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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/2017—Monohydric alcohols branched
• • 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
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
• • 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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/201—Monohydric alcohols linear
• • 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

Definitions

• the present invention relates to an antimicrobial cleaning composition containing surfactant and a hygiene agent, to the use of a specified surfactant to improve the activity of the hygiene agent and to a method of treating surfaces with the said composition.
• Hard-surface cleaning compositions generally comprise one or more surfactants, and, optionally, one or more hygiene agents and/or solvents.
• the surfactants used in such cleaning compositions are selected from anionic, nonionic, amphoteric and cationic surfactants. This large group of surfactants exhibit a broad range of properties. Nonionics are very commonly used due to their effectiveness on fatty soils and the ease with which their foaming can be controlled. The precise function of nonionic surfactants m cleaning compositions depends on the hydrophile/lipophile balance or 'HLB' of the surfactant chosen. In general terms, nonionic surfactants with a relatively low HLB values (7-9) are regarded as wetting agents and are used in combination with solvents where the solvent performs the cleaning function, such as in glass cleaners.
• Nonionic surfactants with relatively high HLB values are regarded as detergents and themselves remove soil from surfaces.
• Nonionic surfactants are reported as showing low biocidal activity, whereas certain anionic, cationic and amphoteric surfactants show biocidal activity under specific conditions of, for example, pH and concentration.
• the biocidal activity of surfactants is, with a few notable exceptions, low and it is commonplace to add a separate hygiene agent to compositions.
• Typical hygiene agents include strong acids, alkali's, phenolics and oxidants such as peracids and hypohalites.
• oxidants of which a typical example is hypochlorite
• hypochlorite are generally highly reactive species which exhibit this reactivity alone or m effective formulations m terms of one or more of, short shelf life, toxic, corrosive and irritant properties. In general, these reactive components are required at relatively high levels m formulations.
• Other less chemically reactive hygiene agents such as 2 , 4, 4 ' -tr ⁇ chloro-2 ' -hydroxy diphenyl ether (available m the marketplace as IRGASAN [RTM] ) , are effective at relatively low concentrations but are more expensive than simpler species and may be specific as regards their spectrum of activity.
• preservatives m cosmetics and some food products, but these preservatives generally show lower biocidal activity than the above-men ioned chemically reactive hygiene agents when used at the same level.
• a 'disinfectant' can be understood to be a hygiene agent which shows a 100,000 fold or better reduction m the number of viable micro-organisms in a specified culture when used at a level of around 0.5 wt%. This is generally known as a 'log 5 kill' . Many of the weaker hygiene agents do not achieve this level of bacterial kill, especially when present in formulations at relatively low levels.
• APG alkyl polyglycoside
• Alcohols such as ethanol and isopropanol (IPA)
• IPA isopropanol
• these are present as solvents at low levels in compositions of near neutral pH.
• GB 1076920 (1966) relates to glass cleaners which comprise -0.25% alkyl phenol polyoxyalkylene ether and 3.5-4% ethanol
• GB 1403919 (1972) relates to vehicle washing compositions which comprise 3-4% nonionic surfactant (an EO/PO system is used in the examples) and 4% isopropanol
• US 4414128 (1981) relates to hard surface cleaners with 0.5-3% Dobanol 91-8 (HLB 13.8 by calculation) and 1-2% ethanol
• GB 2103642 (1981) relates to a spectacle-glass cleaning composition which comprises 1% ethoxylated nonionic surfactant and 10% ethanol: the preferred pH of which is 6-8.
• GB 2167083 (1984) relates to a hard surface cleaner comprising 4% IPA and GB 2173508 (1986) relates to hard surface cleaners which comprise 1% of 3,5- d ⁇ methyl-l-hexyn-3-ol and 0.45% primary alkyl sulphate as anionic surfactant with 2-4% IPA.
• compositions which comprise -12% nonionic surfactants and 3% iso propyl alcohol.
• the compositions which have a pH around 5.5, do not appear to contain alcohol ethoxylate, the surfactant being either betaine or amine oxide.
