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EP0119560B1 - Hypohalite-based bleaching, cleaning and disinfecting agent with storing stability - Google Patents

Hypohalite-based bleaching, cleaning and disinfecting agent with storing stability Download PDF

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Publication number
EP0119560B1
EP0119560B1 EP84102561A EP84102561A EP0119560B1 EP 0119560 B1 EP0119560 B1 EP 0119560B1 EP 84102561 A EP84102561 A EP 84102561A EP 84102561 A EP84102561 A EP 84102561A EP 0119560 B1 EP0119560 B1 EP 0119560B1
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EP
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Prior art keywords
hypohalite
solutions
aqueous solutions
molar ratio
amidosulfonic acid
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EP84102561A
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German (de)
French (fr)
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EP0119560A2 (en
EP0119560A3 (en
Inventor
Jürgen Dr. Schröder
Harald Stabl
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B Braun Holding AG
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B Braun SSC AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3951—Bleaching agents combined with specific additives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • hypohalites preferably hypochlorites
  • hypochlorites have long been used in bleaching, cleaning and disinfecting agents.
  • hypochlorites form solutions of hypochlorous acid in water, which develop their bleaching effect through oxidation, preferably at pH values from 9 to 12.
  • the bleaching effect of the bleaching liquors increases with falling pH and temperature.
  • the disinfectant effect of hypochlorite solutions is based on the property of hypochlorous acid, which can diffuse through the cell walls of the bacteria and thus kill their vital components.
  • the disinfectant power is directly proportional to the concentration of HCIO, i.e. also a function of the pH (E. Heubach, G. Riess, H. Vogt, D. Bergner, Ullmann's Encyclopedia d. Techn. Chem., Vol. 8, 542 ff, Weinheim 1974).
  • hypochlorite-containing solutions The most important parameter for comparing hypochlorite-containing solutions is the mass content (in%) of active or effective chlorine. This is the amount of chlorine that is developed when hydrochloric acid is added: A serious disadvantage of hypohalites, especially hypochlorite, is their unsatisfactory storage stability. In many commercial products, it shows that the hypochlorites decompose with the elimination of oxygen according to the following equation: The effective chlorine content decreases due to the decomposition of the hypochlorite.
  • hypochlorites due to the strong oxidation effect of the hypochlorites, it is particularly difficult to find recipes for bleaching agents, cleaning agents and disinfectants in which stable organic surfactants, water hardness binders and builders are present in the presence of hypochlorite.
  • hypohalite solutions there are already a number of proposals for improving the stability of hypohalite solutions and for the selection of surfactants, water hardness binders and builders with improved storage stability compared to hypochlorite.
  • NH compounds such as, for. B. cyanamide, ethyl carbamate, urea and its derivatives and amides of organic carboxylic acids, sulfuric, phosphoric or boric acid.
  • NH compounds react with hypohalites to form N-halogen compounds, with educts and products being in a pH-dependent equilibrium with one another.
  • amidosulfonate as NH compound
  • hypochlorite ion the following reaction equations are mentioned, for example:
  • the equilibrium of this system favors the formation of N, N-dichlorosulfamate; however, the concentration of free hypochlorite is reduced, e.g. B. by their intended consumption, the balance is shifted back to the starting materials.
  • N, N-dichlorosulfamate formed according to these reaction equations decomposes in a strongly alkaline medium (pH> 11) with the formation of N 2 , sulfate and chloride, but the hydroxide ions released during its formation favor the achievement of a high pH value System added a buffer to adjust the pH in a range between 4 and 11, preferably between 7 and 11.
  • US Pat. No. 3,749,672 also shows that the stability of the N, N-dichlorosulfamate solutions is also influenced by the molar ratio between hypochlorite and N-H compound.
  • hypochlorite amidosulfonate system it is stated that at pH 9.5 the active chlorine content is greatest after 2 weeks' storage when the NaOCI / H2NS03 molar ratio is between 2.05 and 3.
  • US Pat. No. 4,201,687 describes the use of aqueous solutions of chlorimidodisulfate as a bleaching agent. Compared to hypochlorite solutions, these solutions are characterized by better stability.
  • the active chlorine content in the chlorine imidodisulfate systems is significantly higher, particularly at elevated storage temperatures and long storage times.
  • the stability of the solutions is pH-dependent; to maintain a pH of about 10 at which the active chlorine content reaches a maximum Buffering of the solutions to pH values between 9 and 11 is proposed.
  • US-A-2 438 781 discloses a molar ratio of hypohalite: NH compound which is substantially higher than 1: 1.
  • alkaline solutions of hypohalite at a pH-value> 11 can be stabilized by amidosulfonic acids when the molar ratio hypohalite: amidosulfonic acid ⁇ 1, 1.
  • the invention accordingly relates to aqueous solutions of hypohalites stabilized by amidosulfonic acid, which are characterized in that they have a pH> 11 and have a molar ratio of hypohalite: amidosulfonic acid of 1.1.
  • the invention also relates to bleaching agents, cleaning agents and disinfectants which contain such aqueous solutions in addition to conventional auxiliaries desired for these agents, such as surfactants, complexing agents, foam depressors, corrosion inhibitors and / or builders.
  • aqueous solutions according to the invention contain hypohalite in the form of the alkali salts of hypochlorous acid.
  • the solutions an alkali compound, for. B. added sodium hydroxide.
  • solutions of this composition according to the invention are compared with corresponding solutions which do not contain amidosulfonic acid to stabilize hypohaiite after prolonged storage at elevated temperatures, the solutions according to the invention have a significantly higher residual content of active chlorine in all cases.
  • the content of active chlorine is 98.7% of the initial content under identical storage conditions, while in solutions without stabilizing amidosulfonic acid the content decreases to less than 2/3 of the original value .
  • the active chlorine content is greater after a long storage period if amidosulfonic acids are added to the solutions according to the invention and the molar ratio of hypohalite to amidosulfonic acid is 1.1.
  • hypochlorite solutions to which amidosulfonic acid has been added in a molar ratio of hypohalite: amidosulfonic acid ⁇ 1 contain, in the presence of surfactants or other auxiliaries and under the same storage conditions, a residual content of active chlorine that is up to 50% higher than that found in solutions without amidosulfonic acid becomes.
  • selected surfactants show improved hypohalite stability.
  • aqueous solutions according to the composition according to the invention show a significantly reduced corrosion effect against metals. This effect can be further reduced by the targeted use of special corrosion inhibitors.
  • the molar ratio of hypohalite: NH compound was 1.04 in this example.
  • hypochlorite was carried out according to the method given in USP XX, p. 732 by reaction with iodide and titration of the iodine formed with thiosulfate.
  • test germs were examined: The tests were carried out in accordance with the guidelines of the German Society for Hygiene and Microbiology (DGHM). The shortest tested exposure time was 2.5 minutes. Result: With an application concentration of 1%, all test germs could be killed within 2.5 minutes.
  • DGHM German Society for Hygiene and Microbiology
  • test germs were examined: The investigations were carried out according to the guidelines of the DGHM. 20% serum was chosen as protein load. Result: The effectiveness was not significantly impaired by the presence of protein. Here, too, most test germs were killed after 2.5 minutes of exposure to a 1-96 solution.
  • test germs were examined: The investigations were carried out in accordance with the guidelines of the DGHM on batiste patches. In the germ carrier test with batiste lobes as well, the test germs were killed within a short exposure time by a 2% strength solution which had been prepared in accordance with Example 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

