EP0007566A1 - Use of acylated phosphorous or sulphuric acid as cold bleaching activator for washing and cleaning agents containing compounds that deliver active oxygen - Google Patents

Use of acylated phosphorous or sulphuric acid as cold bleaching activator for washing and cleaning agents containing compounds that deliver active oxygen Download PDF

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EP0007566A1
EP0007566A1 EP79102512A EP79102512A EP0007566A1 EP 0007566 A1 EP0007566 A1 EP 0007566A1 EP 79102512 A EP79102512 A EP 79102512A EP 79102512 A EP79102512 A EP 79102512A EP 0007566 A1 EP0007566 A1 EP 0007566A1
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acylated
alkaline earth
earth metal
alkali
active oxygen
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EP0007566B1 (en
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Johannes Dr. Perner
Herbert Dr. Helfert
Rolf Dr. Fikentscher
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BASF SE
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    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/393—Phosphorus, boron- or silicium-containing compounds

Definitions

  • the invention relates to the use of easy-to-produce acylated phosphoric or sulfuric acid as a cold bleach activator for detergents and cleaning agents which contain compounds which release active oxygen as bleaching agents.
  • activators are used that accelerate the process, i.e. it also enables washing processes that take place between approx. 30 and 70 ° C. These activators are therefore, if not entirely true, called “cold bleach activators”.
  • the activators are forming such organic compounds, the organic in alkaline solution with the inorganic peroxy-compounds which themselves again as the inorganic and disintegrate but this already at room p erature. It has long been known that percarboxylic acids have this property. Acyl compounds which form percarboxylic acids in interaction with, for example, perborates were therefore chosen as such activators.
  • acyl compounds for this purpose, mainly N- and -0-acyl compounds, but also acid halides, especially acylated amines, acid chlorides, acid anhydrides, esters etc.
  • the aim of the invention was to find such acyl compounds which are more easily accessible and therefore cheaper, and which are nevertheless not inferior to the previous products in terms of their activity.
  • reaction products are mixed anhydrides which contain at least one O 2 S-OCO or OP-OCO group and at least one OH group with a mobile hydrogen atom capable of salt formation.
  • They are preferably used in the form of their alkali metal or alkaline earth metal salts.
  • the compounds to be used according to the invention can be prepared in a manner known per se:
  • Such a phosphate can also be used e.g. Acylate with acetyl chloride and finally the reaction of acetic acid (alkali or alkaline earth acetate) with phosphorus oxychloride leads to the desired products.
  • acetic acid alkali or alkaline earth acetate
  • Primary alkali or alkaline earth phosphate e.g. primary lithium phosphate at 30 to 70 ° C with about 2 times the molar amount of alkane carboxylic anhydride with 1 to 4 carbon atoms per alkane group, preferably acetic anhydride or propionic anhydride, reacted with the alkali (or alkaline earth) salt of diacyl phosphoric acid with release of acetic acid arises directly.
  • acylated sulfuric acids are expediently obtained from molar amounts of sodium hydrogen sulfate and acetic anhydride with the release of acetic acid. get acid.
  • Output connections are thus e.g. Acetic acid, propionic acid or butyric anhydride on the one hand and phosphoric acid or dihydrogen phosphate or hydrogen sulfate on the other hand.
  • activation value As a measure of the activating effect, i.e. the release of peracid effective in bleaching, a so-called activation value is chosen.
  • the determination method is described in principle in DT-OS 21 38 584.
  • active oxygen-providing compound is mixed with defined amounts of the activator, dissolved, tempered, the solution is mixed with potassium iodide and starch and immediately titrated with thiosulfate.
  • the amount of thiosulfate in ml is the activation value; if the peroxide was activated 100%, it would make up 8.0 ml.
  • Table 1 The values in Table 1 are based on 1 g of activator.
  • Table 2 shows the results of the practical bleaching tests. The test conditions can be found in the legend.
  • the bleaching effect was determined by measuring the degree of whiteness with an Elrepho photometer.
  • the initial values of the test fabric crude nettle, cotton / tea soiling and cotton / red wine soiling were set to 100%.
  • a detergent was used in which sodium sulfate was used instead of the cold bleach activator.
  • the difference between the values without cold bleach activator and the initial value of 100% can be considered as a washable portion. However, this does not apply to the washing test at 95 ° C.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)

Abstract

1. The use of orthophosphoric, metaphosphoric or sulfuric acid acylated with a C1 to C4 -alkanecarboxylic acid or a derivative thereof and containing at least one free hydroxyl group having a hydrogen atom capable of salt formation, or an alkali metal, alkaline earth metal or ammonium salt thereof, as a cold-bleach activator in cleaning agents and detergents containing as a bleach a compound which releases active oxygen.

