JP5092665B2 - Percarboxylic acid composition - Google Patents
Percarboxylic acid composition Download PDFInfo
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- JP5092665B2 JP5092665B2 JP2007260883A JP2007260883A JP5092665B2 JP 5092665 B2 JP5092665 B2 JP 5092665B2 JP 2007260883 A JP2007260883 A JP 2007260883A JP 2007260883 A JP2007260883 A JP 2007260883A JP 5092665 B2 JP5092665 B2 JP 5092665B2
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Description
本発明は、消毒、漂白、洗浄、エポキシ化剤、合成原料、除草剤等に使用されるアミン系過カルボン酸組成物に関する。 The present invention relates to an amine-based percarboxylic acid composition used for disinfecting, bleaching, washing, epoxidizing agents, synthetic raw materials, herbicides and the like.
過カルボン酸組成物は過酸化水素よりも強力な酸化力を有することから、産業上有用な物質として用いられている。また、殺菌力も強く消毒薬や除草剤としても有効に使用可能であることが知られている。特に過酢酸が最も広く利用されているが、強い刺激臭を有することから、用途によって使用が制限されている。この問題を解決するために、低臭気の有機過酸組成物が提案されており、例えば過グルタル酸濃厚液（特許文献１）、過グルタル酸、過コハク酸及び過アジピン酸を含む過ジカルボン酸組成物（特許文献２）がある。しかしながら、過グルタル酸は易水溶性であるが高価であり、過コハク酸、過アジピン酸は溶解度が小さいという欠点を有している。
本発明は、経済性に優れ、易水溶性の低臭気過カルボン酸組成物を提供することにある。 An object of the present invention is to provide a low odor percarboxylic acid composition which is excellent in economic efficiency and easily water-soluble.
本発明者らは、本目的を解決するため鋭意検討を重ねた結果、広く工業的に使われているキレート剤と過酸化水素及び酸触媒を混合することにより易水溶性の過カルボン酸組成物が得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve this object, the present inventors have obtained a highly water-soluble percarboxylic acid composition by mixing a chelating agent, hydrogen peroxide and an acid catalyst, which are widely used industrially. Has been found, and the present invention has been completed.
即ち本発明は、トリエチレンテトラミン六酢酸、１，３−プロパンジアミン四酢酸、グリコールエーテルジアミン四酢酸、タウリン二酢酸、メチルグリシン二酢酸、ニトリロ三酢酸、グルタミン酸二酢酸及びシクロヘキサンジアミン四酢酸、並びにこれらの塩より選ばれた一種以上のキレート剤を８〜２０重量％、相当する過カルボン酸を０．５〜６重量％及び過酸化水素１５〜２５重量％を含有する過カルボン酸組成物に関する。 That is, the present invention relates to triethylenetetramine hexaacetic acid, 1,3-propanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, taurine diacetic acid, methylglycine diacetic acid, nitrilotriacetic acid, glutamic acid diacetic acid and cyclohexanediamine tetraacetic acid, and these The present invention relates to a percarboxylic acid composition containing 8 to 20% by weight of one or more chelating agents selected from the salts of the above, 0.5 to 6% by weight of the corresponding percarboxylic acid, and 15 to 25% by weight of hydrogen peroxide.
本発明によれば、低臭気、安価、水に対する溶解性が高い過カルボン酸組成物が得られる。 According to the present invention, a percarboxylic acid composition having low odor, low cost, and high solubility in water can be obtained.
本発明の組成物は、種々の方法で製造できるが、キレート剤１〜２０重量部、過酸化水素２１〜２８重量部（過酸化水素１００％換算）及び酸触媒１〜１５重量部、残部を水として混合する方法が適用される。 The composition of the present invention can be produced by various methods, but 1 to 20 parts by weight of a chelating agent, 21 to 28 parts by weight of hydrogen peroxide (100% hydrogen peroxide conversion), 1 to 15 parts by weight of an acid catalyst, and the balance A method of mixing as water is applied.
本発明に用いられる過酸化水素には、広く使われている工業用過酸化水素や半導体洗浄の分野で使用される高度に精製された超純過酸化水素が適用可能である。
キレート剤としては、トリエチレンテトラミン六酢酸、１，３−プロパンジアミン四酢酸、グリコールエーテルジアミン四酢酸、タウリン二酢酸、メチルグリシン二酢酸、ニトリロ三酢酸、グルタミン酸二酢酸及びシクロヘキサンジアミン四酢酸、並びにこれらの塩が用いられる。
As the hydrogen peroxide used in the present invention, industrial hydrogen peroxide widely used and highly purified ultrapure hydrogen peroxide used in the field of semiconductor cleaning can be applied.