1. Aqueous solutions of hypohalites stabilized by amidosulfonic acid, characterized in that they have a pH value > 11 and exhibit a molar ratio hypohalite : amidosulfonic acid of =< 1.1.

Description

Hypohalite, bevorzugt Hypochlorite, sind seit langem vielseitig eingesetzte Wirkstoffe in Bleich-, Reinigungs- und Desinfektionsmitteln.Hypohalites, preferably hypochlorites, have long been used in bleaching, cleaning and disinfecting agents.

In den sog. Chlorbleichlaugen, die vor allem in der Papier- und Textilindustrie verwendet werden, bilden Hypochlorite in Wasser Lösungen von hypochloriger Säure, die ihre bleichende Wirkung durch Oxidation, bevorzugt bei pH-Werten von 9 - 12, entfalten. Die Bleichwirkung der Bleichlaugen steigt mit sinkendem pH-Wert und steigender Temperatur. Die desinfizierende Wirkung von Hypochloritlösungen beruht auf der Eigenschaft der hypochlorigen Säure, durch die Zellwände der Bakterien diffundieren und damit ihre vitalen Bestandteile abtöten zu können. Die desinfizierende Kraft ist direkt proportional der Konzentration an HCIO, also auch eine Funktion des pH-Wertes (E. Heubach, G. Riess, H. Vogt, D. Bergner, Ullmann's Encyclopädie d. techn. Chem., Bd. 8, 542 ff, Weinheim 1974).In the so-called chlorine bleach, which is mainly used in the paper and textile industry, hypochlorites form solutions of hypochlorous acid in water, which develop their bleaching effect through oxidation, preferably at pH values from 9 to 12. The bleaching effect of the bleaching liquors increases with falling pH and temperature. The disinfectant effect of hypochlorite solutions is based on the property of hypochlorous acid, which can diffuse through the cell walls of the bacteria and thus kill their vital components. The disinfectant power is directly proportional to the concentration of HCIO, i.e. also a function of the pH (E. Heubach, G. Riess, H. Vogt, D. Bergner, Ullmann's Encyclopedia d. Techn. Chem., Vol. 8, 542 ff, Weinheim 1974).