Description

Die Erfindung betrifft die Verwendung einfach herzustellender acylierter Phosphor- oder Schwefelsäure als Kaltbleichaktivator für Wasch- und Reinigungsmittel, die Aktivsauerstoff abgebende Verbindungen als Bleichmittel enthalten.The invention relates to the use of easy-to-produce acylated phosphoric or sulfuric acid as a cold bleach activator for detergents and cleaning agents which contain compounds which release active oxygen as bleaching agents.

Bekanntlich zerfallen Aktivsauerstoff abgebende Verbindungen, wie Natriumperborat, erst bei Temperaturen über ca. 70°C mit der für einen Waschprozeß notwendigen Geschwindigkeit.As is known, compounds which give off active oxygen, such as sodium perborate, only decompose at temperatures above about 70 ° C. at the speed necessary for a washing process.

Deshalb setzt man sogenannte "Aktivatoren" ein, die den Prozeß beschleunigen, d.h. ihn auch bei Waschprozessen, die zwischen ca. 30 und 70°C ablaufen, ermöglichen. Diese Aktivatoren werden daher, wenn auch nicht ganz zutreffen, "Kaltbleichaktivatoren" genannt.Therefore, so-called "activators" are used that accelerate the process, i.e. it also enables washing processes that take place between approx. 30 and 70 ° C. These activators are therefore, if not entirely true, called "cold bleach activators".

Die Aktivatoren sind solche organische Verbindungen, die in alkalischer Lösung mit den anorganischen Perverbindungen organische Perverbindungen bilden, die selbst wieder wie die anorganischen zerfallen und dies aber bereits bei Raumtem- peratur. Es ist schon lange bekannt, daß Percarbonsäuren diese Eigenschaft besitzen. Man wählte daher Acylverbindungen, die in Wechselwirkung mit beispielsweise Perboraten Percarbonsäuren bilden, als solche Aktivatoren.The activators are forming such organic compounds, the organic in alkaline solution with the inorganic peroxy-compounds which themselves again as the inorganic and disintegrate but this already at room p erature. It has long been known that percarboxylic acids have this property. Acyl compounds which form percarboxylic acids in interaction with, for example, perborates were therefore chosen as such activators.

Als Acylverbindungen sind für diesen Zweck bereits eine große Zahl bekannt geworden, und zwar hauptsächlich N- und -0-Acylverbindungen, aber auch Säurehalogenide, speziell acylierte Amine, Säurechloride, Säureanhydride, Ester etc.A large number have already become known as acyl compounds for this purpose, mainly N- and -0-acyl compounds, but also acid halides, especially acylated amines, acid chlorides, acid anhydrides, esters etc.

Aus der DE-AS 11 62 967 kennt man N-acylierte Verbindungen, wie Tetraacetyläthylendiamin, die als derartige Aktivatoren wirken. Eine nicht einfache technische Herstellungsweise sowie das Ausgangsmaterial Äthylendiamin machen dieses Produkt jedoch sehr kostspielig.DE-AS 11 62 967 discloses N-acylated compounds, such as tetraacetylethylenediamine, which act as such activators. However, a difficult technical production method and the starting material ethylenediamine make this product very expensive.

Aus der DE-AS 11 07 632 sind acylierte Phosphosäureeester bekannt, die ebenfalls als Aktivatoren wirksam sind.From DE-AS 11 07 632 acylated phosphonic acid esters are known which are also effective as activators.

Sie sind flüssige Substanzen und destillativ nicht zu reinigen und dadurch schlecht anwendbar, obwohl sie an sich, wie wir zeigen konnten, im Durchschnitt gute Bleichergebnisse zeigen.They are liquid substances and cannot be purified by distillation and are therefore difficult to use, even though, as we have been able to show, they show good bleaching results on average.

Ziel der Erfindung war es, solche Acylverbindungen zu finden, die leichter zugänglich und damit billiger sind, und die trotzdem hinsichtlich ihrer Aktivität nicht hinter den bisherigen Produkten zurückstehen.The aim of the invention was to find such acyl compounds which are more easily accessible and therefore cheaper, and which are nevertheless not inferior to the previous products in terms of their activity.

