WO2008035081A1

WO2008035081A1 - Cleaning composition

Info

Publication number: WO2008035081A1
Application number: PCT/GB2007/003574
Authority: WO
Inventors: Mokhles Tangestani-Nejad; Ram Singh
Original assignee: Amity Limited
Priority date: 2006-09-22
Filing date: 2007-09-21
Publication date: 2008-03-27
Also published as: GB2444763A; GB2444763B; GB0618713D0

Abstract

The aqueous hard surface cleaning and disinfecting composition comprises a halogen, preferably bromine. It also contains a halogen complex and/or a halogen-releasing compound, together with an alkoxylated tertiary amine oxide compound.

Description

CLEANING COMPOSITION

The present invention relates to a cleaning composition, particularly, but not exclusively, for hard surfaces such as the exterior surfaces of land vehicles or aircraft.

It is well known to clean hard surfaces, such as aircraft bodies, using a foamable aqueous detergent composition. For some areas of the aircraft which are particularly difficult to clean, such as carbonised deposits near the engines, it is known to use a similar composition in the form of a gel. Similar compositions may be used to clean the exterior of land vehicles.

Such compositions are intended to remove grime from the hard surface, such as the build-up of hydrocarbons and other contaminants known in the context of land vehicles as "traffic film", and/or deposits such as bird droppings. This both improves the appearance of the aircraft and obviates the problem of the grime, etc, adding to air resistance and to weight, and hence affecting fuel economy. It has not hitherto been recognised that there are further important reasons to clean aircraft bodies. The spread of epidemic diseases is believed to be promoted by modern air travel. Not only does this include transmission by infected human travellers, but it may also include transmission through contamination of the aircraft body itself. While this might not be a significant hazard to the general public, airport ground staff (and aircraft cleaners in particular) are known to be seriously concerned by this issue. In particular, there is concern about infection with so-called "bird flu" (Avian influenza virus, strain H5N1) carried in contamination on aircraft flying in from regions in which bird flu cases are known.

It is hence an object of the present invention to provide a cleaning agent capable of removing contamination from hard surfaces such as aircraft bodies and having anti-viral and antibacterial activity to deal with such pathogens as may be present in such contamination.

According to a first aspect of the present invention, there is provided an aqueous hard surface cleaning and disinfecting composition comprising a halogen, a halogen complex and/or a halogen-releasing compound, and an alkoxylated tertiary amine oxide compound.

Preferably, the halogen comprises bromine.

Alternatively or additionally, the halogen may comprise iodine.

Alternatively or additionally, the halogen may comprise chlorine.

Advantageously, the composition may comprise up to 0.01% bromine. The composition may comprise up to 0.005% bromine.

The composition may comprise at least 0.0005% bromine.

Optionally, the composition may comprise between 0.001% and 0.003% bromine.

Preferably, said alkoxylated tertiary amine oxide compound comprises a compound having the general formula R¹R²R³NO, where R¹ is a linear or branched alkyl chain containing at least one alkoxylate group.

Advantageously, R¹ is an alkyl chain containing a plurality of alkoxylate groups, optionally comprising a polyalkoxylate group.

R² and R³ may each comprise a hydroxyalkyl chain.

Alternatively or additionally, R² and R³ may each comprise a polyalkoxylate chain.

The composition may comprise between 0.5% and 5% of said alkoxylated tertiary amine oxide compound.

Preferably, the composition further comprises a long-chain alkyl polyamine compound.

Advantageously, said long-chain alkyl polyamine compound comprises a long-chain alkyl triamine compound. - A - The long-chain alkyl triamine compound may comprise a compound having the general formula R⁴-N((CH₂)_mNH)₂)(CH₂)_nNH₂, where R⁴ is a linear or branched alkyl chain comprising at least eight carbon atoms and each of m and n equals 2, 3 or 4.

The long-chain alkyl triamine compound may comprise a compound having the general formula R⁴-N((CH₂)_mNH)₂)_2j i.e. m equals n.

Optionally, each of m and n equals three.

R⁴ may be a linear or branched alkyl chain comprising between ten and sixteen carbon atoms.

Preferably, the composition further comprises a trialkyl amine oxide compound, optionally a trialkyl amine oxide compound in which at least one of the alkyl groups contains at least ten carbon atoms.

