TW201300313A - Weakly acidic hypochlorous acid and apparatus and method for producing the same - Google Patents
Weakly acidic hypochlorous acid and apparatus and method for producing the same Download PDFInfo
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本發明係關於次氯酸水溶液之製造裝置及製造方法。更詳細言之，本發明係關於用以製造次氯酸水溶液之裝置及方法，其不使用酸，且實質上不會產生氯氣。 The present invention relates to a manufacturing apparatus and a manufacturing method of a hypochlorous acid aqueous solution. More specifically, the present invention relates to an apparatus and method for producing an aqueous hypochlorous acid solution which does not use an acid and which does not substantially generate chlorine gas.
先前已知次氯酸具有殺菌作用。因此，次氯酸溶液已被利用於各式各樣領域，亦已利用於自來水之殺菌及食品之殺菌等。 Hypochlorous acid has previously been known to have a bactericidal effect. Therefore, hypochlorous acid solution has been utilized in various fields, and has also been utilized for sterilization of tap water and sterilization of foods.
此次氯酸之殺菌效果係經由次氯酸鈉等次氯酸鹽、水及酸的反應，藉由次氯酸離子與氫離子結合而生成的分子狀次氯酸而產生作用。 The bactericidal effect of chloric acid is caused by the reaction of hypochlorite such as sodium hypochlorite, water and acid, and the molecular hypochlorous acid produced by the combination of hypochlorous acid ions and hydrogen ions.
於殺菌目的上使用次氯酸的情形，一般而言，已知非解離之分子狀次氯酸狀態的殺菌效果最高。又，由次氯酸鈉等製造的次氯酸鹽溶液，已知依其溶液的pH值，殺菌效果會顯著變動。一般而言，於鹼性之pH值，次氯酸呈次氯酸離子而存在，殺菌效果低。另一方面，即使為酸性之pH值，殺菌效果低，又會產生氯氣。通常，關於次氯酸，一般認為其pH值為約3.5~6.5時，分子之次氯酸的存在率高。 In the case where hypochlorous acid is used for sterilization purposes, in general, the non-dissociated molecular state hypochlorous acid state is known to have the highest bactericidal effect. Further, the hypochlorite solution produced from sodium hypochlorite or the like is known to have a significant change in the bactericidal effect depending on the pH of the solution. In general, hypochlorous acid is present as a hypochlorite ion at a pH of alkaline, and the bactericidal effect is low. On the other hand, even if it is an acidic pH value, the bactericidal effect is low, and chlorine gas is generated. In general, regarding hypochlorous acid, it is generally considered that when the pH is about 3.5 to 6.5, the molecular hypochlorous acid is present at a high rate.
另一方面，次氯酸鈉水溶液係被製造為呈鹼性之溶液。又，一般而言，即使將次氯酸鈉水溶液稀釋至作為殺菌水使用的濃度50~100ppm，pH值僅下降至8.5~9.5左右。因此，於殺菌目的上使用次氯酸的情形，有必要將pH值降 低至殺菌效果高的pH值。 On the other hand, an aqueous solution of sodium hypochlorite is produced as an alkaline solution. Further, in general, even if the sodium hypochlorite aqueous solution is diluted to a concentration of 50 to 100 ppm used as the sterilizing water, the pH value is only lowered to about 8.5 to 9.5. Therefore, in the case of using hypochlorous acid for sterilization purposes, it is necessary to lower the pH. Low to a high bactericidal pH.
就降低次氯酸鈉水溶液之pH值的方法而言，已知電解法及二液法等。然而，電解法必須有具備電解槽的裝置，維護費花費高。又，電極為必要的，也需要成本。再者，以電解法僅可製造低濃度的弱酸性次氯酸。另一方面，二液法為藉由將次氯酸鈉水溶液與鹽酸混合，將pH值調製於酸性側的方法。此方法因藉由鹽酸等酸而調整pH值，包含所謂混合次氯酸鈉及酸的步驟，而產生安全性的問題。尤其，混合次氯酸鈉與鹽酸時會產生氯氣，而非常危險。於弱酸性次氯酸之製造，只要將高濃度之次氯酸鈉及酸作為原料來使用，則具有危險的情況不會改變。因此，即使已知降低pH值時殺菌力會上升，但pH值的調節困難，且因過度降低pH值時會產生氯氣，有無法輕鬆地應用的問題。從而冀望根本上不會伴隨氯氣產生的危險之製造方法。 As a method of lowering the pH of the sodium hypochlorite aqueous solution, an electrolytic method, a two-liquid method, and the like are known. However, the electrolysis method must have a device equipped with an electrolytic cell, and the maintenance cost is high. Also, the electrodes are necessary and costly. Further, only a low concentration of weakly acidic hypochlorous acid can be produced by electrolysis. On the other hand, the two-liquid method is a method in which the pH is adjusted to the acidic side by mixing an aqueous sodium hypochlorite solution with hydrochloric acid. This method has a problem of safety by adjusting the pH by an acid such as hydrochloric acid, and includes a step of mixing sodium hypochlorite and an acid. In particular, mixing sodium hypochlorite with hydrochloric acid produces chlorine gas, which is very dangerous. In the production of weakly acidic hypochlorous acid, if a high concentration of sodium hypochlorite and an acid are used as a raw material, the risk is not changed. Therefore, even if it is known that the sterilizing power is increased when the pH is lowered, the adjustment of the pH is difficult, and chlorine gas is generated when the pH is excessively lowered, and there is a problem that it cannot be easily applied. Therefore, it is expected that there will be no manufacturing method that is not accompanied by the danger of chlorine gas.
就為了降低次氯酸鈉水溶液之pH值，不使用鹽酸的方法而言，專利文獻1及專利文獻2已揭示使用離子交換樹脂的方法。專利文獻1已揭示使用將含有礦物質等陽離子的水以氫取代型離子交換樹脂來替代鹽酸而將pH值降低的溶液，來降低次氯酸鈉水溶液之pH值的方法。然而，以此方法，所獲得的酸性溶液與次氯酸鈉混合後，pH值會降低至產生氯氣的值，無法避免氯氣的產生。尤其，已記載將總重量作離子交換的情形，pH值會降低至2.7。因此，藉由離子交換而獲得酸性溶液後，與次氯酸鈉混合的步驟為必要的，故需要勞力。 In order to reduce the pH of the sodium hypochlorite aqueous solution and not to use hydrochloric acid, Patent Document 1 and Patent Document 2 disclose a method of using an ion exchange resin. Patent Document 1 discloses a method of reducing the pH of an aqueous solution of sodium hypochlorite by using a solution containing a cation such as a mineral as a hydrogen-substituted ion exchange resin instead of hydrochloric acid to lower the pH. However, in this way, after the obtained acidic solution is mixed with sodium hypochlorite, the pH value is lowered to the value of generating chlorine gas, and the generation of chlorine gas cannot be avoided. In particular, it has been described that the total weight is ion exchanged, and the pH is lowered to 2.7. Therefore, after the acidic solution is obtained by ion exchange, the step of mixing with sodium hypochlorite is necessary, so labor is required.
又，專利文獻2已揭示以製造一切不含有鹽類的次氯酸為目的，而用以製造次氯酸的方法。此方法中，首先將次氯酸鈉溶液以氫取代型離子交換樹脂來處理而以氫離子取代金屬離子。其次，具有所獲得的溶液以陰離子交換樹脂處理，氯離子以氫氧離子取代的步驟。從而，有必要以兩種類之離子交換樹脂加以處理，此方法亦花費勞力，次氯酸之pH值的調整有困難。又，已揭示次氯酸鈉溶液以氫取代型離子交換樹脂來處理時，液性成為強酸性，殺菌效果會降低。再者，無法避免氯氣的產生。 Further, Patent Document 2 discloses a method for producing hypochlorous acid for the purpose of producing hypochlorous acid which does not contain any salt. In this method, a sodium hypochlorite solution is first treated with a hydrogen-substituted ion exchange resin to replace a metal ion with a hydrogen ion. Next, there is a step of treating the obtained solution with an anion exchange resin and replacing the chloride ions with hydroxide ions. Therefore, it is necessary to treat with two types of ion exchange resins, and this method also takes labor, and it is difficult to adjust the pH of hypochlorous acid. Further, it has been revealed that when the sodium hypochlorite solution is treated with a hydrogen-substituted ion exchange resin, the liquidity becomes strongly acidic and the sterilizing effect is lowered. Furthermore, the generation of chlorine gas cannot be avoided.
如上所述，正冀望不使用酸，且實質上不會產生有毒的氯氣之製造弱酸性次氯酸的裝置及方法。次氯酸尤其於pH值3.5~7左右的情形，不會產生氯氣，具有安全且強力的殺菌效果。因此，正冀望容易且安全地製造如此pH值之弱酸性次氯酸的裝置及方法。 As described above, an apparatus and method for producing weakly acidic hypochlorous acid which does not substantially use an acid and which does not substantially produce toxic chlorine gas are being expected. Hypochlorous acid, especially at a pH of about 3.5 to 7, does not produce chlorine gas and has a safe and strong bactericidal effect. Therefore, an apparatus and method for producing a weakly acidic hypochlorous acid of such pH value is expected to be easily and safely.