Examples of chelating agents include triethylenetetramine hexaacetic acid, 1,3-propanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, taurine diacetic acid, methylglycine diacetic acid, nitrilotriacetic acid, glutamic acid diacetic acid and cyclohexanediamine tetraacetic acid, and these The salt is used.
反応は室温で行ってもよいが、より短時間で平衡に達するように、３０〜６０℃程度に加熱してもよい。ここで、酸触媒を添加するのが好ましい。酸触媒には、硫酸、リン酸、縮合リン酸類、ホスホン酸類、メタンスルホン酸等が好適に使用される。 The reaction may be performed at room temperature, but may be heated to about 30 to 60 ° C. so as to reach equilibrium in a shorter time. Here, it is preferable to add an acid catalyst. As the acid catalyst, sulfuric acid, phosphoric acid, condensed phosphoric acids, phosphonic acids, methanesulfonic acid and the like are preferably used.
本発明の組成物にさらに、過カルボン酸の安定剤として知られているジピコリン酸や１−ヒドロキシエタン−１，１−ジホスホン酸（ＨＥＤＰ）等の化合物も添加することも可能である。また、本発明の組成物の安定性を向上させる目的で、高純度原料を用いて調製することやイオン交換樹脂等に接触させることにより精製することも可能である。 Further, compounds such as dipicolinic acid and 1-hydroxyethane-1,1-diphosphonic acid (HEDP), which are known as stabilizers for percarboxylic acids, may be added to the composition of the present invention. Further, for the purpose of improving the stability of the composition of the present invention, it can be prepared by using a high-purity raw material or by contacting with an ion exchange resin or the like.
以下、実施例により本発明を具体的に説明するが、本発明は、以下の実施例に何らの制限を受けるものではない。
＜過酸化水素及び過カルボン酸濃度の定量＞
過酸化水素濃度は過マンガン酸カリウム法で、過カルボン酸濃度はヨードメトリー法で定量する。
試料を約０．１ｇ精秤した後、滴定中に過酸化水素と過カルボン酸の平衡が変化しないように、氷を加え試料を０℃付近に保つ。４Ｎの硫酸５ｍＬと適量の水を加え、１／１０規定Ｌ過マンガン酸カリウム溶液で滴定する。過マンガン酸カリウムの赤紫色が消えなくなる点を終点とし、過酸化水素濃度を求める。
次いで、ヨウ化カリウム約２ｇ、モリブデン酸アンモニウムの飽和水溶液を２〜３滴を加え、１／４０規定チオ硫酸ナトリウム溶液で滴定する。ヨウ素の黄色が薄くなったところで、デンプン指示薬を加え、紫色が消えたところを終点とする。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention does not receive a restriction | limiting at all to a following example.
<Quantification of hydrogen peroxide and percarboxylic acid concentrations>
The hydrogen peroxide concentration is determined by the potassium permanganate method, and the percarboxylic acid concentration is determined by the iodometry method.
After weighing approximately 0.1 g of the sample, ice is added to keep the sample at around 0 ° C. so that the equilibrium between hydrogen peroxide and percarboxylic acid does not change during the titration. Add 5 mL of 4N sulfuric acid and an appropriate amount of water, and titrate with 1/10 N L potassium permanganate solution. The hydrogen peroxide concentration is obtained with the point where the red purple color of potassium permanganate does not disappear.
Subsequently, about 2 g of potassium iodide and 2-3 drops of a saturated aqueous solution of ammonium molybdate are added and titrated with a 1/40 normal sodium thiosulfate solution. When the yellow color of iodine has decreased, a starch indicator is added, and the point where the purple color disappears is the end point.
過酸化水素濃度(%)=滴定量(mL)×0.1×ｆ／2／1000×34.02／試料(g)×100
過カルボン酸濃度(%)=滴定量(mL)×0.025×ｆ’／2／1000×ＦＷ／試料(g)×100
（ここに、ｆは、過マンガン酸カリウム溶液のファクターを表し、ｆ’は、チオ硫酸ナトリウム溶液のファクター、ＦＷは過カルボン酸の式量を表す。）
Hydrogen peroxide concentration (%) = titration (mL) x 0.1 x f / 2/1000 x 34.02 / sample (g) x 100
Percarboxylic acid concentration (%) = titration (mL) x 0.025 x f '/ 2/1000 x FW / sample (g) x 100
(Here, f represents the factor of the potassium permanganate solution, f ′ represents the factor of the sodium thiosulfate solution, and FW represents the formula amount of the percarboxylic acid.)
