CA2293703A1 - Disinfecting compositions and processes for disinfecting surfaces - Google Patents
Disinfecting compositions and processes for disinfecting surfaces Download PDFInfo
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- CA2293703A1 CA2293703A1 CA002293703A CA2293703A CA2293703A1 CA 2293703 A1 CA2293703 A1 CA 2293703A1 CA 002293703 A CA002293703 A CA 002293703A CA 2293703 A CA2293703 A CA 2293703A CA 2293703 A1 CA2293703 A1 CA 2293703A1
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/22—Peroxides; Oxygen; Ozone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/342—Alcohols having more than seven atoms in an unbroken chain
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/55—Phosphorus compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
- A61Q11/02—Preparations for deodorising, bleaching or disinfecting dentures
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- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
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- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
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- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/92—Sulfobetaines ; Sulfitobetaines
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- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
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- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
-
- 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
- C11D3/39—Organic or inorganic per-compounds
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- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
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- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-compounds
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- 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
- C11D3/50—Perfumes
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Inorganic Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Emergency Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Dermatology (AREA)
- Agronomy & Crop Science (AREA)
- Oncology (AREA)
- Plant Pathology (AREA)
- Communicable Diseases (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract
The present invention relates to the use, in a composition, of a peroxygen bleach and an essential oil or an active thereof or a mixture thereof, for delivering long lasting disinfection to a surface having been treated with said composition.
Description
DISINFECTING COMPOSITIONS AND PROCESSES FOR DISINFECTING SURFACES
Technical field The present invention relates to antimicrobial compositions which can be used to deliver long lasting disinfection on animate surfaces (e.g., human skin, mouth and the like) and inanimate surfaces including, but not limited to, hard surfaces like walls, tiles, table tops, glass, bathroom surfaces, kitchen surfaces, dishes as well as fabrics, clothes, carpets and the like.
Background of the invention AntimicrobiaUantibacterial compositions include materials which have the ability to disinfect. It is generally recognised that a disinfecting material greatly reduces or even eliminates the microorganisms, e.g., bacteria, existing on a surface.
Typical conventional compositions although providing immediate disinfection ' when applied onto a surface to be disinfected are not fully satisfactory when it is also desired to prevent subsequent recontamination from microorganisms on ' such a surface having been first treated with said compositions. Such recontamination may happen when a surface that has been treated with an antimicrobial/antibacterial composition is, later on, touched with contaminated hands or comes in contact with another source of contamination.
!t is therefore an object of the present invention to provide not only effective immediate disinfection, but also effective long lasting disinfection.
This object can be met by combining a peroxygen bleach and an antimicrobial essential oil or an active thereof or a mixture thereof. Indeed, it has surprisingly been found that the incorporation, in a composition, of a peroxygen bleach and an antimicrobial essential oil, or an active thereof, provides long lasting disinfection on a surface treated therewith, even at low total level of active antimicrobial ingredients.
By combining a peroxygen bleach and an antimicrobial essential oil or an active thereof, long lasting disinfection is provided on various surfaces, i.e., animate surfaces {e.g., human skin) and inanimate surfaces. Indeed, this technology is particularly suitable for hard-surfaces applications as well as in laundry applications, e.g., as a laundry detergent or laundry additive in a so called "soaking mode", "through the wash mode", or even as a laundry pretreater in a "pretreatment mode".
An advantage of the present invention is that effective long lasting disinfection is provided on a broad range of bacterial pure strains. Indeed, the growth of Gram positive and Gram negative bacterial strains and more resistant microorganisms like fungi is reduced or even prevented on a surface when said surface has been first treated with a composition comprising a peroxygen bleach and an antimicrobial essential oil or an active thereof.
A further advantage of the present invention is that effective long lasting disinfection is provided by using ingredients which are perceived by the consumers as being safe to the surfaces treated and environmental friendly.