[專利文獻1]特開平6-206076號公報 [Patent Document 1] JP-A-6-206076
[專利文獻2]特開2009-274950號公報 [Patent Document 2] JP-A-2009-274950
因此，本發明之目的係提供不使用酸，且實質上不會產生氯氣之用以製造次氯酸水溶液之裝置及方法。 Accordingly, it is an object of the present invention to provide an apparatus and method for producing a hypochlorous acid aqueous solution which does not use an acid and which does not substantially generate chlorine gas.
本發明提供製造次氯酸水溶液之方法，其藉由使用於氯氣產生的pH值以上具有緩衝作用的弱酸性離子交換體，不使用鹽酸等酸，且使pH值不降低至產生氯氣的值，來製造次氯酸水溶液。 The present invention provides a method for producing a hypochlorous acid aqueous solution which uses a weakly acidic ion exchanger having a buffering action above a pH value generated by chlorine gas, does not use an acid such as hydrochloric acid, and does not lower the pH value to a value at which chlorine gas is generated. To make a hypochlorous acid aqueous solution.
即，本發明提供一種製造方法，其係一種弱酸性次氯酸之製造方法，包含將次氯酸鹽溶液以於氯氣產生的pH值以上具有緩衝作用的弱酸性離子交換體來處理的步驟。 That is, the present invention provides a production method which is a method for producing a weakly acidic hypochlorous acid, which comprises the step of treating a hypochlorite solution with a weakly acidic ion exchanger having a buffering effect above the pH of chlorine gas.
又，本發明提供上述製造方法之特徵係次氯酸鹽為次氯酸鈉、次氯酸鉀或次氯酸鈣。 Further, the present invention provides the above-described production method characterized in that the hypochlorite is sodium hypochlorite, potassium hypochlorite or calcium hypochlorite.
又，本發明提供上述製造方法之特徵係以弱酸性離子交換體處理後的弱酸性次氯酸之pH值為pH3.5~pH7.5。 Further, the present invention provides the above-described production method characterized in that the pH of the weakly acidic hypochlorous acid treated with the weakly acidic ion exchanger is pH 3.5 to pH 7.5.
又，本發明提供上述製造方法之特徵係次氯酸鹽溶液為500ppm以上。 Further, the present invention provides the above production method characterized in that the hypochlorite solution is 500 ppm or more.
再者，本發明提供一種弱酸性次氯酸之製造裝置，其具備於氯氣產生的pH值以上具有緩衝作用的弱酸性離子交換體。 Furthermore, the present invention provides a device for producing a weakly acidic hypochlorous acid, which comprises a weakly acidic ion exchanger having a buffering action at a pH higher than or equal to the chlorine gas.
又，本發明提供上述弱酸性次氯酸之製造裝置，其為上述弱酸性次氯酸之製造裝置，進一步具備次氯酸鹽溶液之稀釋裝置及填充弱酸性離子交換體的容器。 Moreover, the present invention provides the apparatus for producing a weakly acidic hypochlorous acid, which is characterized in that the apparatus for producing a weakly acidic hypochlorous acid further comprises a dilution device of a hypochlorite solution and a container filled with a weakly acidic ion exchanger.
又，本發明提供一種殺菌裝置，其具備於氯氣產生的pH值以上具有緩衝作用的弱酸性離子交換體及用以將弱酸性次氯酸噴霧之噴霧裝置。 Moreover, the present invention provides a sterilizing apparatus comprising a weakly acidic ion exchanger having a buffering action at a pH higher than that of chlorine gas, and a spraying device for spraying weakly acidic hypochlorous acid.
再者，本發明提供一種用以製造弱酸性次氯酸之容器，其含有次氯酸鈣及於產生氯氣的pH值以上具有緩衝作 用的弱酸性離子交換體。 Furthermore, the present invention provides a container for producing weakly acidic hypochlorous acid which contains calcium hypochlorite and has a buffering effect above the pH at which chlorine is generated. A weakly acidic ion exchanger used.
再者，本發明提供由上述製造方法所製造的弱酸性次氯酸。 Further, the present invention provides weakly acidic hypochlorous acid produced by the above production method.
再者，本發明提供一種洗淨劑之製造方法，其為含有弱酸性次氯酸洗淨劑之製造方法，其包含將含有次氯酸鹽及界面活性劑的溶液，以於氯氣產生的pH值以上具有緩衝作用的弱酸性離子交換體加以處理的步驟。 Furthermore, the present invention provides a method for producing a detergent, which comprises a method for producing a weakly acidic hypochlorous acid detergent comprising a solution containing hypochlorite and a surfactant, and a pH generated by chlorine gas. A step of treating a weakly acidic ion exchanger having a buffering value or more.
又，本發明提供包含由上述製造方法所製造的弱酸性次氯酸及界面活性劑之洗淨劑。 Further, the present invention provides a detergent comprising weakly acidic hypochlorous acid and a surfactant prepared by the above production method.
再者，本發明提供一種由次氯酸鹽溶液去除金屬離子之金屬離子去除劑，其含有弱酸性離子交換體。 Furthermore, the present invention provides a metal ion remover for removing metal ions from a hypochlorite solution, which contains a weakly acidic ion exchanger.
又，本發明提供一種方法，其為用以自次氯酸鹽溶液去除金屬離子之方法，其包含將次氯酸鹽溶液以弱酸性離子交換體加以處理的步驟。 Further, the present invention provides a method for removing metal ions from a hypochlorite solution comprising the step of treating a hypochlorite solution with a weakly acidic ion exchanger.
依據本發明，可製造弱酸性次氯酸水溶液，其不使用酸，且不會使pH值降低至產生氯氣的pH值以下。又，依據本發明，可製造高濃度之次氯酸水溶液。再者，依據本發明，因為可製造弱酸性次氯酸，且不會使pH值降低至如先前技術之製造方法般會產生氯氣的pH值以下，故可製造較習知弱酸性次氯酸更少漂白效果之弱酸性次氯酸。又，依據本發明，可防止如習知製造裝置般由於來自次氯酸鹽溶液之礦物質成分所造成的白化現象。 According to the present invention, a weakly acidic aqueous hypochlorous acid solution can be produced which does not use an acid and does not lower the pH below the pH at which chlorine gas is generated. Further, according to the present invention, a high concentration aqueous hypochlorous acid solution can be produced. Furthermore, according to the present invention, since weakly acidic hypochlorous acid can be produced without lowering the pH to below the pH of chlorine gas as produced by the prior art manufacturing method, it is possible to produce a relatively weakly acidic hypochlorous acid. Weak acid hypochlorous acid with less bleaching effect. Further, according to the present invention, it is possible to prevent whitening due to a mineral component derived from a hypochlorite solution as in a conventional manufacturing apparatus.
又，依據本發明，可製造含有弱酸性次氯酸之洗淨劑， 其不使用酸，且不會使pH值降低至氯氣產生的pH值以下。 Moreover, according to the present invention, a detergent containing weakly acidic hypochlorous acid can be produced. It does not use acid and does not lower the pH below the pH produced by chlorine.
又，依據本發明，可生成金屬離子被去除的安定弱酸性次氯酸。 Further, according to the present invention, stable weakly acidic hypochlorous acid in which metal ions are removed can be produced.
本發明者們發現藉由將具有鹼性的次氯酸鈉溶液以弱酸性離子交換體加以處理，可實質上不產生氯氣且獲得pH值3.5~7.5左右的弱酸性次氯酸水溶液。 The present inventors have found that by treating a basic sodium hypochlorite solution with a weakly acidic ion exchanger, substantially no chlorine gas can be generated and a weakly acidic hypochlorous acid aqueous solution having a pH of about 3.5 to 7.5 can be obtained.
於本說明書，氯氣產生的pH值以上係指使次氯酸鹽溶液之pH值降低時，實質上不會產生氯氣的pH值的範圍。 又，於本說明書，弱酸性包含於使鹼性之次氯酸鹽溶液之pH值降低時，實質上不會產生氯氣的pH值之範圍。例如，弱酸性係指於弱酸性~中性之範圍，pH值為約3.5~7.5之值之範圍，尤其是4.0~7.0之值之範圍。實質上不產生氯氣係指實質不會產生對活體有危險程度的氯氣、實質上無法確認使次氯酸鹽溶液之pH值降低時會自溶液產生氯的氣泡、或使次氯酸鹽溶液之pH值降低時實質上不會有由於氯而產生的漂白作用。於本發明所屬技術領域，一般認為即使於pH值4.0實質上亦不產生氯氣，至pH值3.5左右亦不會有氯氣。因此，氯氣產生的pH值係包含如此pH值以下之pH值之範圍。 In the present specification, the pH above the chlorine gas is a range in which the pH of the chlorine gas is substantially not generated when the pH of the hypochlorite solution is lowered. Further, in the present specification, when the weak acidity is included in the pH of the alkaline hypochlorite solution, the pH range of the chlorine gas is not substantially generated. For example, weakly acidic means a range of weakly acidic to neutral, pH is in the range of about 3.5 to 7.5, especially in the range of 4.0 to 7.0. The fact that substantially no chlorine gas is produced means that chlorine gas which does not cause a dangerous degree to the living body is substantially produced, and it is substantially impossible to confirm that a chlorine gas is generated from the solution when the pH of the hypochlorite solution is lowered, or a hypochlorite solution is used. When the pH is lowered, there is substantially no bleaching effect due to chlorine. In the technical field to which the present invention pertains, it is generally considered that chlorine gas is not generated substantially at a pH of 4.0, and chlorine gas is not present at a pH of about 3.5. Therefore, the pH generated by chlorine gas contains a range of pH values below this pH.