Dieses Ziel wurde mit der Verwendung acylierter Phosphor-oder Schwefelsäure erreicht, wie sie aus den Patentansprüchen ersichtlich ist.This goal was achieved with the use of acylated phosphoric or sulfuric acid, as can be seen from the patent claims.

Solche Umsetzungsprodukte stellen gemischte Anhydride dar, die mindestens eine O2S-OCO- bzw. OP-OCO-Gruppierung und mindestens eine OH-Gruppe mit einem zur Salzbildung befähigten beweglichen Wasserstoffatom enthalten.Such reaction products are mixed anhydrides which contain at least one O 2 S-OCO or OP-OCO group and at least one OH group with a mobile hydrogen atom capable of salt formation.

Vorzugsweise werden sie in Form ihrer Alkali- oder Erdalkalimetallsalze eingesetzt.They are preferably used in the form of their alkali metal or alkaline earth metal salts.

Die Verbindungen selbst sind zum Teil bekannt. So werden in der Monographie von Kosolapoff "Organie Phosphorus Compounds", Vol. 6, S. 294-96 und in J. Amer. Chem. Soc. 70, 2183 Mono-Diacetylphosphorsäure und in J. Amer. Soc. 92, 4971 die Monoacetylschwefelsäure bzw. deren Salze beschrieben. Über eine mögliche Verwendung wird aber in den genannten Literaturstellen nichts referiert.Some of the connections themselves are known. Thus in the monograph by Kosolapoff "Organie Phosphorus Compounds", Vol. 6, pp. 294-96 and in J. Amer. Chem. Soc. 70, 2183 mono-diacetylphosphoric acid and in J. Amer. Soc. 92, 4971 describes the monoacetylsulfuric acid or its salts. However, nothing is mentioned in the references mentioned about possible use.

Die Herstellung der erfindungsgemäß zu verwendenden Verbindungen kann in an sich bekannter Weise erfolgen:The compounds to be used according to the invention can be prepared in a manner known per se:

Nach Kosolapoff (s.o.) setzt man z.B. ein sekundäres Silberphosphat mit Keten um.According to Kosolapoff (see above), e.g. a secondary silver phosphate with ketene.

Man kann auch ein solches Phosphat z.B. mit Acetylchlorid acylieren und schließlich führt auch die Umsetzung von Essigsäure (Alkali- oder Erdalkaliacetat) mit Phosphoroxychlorid zu den gewünschten Produkten.Such a phosphate can also be used e.g. Acylate with acetyl chloride and finally the reaction of acetic acid (alkali or alkaline earth acetate) with phosphorus oxychloride leads to the desired products.

Für die erfindungsgemäße Verwendung wird primäres Alkali-oder Erdalkaliphosphat, z.B. primäres Lithiumphosphat bei 30 bis 70°C mit der ca. 2-fachen Molmenge an Alkancarbonsäureanhydrid mit 1 bis 4 C-Atomen pro Alkangruppe, vorzugsweise Acetanhydrid oder Propionsäureanhydrid, umgesetzt, wobei das Alkali- (bzw. Erdalkali-)salz der Diacylphosphorsäure unter Freisetzung von Essigsäure direkt entsteht.Primary alkali or alkaline earth phosphate, e.g. primary lithium phosphate at 30 to 70 ° C with about 2 times the molar amount of alkane carboxylic anhydride with 1 to 4 carbon atoms per alkane group, preferably acetic anhydride or propionic anhydride, reacted with the alkali (or alkaline earth) salt of diacyl phosphoric acid with release of acetic acid arises directly.

Man kann (als Variante) auch NaOH mit Essigsäureanhydrid und Phosphorsäure direkt umsetzen oder Natriumacetat, Phosphorsäure und Acetanhydrid zusammen reagieren lassen.You can (as a variant) also react NaOH directly with acetic anhydride and phosphoric acid or let sodium acetate, phosphoric acid and acetic anhydride react together.

Die acylierten Schwefelsäuren (bzw. deren Salze) werden zweckmäßigerweise aus molaren Mengen Natriumhydrogensulfat und Essigsäureanhydrid unter Freisetzung von Essig- säure erhalten.The acylated sulfuric acids (or their salts) are expediently obtained from molar amounts of sodium hydrogen sulfate and acetic anhydride with the release of acetic acid. get acid.