The composition may also comprise an amphoteric surfactant compound having the general formula R⁵-N((CH₂)_P(COOX))₂, where R⁵ is a linear or branched alkyl chain, and X comprises hydrogen or an alkali metal.

Optionally, p equals two

The composition may also comprise a corrosion inhibiting agent adapted to inhibit corrosion of ferrous metals. Additionally or alternatively, the composition may comprise a corrosion inhibiting agent adapted to inhibit corrosion of non-ferrous metals.

The composition may comprise a flowable liquid composition.

Alternatively, the composition may comprise a paste, gel, cream or the like.

The composition preferably also comprises a degreasing agent.

The composition may also comprise a foam stabilising agent.

The composition may further comprise one or more polyethoxylate compounds and/or one or more alkyl polyethoxylate compounds.

The alkyl groups of said alkyl polyethoxylate compounds may comprise a monobranched alkyl group, such as a Guerbet alcohol derived group.

The composition may contain one or more aliphatic alcohols, optionally ethanol, rø-propanol, wo-propanol or a mixture of any two or all three thereof.

Embodiments of the present invention will now be more particularly described by way of example.

A first foamable composition was made up, containing the following components per 100 kilograms: EDTA, sodium salt 0.20kg Triameen Y12D-30 0.97kg Bromine GPR 0.00075k£

Sodium metasilicate pentahydrate 2.4kg

Dipropylene glycol monomethyl ether, mixed isomers 4.75kg Benzotriazole 0.20kg

Ethanol 0.45kg

«-Propanol 0.20kg

Alcohol ethoxylate (C9-1 1 6EO) 1.00kg

Alcohol ethoxylate (C 13- 15 9EO) 2.0kg

Sodium citrate 2.85kg

Sodium benzoate 1.45kg

Lauryl dimethyl amine oxide 2.8kg

Lakeland AMA 6.65kg

Lakeland RAC 2.8kg

Tomah AO14.5 1.45kg

NTA 89% powder 0.07kg

Topanol O FG 0.028kg

Synperonic A9 (90%) 0.33kg

Synperonic A7 0.17kg

Sandoteric ABD 0.22kg

Water 69kg

The composition appeared as a clear, colourless liquid with a slight detergent odour, and a pH of about 10. EDTA, ethylene diamine tetracetic acid, and its sodium salts are used to soften water by sequestering calcium ions and the like. Triameen Y12D-30 is a long-chain alkyl triamine of the general formula R'-N(C₃H₆NH₂)₂ is a "tallow alkyl" - a naturally-derived mixture of alkyl chains having a range of different lengths. It is sold by Akzo Nobel. Sodium metasilicate is used as an alkalinity builder. Dipropylene glycol monomethyl ether is used as a solvent; the blend of isomers sold as Dowanol DPM by The Dow Chemical Company is a suitable example. (Dowanol is a registered trade mark). Benzotriazole is a corrosion inhibitor for non-ferrous metals. Ethanol and M-propanol are present as solvents but also have bacteriocidal/virucidal properties. The alcohol ethoxylates are present as non-ionic surfactants. Sodium citrate is present as a sequestrant. Sodium benzoate is a corrosion inhibitor for ferrous metals. Lauryl dimethyl amine oxide is an amphoteric surfactant with the additional property of being a foam stabiliser. Lakeland AMA is a shine additive, sold by Lakeland Laboratories Ltd, of the general formula 11"-N(C₂H₄COOM)₂, where R" is a "coco alkyl" and M represents hydrogen or an alkali metal; it is hence also an amphoteric surfactant. Lakeland RAC is a blend of biodegradable surfactants, sold by Lakeland Laboratories Ltd, which acts as both a corrosion inhibitor and a degreaser. Tomah AO 14.5 is an ether amine oxide of the formula (HOC₂H₄)₂(woCi₀H₂i-O-C₃H₆)NO (Tomah is a registered trade mark of Tomah Products, Inc). NTA, or nitrilotriacetic acid trisodium salt, is a buffering agent. Topanol O FG is butylated hydroxytoluene (food grade), an antioxidant, available from Chance & Hunt Ltd (Topanol is a registered trade mark) of ICI pic). Synperonic A9 and Synperonic A7 are polyethoxylate ethers, produced by the Uniqema business of ICI pic and available through Albion Chemicals Ltd (Synperonic is a registered trade mark of ICI Chemicals & Polymers Ltd). Sandoteric ABD is a complex blend of amphoteric surfactants acting as a detergent and having a degree of bacteriocidal activity, sold by Clariant. (Sandoteric is a registered trade mark of Novartis AG).