以下，詳細說明關於本發明中弱酸性次氯酸之製造方法。本發明中弱酸性次氯酸之製造方法包含將次氯酸鹽溶 液以弱酸性離子交換體加以處理的步驟。於本說明書，次氯酸鹽溶液係指包含本項技術領域者一般所認識之次氯酸鈉(NaClO)、次氯酸鉀(KClO)及次氯酸鈣(Ca(ClO)2)等任意次氯酸鹽的溶液。次氯酸鹽可使用市售材料及本發明所屬技術領域中眾所皆知之方法所製造的材料。又，溶液可使用水等任意溶液中者。又，亦可為緩衝液中之溶液。再者，次氯酸鹽溶液可含有任意之添加物。例如，於次氯酸鹽溶液可含有碳酸氫鈉及乳酸鈣等任意之弱酸鹽。藉由含有如此添加物，可將次氯酸鹽溶液調整至殺菌活性高的pH值。 Hereinafter, a method for producing weakly acidic hypochlorous acid in the present invention will be described in detail. The method for producing weakly acidic hypochlorous acid in the present invention comprises the step of treating the hypochlorite solution with a weakly acidic ion exchanger. In the present specification, hypochlorite solution refers to any hypochlorite such as sodium hypochlorite (NaClO), potassium hypochlorite (KClO) and calcium hypochlorite (Ca(ClO) 2 ) generally recognized by those skilled in the art. Solution. Hypochlorite can be made using commercially available materials and materials made by methods well known in the art to which the invention pertains. Further, the solution can be used in any solution such as water. Also, it may be a solution in a buffer. Further, the hypochlorite solution may contain any additives. For example, the hypochlorite solution may contain any weak acid salt such as sodium hydrogencarbonate or calcium lactate. By containing such an additive, the hypochlorite solution can be adjusted to a pH at which the bactericidal activity is high.
於本發明之方法，次氯酸鹽溶液可使用任意濃度之溶液。例如，將市售的12%次氯酸鈉溶液稀釋，可於10~120000ppm以上之濃度，例如可以100、200、500、1000、10000及120000ppm來使用。依據本發明之方法，可製造所謂10000ppm之習知方法所無法製造的濃度之弱酸性次氯酸。又，亦可直接製造於殺菌目的下被實際使用的濃度之50~1000ppm濃度之弱酸性次氯酸。 In the method of the present invention, a solution of any concentration can be used for the hypochlorite solution. For example, a commercially available 12% sodium hypochlorite solution can be used at a concentration of 10 to 120,000 ppm or more, for example, 100, 200, 500, 1000, 10,000, and 120,000 ppm. According to the method of the present invention, a weakly acidic hypochlorous acid of a concentration which cannot be produced by a conventional method of 10,000 ppm can be produced. Further, it is also possible to directly produce a weakly acidic hypochlorous acid having a concentration of 50 to 1000 ppm which is actually used under sterilization purposes.
又，次氯酸鹽溶液亦可於實施本發明之製造方法之際加以調製。不只被製造作為如次氯酸鈉溶液的鹽，亦可使用固體的鹽。例如，藉由將次氯酸鈣等固體添加至水中，可調製次氯酸鹽溶液。 Further, the hypochlorite solution can also be prepared at the time of carrying out the production method of the present invention. Not only a salt such as a sodium hypochlorite solution but also a solid salt can be used. For example, a hypochlorite solution can be prepared by adding a solid such as calcium hypochlorite to water.
本發明之方法係使用於氯氣產生的pH值以上具有緩衝作用的弱酸性離子交換體。弱酸性離子交換體可為例如具有將羧酸基(-COOH)作為交換基之離子交換體。又， 弱酸性離子交換體可交換NaOH等鹼及NaHCO3等弱酸之鹽。於本發明之方法，弱酸性離子交換體可使用本發明所屬技術領域者所習知之任意弱酸性離子交換體。弱酸性離子交換體可為甲基丙烯酸系弱酸性陽離子交換樹脂及丙烯酸系弱酸性陽離子交換樹脂等弱酸性離子交換樹脂。例如，Amberlite IRC-76(Organo股份有限公司)等本發明所屬技術領域者所習知之弱酸性離子交換樹脂。又，弱酸性離子交換樹脂之外亦可使用陶瓷及天然的礦石等具有離子交換作用及pH值緩衝作用的任意材料作為弱酸性離子交換體使用。 The method of the present invention is a weakly acidic ion exchanger having a buffering action above the pH of chlorine gas. The weakly acidic ion exchanger may be, for example, an ion exchanger having a carboxylic acid group (-COOH) as an exchange group. Further, the weakly acidic ion exchanger can exchange a base such as NaOH or a weak acid such as NaHCO 3 . In the method of the present invention, the weakly acidic ion exchanger can be any of the weakly acidic ion exchangers known to those skilled in the art. The weakly acidic ion exchanger may be a weakly acidic ion exchange resin such as a methacrylic weakly acidic cation exchange resin or an acrylic weakly acidic cation exchange resin. For example, Amberlite IRC-76 (Organo Co., Ltd.) is a weakly acidic ion exchange resin known to those skilled in the art. Further, as the weakly acidic ion exchange resin, any material having an ion exchange effect and a pH buffering action such as ceramics and natural ore may be used as the weakly acidic ion exchanger.
又，本發明所使用的弱酸性離子交換體於例如弱酸性~中性之範圍、pH值為約3.5~7.5之範圍，尤其pH值為4.0~7.0之範圍下具有緩衝作用。因此，依據本發明之方法，以弱酸性離子交換體處理後溶液之pH值為pH3.5~7.5，例如pH4.0~6.5之範圍。因此不會有產生氯氣之虞，且殺菌效果亦高。又，具有如此緩衝作用的離子交換體，於吸附過剩氫離子之際，為了一進釋放吸附的鈉離子或鈣離子並一邊吸附，亦不會有部分pH值為產生氯氣的pH值以下。而且，於次氯酸鹽溶液與具有緩衝作用的離子交換體之反應，降低pH值的效果係由此離子交換體負責。因此，本發明所使用的弱酸性離子交換體於降低次氯酸鹽溶液之pH值之際，亦不會有暫時地或部分地成為產生氯氣的pH值以下的情形。如習知之次氯酸之製造方法，使用鹽酸等酸而降低次氯酸鹽溶液之pH值的情形，由於產生氯氣的pH值 之酸與次氯酸鹽溶液混合，一般認為於混合過程中會暫時或局部地使溶液之pH值降低至產生氯氣的pH值為止而產生氯氣。然而，藉由如本發明中使用的弱酸性離子交換體，並不會產生氯氣。又，本發明所使用的弱酸性離子交換體對中性鹽並不會產生影響。 Further, the weakly acidic ion exchanger used in the present invention has a buffering action in a range of, for example, a weakly acidic to a neutral range, a pH of about 3.5 to 7.5, and particularly a pH of 4.0 to 7.0. Therefore, according to the method of the present invention, the pH of the solution after treatment with a weakly acidic ion exchanger is pH 3.5 to 7.5, for example, a pH of 4.0 to 6.5. Therefore, there is no possibility of chlorine gas generation, and the sterilization effect is also high. Further, the ion exchanger having such a buffering action does not have a partial pH value below the pH at which chlorine gas is generated in order to adsorb adsorbed sodium ions or calcium ions while adsorbing excess hydrogen ions. Moreover, the effect of lowering the pH in the reaction of the hypochlorite solution with the buffering ion exchanger is the responsibility of the ion exchanger. Therefore, the weakly acidic ion exchanger used in the present invention does not temporarily or partially become a pH value of chlorine gas when the pH of the hypochlorite solution is lowered. As is known in the production method of hypochlorous acid, the use of an acid such as hydrochloric acid to reduce the pH of the hypochlorite solution, due to the pH of the chlorine gas The acid is mixed with the hypochlorite solution, and it is generally considered that chlorine is generated by temporarily or locally lowering the pH of the solution to a pH at which chlorine is generated during the mixing. However, chlorine gas is not produced by the weakly acidic ion exchanger as used in the present invention. Further, the weakly acidic ion exchanger used in the present invention does not affect the neutral salt.
又，於本發明之方法，弱酸性離子交換體可以任意量來使用。只要為本發明所屬技術領域者，可因應製造的弱酸性次氯酸之濃度及量等而調節弱酸性離子交換體的量。本發明之方法即使使用過量之弱酸性離子交換體來處理次氯酸鹽溶液，生成的弱酸性次氯酸之pH值亦不會降的過低，而非常地安全。 Further, in the method of the present invention, the weakly acidic ion exchanger can be used in an arbitrary amount. As long as it is the technical field of the present invention, the amount of the weakly acidic ion exchanger can be adjusted in accordance with the concentration and amount of the weakly acidic hypochlorous acid to be produced. The method of the present invention, even if an excessively weakly acidic ion exchanger is used to treat the hypochlorite solution, the pH of the weakly acidic hypochlorous acid produced is not lowered too low, and is extremely safe.