Wichtigste Kenngröße zum Vergleich von hypochlorithaltigen Lösungen ist der Massengehalt (in %) an aktivem oder wirksamem Chlor. Darunter versteht man diejenige Menge an Chlor, die beim Zusatz von Salzsäure entwickelt wird:

Figure imgb0001
Ein gravierender Nachteil der Hypohalite, insbesondere des Hypochlorits, ist jedoch deren unbefriedigende Lagerstabilität. Sie zeigt sich bei vielen Handelsprodukten darin, daß sich die Hypochlorite unter Abspaltung von Sauerstoff nach folgender Gleichung zersetzen:
Figure imgb0002
Durch die Zersetzung des Hypochlorits nimmt der wirksame Chlorgehalt ab.The most important parameter for comparing hypochlorite-containing solutions is the mass content (in%) of active or effective chlorine. This is the amount of chlorine that is developed when hydrochloric acid is added:
Figure imgb0001
 A serious disadvantage of hypohalites, especially hypochlorite, is their unsatisfactory storage stability. In many commercial products, it shows that the hypochlorites decompose with the elimination of oxygen according to the following equation:
Figure imgb0002
 The effective chlorine content decreases due to the decomposition of the hypochlorite.

Weiterhin ist es aufgrund der starken Oxidationswirkung der Hypochlorite besonders schwierig, Rezepturen für Bleich-, Reinigungs- und Desinfektionsmittel zu finden, in denen stabile organische Tenside, Wasserhärtebinder und Builder in Gegenwart von Hypochlorit vorliegen.Furthermore, due to the strong oxidation effect of the hypochlorites, it is particularly difficult to find recipes for bleaching agents, cleaning agents and disinfectants in which stable organic surfactants, water hardness binders and builders are present in the presence of hypochlorite.

Daher gibt es bereits eine Vielzahl von Vorschlägen zur Verbesserung der Stabilität von Hypohalit-Lösungen sowie zur Auswahl von Tensiden, Wasserhärtebindern und Buildem mit verbesserter Lagerstabilität gegenüber Hypochlorit.Therefore, there are already a number of proposals for improving the stability of hypohalite solutions and for the selection of surfactants, water hardness binders and builders with improved storage stability compared to hypochlorite.

In der US-A-3 749 672 wird beispielsweise vorgeschlagen, N-H-Verbindungen in Gegenwart von Hypochlorit, Hypobromit, oder Hypoiodit einzusetzen. Als N-H-Verbindungen werden dabei Amide von Brönsted-Säuren sowie damit verwandte Verbindungen mit einer N-H-Bindung bezeichnet, wie z. B. Cyanamid, Ethylcarbamat, Harnstoff und seine Derivate sowie Amide organischer Carbonsäuren, der Schwefel-, Phosphor- oder Borsäure. Diese N-H-Verbindungen setzen sich mit Hypohalogeniten zu N-Halogenverbindungen um, wobei Edukte und Produkte in einem pH-abhängigen Gleichgewicht miteinander stehen. Für das System Amidosulfonat (als NH-Verbindung) und das Hypochlorition werden beispielsweise folgende Reaktionsgleichungen genannt:

Figure imgb0003
Figure imgb0004
Das Gleichgewicht dieses Systems begünstigt die Bildung von N,N-Dichlorsulfamat; wird jedoch die Konzentration an freiem Hypochlorit verringert, z. B. durch deren bestimmungsgemässen Verbrauch, wird das Gleichgewicht wieder zu den Edukten verschoben.For example, US Pat. No. 3,749,672 proposes using NH compounds in the presence of hypochlorite, hypobromite, or hypoiodite. Amides of Bronsted acids and related compounds with an NH bond are referred to as NH compounds, such as, for. B. cyanamide, ethyl carbamate, urea and its derivatives and amides of organic carboxylic acids, sulfuric, phosphoric or boric acid. These NH compounds react with hypohalites to form N-halogen compounds, with educts and products being in a pH-dependent equilibrium with one another. For the system amidosulfonate (as NH compound) and the hypochlorite ion, the following reaction equations are mentioned, for example:
Figure imgb0003
Figure imgb0004
 The equilibrium of this system favors the formation of N, N-dichlorosulfamate; however, the concentration of free hypochlorite is reduced, e.g. B. by their intended consumption, the balance is shifted back to the starting materials.

