EP0079697B1 - Reinigungsmittelzusammensetzungen - Google Patents

Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0079697B1
EP0079697B1 EP82305666A EP82305666A EP0079697B1 EP 0079697 B1 EP0079697 B1 EP 0079697B1 EP 82305666 A EP82305666 A EP 82305666A EP 82305666 A EP82305666 A EP 82305666A EP 0079697 B1 EP0079697 B1 EP 0079697B1
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EP
European Patent Office
Prior art keywords
detergent composition
aqueous detergent
composition according
alkali metal
ionic strength
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Expired
Application number
EP82305666A
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English (en)
French (fr)
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EP0079697A1 (de
EP0079697B2 (de
Inventor
Anthony Francis Martin
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Procter and Gamble Ltd
Procter and Gamble Co
Original Assignee
Procter and Gamble Ltd
Procter and Gamble Co
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Application filed by Procter and Gamble Ltd, Procter and Gamble Co filed Critical Procter and Gamble Ltd
Priority to AT82305666T priority Critical patent/ATE17595T1/de
Publication of EP0079697A1 publication Critical patent/EP0079697A1/de
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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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • This invention relates to aqueous cleaning compositions and especially to chlorine bleach-containing aqueous cleaning compositions useful for the removal of oxidisable stains from and the disinfection of hard surfaces.
  • Compositions in accordance with the invention find particular utility in the cleaning of sanitary fittings such as toilets, bidets, sinks, baths and shower units in addition to the disinfection of drains and the washing of tiled surfaces.
  • Aqueous chlorine bleaching products are well known in the art and have been used for many years in a variety of bleaching and disinfecting applications.
  • the active component of a product of this type is normally an alkali metal hypochlorite, usually at a level of from 1 to 15% by weight, and the physical characteristics of the product are those of a dilute salt solution with a viscosity less than 20 centistokes (20 ⁇ 10 -6 M 2 S -1 ).
  • compositions incorporate one or more bleach stable surfactants as an aid in increasing viscosity and a preferred example of such a surfactant is an amine oxide containing one C 10 ⁇ C 18 alkyl group and two lower alkyl, usually C,-C 4 alkyl groups.
  • a preferred example of such a surfactant is an amine oxide containing one C 10 ⁇ C 18 alkyl group and two lower alkyl, usually C,-C 4 alkyl groups.
  • the compositions also contain a source of alkalinity and alkali metal salts of various kinds.
  • compositions in accordance with the invention display cleaning advantages relative to commercially available chlorine bleach compositions embodying the prior art.
  • a stable single phase aqueous detergent composition incorporating as the sole surfactant species an amine oxide of formula R 1 R 2 R 3 N ⁇ O wherein R, is an alkyl group in which the average number of carbon atoms is such that 13 ⁇ R 1 ⁇ 16 and R 2 and R 3 are C l -C 4 alkyl groups or C Z -C 4 hydroxy alkyl groups together with at least one ionisable water soluble compound wherein the amine oxide is present in an amount of from 1.0% to 2.5% by weight of the composition and in that the at least one ionisable water soluble compound is present in an amount to provide a total ionic strength of the composition of from 3.0 g moles/dm 3 to 7.81 g moles/dm 3 , such that said composition has a viscosity of at least 180 cp (0.18 Pa.sec) at 20°C.
  • R is an alkyl group in which the average number of carbon atoms is such that 13 ⁇ R 1 ⁇ 16 and R 2 and
  • the alkyl group R comprises a mixture of groups containing 13 and 15 carbon atoms and comprising a mixture of moieties of structure, and the group R 4 being predominantly methyl, the composition also being characterised by a total ionic strength of at least 4.7 g moles/dm'.
  • composition incorporates a hypochlorite bleach, R, contains an average of from 14 to 16 carbon atoms and is selected from linear moieties and moieties containing no more than 25% methyl branching.
  • fluid viscosity is expressed as the dynamic viscosity ⁇ in centipoises (10- 3 Pa.sec).
  • the dynamic viscosity is measured by a Brookfield RVT viscometer and for the purposes of this specification measurements are made with Spindle No. 3 at 100 rpm and a liquid temperature of 20°C.
  • compositions in accordance with the present invention have a density in the range from 1.10 to 1.25 g/cm 3 , typically approximately 1.15g/cm', so that the numerical value of the kinematic viscosity in centistokes is slightly less than that of the dynamic viscosity in centipoises.
  • the invention will be described primarily with reference to an aqueous composition containing an alkali metal hypochlorite bleach, the latter providing the majority, and preferably substantially all, of the ionic strength requirement.
  • the invention also embraces non-bleach compositions in which the ionic strength is provided by any ionisable alkali or alkali earth metal compound.
  • Bleach composition embodiments of the present invention therefore comprise an amine oxide of defined structure and an alkali metal hypochlorite there being sufficient ionisable inorganic salt present to provide an ionic strength of at least 3.0 g moles/dm 3 .