如上所述，以本發明之方法即使使用過量之弱酸性離子交換體，亦可維持pH值為一定值。因此，依據本發明之方法使次氯酸鹽溶液之pH值降低後，不去除弱酸性離子交換體而直接殘留於弱酸性次氯酸溶液中，歷經長期間可安定地維持pH值。 As described above, even if an excessive amount of weakly acidic ion exchanger is used in the method of the present invention, the pH can be maintained at a constant value. Therefore, according to the method of the present invention, the pH of the hypochlorite solution is lowered, and the weakly acidic ion exchanger is not removed, but remains directly in the weakly acidic hypochlorous acid solution, and the pH can be stably maintained over a long period of time.
又，弱酸性離子交換體亦具有吸附溶液中之鈣及鎂等礦物質成分的性質。因此，依據本發明之方法使次氯酸鹽溶液之pH值降低後，藉由不去除弱酸性離子交換體而直接殘留於弱酸性次氯酸溶液中，可防止由於裝置內產生的礦物質成分的白化。 Further, the weakly acidic ion exchanger also has the property of adsorbing mineral components such as calcium and magnesium in the solution. Therefore, after the pH of the hypochlorite solution is lowered according to the method of the present invention, it can be directly retained in the weakly acidic hypochlorous acid solution without removing the weakly acidic ion exchanger, thereby preventing the mineral component generated in the device. Whitening.
為了防止白化，例如，將依據本發明之方法使pH值降低的次氯酸鹽溶液，使用加濕器等噴霧裝置加以噴霧之際，裝置內可具備弱酸性離子交換體。具備弱酸性離子交 換體的噴霧裝置，如上所述，可防止來自水中所含的鈣及鎂等所致裝置內之白化及霧化的水滴所致的白化。又，使用時，弱酸性次氯酸溶液以水等稀釋至適當濃度的情形，因應稀釋的水之pH值，稀釋後之次氯酸鹽溶液之pH值可能會變化。然而，依據具備弱酸性離子交換體的噴霧裝置，藉由弱酸性離子交換體之pH值緩衝作用，稀釋後之次氯酸鹽溶液之pH值可適當地維持pH值。因此，藉由使用具備如此弱酸性離子交換體的噴霧裝置，可將稀釋後次氯酸鹽溶液之pH值維持於殺菌效果高的pH值。 In order to prevent whitening, for example, a hypochlorite solution in which the pH is lowered by the method of the present invention is sprayed with a spray device such as a humidifier, and a weakly acidic ion exchanger may be provided in the device. Weakly acidic ion exchange As described above, the replacement spray device can prevent whitening due to whitening and atomized water droplets in the device due to calcium, magnesium, and the like contained in the water. Further, in use, when the weakly acidic hypochlorous acid solution is diluted to an appropriate concentration with water or the like, the pH of the diluted hypochlorite solution may vary depending on the pH of the diluted water. However, according to the spray device having a weakly acidic ion exchanger, the pH of the diluted hypochlorite solution can be appropriately maintained at a pH value by the pH buffering action of the weakly acidic ion exchanger. Therefore, by using a spray device having such a weakly acidic ion exchanger, the pH of the diluted hypochlorite solution can be maintained at a pH at which the bactericidal effect is high.
另一方面，弱酸性陽離子交換樹脂中各種離子的吸附強度，一般而言，價數高的離子選擇性程度變大，尤其對H離子的選擇性係非常地大為特徵。因此，H離子以其他陽離子交換後，使用鹽酸或硫酸水溶液等藥劑而可容易地回到R-COOH的形態。因此，重複使用時之再生為容易，以較理論化學當量多的程度的藥劑量下再生成為可能。 On the other hand, the adsorption strength of various ions in the weakly acidic cation exchange resin is generally such that the degree of ion selectivity is high, and the selectivity to H ions is particularly large. Therefore, after H ions are exchanged with other cations, a form such as hydrochloric acid or a sulfuric acid aqueous solution can be used to easily return to the form of R-COOH. Therefore, it is easy to regenerate at the time of repeated use, and it is possible to regenerate at a dose of a larger amount than the theoretical chemical equivalent.
又，由於次氯酸鈉的漂白一般認為係由於溶存氯的氯化反應所致。又，漂白力一般認為係溶存氯>次氯酸鈉>次氯酸的順序。依據本發明之方法，因可實質上不會產生溶存氯而製造弱酸性次氯酸，故可獲得漂白效果少的弱酸性次氯酸。又，如上所述，因實質上不產生溶存氯，故氯化反應不會發生。溶存氯多的情形，臭氣亦變濃，但依據本發明之方法，可製造實質上不會產生溶存氯之弱酸性次氯酸，故由氯所致的臭氣亦較少。 Further, bleaching of sodium hypochlorite is generally considered to be due to the chlorination reaction of dissolved chlorine. Further, the bleaching power is generally considered to be the order in which chlorine is dissolved > sodium hypochlorite > hypochlorous acid. According to the method of the present invention, weakly acidic hypochlorous acid can be produced without substantially generating dissolved chlorine, so that weakly acidic hypochlorous acid having a small bleaching effect can be obtained. Further, as described above, the chlorination reaction does not occur because substantially no dissolved chlorine is generated. In the case where the amount of dissolved chlorine is large, the odor is also rich. However, according to the method of the present invention, weakly acidic hypochlorous acid which does not substantially generate dissolved chlorine can be produced, so that odor caused by chlorine is also less.
相反地，使用強酸性陽離子樹脂來處理次氯酸鈉溶液 的情形，處理後溶液之pH值會變成3以下。因此，殺菌效果亦降低，又亦會產生氯氣。 Conversely, a strong acid cation resin is used to treat the sodium hypochlorite solution. In the case, the pH of the solution after treatment will become 3 or less. Therefore, the bactericidal effect is also reduced, and chlorine gas is also generated.
次氯酸鹽溶液藉由弱酸性離子交換體之處理可以任意方法來進行。例如，可於填充弱酸性離子交換體的管柱，藉由通過次氯酸鹽溶液來處理。又，藉由含有次氯酸鹽溶液的容器內投入弱酸性離子交換體，亦可以批次法來處理。又，亦可如茶包般於任意袋內填充弱酸性離子交換體，浸漬於次氯酸鹽溶液中。依據本發明之方法，次氯酸鹽溶液僅以弱酸性離子交換體來處理，可容易地獲得殺菌效果高的弱酸性次氯酸。 The hypochlorite solution can be treated by any method by treatment with a weakly acidic ion exchanger. For example, a column packed with a weakly acidic ion exchanger can be treated by passing through a hypochlorite solution. Further, by introducing a weakly acidic ion exchanger into a container containing a hypochlorite solution, it can also be treated by a batch method. Further, a weakly acidic ion exchanger may be filled in any bag as in a tea bag, and immersed in a hypochlorite solution. According to the method of the present invention, the hypochlorite solution is treated only with a weakly acidic ion exchanger, and a weakly acidic hypochlorous acid having a high bactericidal effect can be easily obtained.
再者，可使用含有次氯酸鈣等固體之次氯酸及弱酸性離子交換體兩者的袋子。例如，為了獲得弱酸性次氯酸，可使用於不織布作成的袋中投入次氯酸鈣及弱酸性離子交換體兩者。第1圖顯示預先含有次氯酸鈣及弱酸性離子交換體的容器之一範例。第1圖之上段呈示於不織布1之中置入次氯酸鈣2及弱酸性離子交換體3之際之模式圖。又，第1圖之下段係將上段所示的圖之開口部關閉之際之模式圖。次氯酸鈣及弱酸性離子交換體被密封於不織布之內部。容器可使用任意之材料。藉由不織布等透過水的容器內含有次氯酸鈣及弱酸性離子交換體，僅浸漬於水中可獲得弱酸性次氯酸。容器以不透過水的素材為宜。若為水可置入容器內的形狀，僅浸漬於水使次氯酸鈣與弱酸性離子交換體接觸可獲得弱酸性次氯酸。又，使用時，自容器取出次氯酸鈣及弱酸性離子交換體，亦可投入水中。含有如 此次氯酸鈣等固體之次氯酸及弱酸性離子交換體兩者的袋子，其僅含有固體之次氯酸鈣及弱酸性離子交換體的緣故，使用前，可製造及保存不呈溶液的固體。固體之次氯酸鈣可使用任意形狀者。例如，可使用顆粒及粉末。 Further, a bag containing both solid hypochlorous acid such as calcium hypochlorite and a weakly acidic ion exchanger can be used. For example, in order to obtain weakly acidic hypochlorous acid, both of calcium hypochlorite and a weakly acidic ion exchanger can be introduced into a bag for making a nonwoven fabric. Figure 1 shows an example of a container containing calcium hypochlorite and a weakly acidic ion exchanger in advance. The upper part of Fig. 1 is a schematic view showing the placement of calcium hypochlorite 2 and weakly acidic ion exchanger 3 in the nonwoven fabric 1. Further, the lower part of Fig. 1 is a schematic view showing the opening of the figure shown in the upper stage. Calcium hypochlorite and a weakly acidic ion exchanger are sealed inside the nonwoven fabric. Any material can be used for the container. The calcium hypochlorite and the weakly acidic ion exchanger are contained in a container through which water is not woven or the like, and weakly acidic hypochlorous acid can be obtained only by immersing in water. The container is preferably made of water-impermeable material. If water can be placed in the shape of the container, only weakly acidic hypochlorous acid can be obtained by immersing in water to contact calcium hypochlorite with a weakly acidic ion exchanger. Further, at the time of use, calcium hypochlorite and a weakly acidic ion exchanger are taken out from the container, and may be introduced into water. Contains as The bag of solid hypochlorous acid and weakly acidic ion exchanger such as calcium chlorate contains only solid calcium hypochlorite and weakly acidic ion exchanger, and can be manufactured and stored without being used before use. s solid type. Solid calcium hypochlorite can be used in any shape. For example, granules and powders can be used.