Da sich das nach diesen Reaktionsgleichungen gebildete N,N-Dichlorsulfamat im stark alkalischen Medium (pH > 11) unter Bildung von N2, Sulfat und Chlorid zersetzt, die bei seiner Bildung freiwerdenden Hydroxidionen jedoch das Erreichen eines hohen pH-Wertes begünstigen, wird dem System ein Puffer zugesetzt, um den pH-Wert in einem Bereich zwischen 4 und 11, bevorzugt zwischen 7 und 11, einzustellen.Since the N, N-dichlorosulfamate formed according to these reaction equations decomposes in a strongly alkaline medium (pH> 11) with the formation of N 2 , sulfate and chloride, but the hydroxide ions released during its formation favor the achievement of a high pH value System added a buffer to adjust the pH in a range between 4 and 11, preferably between 7 and 11.

Aus der US-A-3 749 672 geht weiterhin hervor, daß die Stabilität der N,N-Dichlorsulfamat-Lösungen auch durch das Molverhältnis zwischen Hypochlorit und N-H-Verbindung beeinflußt wird. Für das System Hypochlorit-Amidosulfonat wird angegeben, daß bei einem pH von 9,5 der Gehalt an aktivem Chlor nach einer Lagerung von 2 Wochen dann am größten ist, wenn das Molverhältnis NaOCI/H2NS03 zwischen 2,05 und 3 liegt.US Pat. No. 3,749,672 also shows that the stability of the N, N-dichlorosulfamate solutions is also influenced by the molar ratio between hypochlorite and N-H compound. For the hypochlorite amidosulfonate system, it is stated that at pH 9.5 the active chlorine content is greatest after 2 weeks' storage when the NaOCI / H2NS03 molar ratio is between 2.05 and 3.

In der US-A-4 201 687 ist der Einsatz von wässrigen Lösungen von Chlorimidodisulfat als Bleichmittel beschrieben. Im Vergleich zu Hypochlorit-Lösungen zeichnen sich diese Lösungen durch eine bessere Stabilität aus. Insbesondere bei erhöhten Lagertemperaturen und langen Lagerzeiten ist der Gehalt der Lösungen an aktivem Chlor für die Chlorimidodisulfat-Systeme deutlich höher. Auch hier ist die Stabilität der Lösungen pH-abhängig; um einen pH-Wert von etwa 10, bei dem der Gehalt an aktivem Chlor ein Maximum erreicht, einzuhalten, wird eine Pufferung der Lösungen auf pH-Werte zwischen 9 und 11 vorgeschlagen.US Pat. No. 4,201,687 describes the use of aqueous solutions of chlorimidodisulfate as a bleaching agent. Compared to hypochlorite solutions, these solutions are characterized by better stability. The active chlorine content in the chlorine imidodisulfate systems is significantly higher, particularly at elevated storage temperatures and long storage times. Here too, the stability of the solutions is pH-dependent; to maintain a pH of about 10 at which the active chlorine content reaches a maximum Buffering of the solutions to pH values between 9 and 11 is proposed.

Die nach der US-A-3 749 672 auf pH-Werte < 11 begrenzte stabilisierende Wirkung von N-H-Verbindungen auf Hypohalit verbietet den Einsatz starker Alkalien wie KOH oder NaOH in größerer Menge, da sonst der pH-Wert von 11 schnell überschritten wird.The stabilizing effect of N-H compounds on hypohalite, which is limited to pH values <11 according to US Pat. No. 3,749,672, prohibits the use of strong alkalis such as KOH or NaOH in large amounts, since otherwise the pH value of 11 is quickly exceeded.

Andererseits ist gerade der Einsatz starker Alkalien in Reinigungsmitteln oft erwünscht. Es besteht daher ein großes Interesse daran, in stark alkalische Reinigungsmittel Hypohalit in lagerstabiler Form einzuarbeiten. Dabei muß eine Stabilität der Lösungen über längere Zeit auch dann gegeben sein, wenn ein pH-Wert von 11 überschritten wird. Aus wirtschaftlichen wie ökologischen Gründen sollte die zur Stabilisierung der Hypohalit-Lösungen erforderliche Menge an N-H-Verbindung möglichst niedrig gehalten werden.On the other hand, the use of strong alkalis in cleaning agents is often desirable. There is therefore great interest in incorporating Hypohalit in a storage-stable form in strongly alkaline cleaning agents. The solutions must remain stable over a long period of time even if a pH of 11 is exceeded. For economic and ecological reasons, the amount of N-H compound required to stabilize the Hypohalit solutions should be kept as low as possible.