Ausgangsverbindungen sind somit z.B. Essigsäure-, Propionsäure-oder Buttersäureanhydrid einerseits und Phosphorsäure oder Dihydrogenphosphat bzw. Hydrogensulfat andererseits.Output connections are thus e.g. Acetic acid, propionic acid or butyric anhydride on the one hand and phosphoric acid or dihydrogen phosphate or hydrogen sulfate on the other hand.

Ebenso kann man auch von Polyphosphorsäuren ausgehen (R2 = Rest der Formel II) und diese entsprechend umsetzen. Bevorzugt wählt man in diesem Fall Diphosphorsäure, Triphosphorsäure oder Metaphosphorsäure.You can also start from polyphosphoric acids (R 2 = radical of formula II) and implement them accordingly. In this case, preference is given to choosing diphosphoric acid, triphosphoric acid or metaphosphoric acid.

Es wurden folgende Verbindungen geprüft:

Figure imgb0001
Figure imgb0002
Figure imgb0003
 The following connections were checked:
Figure imgb0001
Figure imgb0002
Figure imgb0003

1. Bestimmung der Aktivierungswerte1. Determination of the activation values

Als Maß.für die aktivierende Wirkung, d.h. die Freisetzung von bleichwirksamer Persäure, wird ein sogenannter Aktivierungswert gewählt. Die Bestimmungsmethode ist prinzipiell in der DT-OS 21 38 584 beschrieben. Hierbei werden Aktivsauerstoff liefernde Verbindung mit definierten Mengen des Aktivators vermischt, gelöst, temperiert, die Lösung mit Kaliumjodid und Stärke versetzt und sofort mit Thiosulfat titriert.As a measure of the activating effect, i.e. the release of peracid effective in bleaching, a so-called activation value is chosen. The determination method is described in principle in DT-OS 21 38 584. Here, active oxygen-providing compound is mixed with defined amounts of the activator, dissolved, tempered, the solution is mixed with potassium iodide and starch and immediately titrated with thiosulfate.

Im einzelnen geht man folgendermaßen vor:The procedure is as follows:

Lösungen, die 0,615 g/l NaBO2.H2O2.3H2O (4 mMol/l) und 2,5 g/1 Na4P2O7.10H2O enthielten, wurden nach Erwärmen auf 60°C mit 4 mMol/1 Aktivator versetzt und 5 Minuten unter Rühren bei der angegebenen Temperatur gehalten. Dann gibt man 100 ml dieser Flüssigkeit auf ein Gemisch von 250 g Eis und 15 ml Eisessig und titriert sofort nach Zugabe von 0,35 g Kaliumjodid mit 0,1 g Natriumthiosulfatlösung und Stärke als Indikator; die dabei verbrauchteSolutions containing 0.615 g / l NaBO 2 .H 2 O 2 .3H 2 O (4 mmol / l) and 2.5 g / 1 Na 4 P 2 O 7 . Containing 10 H 2 O, 4 mmol / 1 activator were added after heating to 60 ° C. and the mixture was kept at the stated temperature for 5 minutes with stirring. 100 ml of this liquid are then added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and titrated immediately after adding 0.35 g of potassium iodide with 0.1 g of sodium thiosulfate solution and starch as an indicator; who consumed it

Menge an Thiosulfat in ml ist der Aktivierungswert, bei 100 %iger Aktivierung des Peroxids würde sie 8,0 ml ausmachen.The amount of thiosulfate in ml is the activation value; if the peroxide was activated 100%, it would make up 8.0 ml.

Die Werte in der Tabelle 1 sind auf 1 g Aktivator bezogen.The values in Table 1 are based on 1 g of activator.

Aktivierungswerte:

Figure imgb0004
Activation values:
Figure imgb0004

Tabelle 2 gibt die.Ergebnisse der praxisnahen Bleichversuche wieder. Die Versuchsbedingungen sind der Legende zu entnehmen.Table 2 shows the results of the practical bleaching tests. The test conditions can be found in the legend.