Background art Representative of the prior art is for example EP-B-288 689, which discloses a liquid for hard-surfaces comprising antimicrobial effective amounts of pine oil and at least one oil soluble organic acid. No peroxygen bleaches are disclosed.
US-5,403,587 discloses aqueous antimicrobial compositions which can be used to sanitise, disinfect, and clean hard-surfaces. More particularly, US-5,403,587 discloses aqueous compositions (pH 1 to 12) comprising essential oils (0.02%
to 5%), which exhibit antimicrobial properties efficacy such as thyme oil, eucalyptus oil, clove oil and the like, and a solubilizing or dispersing agent sufficient to form an aqueous solution or dispersion of said essential oils in a water carrier.
No peroxygen bleaches are disclosed.
None of these prior art documents discloses that by combining a peroxygen bleach with an antimicrobial essential oil or an active thereof, in a composition, long lasting disinfection is delivered to a surface having been treated therewith, even at low total levels of antimicrobial ingredients (i.e. under diluted conditions according to the present invention).
Summary of the invention The present invention encompasses the use, in a composition, of a peroxygen bleach and an antimicrobial essential oil or an active thereof or mixture thereof, for long lasting disinfection on a surface treated with said composition.
Detailed description of the invention A first essential ingredient of the present invention is a peroxygen bleach or a mixture thereof. Preferred peroxygen bleach is hydrogen peroxide, or a water soluble source thereof, or mixtures thereof. Hydrogen peroxide is most preferred to be used herein.
The presence of said peroxygen bleach especially hydrogen peroxide, persulfate and the like, in the compositions according to the present invention contribute to the disinfection properties of said compositions. indeed, said peroxygen bleach WO 98!54279 PCT/US97/09260 may attack the vital function of the micro-organism cells, for example, it may inhibit the assembling of ribosomes units within the cytoplasm of the microorganisms cells. Also said peroxygen bleach like hydrogen peroxide, is an oxidiser that generates hydroxyl free radicals which attack proteins and nucleic acids. Furthermore, the presence of said peroxygen bleach, especially hydrogen peroxide, provides strong stain removal benefits which are particularly noticeable for example in laundry and hard surfaces applications.
As used herein a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water.
Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicates, persulphates such as monopersulfate, perborates and peroxyacids such as diperoxydodecandioic acid (DPDA), magnesium perphthalic acid and mixtures thereof.
In addition, other classes of peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof. Suitable classes include dialkylperoxides, diacylperoxides, preformed percarboxylic acids, organic and inorganic peroxides andlor hydroperoxides.
Typically, peroxygen bleach or a mixture thereof is present in the compositions according to the present invention at a level of at least 0.01 % by weight of the total composition, preferably from 0.1 % to 15%, and more preferably from 1 %
to 10%.
A second essential ingredient of the present invention is an antimicrobial essential oil or an active thereof, or a mixture thereof.
Suitable antimicrobial essential oils to be used herein are those essential oils which exhibit antimicrobial activity. By "actives of essential oils", it is meant herein any ingredient of essential oils that exhibit antimicrobial activity. It is speculated that said antimicrobial essential oils and actives thereof act as proteins denaturing agents. Also said antimicrobial oils and actives thereof are compounds which contribute to the safety profile of a composition comprising them when it is used to disinfect any surface. A further advantage of said antimicrobial oils and actives thereof is that they impart pleasant odor to a composition comprising them without the need of adding a perfume.
Such antimicrobial essential oils include, but are not limited to, those obtained . 5 from thyme, lemongrass, citrus, lemons, oranges, anise, clove, aniseed, pine, cinnamon, geranium, roses, mint, lavender, citronella, eucalyptus, peppermint, camphor, ajowan, sandalwood, rosmarin, vervain, fleagrass, lemongrass, ratanhiae, cedar and mixtures thereof. Preferred antimicrobial essential oils to be used herein are thyme oil, clove oil, cinnamon oil, geranium oil, eucalyptus oil, peppermint oil, citronella oil, ajowan oil, mint oil or mixtures thereof.