• the antimicrobial properties of these composition arise from the known antimicrobials, such are chlorhexidine, which are incorporated in the composition.
• a first aspect of the present invention provides a hygienic cleaning composition of pH ⁇ 6 or pH>8 which comprises:
• a second aspect of the present invention of the use of l-30%wt of a C ⁇ C j linear or branched alcohol as a biocidal activity improving additive in a cleaning composition of pH ⁇ 6 or pH>8 which comprises 0.01-30%wt on product of an alkoxylated nonionic surfactant other than an alkyl phenol derivative with an HLB of 10-14.
• a third aspect of the present invention provides a method of cleaning and disinfecting a hard surface which comprises the step of treating said surface with a cleaning composition of pH ⁇ 6 or pH>8 which cleaning composition comprises :
• alkoxylated alcohol surfactants of HLB 10-14 are inhibitors of bacterial growth but are only weakly biocidal at typical formulation pH' s.
• a synergy is maintained and exploited to give a product which is both an effective cleaner and biocidal.
• Effective cleaning and biocidal activity are desirable m a cleaning composition for hygiene purposes as it is important to both to ensure a high kill of bacteria and removal soil so as to retard reinfection and regrowth of bacterial populations.
• the important features of effective microbial kill and improved soil removal are both attained with a relatively simple and hence cost-effective formulation.
• Nonionic, alkoxylated surfactants are present in the compositions of the invention. These surfactants are believed to engage in a synergistic interaction with both the alcohol, to improve cleaning and aid the removal of soil subsequently deposited and with the antimicrobial so as to improve the disinfecting qualities of the compos tion.
• Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of ethylene oxide groups, which are hydrophilic m nature, with an organic hydrophobic compound.
• the length of the hydrophilic or polyoxyethylene radical which is condensed with any particular hydrophobic group can be readily ad3usted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements (HLB) .
• Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 3 to 10 moles of ethylene oxide per mole of coconut alcohol .
• the amount of nonionic detergent active to be employed in the composition of the invention will generally be from 0.1 to 30%wt, preferably from 1 to 20%wt, and most preferably from 3 to 10%wt for non-concentrated products.
• Concentrated products will generally have 10-20%wt nonionic surfactant present, whereas dilute products suitable for spraying will have 0.1-5%wt nonionic surfactant present.
• the alkoxylated nonionic surfactant is an ethoxylated alcohol having a chain length of C ⁇ -C 14 and 4-10 ethoxy groups per molecule. It is however essential that the HLB of the nonionic should fall in the range 10-14.
• HLB can be calculated as a function of the chain length of the molecule and its degree of ethoxylation. According to Griffin (W.C. Griffin J. Soc. Cosmetic Chemists [5, 249, 1954]) the HLB of fatty alcohol ethylene oxide adducts is given as one fifth of the weight percent of oxyethylene content in the adduct .
• CMC critical icellar concentration
• IMBENTIN 91-35 OFA' (TM, ex. Kolb AG) a C 9 alcohol with, on average, five moles of ethoxylation had been found to be a suitable nonionic surfactant in compositions according to the invention.
• This material has a calculated HLB of 11.6 and is believed to have a CMC of l. ⁇ xlO" 1 moles/litre.
• DOBANOL 91-8 (TM) a C,-C n alcohol with on average 8 moles of ethoxylation has also been found to be a suitable material.
• This material has a calculated HLB of 13.8 and is believed to have a CMC of 4.3x10 moles/litre.
• the alcohol is selected from the group comprising propan-2-ol, propanol, ethanol and mixtures thereof.
• Preferred levels of alcohol are l-25%wt on product. At these concentrations alcohols taken alone show little potential as disinfectants. Particularly preferred levels of alcohol range from 5-15%.
• the weight ratio of the alkoxylated nonionic surfactant to the alcohol such that the alcohol is present in weight excess over the alkoxylated nonionic surfactant.
• compositions of the invention further comprise a buffer to maintain the pH of the composition in the desired pH range upon dilution by a factor of 2-5.