Die Bleichwirkung wurde über die Weißgradmessung mit einem Elrepho-Photometer ermittelt. Die Ausgangswerte der Prüfgewebe Rohnessel, Baumwolle/Teeanschmutzung und Baumwolle/ Rotweinanschmutzung wurden dabei jeweils gleich 100 % gesetzt. Als Kontrollversuch diente ein Waschmittel, in welchem anstelle des Kaltbleichaktivators Natriumsulfat verwendet wurde. Die Differenz zwischen den Werten ohne Kalt- bleichaktivator und dem Ausgangswert von 100 % kann als auswaschbarer Anteil gewertet werden. Dies gilt jedoch nicht für den Waschversuch bei 95°C.The bleaching effect was determined by measuring the degree of whiteness with an Elrepho photometer. The initial values of the test fabric crude nettle, cotton / tea soiling and cotton / red wine soiling were set to 100%. As a control test, a detergent was used in which sodium sulfate was used instead of the cold bleach activator. The difference between the values without cold bleach activator and the initial value of 100% can be considered as a washable portion. However, this does not apply to the washing test at 95 ° C.

Bei dieser Temperatur wirkt dann das Natriumperborat für sich bleichend. Die Werte der Tabelle 2 zeigen deutlich, daß die neuen Kaltbleichaktivatoren den Standard TAED erreichen. Die besten Produkte übertreffen es sogar.At this temperature, the sodium perborate has a bleaching effect. The values in Table 2 clearly show that the new cold bleach activators meet the TAED standard. The best products even surpass it.

Für den Einsatz in konfektionierten Wasch- und Reinigungsformulierungen empfiehlt es sich, die Kaltbleichaktivatoren vor unerwünschten Hydrolyse zu schützen. Dies kann beispielsweise durch Beschichten oder Umhüllen geschehen, wie dies z.B. in der DT-AS 11 62 967 für andere Aktivatoren erläutert wird.

Figure imgb0005
Figure imgb0006
 For use in ready-made washing and cleaning formulations, it is advisable to protect the cold bleach activators from undesired hydrolysis. This can be done, for example, by coating or wrapping, as is explained, for example, in DT-AS 11 62 967 for other activators.
Figure imgb0005
Figure imgb0006

Claims (3)

1. Verwendung von mittels C1- bis C4-Alkancarbonsäuren oder deren Derivaten acylierter Orthophosphorsäure, acylierter Metaphosphorsäure und acylierter Schwefelsäure, die mindestens eine Acylgruppe und mindestens eine freie zur Salzbildung befähigtes Wasserstoffatom enthaltende Hydroxylgruppe gebunden enthalten, bzw. deren Alkali-, Erdalkalimetall- oder Ammoniumsalze als Kaltbleichaktivatoren in Wasch- und Reinigungsmitteln, die aktiven Sauerstoff abgebende Verbindungen als Bleichmittel enthalten.1. The use of means C 1 - to C 4 alkanecarboxylic acids or derivatives thereof acylated orthophosphoric acid, metaphosphoric acylated and acylated sulfuric acid, containing at least one acyl group and at least one free UNTRAINED for salt formation hydrogen containing hydroxyl group bonded, or the alkali metal, alkaline earth metal or ammonium salts as cold bleach activators in washing and cleaning agents which contain active oxygen-releasing compounds as bleaching agents. 2. Verwendung von Acylierungsprodukten gemäß Anspruch 1, die der Formel I
Figure imgb0007
gehorchen, in der R1 den Acylrest einer C1- bis C4-Alkancarbonsäure bedeutet, R2 für R1, Wasserstoff oder ein Alkali- oder Erdalkalimetall steht, R3 für Wasserstoff oder ein Alkali- oder Erdalkalimetall und darüber hinaus R1 oder R 2 für die Gruppierung der Formel II
Figure imgb0008
 stehen, in der R4 für den Acylrest einer C1- bis C4-Alkancarbonsäure und R5 für R4 oder Wasserstoff, Alkali- oder Erdalkalimetal stehen, und n für 1 bis 90 steht. 2. Use of acylation products according to claim 1, which of formula I.
Figure imgb0007
 obey in the R 1 is the acyl radical of a C 1 to C 4 alkane carboxylic acid, R 2 represents R 1 , hydrogen or an alkali or alkaline earth metal, R 3 represents hydrogen or an alkali or alkaline earth metal and beyond R 1 or R 2 for the grouping of formula II
Figure imgb0008
 stand in the R 4 for the acyl radical of a C 1 to C 4 alkane carboxylic acid and R 5 represents R 4 or hydrogen, alkali metal or alkaline earth metal, and n stands for 1 to 90. 3. Verwendung von Acylierungsprodukten gemäß Anspruch 1, die der Formel III
Figure imgb0009
gehorchen, in der R 6 den Acylrest einer C1- bis C4-Alkancarbonsäure und R7 für Wasserstoff, Alkali- oder Erdalkalimetall steht. 3. Use of acylation products according to claim 1, which of the formula III
Figure imgb0009
 obey in the R 6 is the acyl radical of a C 1 to C 4 alkane carboxylic acid and R 7 represents hydrogen, alkali or alkaline earth metal.
EP79102512A 1978-07-20 1979-07-18 Use of acylated phosphorous or sulphuric acid as cold bleaching activator for washing and cleaning agents containing compounds that deliver active oxygen Expired EP0007566B1 (en)