Actives of essential oils to be used herein include, but are not limited to, thymol . (present for example in thyme, ajowan), eugenol (present for example in cinnamon and clove), menthol (present for example in mint), geraniol (present for example in geranium and rose, citronella), verbenone (present for example in vervain), eucalyptol and pinocarvone (present in eucalyptus}, cedrol (present for example in cedar}, anethoi (present for example in anise), carvacrol, hinokitiol, berberine, ferulic acid, cinnamic acid, methyl salicylic acid, methyl salycilate, terpineol, limonene and mixtures thereof. Preferred actives of essential oils to be used herein are thymol, eugenol, verbenone, eucalyptoi, terpineol, cinnamic acid, methyl salicylic acid, limonene, geraniol or mixtures thereof.
Thymol may be commercially available for example from Aldrich, eugenol may be commercially available for example from Sigma, Systems - Bioindustries (SBI) Manheimer Inc.
Typically, the antimicrobial essential oil or active thereof or mixture thereof is present in the composition at a level of at least 0.003% by weight of the total composition, preferably from 0.006% to 10%, more preferably from 0.1 % to 8%
and most preferably of from 0.03% to 3%.
It has now been found that combining said antimicrobial essential oil or an active thereof or a mixture thereof with a peroxygen bleach, in a composition, delivers not only excellent immediate disinfecting properties to the surfaces treated with said composition, but also long lasting disinfecting properties. Indeed, it is speculated that peroxygen bleach and said essential oilslactives adsorb on a surface having been treated with said composition and thus reduce or even prevent the contamination of microorganisms over time, typically up to 48 hours after the surface has been treated with said composition, thereby delivering long lasting disinfection. In other words, it is speculated that a microfilm of said active ingredients is deposited on the surface treated with said compositions allowing protection against microorganisms recontamination overtime. Advantageously, this long lasting disinfection benefits is obtained with the compositions of the present invention comprising peroxygen bleach and antimicrobial essential oilslactives even when used under highly diluted conditions, i.e., up to dilution levels of from 1:100 (composition:water}.
Excellent long lasting disinfection is obtained by treating a surface with a composition comprising a peroxygen bleach and an antimicrobial essential oil or active thereof as described herein, on a variety of microorganisms, e.g., the growth of Gram positive bacteria like Staphylococcus aureus, and Gram negative bacteria like Pseudomonas aeroginosa as well as of fungi tike Candida albicans is reduced or even prevented on a surface having been treated with said composition.
Long lasting disinfection properties of the compositions herein may be measured by the bactericidal activity of said compositions. A test method suitable to evaluate the long lasting bactericidal activity of a composition may be as follow:
First, the surfaces (e.g. glass) to be tested are respectively treated with either a composition according to the present invention or a reference composition, e.g., a negative control composed of pure water (for example by spraying the composition directly on the surface or first spraying the composition on a sponge used to clean the surface or when the composition herein is executed in the form of wipe by wiping the surface therewith). After a variable time frame (e.g. 24 hours) each surface is respectively inoculated with bacteria (106-7cfu/slide) cultured in for example TSB (Tryptone Soya Broth) and left typically from a few seconds to 2 hours before evaluating the remaining living bacteria. Then living bacteria (if any) are recovered from the surface {by touching TSA +
neutraliser plates and by re-suspending the bacteria into the neutralisation broth and plating them on agar) and incubated at appropriate temperature, e.g. 37°C to let them grow typically over night. Finally, a visual grading of the living bacteria is made by comparing side by side the cultures and/or dilutions thereof (e.g. 10-2 or 10-1 ) resulting from the surfaces treated with the compositions according to the present invention and the reference composition.