  • the alkali metal hypochlorite may be a lithium, potassium or sodium hypochlorite and the level of hypochlorite in the composition is normally arranged to lie in the range 1-12%, preferably 5-10% by weight.
  • Customarily hypochlorite bleach compositions contain approximately 6% or 9% hypochlorite by weight.
  • the activity of chlorine bleaching compositions is conventionally expressed in terms of the weight percentage of available chlorine in the composition, and the actual weight percentage of bleaching species is arranged to provide the desired level of'available chlorine'.
  • the preferred hypochlorite species is sodium hypochlorite which contains 95.3% available chlorine.
  • Alkali metal hypochlorites are commercially available as aqueous solutions containing 10-15% by weight 'available chlorine' and the bulk suppliers normally produce material having available chlorine contents towards the upper end of this range viz. 12-14% by weight.
  • These commercially available hypochlorite solutions contain other salts as byproducts or contaminants, more specifically free alkalinity in the form of alkali metal hydroxide and alkali metal carbonate, and alkali metal chloride.
  • Low levels of other species such as sodium chlorate are also believed to be formed during hypochlorite manufacture but their chemical stability is sufficiently low that they have largely decomposed by the time the hypochlorite is employed in product formulations.
  • the levels of the byproduct materials depend on the processing conditions employed in the manufacture of the hypochlorite but in general they fall within the ranges
  • Amine oxides useful in the present invention have the formula R 1 R 2 R 3 N ⁇ O wherein R, is an alkyl group in which the number of carbon atoms is 13 ⁇ R 1 ⁇ 16 and R 2 and R 3 are C 1 -C 4 alkyl groups or C 2 -C 4 hydroxy alkyl groups.
  • the amine oxide is present in an amount of from 1.0% to 2.5% and, in preferred embodiments of the invention in which the R i average chain length ⁇ 14 carbon atoms, from 1%to 1.5% by weight of the composition.
  • the R, group may be linear or branched and may be derived from natural or synthetic hydrocarbon sources. For the purposes of the present invention linear groups are defined as including moieties incorporating up to 25% methyl branching, predominantly in the 2-position relative to the nitrogen atom of the amine oxide.
  • Methyl branching on the alkyl chain also predominates in those amine oxides useful in the present invention in which the R, group is branched, rather than linear in nature.
  • amine oxides are normally a mixture of which arises as a result of the processing route used to form the precursor alcohol or aldehyde.
  • This route involves carbonylating or hydroformulating an olefin, preferably a linear a-olefin and leads to a mixture of the desired branched chain aldehyde or alcohol of the same carbon number.
  • the resultant alcohol or aldehyde mixture contains compounds of different carbon number and isomers containing straight chain and 2-alkyl branched chain alkyl groups.
  • a typical mixture useful in the present invention comprises 65 to 75% by weight C 13 and 35 to 25% by weight C, 5 amine oxides with approximately 50% by weight straight chain and 50% by weight 2-alkyl branched chain where the 2-alkyl group is predominantly methyl. These are available from ICI under the trade name Synprolam 35 DMO as a 30% aqueous solution.
  • the branched chain amine oxides and mixtures thereof with linear chain amine oxides are used at levels towards the upper end of the range viz. ⁇ 2% by weight of the composition and typically from 2.0% to 2.5% by weight.
  • the preferred amine oxide structure is one in which R, has an average chain length in the range C, 4 -C, e and is a linear group, linear being defined as including moities containing up to 25% 2-methyl branching.
  • Compositions containing these preferred amine oxides require a lower amine oxide level viz. ⁇ 2.0%, more typically 1.0-1.5% and also a lower ionic strength viz. 3.0 g moles/dm 3 minimum in order to achieve target viscosity. Both of these reductions in ingredient level lead to improved storage stability and also lower the cost of the product.
  • the ionisable water soluble compound which forms the other major component of the compositions of the invention is a non surface active organic, or inorganic, compound which must be present in an amount to provide an ionic strength of at least 3.0 g moles/dm 3 .
  • the ionisable compound(s) can be inorganic in nature e.g. hydroxide sulphate, halide (particularly chloride) carbonate, nitrate, orthophosphate, pyrophosphate, polyphosphate or silicate, or organic such as citrate, formate, acetate or succinate.
  • the hypochlorite bleach in which sodium hypochlorite bleach is incorporated, the hypochlorite itself, together with the sodium hydroxide, chloride and chlorate associated with the bleach provides the, or a major proportion of the ionisable compounds required by the invention.
  • certain inorganic compounds such as silicates, and organic compounds incorporating oxidisable groups are unstable and should be avoided.
  • the ionic strength of the composition is calculated by means of the expression where
  • the function C,Z2 is calculated for each of the ionic species in solution, these functions are summed and divided by two .to give the composition ionic strength.
  • the ionisable alkali metal compound normally comprises a caustic alkali such as sodium or potassium hydroxide either alone or in admixture with alkali metal salts.