Die US-A-2 438 781 offenbart ein Molverhältnis von Hypohalit : -NH-Verbindung, das wesentlich höher als 1 : 1 ist.US-A-2 438 781 discloses a molar ratio of hypohalite: NH compound which is substantially higher than 1: 1.

Überraschenderweise wurde nun gefunden, daß alkalische Lösungen von Hypohalit bei einem pH-Wert > 11 durch Amidosulfonsäuren stabilisiert werden können, wenn das Molverhältnis Hypohalit : Amidosulfonsäure ≤ 1,1 ist.Surprisingly, it has now been found that alkaline solutions of hypohalite at a pH-value> 11 can be stabilized by amidosulfonic acids when the molar ratio hypohalite: amidosulfonic acid ≤ 1, 1.

Die Erfindung betrifft demgemäß wässrige Lösungen von durch Amidosulfonsäure stabilisierten Hypohaliten, die dadurch gekennzeichnet sind, daß sie einen pH-Wert > 11 haben und ein Molverhältnis Hypohalit : Amidosulfonsäure von 1,1 aufweisen.The invention accordingly relates to aqueous solutions of hypohalites stabilized by amidosulfonic acid, which are characterized in that they have a pH> 11 and have a molar ratio of hypohalite: amidosulfonic acid of 1.1.

Die Erfindung betrifft außerdem Bleich-, Reinigungs- und Desinfektionsmittel, die derartige wässrige Lösungen neben üblichen, für diese Mittel erwünschten Hilfsstoffen wie Tensiden, Komplexbildnem, Schaumdepressoren, Korrosionsinhibitoren und/oder Buildem enthalten.The invention also relates to bleaching agents, cleaning agents and disinfectants which contain such aqueous solutions in addition to conventional auxiliaries desired for these agents, such as surfactants, complexing agents, foam depressors, corrosion inhibitors and / or builders.

Die erfindungsgemässen wässrigen Lösungen enthalten Hypohalit in Form der Alkalisalze der unterchlorigen Säure.The aqueous solutions according to the invention contain hypohalite in the form of the alkali salts of hypochlorous acid.

Zur Einstellung des gemäß der Erfindung erforderlichen pH-Wertes wird den Lösungen eine Alkaliverbindung, z. B. Natriumhydroxid zugesetzt.To adjust the pH required according to the invention, the solutions an alkali compound, for. B. added sodium hydroxide.

Vergleicht man Lösungen dieser erfindungsgemässen Zusammensetzung mit entsprechenden Lösungen, die keine Amidosulfonsäure zur Stabilisierung des Hypohaiits enthalten, nach längerer Lagerzeit bei erhöhten Temperaturen, so weisen die erfindungsgemäßen Lösungen in allen Fällen einen deutlich höheren Restgehalt an aktivem Chlor auf. In günstigen Fällen, z. B. bei einem Molverhältnis Hypohalit : Amidosulfonsäure von 0,7 :: 1, beträgt unter identischen Lagerbedingungen der Gehalt an aktivem Chlor 98,7 % des Ausgangsgehaltes, während in Lösungen ohne stabilisierende Amidosulfonsäure der Gehalt auf weniger als 2/3 des ursprünglichen Wertes zurückgeht.If solutions of this composition according to the invention are compared with corresponding solutions which do not contain amidosulfonic acid to stabilize hypohaiite after prolonged storage at elevated temperatures, the solutions according to the invention have a significantly higher residual content of active chlorine in all cases. In favorable cases, e.g. B. at a molar ratio hypohalite: amidosulfonic acid of 0.7 :: 1, the content of active chlorine is 98.7% of the initial content under identical storage conditions, while in solutions without stabilizing amidosulfonic acid the content decreases to less than 2/3 of the original value .

Auch bei Einsatz von Tensiden, Komplexbildnern, Schaumdepressoren und Buildern in alkalischen, wässrigen Desinfektions- und Reinigungslösungen ist der Gehalt an aktivem Chlor nach längerer Lagerzeit dann größer, wenn den Lösungen erfindungsgemäß Amidosulfonsäuren zugesetzt werden und das Molverhältnis Hypohalit zu Amidosulfonsäure s 1,1 ist.Even when surfactants, complexing agents, foam depressors and builders are used in alkaline, aqueous disinfection and cleaning solutions, the active chlorine content is greater after a long storage period if amidosulfonic acids are added to the solutions according to the invention and the molar ratio of hypohalite to amidosulfonic acid is 1.1.

