HK1137117B - Low foaming enhanced biocidal hydrogen peroxide composition - Google Patents

Description

Low foaming enhanced biocidal hydrogen peroxide compositions

The present invention relates to the field of disinfection and cleaning, more particularly to a low foaming enhanced biocidally active composition based on hydrogen peroxide.

Various compounds exhibit varying degrees of biocidal or antimicrobial activity. In particular, there is a need for biocidal compositions for cleaning and disinfecting food (e.g., fruit and vegetable) surfaces, and there is a need in the health care industry (health care industry), the food and beverage industry, and in the household field for cleaning and disinfecting hard surfaces.

Over the past several years, efforts have focused on developing antimicrobial chemicals that are highly effective when diluted, are low toxic to humans and other animals, and are not environmentally harmful.

Among the known disinfectants and biocides, hydrogen peroxide shows particular potential, since the decomposition products water and oxygen are non-toxic and harmless to the environment. And it also tends to have a broad spectrum of biocidal activity. Spectral activity is important in situations where pests are present but their identity is unknown. Hydrogen peroxide based disinfectants are suitable for many different applications, including in hospitals, clinics, laboratories, dental clinics, home care and long term health care facilities. They may also be used in food and beverage processing and preparation, in animal husbandry, in hospitality (health industry) and for general hygiene.

In order to provide a fast, effective action, biocidal hydrogen peroxide solutions must use relatively high concentrations of hydrogen peroxide. However, at higher concentrations, the solution may be subject to hazardous cargo regulations, and special measures may be required for handling and use. For example, at concentrations above about 8 w/w% aqueous solution, hydrogen peroxide is considered corrosive and also a strong oxidizer. Solutions containing less than about 8 w/w% hydrogen peroxide are preferred for their improved safety.

Compositions that have hydrogen peroxide as the only biocidal compound and contain up to 7% hydrogen peroxide by weight of the total compound are not sufficiently effective in disinfecting solid surfaces, such as surfaces that need to be washed and disinfected. In fact, the presence of organic and/or inorganic soils reduces the bactericidal activity of many antimicrobial agents (e.g., peroxide-based agents), resulting in lower bactericidal activity and lower disinfection capacity of compositions containing them.

At low concentrations (e.g. 3% w/w), hydrogen peroxide is not irritating to the skin but shows a lower bactericidal activity. For example, a solution containing 3% w/w hydrogen peroxide takes 20 minutes to reach a log reduction of more than 6 in staphylococcus aureus, which is too long for many applications. Increasing the concentration of hydrogen peroxide increases the rate of disinfection. For example, a 25% w/w aqueous solution of hydrogen peroxide in Staphylococcus aureus requires only 20 seconds to achieve a log reduction of greater than 6. However, solutions are corrosive at this concentration and require special handling steps.

In order to make an antimicrobial composition that can be effectively used in non-industrial or even household environments, the composition must have a technically and commercially attractive set of properties. These properties are as follows: suitable biocidal activity, as low as possible concentration of active ingredient, no irritating odor, no corrosion of materials and skin, ease of application and ability to be used without rinsing. The latter property requires that the composition be low foaming.

Several solutions have been proposed in the art to obtain hydrogen peroxide compositions with enhanced biocidal activity. However, these solutions do not adequately address the above-mentioned problems to achieve very good disinfection results while having a positive effect on wetting properties without having a high foaming character. Highly foamed compositions can cause problems in a variety of situations, for example when the composition is used by devices or facilities such as pumps, nozzles, aerosol devices or spray heads. Because pumping, spraying and other methods cause turbulent motion of the cleaning and sanitizing solutions, agents and solutions that tend to produce foam are totally unsuitable, although they are recommended for use in sanitizing compositions.

In practice, therefore, the use of agents containing highly foaming surfactants, such as sulfonic acids, ether sulfates, sulfosuccinates or sulfonates, is largely avoided in the context of so-called clean-in-place (CIP) processes.

In addition, the wetting characteristics of the biocidal composition are of particular importance. Bacterial problems often occur during disinfection, and despite the use of sufficient active disinfectant, the surface to be disinfected is not reached or does not adhere to the surface for a sufficient period of time because of its low wetting power.

Complete wetting at the required use concentration and maintenance of minimum contact time are absolutely necessary to reliably destroy all harmful microorganisms.

Surfactants are known to improve the wetting ability of solutions. However, many surfactants are also known to show very strong foaming behavior under the application conditions due to their strong wetting action. As previously mentioned, in many sanitizing applications, foamed sanitizing solutions cannot be used or have drawbacks in use. Particularly when the disinfectant solution is used in equipment, pumps, spray nozzles, etc., or when no or only a very low level of rinsing is required.