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AT79102512T ATE28T1 (en) 1978-07-20 1979-07-18 USE OF ACYLATED PHOSPHORIC OR SULPHURIC ACID AS COLD BLEACH ACTIVATOR FOR DETERGENT AND CLEANING AGENTS CONTAINING ACTIVE OXYGEN-RELEASING COMPOUNDS

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DE19782831899 DE2831899A1 (en) 1978-07-20 1978-07-20 USE OF ACYLATED PHOSPHORIC OR SULFURIC ACID AS A CLEAR BLEACH ACTIVATOR FOR DETERGENT-RELEASING COMPONENTS CONTAINING ACTIVE OXYGEN
DE2831899 1978-07-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4545784A (en) * 1983-04-14 1985-10-08 Interox Chemicals Limited Particulate sodium perborate monohydrate containing adsorbed activator

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT406066B (en) * 1998-01-14 2000-02-25 Prokesch Albin COVER DEVICE FOR RECESSING TILED WALLS

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1107632B (en) * 1960-05-27 1961-05-31 Degussa Method for treating textiles
DE2614148A1 (en) * 1976-04-02 1977-10-20 Henkel & Cie Gmbh OXIDIZING AGENTS, BLEACHING AGENTS AND DETERGENTS WITH A BLEACH ACTIVATOR CONTENT
DE2725151A1 (en) * 1976-06-04 1977-12-08 Ugine Kuhlmann PHOSPHORUS ACTIVATORS FOR PERCONNECTIONS
DE2738976A1 (en) * 1976-09-01 1978-03-02 Ugine Kuhlmann ACTIVATORS FOR PERCONNECTIONS
DE2750528A1 (en) * 1976-11-15 1978-05-24 Procter & Gamble METHOD OF KEEPING A TOILET BASIN CLEAN
DE2733849A1 (en) * 1977-07-27 1979-02-15 Basf Ag SOLID COLD BLEACH ACTIVATORS FOR COMPOUNDS RELEASING ACTIVE OXYGEN

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1107632B (en) * 1960-05-27 1961-05-31 Degussa Method for treating textiles
DE2614148A1 (en) * 1976-04-02 1977-10-20 Henkel & Cie Gmbh OXIDIZING AGENTS, BLEACHING AGENTS AND DETERGENTS WITH A BLEACH ACTIVATOR CONTENT
DE2725151A1 (en) * 1976-06-04 1977-12-08 Ugine Kuhlmann PHOSPHORUS ACTIVATORS FOR PERCONNECTIONS
DE2738976A1 (en) * 1976-09-01 1978-03-02 Ugine Kuhlmann ACTIVATORS FOR PERCONNECTIONS
DE2750528A1 (en) * 1976-11-15 1978-05-24 Procter & Gamble METHOD OF KEEPING A TOILET BASIN CLEAN
FR2370832A1 (en) * 1976-11-15 1978-06-09 Procter & Gamble Automatically cleaning water closet basins - using specified soln. of hypohalite and sulpho di:phenyl ether cpd.
DE2733849A1 (en) * 1977-07-27 1979-02-15 Basf Ag SOLID COLD BLEACH ACTIVATORS FOR COMPOUNDS RELEASING ACTIVE OXYGEN

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4545784A (en) * 1983-04-14 1985-10-08 Interox Chemicals Limited Particulate sodium perborate monohydrate containing adsorbed activator

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DE2960198D1 (en) 1981-04-16
ATE28T1 (en) 1981-04-15
DE2831899A1 (en) 1980-02-07
EP0007566B1 (en) 1981-03-18

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