其次，詳細說明關於本發明之弱酸性次氯酸之製造裝置4。本發明之製造裝置係具備弱酸性離子交換體。本發明之製造裝置可為例如第2圖所示之裝置。第2圖之裝置具備用於儲存及稀釋氯酸鹽溶液之稀釋裝置5。稀釋裝置5係與填充離子交換樹脂的管柱等容器6連接。例如，稀釋裝置5具備用以將稀釋裝置之次氯酸鹽溶液導入填充弱酸性離子交換體的容器6之泵，藉由泵與容器6連接。藉由泵，次氯酸鹽溶液自稀釋裝置被導入離子交換管柱，經弱酸性離子交換體處理，可獲得弱酸性次氯酸。 Next, the apparatus 4 for manufacturing the weakly acidic hypochlorous acid of the present invention will be described in detail. The production apparatus of the present invention comprises a weakly acidic ion exchanger. The manufacturing apparatus of the present invention may be, for example, the apparatus shown in Fig. 2. The apparatus of Figure 2 is provided with a dilution device 5 for storing and diluting the chlorate solution. The dilution device 5 is connected to a container 6 such as a column filled with an ion exchange resin. For example, the dilution device 5 is provided with a pump for introducing a hypochlorite solution of the dilution device into the container 6 filled with the weakly acidic ion exchanger, and is connected to the container 6 by a pump. The weakly acidic hypochlorous acid is obtained by a pump, a hypochlorite solution is introduced into the ion exchange column by a dilution device, and treated with a weakly acidic ion exchanger.
又，本發明之製造裝置可為例如第3圖所示之裝置。第3圖所示之裝置具有自次氯酸鹽溶液之稀釋裝置連接填充弱酸性離子交換體的容器6的管道7、不與填充弱酸性離子交換體的容器6連接的管道8。又，可以調節各自管道之流量的方式來構成。例如，藉由於管道7及管道8設置節流閥或開關閥等，可調節通過各別管道的溶液之混合比。藉由作成如此裝置之構成，可以任意量混合離子交換後之弱酸性次氯酸溶液、及離子交換前之次氯酸鹽溶液。例如，製造中性之pH7之溶液的情形，離子交換後之弱酸性次氯酸溶液為pH5時，藉由混合適當量之離子交換前之次氯酸鈉溶液(例如，pH12)，可獲得pH6的溶液。 Further, the manufacturing apparatus of the present invention may be, for example, the apparatus shown in Fig. 3. The apparatus shown in Fig. 3 has a pipe 7 which is connected to a vessel 6 filled with a weakly acidic ion exchanger from a dilution device of a hypochlorite solution, and a pipe 8 which is not connected to a vessel 6 filled with a weakly acidic ion exchanger. Moreover, it is possible to adjust the flow rate of the respective pipes. For example, by providing a throttle valve or a switching valve or the like due to the pipe 7 and the pipe 8, the mixing ratio of the solutions passing through the respective pipes can be adjusted. By forming such a device, the ion exchanged weakly acidic hypochlorous acid solution and the hypochlorite solution before ion exchange can be mixed in an arbitrary amount. For example, in the case of producing a neutral pH 7 solution, when the weakly acidic hypochlorous acid solution after ion exchange is at pH 5, a solution of pH 6 can be obtained by mixing an appropriate amount of a sodium hypochlorite solution (for example, pH 12) before ion exchange.
又，本發明之製造裝置如第3圖所示，可進一步具備用以將通過酸性離子交換體管柱的弱酸性次氯酸加以噴霧的噴霧裝置9。如此，藉由具備噴霧裝置，可使具有殺菌效果的弱酸性次氯酸擴散於空氣中。具備如此噴霧裝置的裝置可裝載於例如空氣清淨機及空調設備等機器，可使用作為殺菌裝置。噴霧裝置可使用本項技術領域者習知之任意裝置。例如，可使用利用超音波的噴霧裝置。 Further, as shown in Fig. 3, the manufacturing apparatus of the present invention may further include a spray device 9 for spraying weakly acidic hypochlorous acid which passes through the column of the acidic ion exchanger. Thus, by providing a spray device, the weakly acidic hypochlorous acid having a bactericidal effect can be diffused into the air. The device having such a spray device can be mounted on a device such as an air cleaner or an air conditioner, and can be used as a sterilizing device. The spray device can employ any of the devices conventionally known to those skilled in the art. For example, a spray device using ultrasonic waves can be used.
又，如上述之弱酸性離子交換體亦具有吸附溶液中之鈣及鎂等礦物質成分的性質。因此，於本發明之裝置，藉由作成使弱酸性次氯酸溶液與弱酸性離子交換體接觸的狀態，可防止裝置內產生的礦物質成分所致的白化。例如，如第3圖所示的裝置之噴霧裝置9，成為弱酸性次氯酸溶液於噴霧裝置9內部被霧化及循環。此時，藉由於噴霧裝置9內部具備弱酸性離子交換體，可使弱酸性次氯酸之溶液中之礦物質成分吸附。因此，防止由於裝置內部之礦物質成分所致的白化，可防止裝置之故障等。再者，亦可使弱酸性次氯酸溶液之pH值安定。 Further, the weakly acidic ion exchanger as described above also has the property of adsorbing mineral components such as calcium and magnesium in the solution. Therefore, in the apparatus of the present invention, whitening caused by the mineral component generated in the apparatus can be prevented by making the weakly acidic hypochlorous acid solution in contact with the weakly acidic ion exchanger. For example, the spray device 9 of the apparatus shown in Fig. 3 is atomized and circulated inside the spray device 9 as a weakly acidic hypochlorous acid solution. At this time, since the weakly acidic ion exchanger is provided inside the spray device 9, the mineral component in the solution of the weakly acidic hypochlorous acid can be adsorbed. Therefore, it is possible to prevent malfunction of the apparatus due to whitening due to mineral components inside the apparatus. Furthermore, the pH of the weakly acidic hypochlorous acid solution can also be stabilized.
如上所述，依據本發明中弱酸性次氯酸之製造方法及製造裝置，可使溶液pH值不降低至產生氯氣的範圍而可容易地獲得弱酸性次氯酸。又，依據本發明中弱酸性次氯酸之製造方法及製造裝置，如下述實施例所示，可獲得500ppm以上高濃度之弱酸性次氯酸。再者，藉由本發明中弱酸性次氯酸之製造方法及製造裝置所獲得的弱酸性次氯酸，如下述實施例所示，與習知之弱酸性次氯酸比較，漂 白活性低。 As described above, according to the method and apparatus for producing weakly acidic hypochlorous acid in the present invention, the pH of the solution can be easily lowered to a range in which chlorine gas is generated, and weakly acidic hypochlorous acid can be easily obtained. Further, according to the method and apparatus for producing weakly acidic hypochlorous acid according to the present invention, as shown in the following examples, a weakly acidic hypochlorous acid having a high concentration of 500 ppm or more can be obtained. Further, the weakly acidic hypochlorous acid obtained by the method and apparatus for producing weakly acidic hypochlorous acid in the present invention is as shown in the following examples, compared with the conventional weakly acidic hypochlorous acid. White activity is low.
其次，詳細說明關於含有本發明中弱酸性次氯酸及界面活性劑的洗淨劑。本發明之洗淨劑包含如上所述之弱酸性次氯酸溶液及界面活性劑之混合物。 Next, the detergent containing the weakly acidic hypochlorous acid and the surfactant in the present invention will be described in detail. The detergent of the present invention comprises a mixture of a weakly acidic hypochlorous acid solution and a surfactant as described above.