The composition is both a highly effective cleaner of hydrocarbon-based and other surface contamination from hard surfaces, such as aircraft or land vehicle bodies, and has a biocidal effect against viruses, bacteria and other pathogens that might be incorporated into or adhered to the surface contamination.

Much of the virucidal and/or bacteriocidal effect is believed to stem from the bromine, which is complexed by some or all of the various alkoxylated species present in the composition. However, the long-chain alkyl triamine, which is believed to form a cationic species at a pH such as that of the composition, appears to have a synergistic effort with the bromine, particularly against the more resistant pathogens. The presence of low levels of short-chain alcohols is also believed to add to the effectiveness of the composition, which may be because they would attack viral RNA chains or bacterial DNA chains at different sites to those at which the cationic triamine is believed to attack. This combination is believed to give a broad-spectrum biocidal effect against almost any class of pathogens that might be carried in or on hard surface grime.

A second, preferred, foamable composition was made up, containing the following components per 100 kilograms:

EDTA, sodium salt, 38% ^w/w 0.75kg

Triameen Y12D-30 1.00kg

Bromine water, 1 % ^w/w 0.125kg Deionised water 0.625kg

Sodium metasilicate pentahydrate 2.375kg

Dipropylene glycol monomethyl ether, mixed isomers 4.75kg

Benzotriazole 0.191kg

Ethanol 0.25kg

Alcohol ethoxylate (C9-1 1 6EO) 0.95kg

Alcohol ethoxylate (C 13- 15 9EO) 1.90kg

Sodium citrate 2.85kg

Sodium benzoate 1.425kg

Lauryl dimethyl amine oxide 2.85kg

Lakeland AMA 6.65kg

Lakeland RAC 2.85kg

Tomah AO14.5 1.425kg

Lutensol XL90 0.15kg

Didecyl dimethyl ammonium chloride (DDAC), 50% ^w/w 0.50kg

Water 68.334kg

The composition appeared as a clear, colourless liquid with a slight detergent odour. The pH was adjusted to 10 with citric acid, where necessary.

Bromine water at 1% w/w bromine, further diluted with deionised water, was used as a convenient source of bromine. The second composition contains 0.00125kg bromine per 100 kg, calculated as neat bromine. Lutensol XL90 is a monbranched Ci₀ fatty alcohol polyethoxylate, with an average of nine ethoxylate groups per molecule. The monobranched fatty alcohol moiety is a Guerbet alcohol, a primary alcohol with the branched chain attached at the 2 (or β) position. These structures are believed to obviate the environmental problems ascribed to some other alkyl and alkylphenol moieties. DDAC is a quaternary ammonium cationic detergent, with a degree of bacteriocidal activity.

This composition is at least as effective as the first composition, both as a cleaner of hydrocarbon-based and other surface contamination from hard surfaces, and as a biocidal agent against viruses, bacteria and other pathogens. The mode of action is substantially the same in each case.

A third foamable composition was made up, containing the following components per 100 kilograms:

EDTA, sodium salt, 38% 7w 0.974kg

Triameen Y 12D-30 2.00kg

Bromine water, 1% 7w 0.250kg

Deionised water 1.25kg

Sodium metasilicate pentahydrate 2.25kg

Dipropylene glycol monomethyl ether, mixed isomers 4.50kg

Benzotriazole 0.183kg

Ethanol 0.50kg

Alcohol ethoxylate (C9- 1 1 6EO) 0.90kg

Alcohol ethoxylate (C 13- 15 9EO) 1.80kg Sodium citrate 2.70kg

Sodium benzoate 1.35kg

Lauryl dimethyl amine oxide 2.70kg

Lakeland AMA 6.30kg

Tomah AO14.5 1.35kg

Lutensol XL90 0.30kg

Water 66.894kg

This composition contains higher levels of bromine, the long-chain alkyl triamine and ethanol than the second composition, e.g. for situations in which a particularly high risk of biological contamination is expected. The third composition contains 0.0025kg bromine per 100kg, calculated as neat bromine.