For example, the compositions disclosed in WO 03/067989, which comprise certain anionic sulphonic acid based surfactants and hydrogen peroxide, although highly effective as disinfecting compositions, are not suitable for use where low foaming is required.

It is therefore an object of the present invention to provide compositions which provide excellent biocidal activity using as low a hydrogen peroxide concentration as possible and/or as few other biocidal additives as possible. It is also an object to provide compositions which can be applied directly without precautions and safety measures in handling or in use and which do not require rinsing after application or require only a small amount of rinsing. It is also an object of the present invention to prepare synergistic, spectroscopic biocidal solutions without the use of peracetic acid, which causes pungent odors and is not suitable for use in home cleaning, skin disinfection, food processing, oral care and personal care applications.

The present invention surprisingly shows that compositions comprising hydrogen peroxide and certain alkyl ether carboxylic esters show enhanced biocidal activity, low foaming behaviour and still have good wetting ability.

The compositions of the present invention need not include disinfectants such as peracetic acid and/or acetic acid (which make the odor of the composition less acceptable for non-professional use), but the spectral antimicrobial efficacy is still sufficient to meet the required industry standards.

WO 97/28691 discloses a fast acting room temperature disinfectant solution which is primarily suitable for disinfecting medical devices. The composition comprises hydrogen peroxide and from about 1% to 30% by weight of a water soluble organic acid or salt form thereof, said acid preferably being selected from the group consisting of malonic acid and succinic acid. Which may optionally contain surfactants including alkyl sulfates, amine oxides, and alkyl polyethoxy carboxylates (having 8 to 22 carbon atoms and 0 to 10 ethoxy groups). An exemplary surfactant is sodium olefin sulfonate.

EP 0423922 discloses antimicrobial surface sanitizing compositions comprising an alpha-hydroxy substituted mono-or dicarboxylic acid, preferably lactic acid, and hydrogen peroxide, wherein the antimicrobial composition leaves non-staining residues on the intended surface after contact with the surface. The composition may also contain a surfactant such as a polyalkyloxycarboxylate or sulfonate.

US 6,444,230 discloses improved antimicrobial activity of a combination of a peroxide (peroxide compound) and an amine oxide. Optionally, ethoxylated carboxylic acid ethers may be included in the composition. However, US 6,444,230 therefore emphasizes that the excellent fungicidal results are due to a synergistic effect in the composition caused by the simultaneous presence of peracetic acid and amine oxide.

WO 02/50233 discloses a composition for CIP disinfection comprising a surfactant in combination with a peroxycarboxylic acid. The surfactant is preferably an alkyl benzene sulphonic acid or sulphonate and/or an ether carboxylic acid. Exemplary are compositions comprising substantial amounts of acetic acid, hydrogen peroxide, C10-13 alkylbenzene sulfonic acid and unspecified ether carboxylic acid.

JP 9-137192 discloses a composition comprising hydrogen peroxide, a specific bleach activator and a specific polyoxyalkylene compound. Among the polyoxyalkylene compounds, ether carboxylic acids may be selected. These ether carboxylic acids may have alkyl or alkylene groups of 1 to 20C atoms and may have 1 to 50 alkylene oxide units. Two exemplary ether carboxylic acids have 14 and 20 ethoxy groups, respectively, and a C12 alkyl or C18 alkenylene group. The examples therefore show a clear preference for long-tailed molecules. This is because the long-tailed molecule is naturally able to play an important role in the bleaching composition to solubilize the strain and keep the particles suspended. Having relatively short carbon chains (C6-C12) and low degrees of alkoxylation (n is 3-10) is a particular preference of the present invention in order to balance foaming behavior, biocidal activity and synergistic activity with hydrogen peroxide in antimicrobial applications.

Accordingly, the present invention provides, in a first aspect, a composition comprising hydrogen peroxide in a concentration of 0.05-50% (w/w) and hydrogen peroxide in a concentration of 0.01-60% (w/w) having the formula I: R-O- (CH (Y) -CH₂-O)_n-CH₂A compound of the structure-COOH, in which R is an alkyl or alkenylene radical having 6 to 12 carbon atoms and Y is H or CH₃And n is 3 to 10, provided that the composition does not contain acetic acid at a concentration of 0.001% or more and/or peroxyacetic acid at a concentration of 0.0005% or more.

Preferably, R is a straight chain alkyl group. Also preferably, R is an alkyl group of 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.

The individual compounds having the structure of formula I may also contain only propoxy groups or only ethoxy groups, or may contain a mixture of ethoxy and propoxy groups. Preferably, n is 3-8 and/or Y is H.