界面活性劑例如可使用多元醇衍生物型界面活性劑、陽離子界面活性劑及兩性界面活性劑。多元醇衍生物型界面活性劑可使用甘油脂肪酸酯、聚甘油脂肪酸酯、丙二醇脂肪酸酯、聚丙二醇脂肪酸酯、蔗糖脂肪酸酯、山梨糖醇酐脂肪酸酯及烷基多糖苷等。脂肪酸酯型者中脂肪酸部分之碳數或烷基多糖苷中烷基之碳數可使用任意的碳數，例如可使用6~28及6~18者。 As the surfactant, for example, a polyol derivative type surfactant, a cationic surfactant, and an amphoteric surfactant can be used. As the polyol derivative type surfactant, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polypropylene glycol fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, alkyl polyglycoside, etc. can be used. . In the fatty acid ester type, the carbon number of the fatty acid moiety or the carbon number of the alkyl group in the alkylpolyglycoside may be any carbon number, and for example, 6 to 28 and 6 to 18 may be used.
陽離子界面活性劑可使用第一級胺鹽系陽離子界面活性劑、第二級胺鹽系陽離子界面活性劑、第三級胺鹽系陽離子界面活性劑、第四級胺鹽系陽離子界面活性劑。此等中以第四級胺鹽系陽離子界面活性劑為特佳。第四級胺鹽系陽離子界面活性劑為例如四個取代基之至少一個為總碳數為8~28之烷基或烯基，殘餘者可使用選自苄基、碳數1~8之烷基及碳數1~5之羥基烷基之基的化合物。 As the cationic surfactant, a first-order amine salt-based cationic surfactant, a second-grade amine salt-based cationic surfactant, a third-order amine salt-based cationic surfactant, and a fourth-grade amine salt-based cationic surfactant can be used. Among these, a fourth-order amine salt-based cationic surfactant is particularly preferred. The fourth-stage amine salt-based cationic surfactant is, for example, at least one of the four substituents is an alkyl or alkenyl group having a total carbon number of 8 to 28, and the residue may be an alkyl group selected from the group consisting of a benzyl group and a carbon number of 1 to 8. a compound having a group of a hydroxyalkyl group having 1 to 5 carbon atoms.
兩性界面活性劑係可使用胺基酸系、甜菜鹼(betaine)系、咪唑啉(imidazoline)系、胺氧化物系之兩性界面活性劑。 As the amphoteric surfactant, an amphoteric surfactant, an betaine system, an imidazoline system, or an amine oxide-based amphoteric surfactant can be used.
胺基酸系兩性界面活性劑可使用例如醯基胺基酸鹽、醯基肌胺酸鹽、丙烯醯基甲基胺基丙酸鹽、烷基胺基丙酸鹽及醯基醯胺乙基羥基乙基甲基羧酸鹽等。 As the amino acid amphoteric surfactant, for example, a mercaptoamine salt, a mercaptocreatine, an acrylmethylaminopropionate, an alkylaminopropionate, and a mercaptoguanidinium ethyl group can be used. Hydroxyethyl methylcarboxylate and the like.
甜菜鹼系兩性界面活性劑可使用烷基二甲基甜菜鹼、烷基羥基乙基甜菜鹼、醯基醯胺丙基羥基丙基氨磺基甜菜鹼及蓖麻油酸醯胺丙基二甲基羧基甲基氨甜菜鹼等。 The betaine-based amphoteric surfactant can be used as alkyl dimethyl betaine, alkyl hydroxyethyl betaine, mercaptoguanidinopropyl hydroxypropyl sulfamobetaine and ricinoleic propyl decyl propyl methacrylate. Carboxymethylaminobetaine and the like.
咪唑啉系兩性界面活性劑可使用例如烷基羧基甲基羥基乙基咪唑鎓甜菜鹼及烷基乙氧基羧基甲基咪唑鎓甜菜鹼等。 As the imidazoline-based amphoteric surfactant, for example, an alkylcarboxymethylhydroxyethylimidazolium betaine, an alkylethoxycarboxymethylimidazolium betaine or the like can be used.
胺氧化物系兩性界面活性劑可使用例如烷基胺氧化物、烷基二甲基胺氧化物、烷基二乙醇胺氧化物及烷基醯胺丙基胺氧化物等。 As the amine oxide-based amphoteric surfactant, for example, an alkylamine oxide, an alkyldimethylamine oxide, an alkyldiethanolamine oxide, a alkylguanamine propylamine oxide or the like can be used.
本發明之洗淨劑可以任意比率含有弱酸性次氯酸溶液及界面活性劑。例如，弱酸性次氯酸溶液/界面活性劑以20/1~1/10之重量比含有，較佳為10/1~1/10，更佳為10/1~1/5，再更佳為5/1~1/5，例如以2/1~1/2含有。 The detergent of the present invention may contain a weakly acidic hypochlorous acid solution and a surfactant in an arbitrary ratio. For example, the weakly acidic hypochlorous acid solution/surfactant is contained in a weight ratio of 20/1 to 1/10, preferably 10/1 to 1/10, more preferably 10/1 to 1/5, and even more preferably. It is 5/1~1/5, for example, it is contained in 2/1~1/2.
又，本發明之洗淨劑除了上述成分之外，可含有防鏽劑。防鏽劑可為例如磷酸、多磷酸及膦酸等。又，相對於弱酸性次氯酸，本發明之洗淨劑可以含有任意重量比之防鏽劑，例如以10/1~1/10之重量比含有弱酸性次氯酸/防鏽劑，例如10/1~1/5及5/1~1/5之重量比。 Further, the detergent of the present invention may contain a rust inhibitor in addition to the above components. The rust inhibitor may be, for example, phosphoric acid, polyphosphoric acid, phosphonic acid or the like. Further, the detergent of the present invention may contain an arsenic inhibitor of any weight ratio with respect to the weakly acidic hypochlorous acid, for example, a weak acid hypochlorous acid/rust inhibitor in a weight ratio of 10/1 to 1/10, for example, Weight ratio of 10/1~1/5 and 5/1~1/5.
又，製造本發明中洗淨劑之際，界面活性劑及任意之防鏽劑亦可於藉由弱酸性離子交換體處理次氯酸塩溶液之前及之後任一之階段中混合。例如，混合次氯酸鹽溶液及界面活性劑後，可藉由弱酸性離子交換體使溶液之pH值降低。又，將不含有界面活性劑的次氯酸鹽溶液藉由弱酸性離子交換體加以處理後，亦可混合界面活性劑。 Further, when the detergent of the present invention is produced, the surfactant and any rust preventive agent may be mixed in any of the stages before and after the treatment of the ruthenium hypochlorite solution by the weakly acidic ion exchanger. For example, after mixing the hypochlorite solution and the surfactant, the pH of the solution can be lowered by the weakly acidic ion exchanger. Further, the hypochlorite solution containing no surfactant may be treated with a weakly acidic ion exchanger, or a surfactant may be mixed.
本發明之洗淨劑係如上所述，於其製造過程溶液之pH值不會降低至氯氣產生的pH值以下。因此，可製造含有次氯酸水溶液的洗淨劑，其不使用酸，且不會產生氯氣。 The detergent of the present invention is as described above, and the pH of the solution during the production process is not lowered below the pH of the chlorine gas. Therefore, a detergent containing an aqueous hypochlorous acid solution which does not use an acid and which does not generate chlorine gas can be produced.
又，本發明之弱酸性次氯酸之製造方法包含將次氯酸鹽溶液以於產生氯氣的pH值以上具有緩衝作用的弱酸性離子交換體加以處理的步驟。因此，依據本發明中方法所產生的弱酸性次氯酸係藉由弱酸性離子交換體將次氯酸鹽溶液中所含的金屬離子交換成H離子。 Further, the method for producing weakly acidic hypochlorous acid of the present invention comprises the step of treating the hypochlorite solution with a weakly acidic ion exchanger having a buffering effect above the pH of the chlorine gas. Therefore, the weakly acidic hypochlorous acid produced by the method of the present invention exchanges metal ions contained in the hypochlorite solution into H ions by a weakly acidic ion exchanger.
金屬離子已被報告具有次氯酸之分解活性。然而，依據本發明中弱酸性次氯酸之製造方法，可生成金屬離子被去除的弱酸性次氯酸。因此，依據本發明之方法，可生成金屬離子被去除、無弱酸性次氯酸之分解活性、且安定的弱酸性次氯酸溶液。 Metal ions have been reported to have the decomposition activity of hypochlorous acid. However, according to the method for producing weakly acidic hypochlorous acid in the present invention, weakly acidic hypochlorous acid in which metal ions are removed can be produced. Therefore, according to the method of the present invention, a weakly acidic hypochlorous acid solution in which metal ions are removed, has no decomposing activity of weakly acidic hypochlorous acid, and is stable can be produced.
只要未特別指明，實驗使用以下之材料。弱酸性離子交換樹脂係使用Amberlite IRC-76(Organo股份有限公司)。將500ml之量之弱酸性離子交換樹脂填充於11之管柱來使用。次氯酸鈉溶液係將市售之12%次氯酸鈉溶液(Tsuruchlone Super，鶴見曹達股份有限公司)稀釋或未稀釋來使用。次氯酸鈣係使用市售之顆粒劑(TOSOH股份有限公司)。重碳酸鈉係使用市售之重碳酸鈉(高杉製藥股份有限公司)。乳酸鈣係使用市售之乳酸鈣(內藤商店股份有限公司)。 The following materials were used in the experiment unless otherwise specified. As the weakly acidic ion exchange resin, Amberlite IRC-76 (Organo Co., Ltd.) was used. A 500 ml portion of the weakly acidic ion exchange resin was filled in a column of 11 for use. The sodium hypochlorite solution was used by diluting or undiluting a commercially available 12% sodium hypochlorite solution (Tsuruchlone Super, Tsurumi Soda Co., Ltd.). As the calcium hypochlorite, a commercially available granule (TOSOH Co., Ltd.) was used. As the sodium bicarbonate, commercially available sodium bicarbonate (Kumuzoku Pharmaceutical Co., Ltd.) was used. Calcium lactate is a commercially available calcium lactate (Naito Store Co., Ltd.).