  • the level of sodium hydroxide necessary to provide a total composition ionic strength of 3.0 g moles/dm 3 where the composition contains only the amine oxide would be approximately 11 % to 12% by weight of the composition dependent on the density of the solution.
  • the at least one ionisable compound comprises a mixture of a caustic alkali in an amount of from 0.5% to 2% by weight of the composition together with one or more alkali metal salts in an amount of at least 10% by weight, more usually at least 15-20%.
  • the ionisable compound can include any of the water soluble inorganic and organic builder and sequestrant salts normally incorporated in such products.
  • Compounds classifiable and well-known in the art as detergent builder salts include the nitrilotriacetates, polycarboxylates, citrates, ortho- and pyro-phosphates, and mixtures of any of these.
  • Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino- polyphosphonates and phosphates.
  • a wide variety of poly-functional organic acids and salts is disclosed in European Patent Application Publication No. 0040882 which contains examples of the use of such materials in various cleaning compositions.
  • the builder/sequestrant will comprise from 1 % to 25% of the composition. Citric acid (2%-20% as sodium citrate) is a preferred builder.
  • a highly preferred bleach composition embodiment of the invention therefore comprises from 1 % to 1.5% C 14 linear alkyl dimethyl amine oxide, from 9.0% to 9.5% sodium hypochlorite, from 9.0% to 9.5% sodium chloride and from 0.5% to 1.5% sodium hydroxide.
  • a desirable optional component of compositions in accordance with the invention is a perfume which is present at a level of from 0.01% to 0.5% preferably from 0.05% to 0.25% by weight of the composition.
  • compositions are made by conventional mixing techniques. Although any order of mixing can be used, presolution of the alkali metal hydroxide and any alkali metal salt is desirable and these are normally added to a solution of the amine oxide. Perfume is then added under high shear agitation together with any additional water to provide the desired product concentration. In the aspect of the invention in which an alkali metal hypochlorite bleach is included, this component is added last.
  • This composition had the following analysis, in percent by weight and had a density of 1.25 g/cm 2 .
  • This product was a single phase solution having a dynamic viscosity as measured at 20°C with a 'Supplied by British Drug Houses Ltd. as GPR hypochlorite. Brookfield viscometer using the No. 3 spindle at 100 rpm was 165 cp (0.165 Pa . sec) fresh and 180 cp (0.1 Pa . sec) after 24 hours.
  • the ionic strength of this composition was calculated as follows:
  • the ionic strength I of this composition was found to be 5.61 g moles/dm 3 and the dynamic viscosity, measured by means of a Brookfield RVT viscometer (Spindle No. 3 at 100 rpm) at 20°C was 220 cp as (0.22 Pa . sec) as measured 24 hours after the solution was prepared.
  • the density of the solution was 1.25 g/cm 3 so that the calculated kinematic viscosity v was 215.6 centistokes (2.15 ⁇ 10 -4 m 2 /sec).
  • the density of this solution was 1.25 g/cm 3 and on this basis the ionic strength of the composition was calculated to be 5.50 g moles/dm 3. Its viscosity (after 24 hours) was 220 centipoises (0.22 Pa . sec).
  • compositions prepared according to the technique of Example 1 illustrate the criticality of the various features of the invention.
  • composition (a) is in accordance with the present invention whilst compositions (b), (c) and (d) are illustrative of prior art products.
  • Comparison of compositions (a) and (b) demonstrates the different viscosity behaviour of products containing a) amine oxides of average chain length ⁇ C, 3 and b) amine oxide of average chain length >C i3 both products being at the same ionic strength.
  • Comparison of compositions (a) and (c) illustrates the role of ionic strength in providing the product viscosities of the present invention.
  • Example 4(a) The composition set out in Example 4(a) and designated I was tested for its hard surface cleaning ability relative to a commercially available chlorine bleach product designated II and having the following approximate analysis:
  • a synthetic soil was made up comprising by volume 8 parts ground garden soil, 4 parts roast lamb fat and 1 part milk.
  • the soil was made up by mixing the fat and garden soil, heating and stirring to melt the fat and then dispersing the milk in the mixture.
  • a soiled tile was then clamped with the soiled surface uppermost at an angle of 30° to the vertical and the soiled surface was divided equally into Left hand and Right hand areas.
  • 14 ml of Product I was applied by syringe on to the Left Hand area and the same volume of Product II was applied to the Right Hand area, each application being arranged to cover the whole surface of the respective area.
  • the areas were then left to drain for 10 minutes or overnight (18 hours) before being rinsed for 10 seconds with water at a rate of 8.5 liters/minute and a temperature of 20°C using a split rinsing head to treat both LH and RH areas simultaneously.
  • Four replicate tests were carried out in two of which the tile areas to which the products were applied were also reversed.
  • the density of each of these compositions was 1.15 g/ml and the ionic strength for each composition was calculated to be 3.5 g moles/dm 3 .
  • the product viscosity was measured at 20°C using the technique of Example 1.
  • compositions are in accordance with the invention.
  • compositions exhibit viscosities in excess of 200 cp (0.20 Pa . sec.) at 20°C after 24 hours.