Such compositions unexpectedly have excellent biocidal activity even when diluted to compositions comprising 0.1-8% hydrogen peroxide and 0.01-10% of a compound having the structure of formula I. The combination of hydrogen peroxide and the compound of formula I provides a more effective biocide than can be obtained using the two compounds alone. The composition has good wetting characteristics and does not produce excessive foaming.

Percentages used throughout the present invention are weight percentages based on the total weight of the composition, unless otherwise indicated.

The skilled person will appreciate that mixtures of compounds of formula I are also encompassed by the present invention. Examples of such mixtures include compounds of formula I wherein Y is H, and R is C8 and n is 8, and R is C6 and n is 3.

Preferred structures of formula I are those wherein Y is H, R is a straight chain C6 and n is 3; r is a straight chain C8 and n is 8; a structure wherein R is linear C8 and n is 5, and combinations thereof. These preferred structures of formula I are provided, for example, by surfactants marketed under the trade names AKYPO LF1, LF2, LF4 and LF6 (from KAO Chemicals).

The compositions of the present invention may preferably be sold as concentrates comprising hydrogen peroxide at a concentration in the range of about 10-50% and a compound having the structure of formula I at a concentration in the range of about 5-60%. The concentrate may be suitably diluted to an effective concentration for use in the final application.

After dilution, the effective hydrogen peroxide concentration of the composition of the invention may be 0.05-8% (w/w), preferably 0.1-5%, more preferably 0.2-3%, most preferably 0.3-2%. Depending on the intended use of the composition of the invention, the hydrogen peroxide concentration may be in a higher range (e.g. from 1 to 8%) or in a lower range (e.g. from 0.05 to 1%). The concentration of the compound having the structure of formula I may be 0.01-10% (w/w), preferably 0.02-5%, more preferably 0.05-2%.

The concentrations of hydrogen peroxide and the compound having the structure of formula I in the composition of the invention are selected in the following manner: the weight ratio between hydrogen peroxide and the compound having the structure of formula I varies between 10 and 0.1, preferably between 5 and 0.2, more preferably between 2 and 0.5.

Compounds having the structure of formula I have several advantages that are particularly useful for the applications described herein. In acidic aqueous solutions, the compounds having the structure of formula I act as nonionic surfactants. In their neutralized form, they act as anionic surfactants (the latent anionic character of alkyl ether carboxylic acids). It was found that the non-ionic behaviour in the slightly acidic range provides a simple, but highly synergistic mixture with high antimicrobial activity and enhanced wetting ability when combined with hydrogen peroxide.

The main advantage of the composition comprising the structure of formula I is that low foaming behaviour is observed at different temperatures, whereas such foam levels only occur around the cloud point when non-ionic surfactants are used. This makes them particularly suitable for use where the compositions are used as rinses in the food, beverage, ice cream and dairy industries.

Because of the effectiveness of the combination of hydrogen peroxide and the compound having the structure of formula 1, the composition of the present invention can be used as a formulation that is as simple as possible. For many applications, it is not necessary to supplement the composition with additional compounds that affect (enhance) its biocidal activity. Thus, in such embodiments, the composition consists essentially of hydrogen peroxide and a compound having the structure of formula 1 as the compound having biocidal activity.

The biocidal activity of the compositions of the present invention is preferably determined by a controlled bactericidal suspension test, european standard EN1276 for chemical disinfectants and antibacterial agents (EN1276: quantitative suspension test for evaluation of bactericidal activity of chemical disinfectants and antibacterial agents used in food, industrial, cosmetic and public areas: test methods and requirements).

Advantageously, the compositions of the present invention exhibit not only good bactericidal activity but also good fungicidal, mycobacterial and virucidal activity.

The biocidal peroxide composition of the present invention is preferably an aqueous solution.

In a preferred embodiment, the biocidal peroxide composition of the present invention is a ready-to-use aqueous solution comprising 0.1-5% hydrogen peroxide and 0.05-5% of a compound having the structure of formula I, such as AKYPO LF4 from KAO Chemicals. The pH of the solution is preferably 1-7, more preferably 1.5-6, most preferably 1.5-5.

Such compositions are also very eco-friendly.

In one embodiment of the invention, the compositions of the invention are supplemented with compounds that enhance their practical utility, such as nonionic, cationic and/or anionic surfactants, solvents, stabilizers, preservatives, colorants, fragrances and the like.

For example, a pH adjusting acid (organic or inorganic) or base or an appropriate buffer may be added as appropriate to provide the selected pH to the composition of the invention. Suitable acids for adjusting the pH are for example citric acid or potassium hydroxide. Preferably, the composition of the invention has a pH in the acidic region, more preferably a pH of 1 to 7, even more preferably a pH of 1.5 to 6, most preferably a pH of 1.5 to 5.