次氯酸鈉溶液以弱酸性離子交換樹脂之處理係使用將泵與弱酸性離子交換樹脂管柱連接的裝置。儲存部之次氯酸鈉溶液以所欲濃度通過弱酸性離子交換樹脂的方式，依指定水量使用泵，而將次氯酸鈉溶液導入弱酸性離子交換樹脂管柱。使用自來水、pH值7.5用於稀釋。 The sodium hypochlorite solution is treated with a weakly acidic ion exchange resin using a device that connects the pump to a weakly acidic ion exchange resin column. The sodium hypochlorite solution in the storage portion is passed through the weakly acidic ion exchange resin at a desired concentration, and the sodium hypochlorite solution is introduced into the weakly acidic ion exchange resin column by using a pump according to the specified amount of water. Use tap water, pH 7.5 for dilution.
溶液pH值使用可攜帶式pH值計HM-30P(東亞DKK股份有限公司)或使用pH值試驗紙來測量。次氯酸濃度係使用Aqua Check HC(日產化學工業股份有限公司)，測量游離殘留氯濃度。 The pH of the solution was measured using a portable pH meter HM-30P (East Asia DKK Co., Ltd.) or using a pH test paper. The hypochlorous acid concentration was measured using Aqua Check HC (Nissan Chemical Industries, Ltd.) to measure the free residual chlorine concentration.
將上述12%次氯酸鈉溶液以水稀釋為濃度200ppm，測量通過弱酸性離子交換樹脂管柱後之pH值。樹脂通過水量為2.3公升/分鐘。被導入管柱時該次氯酸鈉溶液(稀釋水)之濃度為約150~200ppm，pH值為8.7。通過弱酸性離子交換樹脂後該弱酸性次氯酸(樹脂生成水)之濃度為約150~200ppm，pH值為6.1~7.4。以下表1呈現一部份結果。 The above 12% sodium hypochlorite solution was diluted with water to a concentration of 200 ppm, and the pH value after passing through the weakly acidic ion exchange resin column was measured. The amount of resin passing through the water was 2.3 liters/min. The concentration of the sodium hypochlorite solution (dilution water) when introduced into the column is about 150 to 200 ppm, and the pH is 8.7. The concentration of the weakly acidic hypochlorous acid (resin-forming water) after the weakly acidic ion exchange resin is about 150 to 200 ppm, and the pH is 6.1 to 7.4. Table 1 below presents some of the results.
將上述12%次氯酸鈉溶液以水稀釋為濃度100ppm，測量通過弱酸性離子交換樹脂管柱後之pH值。樹脂通過水量為2.3公升/分鐘。被導入管柱時該次氯酸鈉溶液之濃度為約100ppm，pH值為8.5~8.9。通過弱酸性離子交換樹脂後 該弱酸性次氯酸之濃度為約100ppm，pH值為6.0~6.3。以下表2呈現一部份的結果。 The above 12% sodium hypochlorite solution was diluted with water to a concentration of 100 ppm, and the pH value after passing through the weakly acidic ion exchange resin column was measured. The amount of resin passing through the water was 2.3 liters/min. The concentration of the sodium hypochlorite solution when introduced into the column is about 100 ppm, and the pH is 8.5 to 8.9. After weakly acidic ion exchange resin The weakly acidic hypochlorous acid has a concentration of about 100 ppm and a pH of 6.0 to 6.3. Table 2 below presents a partial result.
將上述12%次氯酸鈉溶液以水稀釋為濃度500ppm，測量通過弱酸性離子交換樹脂管柱後之pH值。樹脂通過水量為2.3公升/分鐘。如以下表3所示，被導入管柱時該次氯酸鈉溶液之pH值為9.1~9.2。通過弱酸性離子交換樹脂後該弱酸性次氯酸之pH值為6.1。 The above 12% sodium hypochlorite solution was diluted with water to a concentration of 500 ppm, and the pH value after passing through the weakly acidic ion exchange resin column was measured. The amount of resin passing through the water was 2.3 liters/min. As shown in Table 3 below, the pH of the sodium hypochlorite solution was 9.1 to 9.2 when introduced into the column. The pH of the weakly acidic hypochlorous acid after passing through the weakly acidic ion exchange resin was 6.1.
將上述12%次氯酸鈉溶液以水稀釋為濃度10,000ppm，測量通過弱酸性離子交換樹脂管柱後之pH值。樹脂通過水量為2.3公升/分鐘。如以下表4所示，被導入管柱時該次氯酸鈉溶液之pH值為11.4~11.9。通過弱酸性離子交換樹脂後該弱酸性次氯酸之pH值為7.1。 The above 12% sodium hypochlorite solution was diluted with water to a concentration of 10,000 ppm, and the pH value after passing through the weakly acidic ion exchange resin column was measured. The amount of resin passing through the water was 2.3 liters/min. As shown in Table 4 below, the pH of the sodium hypochlorite solution was 11.4 to 11.9 when introduced into the column. The pH of the weakly acidic hypochlorous acid after passing through the weakly acidic ion exchange resin was 7.1.
使於上述步驟中由濃度10,000ppm之次氯酸鈉溶液所獲得的弱酸性次氯酸再通過樹脂。如以下表5所示，被導入管柱時該次氯酸鈉溶液之pH值為7.2。通過弱酸性離子交換樹脂後該弱酸性次氯酸之pH值為5.8~6.5。 The weakly acidic hypochlorous acid obtained from the sodium chlorate solution having a concentration of 10,000 ppm in the above step was passed through the resin. As shown in Table 5 below, the pH of the sodium hypochlorite solution was 7.2 when introduced into the column. The pH of the weakly acidic hypochlorous acid after passing through the weakly acidic ion exchange resin is 5.8 to 6.5.
依據本發明之方法及裝置，即使於所謂10,000ppm的非常高濃度，亦可製造具有抗菌效果的pH值5.8~6.5範圍的弱酸性次氯酸。如此高濃度之弱酸性次氯酸無法以習知的製法來製造。又，於上述實驗之任一者皆未成為會產生氯氣的低pH值。 According to the method and apparatus of the present invention, a weakly acidic hypochlorous acid having a pH value of 5.8 to 6.5 having an antibacterial effect can be produced even at a very high concentration of 10,000 ppm. Such a high concentration of weakly acidic hypochlorous acid cannot be produced by a known method. Moreover, none of the above experiments did not have a low pH value which would generate chlorine gas.
其次，使用丙烯酸系Diaion(註冊商標)WK40L(三菱化學股份有限公司)作為弱酸性離子交換樹脂，自200ppm濃度之次氯酸鈉溶液獲得弱酸性次氯酸。此弱酸性離子交換樹脂於pH值5.0附近具有緩衝作用。 Next, acrylic acid Diaion (registered trademark) WK40L (Mitsubishi Chemical Co., Ltd.) was used as a weakly acidic ion exchange resin, and weakly acidic hypochlorous acid was obtained from a 200 ppm sodium hypochlorite solution. This weakly acidic ion exchange resin has a buffering effect near pH 5.0.
上述12%次氯酸鈉溶液以水稀釋為濃度200ppm，測量通過弱酸性離子交換樹脂管柱後之pH值。樹脂通過水量為2.3公升/分鐘。被導入管柱時該次氯酸鈉溶液之濃度為200ppm，pH值為8.7。通過弱酸性離子交換樹脂後該弱酸性次氯酸之濃度為200ppm，pH值為4.9。經由混合所獲得的pH值4.9之弱酸性次氯酸與樹脂通過前pH值為8.7之次氯酸鈉溶液，可獲得pH值6.0之弱酸性次氯酸。 The above 12% sodium hypochlorite solution was diluted with water to a concentration of 200 ppm, and the pH value after passing through the weakly acidic ion exchange resin column was measured. The amount of resin passing through the water was 2.3 liters/min. The sodium hypochlorite solution had a concentration of 200 ppm and a pH of 8.7 when it was introduced into the column. The weakly acidic hypochlorous acid had a concentration of 200 ppm and a pH of 4.9 after passing through a weakly acidic ion exchange resin. The weakly acidic hypochlorous acid having a pH of 4.6 was obtained by mixing the weakly acidic hypochlorous acid having a pH of 4.9 and the resin through a sodium hypochlorite solution having a pH of 8.7.