• the acidic compositions according to the invention have a pH of 3.2-4.5. It is believed that the above pH 4.5 the hygiene benefit of the compositions is much reduced and below pH 3.0 surface damage may occur.
• the most preferred pH m the acid range is around 3.5.
• citrate at a level of 3.5% will be sufficient to reduce the pH on addition of the product of the present invention at 3.3g/l to a pH below 4.0.
• For sprayable products less steps need be taken to maintain the pH.
• the alkaline products according to the invention have a preferred pH of 8-11, more preferably 9.5-11. Below pH 9.5, compositions show reduced bacterial kill, whilst above pH 11, compositions are considered unacceptably hazardous for many uses.
• Sodium bicarbonate/carbonate buffers are suitable to maintain pH in the preferred range. Acid products are preferred to alkaline products, as while the antibacterial action can be seen in the higher pH range it is more marked in the acid pH range.
• composition according to the invention can contain other minor, unessential ingredients which aid in their cleaning performance and maintain the physical and the chemical stability of the product.
• the composition can contain detergent builders.
• the builder when employed, preferably will form from 0.1 to 25% by weight of the composi ion.
• the composition can include one or more amphoteric surfactants, preferably betaines, or other surfactants such as arnine-oxide and alkyl-amino-glycinates.
• amphoteric surfactants preferably betaines, or other surfactants such as arnine-oxide and alkyl-amino-glycinates.
• Betaines are preferred for reasons of cost, low toxicity (especially as compared to amine oxides) and wide availability.
• betaines in compositions according to the invention are the amido-alkyl betaines, particularly the amido-propyl betaines, preferably having an aliphatic alkyl radical of from 8 to 18 carbon atoms and preferably having a straight chain.
• betaines are preferred as they are believed to comprise relatively low levels of nitrosamine precursors although other betaines, such as alkyl betaines, can be used in the compositions of the invention.
• Typical levels of amphoteric range from 0.01 to 8%, with levels of l-5wt%, particularly around 2% being preferred for normal compositions and up to four times the concentration being present in so called, concentrated products.
• levels of l-5wt%, particularly around 2% being preferred for normal compositions and up to four times the concentration being present in so called, concentrated products.
• lower levels of around 0.05-1% will be employed in sprayable products and higher levels of, typically, around 4%wt in concentrates.
• Metal ion sequestrants including ethylene-diamme-tetra- acetates, ammo-poly-phosphonates (such as those in the DEQUEST R range) and phosphates and a wide variety of other poly-functional organic acids and salts, can also be employed. It is believed that the hygiene performance of the composition is improved by the presence of a metal ion sequesterant .
• citric acid s particularly preferred as a metal ion binding agent as this also functions as a buffer maintaining the composition at a pH in the range 3-5 on dilution.
• Typical levels of citrate range from 0.5-5%, with higher levels of 5-10% being used in concentrates and lower levels of 0.1-1% being used in sprayable products.
• Citric can be replaced by other suitable buffering agents to maintain the pH in this range. Citric is also preferred for environmental reasons and a lack of residues as it is believed to be the most cost/weight effective acid.
• Suitable additional hydrotropes include, alkali metal toluene sulphonates, urea, alkali metal xylene and cumene sulphonates, polyglycols, >20EO ethoxylated alcohols and glycols. Preferred amongst these hydrotropes are the sulphonates, particularly the cumene, xylene and toluene sulphonates. Typical levels of additional hydrotrope range from 0-5% for the sulphonates.
• Hydrotropes are not always required for dilute, sprayable products, but may be required if lower EO or longer alkyl ethoxylates are used or the cloud point needs to be raised considerably.
• the cumene sulphonate is the most preferred hydrotrope.
• compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as, further solvents, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, further bacte ⁇ cides, perfumes and opacifiers.
• various other optional ingredients such as, further solvents, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, further bacte ⁇ cides, perfumes and opacifiers.
• compositions according to the present invention comprise:
• l-30%wt of an alcohol is selected from the group comprising propan-2-ol, propanol, ethanol and mixtures thereof, wherein the ethoxylated alcohol (b) is present in weight excess over the alcohol (a), and,
• a preferred method according to the present invention comprises the step of treating a surface with a composition as disclosed herein by means of a spray.