So enthalten Hypochloritlösungen, denen Amidosulfonsäure in einem Molverhältnis Hypohalit : Amidosulfonsäure < 1 zugesetzt wurde, in Gegenwart von Tensiden bzw. anderen Hilfsstoffen bei gleichen Lagerbedingungen einen Restgehalt an aktivem Chlor, der bis zu 50 % über dem Gehaft liegt, der in Lösungen ohne Amidosulfonsäure gefunden wird. Zudem zeigen ausgesuchte Tenside eine verbesserte Hypohalitstabilität.For example, hypochlorite solutions to which amidosulfonic acid has been added in a molar ratio of hypohalite: amidosulfonic acid <1 contain, in the presence of surfactants or other auxiliaries and under the same storage conditions, a residual content of active chlorine that is up to 50% higher than that found in solutions without amidosulfonic acid becomes. In addition, selected surfactants show improved hypohalite stability.

Als ein weiterer Vorteil der wässrigen Lösungen entsprechend der erfindungsgemäßen Zusammensetzung ist es anzusehen, daß sie eine deutlich verringerte Korrosionswirkung gegen Metalle zeigen. Diese Wirkung kann durch den gezielten Einsatz spezieller Korrosionsinhibitoren weiter verringert werden.Another advantage of the aqueous solutions according to the composition according to the invention is that they show a significantly reduced corrosion effect against metals. This effect can be further reduced by the targeted use of special corrosion inhibitors.

Die Erfindung wird durch die nachstehenden Beispiele näher erläutert.The invention is illustrated by the examples below.

Beispiel 1example 1

30,77 kg Natronbleichlauge mit einem Gehalt von 13 Gew.-% NaOCI wurden mit 50 kg Wasser versetzt, dann wurden 12 kg 50-%-ige Natronlauge eingerührt. Jetzt wurden 6,13 kg Amidosulfonsäure-Na-Salz zugegeben und unter Rühren gelöst. Dann wurden 1,1 kg einer handelsüblichen Lösung von Diphenyloxid-Disulfonat-Na-Salz (45 % Aktivgehalt) sowie 0,5 kg eines handelsüblichen Phosphorsäureesters von linearen Fettalkoholen in neutralisierter Form zugegeben und mit Wasser auf 100 kg aufgefüllt.30.77 kg of sodium bleaching solution containing 13% by weight of NaOCl were mixed with 50 kg of water, then 12 kg of 50% strength sodium hydroxide solution were stirred in. Now 6.13 kg of amidosulfonic acid Na salt were added and dissolved with stirring. Then 1.1 kg of a commercial solution of diphenyl oxide disulfonate sodium salt (45% active content) and 0.5 kg of a commercial phosphoric acid ester of linear fatty alcohols in neutralized form were added and made up to 100 kg with water.

Das Molverhältnis Hypohalit : NH-Verbindung betrug in diesem Beispiel 1,04.The molar ratio of hypohalite: NH compound was 1.04 in this example.

Die Bestimmung des Hypochlorit wurde nach dem in USP XX, S. 732 angegebenen Verfahren durch Umsetzung mit Iodid und Titrieren des entstandenen lod mit Thiosulfat durchgeführt.The determination of the hypochlorite was carried out according to the method given in USP XX, p. 732 by reaction with iodide and titration of the iodine formed with thiosulfate.

Dieser Ansatz hatte nach einer Lagerzeit von 6 Monaten bei Zimmertemperatur noch einen Gehalt von 91,5 % des Ausgangsgehaltes an aktivem Chlor.After a storage period of 6 months at room temperature, this approach still contained 91.5% of the starting content of active chlorine.

Vergleichsbeispiel 1Comparative Example 1

Vergleichsbeispiel nach dem Stand der Technik:

  • Es wurde ein Ansatz wie in Beispiel 1 hergestellt, jedoch wurden anstelle der 6,13 kg Amidosulfonsäure-Na-Salz die gleiche Menge Wasser zugesetzt. Dieser Ansatz hatte nach 6 Monaten Lagerung bei Zimmertemperatur nur noch einen Aktivgehalt von 77 % des Ausgangswertes.
Comparative example according to the prior art:
  • A batch was prepared as in Example 1, but the same amount of water was added instead of the 6.13 kg of amidosulfonic acid Na salt. After 6 months of storage at room temperature, this approach only had an active content of 77% of the initial value.