於上述12%次氯酸鈉溶液100ml中添加一湯匙(約5g)之碳酸氫鈉而混合。此時，因殘留未溶解的碳酸氫鈉，確認為飽和溶液。稀釋此溶液，而製作濃度200ppm之碳酸氫鈉飽和次氯酸鈉溶液，測量通過弱酸性離子交換樹脂管柱後之pH值。樹脂通過水量為2.3公升/分鐘。如以下表6所示，被導入管柱時該次氯酸鈉溶液(飽和稀釋水)之濃度為約200ppm，pH值為8.8~8.9。通過弱酸性離子交換樹脂後該弱酸性次氯酸之濃度為約200ppm，pH值為5.8~6.1。 One tablespoon (about 5 g) of sodium hydrogencarbonate was added to 100 ml of the above 12% sodium hypochlorite solution and mixed. At this time, it was confirmed that it was a saturated solution because the undissolved sodium hydrogencarbonate remained. The solution was diluted to prepare a sodium bicarbonate saturated sodium hypochlorite solution having a concentration of 200 ppm, and the pH value after passing through the weakly acidic ion exchange resin column was measured. The amount of resin passing through the water was 2.3 liters/min. As shown in Table 6 below, the concentration of the sodium hypochlorite solution (saturated dilution water) when introduced into the column was about 200 ppm, and the pH was 8.8 to 8.9. The concentration of the weakly acidic hypochlorous acid after passing through the weakly acidic ion exchange resin was about 200 ppm, and the pH was 5.8 to 6.1.
進行以下三個實驗。 Perform the following three experiments.
1.將顆粒劑之次氯酸鈣0.03g置入已放入100ml純水的不織布袋中。游離殘留氯濃度為約200ppm，pH值為8.6。 1. A granule of calcium hypochlorite (0.03 g) was placed in a non-woven bag that had been placed in 100 ml of pure water. The free residual chlorine concentration was about 200 ppm and the pH was 8.6.
2.將顆粒劑之次氯酸鈣0.03g與弱酸性離子交換樹脂0.6g置入已放入100ml純水的不織布袋中。游離殘留氯濃度為約200ppm，pH值為7.3。 2. A granule of calcium hypochlorite (0.03 g) and a weakly acidic ion exchange resin (0.6 g) were placed in a non-woven bag which had been placed in 100 ml of pure water. The free residual chlorine concentration was about 200 ppm and the pH was 7.3.
3.將顆粒劑之次氯酸鈣0.03g、弱酸性離子交換樹脂0.6g、及乳酸鈣0.6g置入已放入100ml純水的不織布袋中。游離殘留氯濃度為約200ppm，pH值為5.2。 3. The granules of calcium hypochlorite 0.03 g, weakly acidic ion exchange resin 0.6 g, and calcium lactate 0.6 g were placed in a non-woven bag which had been placed in 100 ml of pure water. The free residual chlorine concentration was about 200 ppm and the pH was 5.2.
如上所述，藉由使次氯酸鈣與弱酸性離子交換樹脂反應，可容易獲得pH值5.2~7.3之弱酸性次氯酸。又，藉由使用弱酸性離子交換樹脂，為了調整次氯酸鈣之溶液中的pH值，不須考慮化學反應上之調合比率，而可獲得弱酸性次氯酸。 As described above, weakly acidic hypochlorous acid having a pH of 5.2 to 7.3 can be easily obtained by reacting calcium hypochlorite with a weakly acidic ion exchange resin. Further, by using a weakly acidic ion exchange resin, in order to adjust the pH value in the solution of calcium hypochlorite, it is possible to obtain weakly acidic hypochlorous acid without considering the blending ratio on the chemical reaction.
調查由本發明方法所獲得的弱酸性次氯酸是否具有漂白效果。 It was investigated whether the weakly acidic hypochlorous acid obtained by the method of the present invention has a bleaching effect.
將已著色的綿絲浸漬於將上述12%次氯酸鈉溶液稀釋為濃度500ppm及1000ppm之溶液的情形，其被漂白。另一方面，將已著色的綿絲浸漬於上述實驗所獲得的濃度500ppm及1000ppm之弱酸性次氯酸中一日。即使一日後亦難以被漂白。 The colored cotton yarn was immersed in a case where the above 12% sodium hypochlorite solution was diluted to a solution having a concentration of 500 ppm and 1000 ppm, which was bleached. On the other hand, the colored cotton yarn was immersed in the weakly acidic hypochlorous acid having a concentration of 500 ppm and 1000 ppm obtained in the above experiment for one day. Even after one day, it is difficult to be bleached.
如上所述，將12%次氯酸鈉溶液以水稀釋為濃度500ppm，藉由通過弱酸性離子交換樹脂管柱，調整濃度500ppm之弱酸性次氯酸水溶液。將此溶液保存於暗處，隨著時間經過測量弱酸性次氯酸之濃度歷時變化。弱酸性次氯酸之水溶液保存於室溫，為約5℃~約35℃範圍。結果顯示於以下表7。 As described above, the 12% sodium hypochlorite solution was diluted with water to a concentration of 500 ppm, and a weak acid hypochlorite aqueous solution having a concentration of 500 ppm was adjusted by passing through a weakly acidic ion exchange resin column. The solution was stored in the dark and the concentration of weakly acidic hypochlorous acid was measured over time as a function of time. The aqueous solution of weakly acidic hypochlorous acid is stored at room temperature and ranges from about 5 ° C to about 35 ° C. The results are shown in Table 7 below.
已知藉由本發明之方法所製造的弱酸性次氯酸歷經十二個月以上的期間為非常地安定，且分解少。 It is known that the weakly acidic hypochlorous acid produced by the method of the present invention is extremely stable over a period of twelve months or more, and has less decomposition.
依據本發明，可不使用酸，且不產生氯氣來製造次氯酸水溶液。 According to the present invention, an aqueous solution of hypochlorous acid can be produced without using an acid and without generating chlorine gas.
1‧‧‧不織布 1‧‧‧nonwoven
2‧‧‧次氯酸鈣 2‧‧‧ calcium hypochlorite
3‧‧‧弱酸性離子交換體 3‧‧‧Weakly acidic ion exchanger
4‧‧‧弱酸性次氯酸之製造裝置 4‧‧‧Manufacture of weakly acidic hypochlorous acid
5‧‧‧稀釋裝置 5‧‧‧Dilution device
6‧‧‧容器 6‧‧‧ Container
7‧‧‧管道 7‧‧‧ Pipes
8‧‧‧管道 8‧‧‧ Pipes
9‧‧‧噴霧裝置 9‧‧‧Spray device
第1圖為顯示含有次氯酸鈣及弱酸性離子交換體之容器之一範例圖。 Figure 1 is a diagram showing an example of a container containing calcium hypochlorite and a weakly acidic ion exchanger.
第2圖為顯示本發明之裝置之一範例的概略圖。 Fig. 2 is a schematic view showing an example of the apparatus of the present invention.
第3圖為顯示本發明之裝置之一範例的概略圖。 Fig. 3 is a schematic view showing an example of the apparatus of the present invention.
1‧‧‧不織布 1‧‧‧nonwoven
2‧‧‧次氯酸鈣 2‧‧‧ calcium hypochlorite
3‧‧‧弱酸性離子交換體 3‧‧‧Weakly acidic ion exchanger
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| CN111565570A (en) * | 2018-01-12 | 2020-08-21 | 吉武亨将 | Insect repellent and method and apparatus for producing hypochlorous acid aqueous solution |
| CN112739309A (en) * | 2018-09-13 | 2021-04-30 | 株式会社德山齿科 | Composition for cleaning teeth, tooth cleaning agent and dental calculus removal promoter, and method for cleaning teeth |
| CN114173792A (en) * | 2019-08-09 | 2022-03-11 | 西科姆医疗系统株式会社 | Anticancer agent decomposition agent and anticancer agent decomposition method |
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| JP6798045B2 (en) * | 2018-01-16 | 2020-12-09 | 株式会社トクヤマ | Processing liquid for semiconductor wafers containing hypochlorite ions |
| JP6811967B2 (en) * | 2018-05-22 | 2021-01-13 | 株式会社トクヤマデンタル | Manufacturing method of weakly acidic hypochlorous acid water |
| US20210188634A1 (en) * | 2018-05-22 | 2021-06-24 | Tokuyama Dental Corporation | Method for producing weakly acidic hypochlorous acid aqueous solution |
| JP6808201B2 (en) * | 2019-01-25 | 2021-01-06 | 株式会社トクヤマデンタル | Manufacturing method of weakly acidic hypochlorous acid water |
| JPWO2021090916A1 (en) * | 2019-11-08 | 2021-05-14 | ||
| CN111020621A (en) * | 2019-12-30 | 2020-04-17 | 肇庆钜晨化工有限公司 | Device and method for preparing weak hypochlorous acid aqueous solution for disinfection |
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| JP5237913B2 (en) * | 2009-09-27 | 2013-07-17 | 株式会社微酸性電解水研究所 | Preparation method of molecular hypochlorous acid solution by ion exchange and molecular hypochlorous acid solution |
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| CN112739309A (en) * | 2018-09-13 | 2021-04-30 | 株式会社德山齿科 | Composition for cleaning teeth, tooth cleaning agent and dental calculus removal promoter, and method for cleaning teeth |
| CN114173792A (en) * | 2019-08-09 | 2022-03-11 | 西科姆医疗系统株式会社 | Anticancer agent decomposition agent and anticancer agent decomposition method |
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