The combination of ingredients according to the present invention, i.e., a peroxygen bleach and an antimicrobiai essential oil and/or active thereof, may be formulated in a composition being either in a solid, pasty or liquid form. In the case where the compositions according to the present invention are formulated as solids, they will be mixed with an appropriate solvent, typically water, before use. In liquid form, the compositions are preferably but not necessarily formulated as aqueous compositions. Liquid compositions are preferred herein for convenience of use.
In a preferred embodiment the liquid compositions according to the present invention are aqueous compositions typically comprising from 50% to 99% by weight of the total composition of water, preferably from 70% to 99% and more preferably from 80% to 99%. These aqueous compositions preferably have a pH
as is of not more than 12.0, more preferably from 1 to 10, and most preferably from 2 to 9. The pH of the compositions can be adjusted by using organic or inorganic acids, or alkalinising agents.
Optional ingredients In a preferred embodiment of the present invention, as effective long lasting disinfection is provided with the combination of ingredients of the present invention the compositions comprising said combination do not require the addition of other antimicrobial compounds. However, in particular embodiments of the present invention, depending on the end use desired with said compositions they may further comprise, as optional ingredients, other antimicrobial compounds that further contribute to the antimicrobial/antibacterial activity of the compositions according to the present invention. Such antimicrobial ingredients include parabens like ethyl paraben, propyl paraben, methyl paraben, glutaraldehyde or mixtures thereof.
The compositions herein may further comprise a variety of other optional ingredients such as surfactants, chelants, solvents, builders, stabilisers, bleach activators, soil suspenders, dye transfer agents, brighteners, perfumes, anti dusting agents, enzymes, dispersant, dye transfer inhibitors, pigments, perfumes, radical scavengers, pH buffers, dyes or mixtures thereof.
The compositions according to the present invention may comprise any surfactant known to those skilled in the art including nonionic, anionic, cationic, amphoteric and/or zwitterionic surfactants. Said surfactants are suitable as they contribute to the cleaning performance of the compositions herein.
Typically, the compositions according to the present invention comprise up to 50%
by weight of the total composition of a surfactant, or mixtures thereof, preferably from 0.3 % to 30 % and more preferably from 0.4 % to 25 %.
Particularly suitable anionic surfactants for use herein include water-soluble salts or acids of the formula ROS03M wherein R is preferably a Cg-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cg-C20 alkyl component, more preferably a Cg-C16 alkyl or hydroxyalkyl, and M is H or a ration, e.g., an alkali metal ration {e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium rations and quaternary ammonium rations, such as tetramethyl-ammonium and dimethyl piperdinium rations and quaternary ammonium rations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Other suitable anionic surfactants for use herein include alkyl-Biphenyl-ether-sulphonates and alkyl-carboxylates. Other anionic surfactants can include salts {including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C20 linear alkylbenzenesulfonates, Cg-C22 primary or secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as 16 methyl ester sulfonates; aryl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin suffonates, alkyl phosphates, isethionates such as the aryl isethionates, N-aryl taurates, alkyl succinamates ahd sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C1g monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cg-C14 diesters), aryl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkyipolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH20)kCH2C00-M+ wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming ration. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" {Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al.
at Column 23, line 58 through Column 29, line 23.
Preferred anionic surfactants for use herein are the C8-C16 alkyl sulfonates, C16 alkyl sulfates, C8-C16 alkyl alkoxylated sulfates (e.g., C8-C16 alkyl ethoxylated sulfates), and mixtures thereof. Such anionic surfactants are preferred herein as it has been found that they contribute to the disinfecting properties of a disinfecting composition herein. For example, C8-C16 alkyl sulfate acts by disorganizing the bacteria cell membrane, inhibiting enzymatic activities, interrupting the cellular transport and/or denaturing cellular proteins.
Indeed, it is speculated that the improved disinfecting performance further associated with the addition of an anionic surfactant, especially a C8-C16 alkyl sulfonate, a C8-C16 alkyl sulfate and/or a C8-C16 alkyl alkoxylated sulfate, in a composition according to the present invention, is likely due to multiple mode of attack of said surfactant against the bacteria.