• the following examples are suspension tests against a range or microbes at a range of pH' s.
• the following bacterial strains were used in these suspension tests.
• Example 1 against Ps aeruginosa and S. aureus
• Micro-organisms were taken from slopes using 10 microliter sterile loops and cultured m Nutrient Broth No. 2 (supplied by Oxoid Unipath [TM] ) at 37°C with constant agitation for 24 hours in a shaking waterbath. Cells were recovered by transferring into 50ml centrifuge tubes, centrifugation in a Mistral [TM] 2000 Centrifuge for 10 mm at 4100 rpm and re-suspended m l A strength Ringer's buffer. This procedure is believed to give a bacterial suspension of 10 Q -10 10 cfus/ml.
• the nonionic surfactant used was Imbentm C91-35 ( [TM] ex. Kolb) and the alcohol was isopropanol.
• Test solutions (9ml) were buffered with 0.02% citric acid and 0.01% sodium citrate and inoculated with lml bacterial suspension.
• Viable organisms were determines by culturing on Nutrient or Tryptone-soya agar for 48 hours at 37°C. Log decimal reductions were determined from the viable counts.
• Table 1 shows the selective synergy between nonionic surfactant and alcohol at pH 4.0 against Pseudomonas aeruginosa and Staphylococcus aureus as identified above.
• Figure 1 shows the effect of pH in the acid region. It can be seen that effective synergy is only seen at pH below 6. As the pH is increased towards the neutral, physiological range, the combined effect of the alcoholic solvent and the alcohol ethoxylate surfactant is reduced.
• Bacterial suspension was prepared as follows. Incubate bacterial culture (tryptone soya broth) for 24 hours. Spin down (50 ml tubes, Mistral 1000 centrifuge, 4100rpm, 10 min) . Resuspend pellets in peptone water (20ml) and mix using a vortex mixer for 15-30 seconds. Adjust cell density with sterile peptone water to required inoculum size using a calibrated densitometer. Cell suspension is stored at 20 °C (+/- 1°C) and used within 2 hours
• Acidic formulations (pH 3.5) were buffered with citric acid (0.02 percent) and sodium citrate (0.01 percent) .
• Alkaline formulations (pH 10.5) were buffered with a mixture of sodium carbonate (1.14 w/v percent decahydrate) and sodium hydrogen carbonate (0.08 w/v percent) .
• reaction 30 ⁇ l of each reaction mixture was transferred into 270 ⁇ l of a quench solution using a multip pette and mixed as previously indicated.
• the composition of quench solution was as follows:
• Table 2 shows that under both acid and alkaline conditions a significant increase in the biocidal activity of the composition is achieved when both the alcohol and the alcohol ethoxylate are present .
• Example 3 further examples
• Tables 3a and 3b below show further examples, using two nonionic surfactants and two microbes, for which the results were obtained using the method as described above in example 2.
• the formulations contained 10% iso-propyl alcohol, 0.7% non-ionic surfactant, and were prepared at pH 11.0

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• 1995
  • 1995-12-08 GB GBGB9525155.9A patent/GB9525155D0/en active Pending
• 1996
  • 1996-11-05 BR BR9611979A patent/BR9611979A/pt not_active Application Discontinuation
  • 1996-11-05 AU AU75673/96A patent/AU699602B2/en not_active Ceased
  • 1996-11-05 WO PCT/EP1996/004876 patent/WO1997021795A1/en not_active Application Discontinuation
  • 1996-11-05 DE DE69607391T patent/DE69607391T2/de not_active Revoked
  • 1996-11-05 ES ES96938139T patent/ES2146421T3/es not_active Expired - Lifetime
  • 1996-11-05 EP EP96938139A patent/EP0874887B1/de not_active Revoked
  • 1996-11-05 CA CA002235680A patent/CA2235680C/en not_active Expired - Fee Related
  • 1996-11-12 ZA ZA9609481A patent/ZA969481B/xx unknown

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