The composition of the invention may also comprise a hydrogen peroxide stabilizer, preferably in the form of a cationic sequestering agent (sequencing agent), more preferably present at a concentration of 0.01 to 20% (w/w). The cation sequestering agent may be selected from ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N- (hydroxyethyl) -ethylenediaminetetraacetic acid (HEDTA), nitrilotriacetic acid (NTA), 2-hydroxyethyliminodiacetic acid (HEIDA) and salts thereof, or from benzoic acid, aminobenzoic acid, citric acid, phosphoric acid, iminodisuccinic acid (iminodisuccic acid), and polyaspartic acid. More preferably, the cationic masking agent is a (colloidal) stannate, even more preferably selected from acetanilide, trisodium ethylene disuccinate (e.g. OctaQuest E30 or a65(Octel)), phosphoric acid derivatives having 1 to 5 phosphoric acid groups (e.g. dequest phosphate (solutia), 1-hydroxyethylene-1, 1-diphosphonic acid, aminotri (methylenephosphoric acid), diethylenetriamine-penta (methylenephosphoric acid), 2-hydroxyethyliminodi (methylenephosphoric acid) and ethylenediaminetetra (methylenephosphoric acid)).

The compositions of the present invention may also comprise a corrosion inhibitor, preferably present at a concentration of 0.01% to 20% w/w. Preferably, the corrosion inhibitor is selected from the group consisting of 1, 2, 3 benzotriazole, sodium molybdate, sodium nitrite, sodium bisulfate, sodium sulfite, chromate, borate, phosphate, polyphosphate, sodium benzoate, sodium gluconate, and sodium silicate.

The composition may also comprise a surfactant compatible with hydrogen peroxide. The surfactant may be an anionic, cationic, nonionic and/or amphoteric surfactant, preferably a nonionic and/or cationic and/or anionic surfactant. The concentration of the surfactant may be from 0.005 to 40% w/w.

Exemplary hydrogen peroxide compatible nonionic surfactants are ethoxylated alcohols, alkyl polyalkylene glycol ethers and alkyl polyglucosides having a hydrophilic-lyophilic balance (hydrophene lyophile balance) from 5 to 15 and/or sufficiently water soluble ethylene oxide or propylene oxide block copolymers, C6-C14 alkyl, 3-8 moles Ethylene Oxide (EO) alcohol ethoxylate or combinations thereof.

Exemplary hydrogen peroxide compatible anionic surfactants (of which the low foaming type is most preferred) are alkyl sulfates such as C8-C16 alkyl sulfates, C8-C16 alkyl phosphates, alkyl ether sulfates, alkali metal, alkaline earth metal, ammonium or alkylammonium salts of alkylbenzene sulfonic acids (e.g., C8-C16 alkylbenzene sulfonic acids), alkylsulfonic acids (e.g., C8-C18 alkylsulfonic acids), alkyldiphenyloxysulfonic acids, C6-C12 alkyldiphenylsulfonates, naphthalenesulfonic acids, alkyl or alkenyl esters or diesters of sulfosuccinic acid, and salts thereof.

Preferred surfactants may also be selected from the group consisting of alkyl betaines, alkyl amidopropyl betaine amides, alkyl amidopropyl betaines and amine oxides, and derivatives thereof, at a concentration of about 0.01-40% w/w.

Additionally, the composition may comprise at least one C1 to C8 alcohol, preferably present at a concentration of about 0.01 to about 10% w/w. The alcohol may be selected from benzyl alcohol, ethanol, n-butanol, 1-propanol, isopropanol and glycols, such as ethylene glycol, propylene glycol and butylene glycol.

Other additives may be added to the biocidal peroxide composition of the present invention to provide the composition with properties suitable for its use. Examples of such additives are emulsifiers, hydrotropes, glycerol, thickeners, flavorings, colouring chemicals, preservatives and antifoams.

In another aspect, the present invention relates to the use of the biocidal hydrogen peroxide composition of the present invention for any purpose where disinfecting and/or sanitizing and/or preserving activity is required, optionally in combination with cleaning and/or bleaching activity, including but not limited to use as biocidal and sterilizing liquids, and as disinfectants and sanitizers.

The biocidal peroxides of the present invention are particularly useful in applications where it is important to obtain disinfecting and/or sanitizing and/or preservative activity with the mildest possible medicament, such as cosmetic use, medical use, personal care, oral care, food, clean room (clean room) and the like. Also used in the following applications: wherein preferably no or insufficient rinsing after application, or wherein the solution may come into contact with food.

Since the biocidal peroxide composition of the present invention is non-irritating, free of odors or volatile gases, and skin friendly, it is also most suitable for situations where the user is not wearing any protective clothing, where the safety of the workers is a high priority, or for personal applications such as wound disinfection or prevention of gingivitis.

