐｐｂとなるように添加した過酸
化水素水溶液を調製し、更に硝酸を１重量ｐｐｍ添加
後、実施例１と同様の方法で安定度試験を実施した。そ
の結果、安定度は９７．３％であった。Comparative Example 3 The commercially available aqueous solution of hydrogen peroxide used in Example 1 was mixed with iron and chromium having a catalytic activity for decomposing hydrogen peroxide (1,000 ppm of an atomic absorption spectrometer manufactured by Kanto Chemical Co., Ltd.). An aqueous hydrogen peroxide solution was added to each of the solutions to give a weight of 1 ppb (using a standard stock solution), and 1 ppm by weight of nitric acid was further added. Then, a stability test was performed in the same manner as in Example 1. As a result, the stability was 97.3%.
【００２７】[0027]
【発明の効果】本発明によれば、過酸化水素水溶液に、
微量のタンタル、ニオブ又はジルコニウム金属元素種の
イオン又は化合物を添加することにより、保存安定性、
熱安定性に優れた過酸化水素水溶液を提供することがで
きた。また、これらの添加剤は、微量であり、しかも従
来の高価な有機キレート化合物等に比べて、安価である
ことから経済性にも優れた過酸化水素水溶液の安定化剤
である。According to the present invention, the aqueous hydrogen peroxide solution
By adding a trace amount of tantalum, niobium or zirconium metal element species ions or compounds, storage stability,
An aqueous hydrogen peroxide solution having excellent thermal stability was provided. In addition, these additives are trace amounts and are inexpensive as compared with conventional expensive organic chelate compounds and the like, and thus are excellent in economical efficiency of hydrogen peroxide aqueous solution.
フロントページの続き (72)発明者 西沢 千春 三重県四日市市日永東２丁目４番16号 三 菱瓦斯化学株式会社四日市工場内 (72)発明者 岡部 哲 三重県四日市市日永東２丁目４番16号 三 菱瓦斯化学株式会社四日市工場内 (72)発明者 松家 直子 三重県四日市市日永東２丁目４番16号 三 菱瓦斯化学株式会社四日市工場内Continuation of the front page (72) Inventor Chiharu Nishizawa 2-4-1-16 Hinagahigashi, Yokkaichi City, Mie Prefecture Inside the Yokkaichi Plant of Sanrishi Gas Chemical Co., Ltd. No. 16 Sanyo Gas Chemical Co., Ltd. Yokkaichi Plant (72) Inventor Naoko Matsuya 2-4-1 Hinagahigashi Yokkaichi City, Mie Prefecture
Claims (6)
なる群から選ばれた少なくとも一種の金属元素種を含有
することを特徴とする安定化された過酸化水素水溶液。1. A stabilized aqueous hydrogen peroxide solution containing at least one metal element selected from the group consisting of tantalum, zirconium and niobium.
コニウム及びニオブからなる群から選ばれた少なくとも
一種の金属元素種がイオン又は化合物として存在するこ
とを特徴とする請求項１記載の過酸化水素水溶液。2. The hydrogen peroxide according to claim 1, wherein at least one kind of metal element selected from the group consisting of tantalum, zirconium and niobium is present as an ion or a compound in the aqueous hydrogen peroxide solution. Aqueous solution.
ニウム及びニオブからなる群から選ばれた少なくとも一
種の金属元素種の元素濃度が、０．０１〜５０重量ｐｐ
ｍの範囲にある請求項１記載の過酸化水素水溶液。3. An aqueous hydrogen peroxide solution wherein the element concentration of at least one metal element selected from the group consisting of tantalum, zirconium and niobium is 0.01 to 50 parts per weight (pp).
2. The aqueous solution of hydrogen peroxide according to claim 1, which is in the range of m.
度が、０．０５〜５０重量ｐｐｍの範囲にある請求項３
記載の過酸化水素水溶液。4. The elemental concentration of tantalum in an aqueous hydrogen peroxide solution is in the range of 0.05 to 50 ppm by weight.
An aqueous hydrogen peroxide solution as described above.
素濃度が、０．０５〜２０重量ｐｐｍの範囲にある請求
項３記載の過酸化水素水溶液。5. The aqueous hydrogen peroxide solution according to claim 3, wherein the elemental concentration of zirconium in the aqueous hydrogen peroxide solution is in the range of 0.05 to 20 ppm by weight.
が、０．１０〜３０重量ｐｐｍの範囲にある請求項３記
載の過酸化水素水溶液。6. The aqueous hydrogen peroxide solution according to claim 3, wherein the elemental concentration of niobium in the aqueous hydrogen peroxide solution is in a range of 0.10 to 30 ppm by weight.
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|---|---|---|---|
| JP15161198A JP4120716B2 (en) | 1997-06-19 | 1998-06-01 | Stabilized hydrogen peroxide solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16263297 | 1997-06-19 | ||
| JP9-162632 | 1997-06-19 | ||
| JP15161198A JP4120716B2 (en) | 1997-06-19 | 1998-06-01 | Stabilized hydrogen peroxide solution |
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| Publication Number | Publication Date |
|---|---|
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| JP4120716B2 JP4120716B2 (en) | 2008-07-16 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053838A (en) * | 2000-08-09 | 2002-02-19 | Nankyou Efunika Kk | Composition for removing aldehyde |
| JP2020523253A (en) * | 2017-06-13 | 2020-08-06 | テクノロジー・フォー・プロパルジョン・アンド・イノベーション・ソシエタ・ペル・アチオニＴｅｃｈｎｏｌｏｇｙ Ｆｏｒ Ｐｒｏｐｕｌｓｉｏｎ Ａｎｄ Ｉｎｎｏｖａｔｉｏｎ Ｓ．Ｐ．Ａ． | Groups or systems for the rapid emergence of submarines or submarines |
-
1998
- 1998-06-01 JP JP15161198A patent/JP4120716B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053838A (en) * | 2000-08-09 | 2002-02-19 | Nankyou Efunika Kk | Composition for removing aldehyde |
| JP2020523253A (en) * | 2017-06-13 | 2020-08-06 | テクノロジー・フォー・プロパルジョン・アンド・イノベーション・ソシエタ・ペル・アチオニＴｅｃｈｎｏｌｏｇｙ Ｆｏｒ Ｐｒｏｐｕｌｓｉｏｎ Ａｎｄ Ｉｎｎｏｖａｔｉｏｎ Ｓ．Ｐ．Ａ． | Groups or systems for the rapid emergence of submarines or submarines |
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