Suitable nonionic surfactants for use herein are fatty alcohol ethoxylates and/or propoxylates which are commercially available with a variety of fatty alcohol chain lengths and a variety of ethoxyiation degrees. Indeed, the HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation.
Surfactant catalogues are available which list a number of surfactants, including nonionics, together with their respective HLB values.
Particularly suitable for use herein as nonionic surfactants are hydrophobic nonionic surfactants having an HLB {hydrophilic-lipophilic balance) below 16, preferably below 15 and more preferably below 14. Those hydrophobic nonionic surfactants have been found to provide good grease cutting properties.
Technical field The present invention relates to antimicrobial compositions which can be used to deliver long lasting disinfection on animate surfaces (e.g., human skin, mouth and the like) and inanimate surfaces including, but not limited to, hard surfaces like walls, tiles, table tops, glass, bathroom surfaces, kitchen surfaces, dishes as well as fabrics, clothes, carpets and the like.
Background of the invention AntimicrobiaUantibacterial compositions include materials which have the ability to disinfect. It is generally recognised that a disinfecting material greatly reduces or even eliminates the microorganisms, e.g., bacteria, existing on a surface.
Typical conventional compositions although providing immediate disinfection ' when applied onto a surface to be disinfected are not fully satisfactory when it is also desired to prevent subsequent recontamination from microorganisms on ' such a surface having been first treated with said compositions. Such recontamination may happen when a surface that has been treated with an antimicrobial/antibacterial composition is, later on, touched with contaminated hands or comes in contact with another source of contamination.
!t is therefore an object of the present invention to provide not only effective immediate disinfection, but also effective long lasting disinfection.
This object can be met by combining a peroxygen bleach and an antimicrobial essential oil or an active thereof or a mixture thereof. Indeed, it has surprisingly been found that the incorporation, in a composition, of a peroxygen bleach and an antimicrobial essential oil, or an active thereof, provides long lasting disinfection on a surface treated therewith, even at low total level of active antimicrobial ingredients.
By combining a peroxygen bleach and an antimicrobial essential oil or an active thereof, long lasting disinfection is provided on various surfaces, i.e., animate surfaces {e.g., human skin) and inanimate surfaces. Indeed, this technology is particularly suitable for hard-surfaces applications as well as in laundry applications, e.g., as a laundry detergent or laundry additive in a so called "soaking mode", "through the wash mode", or even as a laundry pretreater in a "pretreatment mode".
An advantage of the present invention is that effective long lasting disinfection is provided on a broad range of bacterial pure strains. Indeed, the growth of Gram positive and Gram negative bacterial strains and more resistant microorganisms like fungi is reduced or even prevented on a surface when said surface has been first treated with a composition comprising a peroxygen bleach and an antimicrobial essential oil or an active thereof.
A further advantage of the present invention is that effective long lasting disinfection is provided by using ingredients which are perceived by the consumers as being safe to the surfaces treated and environmental friendly.
Background art Representative of the prior art is for example EP-B-288 689, which discloses a liquid for hard-surfaces comprising antimicrobial effective amounts of pine oil and at least one oil soluble organic acid. No peroxygen bleaches are disclosed.
US-5,403,587 discloses aqueous antimicrobial compositions which can be used to sanitise, disinfect, and clean hard-surfaces. More particularly, US-5,403,587 discloses aqueous compositions (pH 1 to 12) comprising essential oils (0.02%
to 5%), which exhibit antimicrobial properties efficacy such as thyme oil, eucalyptus oil, clove oil and the like, and a solubilizing or dispersing agent sufficient to form an aqueous solution or dispersion of said essential oils in a water carrier.
No peroxygen bleaches are disclosed.
None of these prior art documents discloses that by combining a peroxygen bleach with an antimicrobial essential oil or an active thereof, in a composition, long lasting disinfection is delivered to a surface having been treated therewith, even at low total levels of antimicrobial ingredients (i.e. under diluted conditions according to the present invention).
