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.
• 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 Cl - C4 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 Cl - C4 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 compositicns embodying the prior art.
• a stable single phase aqueous detergent composition incorporating an amine oxide of formula R 1 R 2 R 3 N ⁇ O wherein R 1 is an alkyl group in which the average number of carbon atoms is such that 13 ⁇ R 1 ⁇ 18 and R 2 and R 3 are C l -C 4 alkyl groups or C 2 -C 4 hydroxy alkyl groups together with at least one ionisable water soluble compound wherein the amine oxide comprises the sole surfactant and is present in an amount of not more than 2.5% by weight of the composition and in that the at least one water soluble inorganic salt is present in an amount to provide a total ionic strength of the composition of at least 3.0 g moles/dm 3 , such that said composition has a viscosity of at least 180 cp at 20°C.
• R 1 is an alkyl group in which the average number of carbon atoms is such that 13 ⁇ R 1 ⁇ 18 and R 2 and R 3 are C l -C 4 alkyl groups or C 2
• the alkyl group R 1 comprises a mixture of groups containing 13 and 15 carbon atoms and comprising a mixture of moieties of structure, and the group P 4 being predominantly methyl, the composition also being characterised by a total ionic strength of at least 4.7 g moles/dm 3 .
• R 1 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 n in centipoises.
• 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 1.15 g/cm 3 ; 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 .
• 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 expressed as a weight percentage of the hypochlorite solution as supplied.
• Amine oxides useful in the present invention have the formula R 1 R 2 R 3 N ⁇ O wherein R 1 is an alkyl group in which the number of carbon atoms is 13 ⁇ R 1 ⁇ 18 and R 2 and R3 are Cl - C4 alkyl groups or C 2 -C 4 hydroxy alkyl groups.
• the amine oxide is present in an amount of from 0.5% to 5%, more preferably from 0.5% to 2.5% and,in preferred embodiments of the invention in which the R 1 average chain length ⁇ 14 carbon atoms, from 1% to 1.5% by weight of the composition.
• the R 1 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 1 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 hydroformylating an olefin, preferably a linearor ⁇ -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 C15 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 hypochlorite bleach aspect of the composition is one in which R 1 has an average chain length in the range C 14 -C 16 and is a linear group, linear being defined as including moieties 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 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 eg. 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
• 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 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 pyre-phosphates, and mixtures of any of these.
• Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-polyphosphonates and phosphates (DEQUEST).
• 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.
• the bleach itself in which a hypochlorite bleach is incorporated the bleach itself, containing the range of by-product materials previously mentioned, provides a major portion of the ionic strength requirement, viz at least 3.0 g moles/dm 3 assuming an available chlorine level of 9% in the composition. In practice therefore it is usually only necessary to add alkali metal hydroxide on a total composition basis.
• the, or the major part of the, amine oxide should have an R l alkyl chain length in the range 14 to 16 carbon atoms.
• 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 Brookfield viscometer using the No. 3 spindle at 100 rpm was 165 cp fresh and 180 cp after 24 hours.
• Example 2 The following composition was prepared using the technique employed in Example 2. The density of this solution was 1.25 g/cm and on this basis the ionic strength of the composition was calculated to be 5.50 g moles/dm3. Its viscosity (after 24 hours) was 220 centipoises.
• compositions (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 13 and b) amine oxide of average chain length > C 13 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 litres/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 3 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 centipoises at 20°C after 24 hours.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

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Cited By (15)

Citations (6)

• 1982
  • 1982-10-26 DE DE8282305666T patent/DE3268705D1/de not_active Expired
  • 1982-10-26 AT AT82305666T patent/ATE17595T1/de not_active IP Right Cessation
  • 1982-10-26 EP EP82305666A patent/EP0079697B2/de not_active Expired - Lifetime
  • 1982-11-05 CA CA000415030A patent/CA1202853A/en not_active Expired

Patent Citations (6)

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