本発明のキレート剤は、分子内に２以上のカルボキシル基を有すため、ジ過カルボン酸、トリペルオキシ酸となる可能性があるが、当該明細書においては、便宜的にモノペルオキシ酸として過カルボン酸の濃度を算出している。 Since the chelating agent of the present invention has two or more carboxyl groups in the molecule, it may be a dipercarboxylic acid or a triperoxy acid. The concentration of carboxylic acid is calculated.
＜イースト菌を用いた殺菌試験方法＞
本発明の過カルボン酸組成物の殺菌力を調べるため、以下の方法で殺菌試験を実施した。使用したイースト菌と培地は以下の通りである。
イースト菌（パン酵母）：日清フーズ株式会社製 日清スーパーカメリア
培養用培地：三愛石油株式会社製 サンアイバイオチェッカーＭ
殺菌方法
（１）イースト菌１００ｍｇに超純水１０ｍＬを加える［１］。
（２）被検液９ｍＬに［１］１ｍＬを加え１分間放置する［２］。
（３）［２］１ｍＬに不活性化剤９ｍＬを加える［３］。
（４）［３］に超純水を加え全量を１００ｍＬとする［４］。
（５）バイオチェッカーＭを［４］に浸す。
（６）３０℃にて４８時間培養する。
（７）対照表により菌数を測定する。
注１）不活性化剤として１％チオ硫酸ナトリウム溶液を用いた。
注２）ブランクでは、被検液の替わりに超純水を用いた。
<Bactericidal test method using yeast>
In order to investigate the bactericidal activity of the percarboxylic acid composition of the present invention, a bactericidal test was carried out by the following method. The yeast and medium used are as follows.
Yeast bacteria (Ban yeast): Nisshin Foods Co., Ltd. Nisshin Super Camellia Culture medium: Sanai Oil Co., Ltd. Sun Eye Bio Checker M
Sterilization method (1) Add 10 mL of ultrapure water to 100 mg of yeast [1].
(2) Add 1 mL of [1] to 9 mL of the test solution and leave it for 1 minute [2].
(3) [2] Add 9 mL of deactivator to 1 mL [3].
(4) Add ultrapure water to [3] to make the total volume 100 mL [4].
(5) Soak biochecker M in [4].
(6) Incubate at 30 ° C. for 48 hours.
(7) Measure the number of bacteria according to the control table.
Note 1) A 1% sodium thiosulfate solution was used as an inactivating agent.
Note 2) In the blank, ultrapure water was used instead of the test solution.
実施例１〜３
アミン系キレート剤としてキレスト株式会社製のトリエチレンテトラミン六酢酸（ＴＴＨＡ）、１，３−プロパンジアミン四酢酸（ＰＤＴＡ）、グリコールエーテルジアミン四酢酸（ＧＥＤＴＡ）、を用いた。
アミン系キレート剤２．０ｇ、３５％過酸化水素水溶液（三菱ガス化学製）９．０ｇ、硫酸（和光純薬製）１．０ｇを３０ｍＬねじ口瓶に仕込み、３５℃恒温槽中に一晩放置した。各キレート剤から得た過カルボン酸溶液の組成を表１に示す。
Examples 1-3
Triethylenetetramine hexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), and glycol etherdiaminetetraacetic acid (GEDTA) manufactured by Kirest Co., Ltd. were used as the amine chelating agent.
Charge 2.0g of amine chelating agent, 9.0g of 35% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd.), 1.0g of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) into a 30mL screw cap bottle and put it in a 35 ℃ constant temperature bath overnight. I left it alone. Table 1 shows the composition of the percarboxylic acid solution obtained from each chelating agent.
実施例４
アミン系キレート剤としてキレスト株式会社製のタウリン二酢酸三ナトリウム（ＥＳＤＡ）の３０％溶液を用いた。
アミン系キレート剤溶液６．７ｇ、３５％過酸化水素水溶液（三菱ガス化学製）９．０ｇ、硫酸（和光純薬製）２．０ｇを３０ｍＬねじ口瓶に仕込み、３５℃恒温槽中に一晩放置した。各キレート剤から得た過カルボン酸溶液の組成を表１に示す。
Example 4
A 30% solution of trisodium taurine diacetate (ESDA) manufactured by Kirest Co., Ltd. was used as an amine chelating agent.
6.7 g of amine-based chelating agent solution, 9.0 g of 35% hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical), 2.0 g of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) are charged into a 30 mL screw cap bottle and placed in a constant temperature bath at 35 ° C. Left overnight. Table 1 shows the composition of the percarboxylic acid solution obtained from each chelating agent.