The compositions of the present invention may be used as low foaming compositions, alone or in combination with the compounds described herein, for use in the household, professional and public areas. They are very user friendly because of the following properties: hard water stability, electrolyte stability, enhanced corrosion resistance, and skin mildness.

In addition, the compositions of the invention are particularly suitable for use in situations where strong foaming behaviour is not desired, such as in-situ cleaning processes and disinfection of equipment and surfaces in the medical field and in the food, dairy, poultry, meat, fish and soft drink industries.

The present invention therefore relates to the use of the composition according to the invention for disinfecting and/or sanitizing and/or preserving substrates. This may be accomplished by contacting the substrate with an effective amount of the biocidal composition of the present invention. The contacting may be accomplished by spraying, dipping, atomizing and/or rinsing. In addition to disinfection, the composition is particularly effective in removing stains and soils. The substrate may be any surface, space, material, animate object and/or inanimate object. For example, the substrate may be a medical instrument or device, a hospital or industrial facility, a surface of a wall, ceiling and/or floor, a food product, an agricultural product, human or animal skin, and the like. Preferably, the substrate is a substrate in which a (pathogenic) microorganism is suspected to be present.

The compositions of the present invention can be effectively used for food preservation, as rinses in beer and dairy production, in veterinary and bovine applications such as the prevention and treatment of mastitis, and in water treatment and water disinfection. One preferred use of the composition of the present invention relates to the use of the composition for rinsing fruits, vegetables, fish, poultry and meat. The compositions of the present invention can be advantageously used in food processing and anti-microbial rinses due to low foaming and low rinse requirements.

The good dermatological properties of the compounds having the structure of formula I begin to function adequately when used in neutral household or non-industrial cleaners. The compositions of the present invention comprising a compound of formula I and hydrogen peroxide are also readily biodegradable according to the OECD guidelines.

The invention also relates to the use of the biocidal peroxide composition in specific device embodiments and by application in the form of an impregnation, such as a spray device (e.g. spray bottle, aerosol can, aerosol generating device) for room disinfection.

Another use of the biocidal hydrogen peroxide composition of the present invention relates to its use as a skin disinfectant, preferably a hand disinfectant.

The compositions of the present invention are capable of providing adequate levels of disinfection while not irritating the skin. The composition does not stimulate the mild nature of the structure due to the low levels of hydrogen peroxide, formula I, and low concentrations of other mild additives that may be used as described above.

Another use of the composition of the present invention relates to use in dentistry and as a mouthwash. Infection and inflammation control in the mouth and oral cavity remains an important area, which until today is dominated by products based on chlorine, alcohols and phenols. Many of these products have significant disadvantages and have negative effects on living tissue. The compositions of the present invention can effectively replace such products.

To obtain an effective composition for use in dentistry and mouthwashes, a variety of compounds can be added to the compositions of the present invention to enhance their antimicrobial efficacy, such as antimicrobial essential oils and zinc salts (i.e., zinc chloride, zinc oxide, zinc lactate), or compounds that enhance practical utility such as glycols, alcohols, edible surfactants, flavors, fragrances, and the like.

Examples

The bactericidal activity of the example compositions was tested using a controlled bactericidal suspension test, which is the european standard EN1276 for chemical disinfectants and antibacterial agents (EN1276: quantitative suspension test for evaluation of bactericidal activity of chemical disinfectants and antibacterial agents used in food, industrial, cosmetic and public areas: test methods and requirements). To 8ml of the composition to be tested was added a solution containing about 10 per ml⁸cfu test 1ml test suspension of microorganisms and 1ml milli-Q water was added. After a contact time of 1, 2, 3 and/or 4 and 5 minutes, the amount of viable bacteria is determined by: 0.1ml was placed on the plate containing the medium, after which the plate was incubated for at least 24 hours.

Similarly, fungicidal activity was tested in the EN 1650 suspension test, mycobacterial activity in the EN 14348 suspension test, and virucidal activity in the EN 14476 suspension test tailored to the particular virus.

In some experiments, protein load was added to the suspension according to the EN1276, EN 1650 or EN 14348 steps to simulate an unclean practical situation. To provide clean conditions, 0.3% Bovine serum Albumin (Bovine Albumin) was added, and to provide dirty conditions, 3% Bovine serum Albumin was added.

Description of the compounds used:

AKYPO LF 2C 8; n-8 from KAO Corporation

AKYPO LF 4C 6-8; n-4-9 (average 7) from KAO Corporation

Monafax 1214C 8-C10, 5EO alkyl ether phosphate from Uniqema

Barlox 10s N, N-dimethyldecylamine N-oxide, available from Lonza Inc.