The second composition has been subjected to two sets of standard tests, used to certify that cleaning formulations are suitable for use on aircraft.

The first of these sets is known as Boeing D6- 17487 Revision P, "Exterior and General Cleaners and Liquid Waxes, Polishes and Polishing Compounds", and comprises four tests, each performed according to an ASTM (American Society for Testing and Materials) standard method. The Sandwich Corrosion Test, in accordance with ASTM Fl I lO, tests the corrosive effect of the composition, both in concentrated form as supplied and diluted to 10% with water, on standard samples of bare anodised aluminium alloy and clad aluminium alloy, typical of those used in aircraft structures. To pass, a rating of 1 must be achieved (no more than 5% of the surface area corroded) and the samples must be no more corroded than control samples exposed to water alone. The composition of the present invention rated 1 on both substrates, both in concentrated and diluted forms, and the controls also rated 1. The test was thus passed.

The Acrylic Crazing Test, in accordance with ASTM F484, tests whether a standard stretched acrylic polymer sample is crazed, cracked or etched on exposure to the composition. No crazing, cracking or etching was noted for either the concentrated or diluted compositions, so the test was passed.

The Paint Softening Test, in accordance with ASTM F502, tests for a decrease in paint film hardness on exposure to the composition, and/or discolouration or staining. Two standard primer/topcoat paint systems were tested. To pass the test, a decrease in pencil hardness must be no greater than two pencils, and there must be no discolouration or staining. For each paint system, with both the concentrated and the diluted compositions, there was no change in pencil hardness and no reported discolouration or staining. The test was passed.

The Hydrogen Embrittlement Test, in accordance with ASTM F519-93, tests cadmium-plated steel specimens for mechanical embrittlement in the presence of the composition, which might potentedly act as a hydrogen source. For both the concentrated and diluted compositions, there were no failures under tension within 150 hours testing, which constitutes a pass.

The second set of tests is known as AMS 1527B "Cleaner for Aircraft Exterior Surfaces: Water-Miscible, Foam-On, Pressure Spraying". It comprises ten tests, each performed in accordance with ASTM or MIL (US Military) standard methods. Several of these tests are also present in the Boeing set of tests, above.

The Sandwich Corrosion Test, in accordance with ASTM F1110, was carried out as described above, using two different bare anodised aluminium alloy samples and two different alclad aluminium alloy samples. In each case, the corrosion rating was 1 , a pass.

The Total Immersion Corrosion Test, in accordance with ASTM F483, tests for a weight gain or loss for standard samples immersed in the composition for 24 hours. Three different aluminium alloys, a magnesium alloy, a titanium alloy and a carbon steel sample were tested in both the concentrated and the diluted composition. In each case, the weight change per unit area was well within permissible limits, in most cases by a factor of ten. The test was passed.

The Low-Embrittlement Cadmium Plate Test, in accordance with ASTM Fl 111, tests for a weight change on immersion in both the concentrated and the dilute composition. The weight change per unit area in the concentrated composition was just below the pass limit, while that in the diluted composition was only a third of the pass limit. The test was passed. The Hydrogen Embrittlement Test in accordance with ASTM F519 was carried out as described above and was again passed with no failures.

The Flash Point Test in accordance with ASTM D56 requires that the flash point of the composition should be not lower than 60°C/140°F. No flash was produced for the composition as supplied, up to the highest test temperature of 141 °F, so the test was passed.

The Effect on Transparent Acrylic Plastics Test, in accordance with ASTM 484, corresponds substantially to the Acrylic Crazing Test, above. There was no crazing or staining of a stretched standard acrylic polymer sample, in either the concentrated or the diluted composition. The test was passed.

The Effect on Painted Surfaces Test, in accordance with ASTM F502, corresponds substantially to the Paint Softening Test, described above. For each of the concentrated and the diluted compositions, there was no hardness decrease and no streaking, discolouration or blistering. The test was passed.

The Effect on Unpainted Surfaces Test, in accordance with ASTM F485, tests for residual streaking or stains requiring to be polished off, resulting from the concentrated or the diluted composition. No streaking or staining was noted, so the test was passed.

The Storage Stability Test was considered not to be necessary.