Vergleichsbeispiel 2Comparative Example 2

Vergleichsbeispiel für ein Molverhältnis Hypohalit : NH-Verbindung außerhalb der Patentansprüche:

  • Es wird ein Ansatz wie in Beispiel 1 hergestellt, jedoch werden anstelle von 6,13 kg Amidosulfonsäure-Na-Salz nur 4,90 kg Amidosulfonsäure-Na-Salz zugesetzt. Der Gewichtsausgleich erfolgt über die Wassermenge. Das Molverhältnis Hypohalit : NH-Verbindung betrug 1,30. Dieser Ansatz ist derart instabil, daß nach einer Lagerzeit von 24 Stunden bei 40°C nur noch 59 % des Ausgangsgehaftes an aktivem Chlor vorhanden sind.
Comparative example of a molar ratio of hypohalite: NH compound outside the claims:
  • It is an approach prepared as in Example 1, except that instead of 6.13 kilograms of sulfamic acid sodium salt only 4, 9 0 kg sulfamic acid sodium salt was added. The weight is balanced by the amount of water. The molar ratio hypohalite: NH compound was 1.30. This approach is so unstable that after a storage time of 24 hours at 40 ° C only 59% of the initial content of active chlorine is still present.

Beispiel 2Example 2

Anwendung der erfindungsgemässen Ansätze:

  • In klinischen Laboratorien fallen oftmals mit eingetrocknetem Blut verkrustete Pipetten an, deren Reinigung ein erhebliches Problem darstellt.
Application of the approaches according to the invention:
  • In clinical laboratories, there are often pipettes encrusted with dried blood, the cleaning of which is a considerable problem.

Derartige Pipetten wurden nur 5 Minuten in eine 3-%-ige Lösung des Ansatzes nach Beispiel 1 getaucht; es waren nach dieser Zeit alle Verkrustungen selbsttätig abgelöst.Such pipettes were immersed in a 3% solution of the batch according to Example 1 for only 5 minutes; after this time, all incrustations were automatically removed.

Beispiele zur mikrobiologischen Wirkung der erfindungsgemäßen Lösungen:Examples of the microbiological effect of the solutions according to the invention:

Beispiel 3Example 3

Bakterizide und fungizide Wirkung einer gemäß Beispiel 1 hergestellten Lösung im Suspensionsversuch.Bactericidal and fungicidal activity of a solution prepared according to Example 1 in a suspension test.

Es wurden folgende Testkeime untersucht:

Figure imgb0005
Die Untersuchungen wurden entsprechend den Richtlinien der Deutschen Gesellschaft für Hygiene und Mikrobiologie (DGHM) durchgeführt. Die kürzeste geprüfte Einwirkungszeit betrug 2,5 Minuten.
Figure imgb0006
Ergebnis: Bei einer Anwendungskonzentration von 1 % konnten alle Testkeime innerhalb von 2,5 Minuten abgetötet werden.The following test germs were examined:
Figure imgb0005
 The tests were carried out in accordance with the guidelines of the German Society for Hygiene and Microbiology (DGHM). The shortest tested exposure time was 2.5 minutes.
Figure imgb0006
 Result: With an application concentration of 1%, all test germs could be killed within 2.5 minutes.

Belspiel 4Example 4

Bakterizide und fungizide Wirkung einer gemäß Beispiel 1 hergestellten Lösung im Suspensionsversuch unter Eiweißbelastung.Bactericidal and fungicidal activity of a solution prepared according to Example 1 in a suspension test under protein load.

Es wurden folgende Testkeime untersucht:

Figure imgb0007
Die Untersuchungen wurden entsprechend den Richtlinien der DGHM durchgeführt. Als Eiweißbelastung wurde 20 % Serum gewählt.
Figure imgb0008
Ergebnis: Durch die Anwesenheit von Eiweiß wurde die Wirksamkeit nicht wesentlich beeinträchtigt. Auch hier wurden die meisten Testkeime nach Einwirkungszeiten einer 1-96-igen Lösung von 2,5 Minuten abgetötet.The following test germs were examined:
Figure imgb0007
 The investigations were carried out according to the guidelines of the DGHM. 20% serum was chosen as protein load.
Figure imgb0008
 Result: The effectiveness was not significantly impaired by the presence of protein. Here, too, most test germs were killed after 2.5 minutes of exposure to a 1-96 solution.

Beispiel 5Example 5

Bestimmung der bakteriziden Wirkung einer gemäß Beispiel 1 hergestellten Lösung im Keimträgertest.Determination of the bactericidal activity of a solution prepared according to Example 1 in the germ carrier test.