Mackam LHS Lauryl hydroxysulfobetaine (Lauryl hydroxysultaine) from McIntyre

Dequest 2010 hydroxyethylidene 1, 1-diphosphonic acid from Solutia

Zetesol NL-U sodium lauryl Ether sulfate from Zschimmer & Schwarz

Mackam CB 818 Cocamidopropyl Betaine (Cocamidopropyl Betaine), from McIntyre

Example 1

Various compositions were tested for biocidal activity and were compared to standard solutions (commercially available H without any addition of stabilizers added by the manufacturer)₂O₂Solution) of the two phases. The compositions of the invention tested included various forms of the compound of formula I from KAO Chemicals (trade names AKYPOLF2 and AKYPO LF 4). The pH of such solutions varies in the range between 2.5 and 3.5. The test results are shown in table 1 below. The results show that the addition of the compound according to formula I significantly enhances the biocidal activity of the composition.

TABLE 1

CFU′s

Strain name type suspension 1 min 3 min 5 min

1.30% hydrogen peroxide

0.5％AKYPO LF 2

Salmonella typhimurium ATCC 27853 8，20E+08 0 0 0

Escherichia coli ATCC 25922 7，50E+07 0 0 0

Pseudomonas aeruginosa ATCC 27853 3，34E+09 0 0 0

Staphylococcus aureus ATCC 25923 1，43E+10 0 0 0

Enterobacter cloacae ATCC 13047 1，27E+10 2 0 0

Lysteria monocytogenes ATCC 7644 4，22E+09 0 0 0

Micrococcus luteus ATCC 9341 3，93E+09 0 0 0

Proteus vulgaris ATCC 6380 2，08E+09 0 0 0

1.50% hydrogen peroxide

0.2％AKYPO LF 2

Salmonella typhimurium ATCC 27853 8，20E+08 0 0 0

Escherichia coli ATCC 25922 7，50E+07 0 0 0

Pseudomonas aeruginosa ATCC 27853 3，34E+09 0 0 0

Staphylococcus aureus ATCC 25923 1，43E+10 0 0 0

Enterobacter cloacae ATCC 13047 1，27E+10 5 0 0

Lysteria monocytogenes ATCC 7644 4，22E+09 0 0 0

Micrococcus luteus ATCC 9341 3，93E+09 0 0 0

Proteus vulgaris ATCC 6380 2，08E+09 0 0 0

0.50% hydrogen peroxide

0.20％AKYPO LF 2

Salmonella typhimurium ATCC 27853 1，45E+09 3 0 0

Escherichia coli ATCC 25922 1，40E+07 0 0 0

Pseudomonas aeruginosa ATCC27853 1，05E+08 0 0 0

Staphylococcus aureus ATCC 25923 7，00E+09 0 0 0

Enterobacter cloacae ATCC 13047 1，37E+10 0 0 0

1.00% hydrogen peroxide

0.50％AKYPO LF 4

Salmonella typhimurium ATCC 27853 3，20E+08 0 0 0

Escherichia coli ATCC 25922 1，50E+07 0 0 0

Pseudomonas aeruginosa ATCC 27853 2，30E+08 0 0 0

Staphylococcus aureus ATCC 25923 7，50E+07 0 0 0

Enterobacter cloacae ATCC 13047 2，15E+08 0 0 0

Lysteria monocytogenes ATCC7644 3，40E+08 0 0 0

1.50% hydrogen peroxide

0.10％AKYPO LF 4

Salmonella typhimurium ATCC27853 3，20E+08 0 0 0

Escherichia coli ATCC25922 1，50E+07 7 0 0

Pseudomonas aeruginosa ATCC27853 2，30E+08 0 0 0

Staphylococcus aureus ATCC25923 7，50E+07 10 0 0

Enterobacter cloacae ATCC13047 2，15E+08 0 0 0

Lysteria monocytogenes ATCC7644 3，40E+08 23 0 0

0.50% hydrogen peroxide

0.10％AKYPO LF 4

Salmonella typhimurium ATCC27853 1，45E+09 664 126 4

Escherichia coli ATCC25922 1，40E+07 0 0 0

Pseudomonas aeruginosa ATCC27853 1，05E+08 0 0 0

Staphylococcus aureus ATCC25923 7，00E+09 0 0 0

Enterobacter cloacae ATCC13047 1，37E+10 178 0 0

0.50% hydrogen peroxide

0.20％AKYPO LF4

Salmonella typhimurium ATCC27853 1，45E+09 4 0 0

Escherichia coli ATCC25922 1，40E+07 0 0 0

Pseudomonas aeruginosa ATCC27853 1，05E+08 0 0 0

Staphylococcus aureus ATCC25923 7，00E+09 0 0 0

Enterobacter cloacae ATCC13047 1，37E+10 0 0 0

The antimicrobial efficacy of the following concentrations of hydrogen peroxide (table 2) was tested using pure hydrogen peroxide as a control. The solution was buffered to pH3 with phosphoric acid. As can be seen from tables 1 and 2, the addition of the compound of formula I significantly enhanced the biocidal activity of the composition.