The Foaming Properties Test, in accordance with MIL-PRF-85570D Type II, tests for foam retention. A 100ml sample comprising 1 part concentrated composition to 14 parts hard water is whipped up into a foam, under standard conditions, and left to stand for six minutes.

A pass requires a maximum of 80ml clear liquid separated out beneath the foam at this point, and less than 80ml was observed, a clear pass.

The compositions of the present invention are thus fully suitable for use for cleaning aircraft exteriors, and the non-standard components such as bromine have no detectable harmful effect on the paint, plastics and metal surfaces with which the composition would come into contact.

Although the compositions described are formulated to be employed as liquid cleaning/disinfecting agents, it should be relatively straightforward to reformulate any of them, using conventional cleaning agent formulation methods, to produce a gel composition having the same cleaning and anti-pathogen properties. Gel compositions are often used on particularly difficult contamination, such as partially or wholly carbonised deposits near aircraft engines.

Claims

1. An aqueous hard surface cleaning and disinfecting composition comprising a halogen, a halogen complex and/or a halogen-releasing compound, and an alkoxylated tertiary amine oxide compound.

2. A composition as claimed in claim 1 , wherein the halogen comprises bromine.

3. A composition as claimed in either claim 1 or claim 2, wherein the halogen comprises iodine.

4. A composition as claimed in any one of the preceding claims, wherein the halogen comprises chlorine.

5. A composition as claimed in any one of claims 2 to 4, comprising up to 0.01% bromine.

6. A composition as claimed in claim 5 comprising up to 0.005% bromine.

7. A composition as claimed in any one of claims 2 to 6, comprising at least 0.0005% bromine.

8. A composition as claimed in either claim 6 or claim 7 comprising between 0.001% and 0.003% bromine.

9. A composition as claimed in any one of the preceding claims, wherein said alkoxylated tertiary amine oxide compound has the general formula R¹R²R³NO, where R¹ is a linear or branched alkyl chain containing at least one alkoxylate group.

10. A composition as claimed in claim 9 wherein R¹ is an alkyl chain containing a plurality of alkoxylate groups, optionally comprising a polyalkoxylate group.

1 1. A composition as claimed in either claim 9 or claim 10, wherein R² and R³ each comprise a hydroxyalkyl chain.

12. A composition as claimed in any one of claims 9 to 11, wherein R² and R³each comprise a polyalkoxylate chain.

13. A composition as claimed in any one of the preceding claims, comprising between 0.5% and 5% of said alkoxylated tertiary amine oxide compound.

14. A composition as claimed in any one of the preceding claims further comprising a long-chain alkyl polyamine compound.

15. A composition as claimed in claim 14, wherein said long-chain alkyl polyamine compound comprises a long-chain alkyl triamine compound.

16. A composition as claimed in either claim 14 or claim 15, wherein long-chain alkyl triamine compound comprises a compound having the general formula R⁴- N((CH₂)_mNH)₂)(CH₂)_nNH₂, where R⁴ is a linear or branched alkyl chain comprising at least eight carbon atoms and each of m and n equals 2, 3 or 4.

17. A composition as claimed in either claim 14 or claim 15, wherein the long-chain alkyl triamine compound has the general formula R⁴-N((CH₂)_mNH)₂)_2. i.e. m equals n.

18. A composition as claimed in any one of claims 14 to 17, wherein each of m and n equals three.

19. A composition as claimed in any one of claims 16 to 18, wherein R⁴ is a linear or branched alkyl chain comprising between ten and sixteen carbon atoms.

20. A composition as claimed in any one of the preceding claims, further comprising an amphoteric surfactant compound having the general formula R⁵-N((CH₂)_P(COOX))₂, where R⁵ is a linear or branched alkyl chain, and X comprises hydrogen or an alkali metal.

21. A composition as claimed in claim 20 wherein p equals two.

22. A composition as claimed in any one of the preceding claims, further comprising a corrosion inhibiting agent adapted to inhibit corrosion of ferrous metals.

23. A composition as claimed in any one of the preceding claims, further comprising a degreasing agent.

24. A composition as claimed in any one of the preceding claims, further comprising one or more aliphatic alcohols, optionally ethanol, «-propanol, /.rø-propanol or a mixture of any two or all three thereof.