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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)

Claims (9)

1. Eine stabile einphasige wässerige Reinigungsmittelzusammensetzung, die als einzige Sorte von oberflächenaktivem Mittel ein Aminoxid der Formel R1R2R3N→O, worin R, eine Alkylgruppe ist, in welcher die mittlere Zahl von Kohlenstoffatomen derart ist, daß 13<R1≤16, und R2 und R3 C1-C4-Alkylgruppen oder C2-C4-Hydroxyalkylgruppen sind, zusammen mit wenigstens einer ionisierbaren, wasserlöslichen Verbindung einverleibt enthält, dadurch gekennzeichnet, daß das Aminoxid in einer Menge von 1,0 Gew.-% bis 2,5 Gew.-% der Zusammensetzung vorliegt, und daß sie wenigstens eine ionisierbare, wasserlösliche Verbindung in einer Menge vorliegt, um eine Gesamtionenstärke der Zusammensetzung von 3,0 g-Mol/dm3 bis 7,81 g-Mol/dm3 einzustellen, sodaß die genannte Zusammensetzung eine Viskosität von wenigstens 0,18 Pa . sec (180 cP) bei 20°C hat.
2. Eine wässerige Reinigungsmittelzusamennsetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Alkylgruppe R, ein Gemisch von 13 und 15 Kohlenstoffatome enthaltenden Gruppen umfaßt, die ein Gemisch von Resten der Struktur
Figure imgb0018
und
Figure imgb0019
enthalten, wobei die Gruppe R4 überwiegend Methyl ist und die Zusammensetzung auch durch eine Gesamtionenstärke von wenigstens 4,7 g-Mol/dm3 gekennzeichnet ist.
3. Eine wässerige Reinigungsmittelzusammensetzung nach Anspruch 2, in der a) und b) in annähernd gleichen Gewichtsanteilen vorliegen.
4. Eine wässerige Reinigungsmittelzusammensetzung nach Anspruch 1, worin R, im Mittel 14 bis 16 Kohlenstoffatome enthält und aus geraden Resten und Resten, die nich mehr als 25% 2-Methyl-Verzweigung aufweisen, ausgewählt ist.
5. Eine wässerige Reinigungsmittelzusamennsetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die ionisierbare, wasserlösliche Verbindung ein organisches oder anorganisches Gerüststoff- oder komplexbildendes Salz ist.
6. Eine wässerige Reinigungsmittelzusammensetzung nach Anspruch 5, worin die wasserlösliche Verbindung aus Alkalimetallcarbonaten, -citraten, pyrophosphaten, -aminopolyacetaten und -aminopolyphosphaten ausgewählt ist.
7. Eine wässerige Reinigungsmittelzusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß im wesentlichen die gesamte Ionenstärke durch ein Gemisch aus Alkalimetyllhypochlorit, Alkalimetallchlorid und Alkalimetallhydroxid geliefert wird.
8. Eine wässerige Reinigungsmittelzusammensetzung nach Anspruch 7, in Abhängigkeit von Anspruch 4, dadurch gekennzeichnet, daß sie 1% bis 1,5% . C14-linear-Alkyldimethylaminoxid, 9,0% bis 9,5% Natriumhypochlorit, 9,0% bis 9,5% Natriumchlorid und 0,5% bis 1,5% Natriumhydroxid enthält.
9. Eine wässerige Reinigungsmittelzusammensetzung nach einem der Ansprüche 7 oder 8, wobei die Zusammensetzung ein Bleichmittel-stabiles Parfum einverleibt enthält.
EP82305666A 1981-11-07 1982-10-26 Reinigungsmittelzusammensetzungen Expired - Lifetime EP0079697B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82305666T ATE17595T1 (de) 1981-11-07 1982-10-26 Reinigungsmittelzusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8133642 1981-11-07
GB8133642 1981-11-07