TABLE 2

CFU＇s

Strain name suspension 1 min 3 min 5 min

Salmonella 4，00E+07 0，5％H₂O₂ >1000 >1000 448

typhimurium 3，20E+08 1％H₂O₂ >1000 >1000 1008

4，80E+08 1，5％H₂O₂ >1000 >1000 1000

4，80E+08 1，75％H₂O₂ >1000 >1000 >1000

4，80E+08 2％H₂O₂ >1000 >1000 1000

Escherichia 5，50E+07 0，5％H₂O₂ >1000 1000 420

coli 1，50E+07 1％H₂O₂ 1000 1000 768

6，00E+07 1，5％H₂O₂ 1000 430 688

6，00E+07 1，75％ 688 102 54

5，50E+07 2％H₂O₂ 69 54 4

Pseudomonas 1，25E+08 0，5％H₂O₂ >1000 221 3

aeruginosa 1，25E+08 1％H₂O₂ >1000 431 72

1，25E+08 1，5％H₂O₂ 130 13 0

1，25E+08 1，75％H₂O₂ 27 4 2

1，25E+08 2％H₂O₂ 35 23 0

Staphylococcus 1，50E+08 0，5％H₂O₂ >1000 >1000 >1000

aureus 7，50E+07 1％H₂O₂ >1000 1072 608

5，35E+08 1，5％H₂O₂ >1000 >1000 419

5，35E+08 1，75％H₂O₂ 672 344 22

5，35E+08 2％H₂O₂ 592 328 92

Enterobacter 2，15E+08 0，5％H₂O₂ >1000 >1000 892

cloacea 7，50E+08 1％H₂O₂ >1000 >1000 1000

7，50E+08 1，5％H₂O₂ >1000 >1000 664

7，50E+08 1，75％H₂O₂ >1000 >1000 320

2，15E+08 2％H₂O₂ >1000 200 120

It has surprisingly been found that the compositions of the present invention not only show good bactericidal activity but also good fungicidal, mycobacterial and virucidal activity, whereas other known antimicrobial combinations of hydrogen peroxide and specific phosphate surfactants do not show any relevant reduction, in particular against fungi and mycobacteria.

Example 2

Compositions consisting of 5% hydrogen peroxide and 2.5% Akypo LF2 were tested against Mycobacterium terrae ATCC 15755 and showed >5 log reduction in contact time over 15 minutes both under clean and dirty conditions according to EN 14348. The combination of 5% hydrogen peroxide with known antimicrobial activity and 3% of a surfactant, i.e., Monamax 1214 from Uniqema (a C8-C10, 5EO alkyl ether phosphate), showed only a log 1.5 reduction after 15 minutes and a log 2-3 reduction after 30 minutes. Thus, the composition may be advantageously used as a High Level Disinfectant (HLD) in, for example, health care applications.

Example 3

To enhance cleaning efficacy, the compositions may be supplemented with nonionic or amphoteric surfactants. Compositions consisting of 2% hydrogen peroxide, 0.9% Akypo LF4 and 0.6% amine oxide (Barlox 10s by Lonza inc.) were tested for enhanced degreasing and cleaning efficacy against a variety of microbial strains, which showed the following log reductions after 3 minutes contact time in the EN1276 suspension test:

Escherichia coli ATCC 10536 >6.7

Pseudomonas aeruginosa ATCC 15442 >6.3

Staphylococcus aureus ATCC 6538 >6.6

Enterococcus hirae ATCC 10541 >6.5

example 4

Compositions consisting of 1.8% hydrogen peroxide, 0.6% Akypo LF2 and 0.8% hydroxysulfobetaine (hydroxysultaine) (MackamLHS by McIntyre) were tested against Candida Albicans ATCC 12031 and showed a reduction in log4 after 15 minutes and > log5.3 after 30 minutes.

Example 5

Compositions consisting of 4.5% hydrogen peroxide and 2% Akypo LF4 were tested in the EN 1650 european suspension test, showing > log5 reduction after 5 minutes for Candida albicans ATCC 12031 and > log5 reduction after 15 minutes for Aspergillus niger ATCC 16404. Solutions of 4.5% hydrogen peroxide were tested under similar conditions (EN 1650) and did not show any significant log reduction against Candida albicans and Aspergillus niger after 15 minutes. Thus, the composition can be used as a broad spectrum disinfectant.