実施例５
アミン系キレート剤としてキレスト株式会社製の純度８５％のメチルグリシン二酢酸三ナトリウム（ＭＧＤＡ）を用いた。
アミン系キレート剤２．３ｇ、３５％過酸化水素水溶液（三菱ガス化学製）９．０ｇ、硫酸（和光純薬製）２．０ｇを３０ｍＬねじ口瓶に仕込み、３５℃恒温槽中に一晩放置した。各キレート剤から得た過カルボン酸溶液の組成を表１に示す。
Example 5
As the amine chelating agent, 85% pure methylglycine diacetate (MGDA) manufactured by Kirest Co., Ltd. was used.
Charge 2.3g of amine chelating agent, 9.0g of 35% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd.), 2.0g of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) into a 30mL screw cap bottle and put it in a 35 ℃ constant temperature bath overnight. I left it alone. Table 1 shows the composition of the percarboxylic acid solution obtained from each chelating agent.
実施例６
アミン系キレート剤としてＢＡＳＦ製のニトリロ三酢酸三ナトリウム（ＮＴＡ）を用いた。 アミン系キレート剤２．０ｇ、３５％過酸化水素水溶液（三菱ガス化学製）１２．０ｇ、硫酸（和光純薬製）２．１ｇを３０ｍＬねじ口瓶に仕込み、３５℃恒温槽中に５日間放置した。各キレート剤から得た過カルボン酸溶液の組成を表１に示す。
Example 6
As the amine-based chelating agent, trisodium nitrilotriacetate (NTA) manufactured by BASF was used. Charge 2.0g of amine chelating agent, 12.0g of 35% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd.), 2.1g of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) into a 30mL screw cap bottle, and keep it in a 35 ℃ constant temperature bath for 5 days I left it alone. Table 1 shows the composition of the percarboxylic acid solution obtained from each chelating agent.
実施例７
アミン系キレート剤としてキレスト株式会社製のグルタミン酸二酢酸四ナトリウム（ＧＬＤＡ）の４０％溶液を用いた。
アミン系キレート剤溶液５．０ｇ、３５％過酸化水素水溶液（三菱ガス化学製）１２．０ｇ、硫酸（和光純薬製）２．１ｇを３０ｍＬねじ口瓶に仕込み、３５℃恒温槽中に一晩放置した。各キレート剤から得た過カルボン酸溶液の組成を表１に示す。
Example 7
A 40% solution of tetrasodium glutamate diacetate (GLDA) manufactured by Kirest Co., Ltd. was used as an amine chelating agent.
An amine chelating agent solution (5.0 g), 35% hydrogen peroxide aqueous solution (Mitsubishi Gas Chemical Co., Ltd.) (12.0 g) and sulfuric acid (Wako Pure Chemical Industries, Ltd.) (2.1 g) were charged into a 30 mL screw cap bottle and placed in a 35 ° C. constant temperature bath. Left overnight. Table 1 shows the composition of the percarboxylic acid solution obtained from each chelating agent.
実施例８
アミン系キレート剤としてキレスト株式会社製のシクロヘキサンジアミン四酢酸（ＣｙＤＴＡ）を用いた。
アミン系キレート剤１．６ｇ、３５％過酸化水素水溶液（三菱ガス化学製）１２．０ｇ、硫酸（和光純薬製）１．０ｇを３０ｍＬねじ口瓶に仕込み、３５℃恒温槽中に５日間放置した。各キレート剤から得た過カルボン酸溶液の組成を表１に示す。
Example 8
Cyclohexanediaminetetraacetic acid (CyDTA) manufactured by Kirest Co., Ltd. was used as the amine chelating agent.
1.6 g of amine chelating agent, 12.0 g of 35% aqueous hydrogen peroxide solution (Mitsubishi Gas Chemical Co., Ltd.), 1.0 g of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) are charged into a 30 mL screw cap bottle and placed in a 35 ° C constant temperature bath for 5 days. I left it alone. Table 1 shows the composition of the percarboxylic acid solution obtained from each chelating agent.
実施例３〜７の過カルボン酸溶液を希釈し、２、１、０．５、０．２５％の各過カルボン酸濃度について、イースト菌を用いた殺菌試験を行った結果を表２に示す。 Table 2 shows the results of diluting the percarboxylic acid solutions of Examples 3 to 7 and performing a sterilization test using yeast for each of the percarboxylic acid concentrations of 2, 1, 0.5 and 0.25%.
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| JP2015533375A (en) * | 2012-10-18 | 2015-11-24 | シーエイチディー・バイオサイエンス，インコーポレーテッド | Composition comprising peroxy acid |
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| JP2871124B2 (en) * | 1991-01-23 | 1999-03-17 | 日本パーオキサイド株式会社 | Safe peracetic acid composition |
| JP2002155048A (en) * | 2000-11-22 | 2002-05-28 | Mitsubishi Chemicals Corp | Method for stabilizing organic peracid |
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