Es wurden folgende Testkeime untersucht:

Figure imgb0009
Die Untersuchungen wurden entsprechend den Richtlinien der DGHM an Batistläppchen durchgeführt.
Figure imgb0010
Auch im Keimträgerversuch mit Batistläppchen wurden die Testkeime durch eine 2-%-ige Lösung, die entsprechend Beispiel 1 hergestellt worden war, innerhalb kurzer Einwirkungszeiten abgetötet.The following test germs were examined:
Figure imgb0009
 The investigations were carried out in accordance with the guidelines of the DGHM on batiste patches.
Figure imgb0010
 In the germ carrier test with batiste lobes as well, the test germs were killed within a short exposure time by a 2% strength solution which had been prepared in accordance with Example 1.

Claims (5)

1. Aqueous solutions of hypohalites stabilized by amidosulfonic acid, characterized in that they have a pH value > 11 and exhibit a molar ratio hypohalite : amidosulfonic acid of s 1.1.
2. Aqueous solutions according to claim 1, characterized in that hypochlorite is preferably used as the hypohalite.
3. Aqueous solutions according to claims 1 to 2, characterized in that they have a pH value > 11, and preferably a pH-value > 13.
4. Aqueous solutions according to claims 1 to 3, characterized in that the molar ratio hypohalite : amidosulfonic acid is from 1.04 to 0.70 : 1.
5. Bleaching agent, cleanser or disinfectant, containing aqueous solutions according to claims 1 to 4 and conventional auxiliary material desired for said agents, such as surfactants, complexing agents, antifoaming agents, corrosion inhibitors and/or builders.
EP84102561A 1983-03-12 1984-03-09 Hypohalite-based bleaching, cleaning and disinfecting agent with storing stability Expired - Lifetime EP0119560B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84102561T ATE51207T1 (en) 1983-03-12 1984-03-09 HYPOHALITE BASED BLEACH, CLEANER AND DISINFECTANT WITH IMPROVED STORAGE STABILITY.

Applications Claiming Priority (2)

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DE3308850 1983-03-12
DE3308850A DE3308850C2 (en) 1983-03-12 1983-03-12 Hypohalite-based bleaching, cleaning and disinfecting agents with improved storage stability

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EP0119560A3 EP0119560A3 (en) 1986-07-30
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DE3400989A1 (en) * 1984-01-13 1985-07-18 Basf Ag, 6700 Ludwigshafen METHOD FOR DECOLEATING COTTON AND COTTON-FABRIC FABRICS
DE3910921C1 (en) * 1989-04-05 1990-05-17 Bayer Ag, 5090 Leverkusen, De
US5380458A (en) * 1992-10-02 1995-01-10 Colgate-Palmolive Co. Stabilized hypohalite compositions
EP0813588A1 (en) * 1995-03-03 1997-12-29 The Procter & Gamble Company Cleaning compositions with reduced skin malodor
EP0743279A1 (en) * 1995-05-16 1996-11-20 The Procter & Gamble Company Process for the manufacture of hypochlorite bleaching compositions
EP0743280A1 (en) * 1995-05-16 1996-11-20 The Procter & Gamble Company Process for the manufacture of hypochlorite bleaching compositions
EP0783036A1 (en) * 1995-12-07 1997-07-09 The Procter & Gamble Company Sprayable bleaching compositions for reduced irritation of the respiratory systems
US6015782A (en) * 1995-12-07 2000-01-18 The Procter & Gamble Company Process for manufacturing bleaching compositions
EP0778341A1 (en) * 1995-12-07 1997-06-11 The Procter & Gamble Company Use of amido compounds in halogen bleach-comprising compositions for improved mildness to the skin
US5723095A (en) * 1995-12-28 1998-03-03 Steris Corporation Cleaner concentrate formulation for biological waste fluid handling systems
US6037318A (en) * 1996-05-15 2000-03-14 The Procter & Gamble Company Process for manufacturing bleaching compositions comprising chlorine and bromine sources and product thereof
JPH11511779A (en) * 1996-05-15 1999-10-12 ザ、プロクター、エンド、ギャンブル、カンパニー Method for producing bleaching composition comprising chlorine source and bromine source and product thereof
EP0905225B1 (en) * 1997-09-19 2006-11-08 The Procter & Gamble Company Processes of bleaching fabrics
CN1954267B (en) * 2004-02-11 2010-12-08 马林克罗特贝克公司 Microelectronic cleaning composition containing halogen oxygen acids, salts and derivatives thereof
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DE3308850A1 (en) 1984-09-13
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DE3481702D1 (en) 1990-04-26
EP0119560A3 (en) 1986-07-30
ATE51207T1 (en) 1990-04-15

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