Example 6

To evaluate the virucidal activity of the compositions, compositions consisting of low concentrates of 1% hydrogen peroxide and 0.4% Akypo LF2 were tested against the following enveloped viruses: vaccinia virus and Bovine Viral Diarrhea Virus (BVDV), which showed a greater than log4 reduction after only 1 minute in the EN 14476 suspension test.

Example 7

Compositions I-X (table 3) were prepared and tested for bactericidal activity in order to compare the bactericidal activity of compositions comprising hydrogen peroxide and any of an ether carboxylic acid, a carboxylic acid, an anionic surfactant, or an amphoteric surfactant. It is clearly shown (table 4) that the compositions comprising hydrogen peroxide in combination with ether carboxylic acid show the highest antibacterial activity.

TABLE 3

Composition pH of No. 2

I 1.5％H₂O₂+0.3％Akypo LF 4 2.8

II 1.5％H₂O₂+ 0.3% 2-Furanecarboxylic acid 2.4

III 1.5％H₂O₂+ 0.3% glycolic acid 2.6

IV 1.5％H₂O₂+0.3％Dequest 2010 2.3

V 1.5％H₂O₂+ 0.3% citric acid 2.3

VI 1.5％H₂O₂+ 0.4% lactic acid 2.5

VII 1.5％H₂O₂+0.4％Akypo LF4 2.9

VIII 1.5％H₂O₂+0.4％Zetesol NL-U(+H₃PO₄To pH3) 2.9

IX 1.5％H₂O₂+0.4％Mackam CB818(+H₃PO₄To pH3) 3.0

X 2％H₂O₂(+ HCl to pH2.5) 2.5

TABLE 4

EN1276 dirty Condition

E.coli Staph.aureus Ent.cloacae

Starting 1.6x10⁸ 3.3x10⁷ 2.4x10⁷

1 minute 3 minute

I 164 0 432 165 58 0

II >1000 101 >1000 >1000 >1000 104

III >1000 260 >1000 >1000 >1000 >1000

IV >1000 150 >1000 >1000 >1000 >1000

V >1000 280 >1000 >1000 >1000 >1000

VI >1000 290 >1000 >1000 >1000 >1000

VII 18 0 6 0 0 0

VIII 68 9 >1000 >1000 42 6

IX >1000 >1000 >1000 280 >1000 >1000

X >1000 >1000 >1000 >1000 >1000 >1000

Claims (17)

1. A composition comprising hydrogen peroxide at a concentration of 0.05-50% (w/w) and hydrogen peroxide at a concentration of 0.01-60% (w/w) having formula I: R-O- (CH)₂-CH₂-O)_n-CH₂-a compound of the structure COOH, wherein R is an alkyl or alkenylene group containing 6 to 10 carbon atoms, and n is 3 to 10, with the proviso that the composition does not contain acetic acid at a concentration of 0.001% or more and/or peroxyacetic acid at a concentration of 0.0005% or more.

2. The composition of claim 1 wherein R is an alkyl or alkenylene group containing 6 to 8 carbon atoms.

3. The composition of claim 1 or 2, wherein R is a straight chain alkyl group.

4. The composition of claim 1, wherein n is 3-8.

5. The composition of claim 1, wherein the hydrogen peroxide concentration is 0.05-8% (w/w).

6. The composition of claim 1, wherein the concentration of the compound having the structure of formula I is 0.01-10% (w/w).

7. The composition of claim 1, wherein the concentrations of hydrogen peroxide and the compound having the structure of formula I are selected in the following manner: the weight ratio between hydrogen peroxide and said compound having the structure of formula I varies between 10 and 0.1.

8. The composition of claim 1, wherein the pH has a value of 1-7.

9. The composition of claim 1, further comprising a hydrogen peroxide stabilizer.

10. The composition of claim 1, further comprising a carboxylic acid.

11. The composition of claim 1, further comprising a nonionic, cationic, amphoteric, and/or anionic surfactant.

12. The composition of claim 11 wherein the surfactant is selected from the group consisting of alkyl betaines, alkyl amidopropyl betaine amides, alkyl amidopropyl betaines, and amine oxides.

13. The composition of claim 1, further comprising a skin emollient or skin moisturizer.

14. The composition of claim 1, further comprising a corrosion inhibitor.

15. Use of a composition according to claim 1 for any purpose where disinfecting and/or sanitizing and/or preserving activity is required, optionally in combination with cleaning and/or bleaching activity.

16. A method for disinfecting and/or sanitizing and/or preserving a substrate comprising contacting the substrate with an effective amount of a biocidal composition according to any one of claims 1 to 14.

17. The method of claim 16, wherein the contacting comprises spraying, dipping, atomizing, and/or rinsing.