Publications (3)

Publication Number Publication Date
EP0079697A1 EP0079697A1 (de) 1983-05-25
EP0079697B1 true EP0079697B1 (de) 1986-01-22
EP0079697B2 EP0079697B2 (de) 1990-03-14

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EP82305666A Expired - Lifetime EP0079697B2 (de) 1981-11-07 1982-10-26 Reinigungsmittelzusammensetzungen

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AT (1) ATE17595T1 (de)
CA (1) CA1202853A (de)
DE (1) DE3268705D1 (de)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0110544A1 (de) * 1982-11-02 1984-06-13 Imperial Chemical Industries Plc Bleichmittelzusammensetzungen
EP0137871B1 (de) * 1983-10-14 1989-10-18 The Procter & Gamble Company Reinigungsmittelzusammensetzungen
GB8330158D0 (en) * 1983-11-11 1983-12-21 Procter & Gamble Ltd Cleaning compositions
GB8332271D0 (en) * 1983-12-02 1984-01-11 Unilever Plc Bleaching composition
GB8333426D0 (en) * 1983-12-15 1984-01-25 Ici Plc Bleaching compositions
GB8630845D0 (en) * 1986-12-24 1987-02-04 Ici Plc Bleaching compositions
US4946619A (en) * 1988-07-19 1990-08-07 The Clorox Company Solubilization of brighter in liquid hypochlorite
US5034150A (en) * 1989-05-03 1991-07-23 The Clorox Company Thickened hypochlorite bleach solution and method of use
US5705467A (en) * 1991-10-22 1998-01-06 Choy; Clement K. Thickened aqueous cleaning compositions and methods of use
US5279758A (en) * 1991-10-22 1994-01-18 The Clorox Company Thickened aqueous cleaning compositions
GB9213578D0 (en) * 1992-06-26 1992-08-12 Unilever Plc Improvements to bleaching compositions
HU219162B (hu) * 1993-07-23 2001-02-28 The Procter And Gamble Company Rövid szénláncú felületaktív anyagokat tartalmazó, javított tisztító hatású viszkózus, vizes mosószerkészítmény és alkalmazása
CA2179409C (en) * 1993-12-29 2000-04-18 David L. Chang Thickened alkali metal hypochlorite compositions
US9133417B2 (en) 2012-03-23 2015-09-15 The Procter & Gamble Company Liquid cleaning and disinfecting compositions comprising an assymetrically branched amine oxide
US8470755B1 (en) 2012-03-23 2013-06-25 The Procter & Gamble Company Liquid cleaning and disinfecting compositions comprising a zinc inorganic salt

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA797201A (en) * 1965-06-22 1968-10-22 The Procter & Gamble Company Liquid detergent composition
BE755338A (fr) * 1969-08-29 1971-02-26 Unilever Nv Compositions de blanchiment
GB2003522B (en) * 1977-09-02 1982-02-24 Ici Ltd Bleaching and cleaning compositions
US4352678A (en) * 1978-10-02 1982-10-05 Lever Brothers Company Thickened abrasive bleaching compositions
GB2051162A (en) * 1979-05-30 1981-01-14 Reckitt & Colmann Prod Ltd Thickened aqueous alkali metal hypochlorite solutions
NL7908798A (nl) * 1979-12-05 1981-07-01 Unilever Nv Vloeibaar, verdikt chloorbleekmiddel.

Also Published As

Publication number Publication date
ATE17595T1 (de) 1986-02-15
EP0079697A1 (de) 1983-05-25
DE3268705D1 (en) 1986-03-06
EP0079697B2 (de) 1990-03-14
CA1202853A (en) 1986-04-08

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