Summary of the invention The present invention encompasses the use, in a composition, of a peroxygen bleach and an antimicrobial essential oil or an active thereof or mixture thereof, for long lasting disinfection on a surface treated with said composition.
Detailed description of the invention A first essential ingredient of the present invention is a peroxygen bleach or a mixture thereof. Preferred peroxygen bleach is hydrogen peroxide, or a water soluble source thereof, or mixtures thereof. Hydrogen peroxide is most preferred to be used herein.
The presence of said peroxygen bleach especially hydrogen peroxide, persulfate and the like, in the compositions according to the present invention contribute to the disinfection properties of said compositions. indeed, said peroxygen bleach WO 98!54279 PCT/US97/09260 may attack the vital function of the micro-organism cells, for example, it may inhibit the assembling of ribosomes units within the cytoplasm of the microorganisms cells. Also said peroxygen bleach like hydrogen peroxide, is an oxidiser that generates hydroxyl free radicals which attack proteins and nucleic acids. Furthermore, the presence of said peroxygen bleach, especially hydrogen peroxide, provides strong stain removal benefits which are particularly noticeable for example in laundry and hard surfaces applications.
As used herein a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water.
Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicates, persulphates such as monopersulfate, perborates and peroxyacids such as diperoxydodecandioic acid (DPDA), magnesium perphthalic acid and mixtures thereof.
In addition, other classes of peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof. Suitable classes include dialkylperoxides, diacylperoxides, preformed percarboxylic acids, organic and inorganic peroxides andlor hydroperoxides.
Typically, peroxygen bleach or a mixture thereof is present in the compositions according to the present invention at a level of at least 0.01 % by weight of the total composition, preferably from 0.1 % to 15%, and more preferably from 1 %
to 10%.
A second essential ingredient of the present invention is an antimicrobial essential oil or an active thereof, or a mixture thereof.
Suitable antimicrobial essential oils to be used herein are those essential oils which exhibit antimicrobial activity. By "actives of essential oils", it is meant herein any ingredient of essential oils that exhibit antimicrobial activity. It is speculated that said antimicrobial essential oils and actives thereof act as proteins denaturing agents. Also said antimicrobial oils and actives thereof are compounds which contribute to the safety profile of a composition comprising them when it is used to disinfect any surface. A further advantage of said antimicrobial oils and actives thereof is that they impart pleasant odor to a composition comprising them without the need of adding a perfume.
Such antimicrobial essential oils include, but are not limited to, those obtained . 5 from thyme, lemongrass, citrus, lemons, oranges, anise, clove, aniseed, pine, cinnamon, geranium, roses, mint, lavender, citronella, eucalyptus, peppermint, camphor, ajowan, sandalwood, rosmarin, vervain, fleagrass, lemongrass, ratanhiae, cedar and mixtures thereof. Preferred antimicrobial essential oils to be used herein are thyme oil, clove oil, cinnamon oil, geranium oil, eucalyptus oil, peppermint oil, citronella oil, ajowan oil, mint oil or mixtures thereof.
Actives of essential oils to be used herein include, but are not limited to, thymol . (present for example in thyme, ajowan), eugenol (present for example in cinnamon and clove), menthol (present for example in mint), geraniol (present for example in geranium and rose, citronella), verbenone (present for example in vervain), eucalyptol and pinocarvone (present in eucalyptus}, cedrol (present for example in cedar}, anethoi (present for example in anise), carvacrol, hinokitiol, berberine, ferulic acid, cinnamic acid, methyl salicylic acid, methyl salycilate, terpineol, limonene and mixtures thereof. Preferred actives of essential oils to be used herein are thymol, eugenol, verbenone, eucalyptoi, terpineol, cinnamic acid, methyl salicylic acid, limonene, geraniol or mixtures thereof.
Thymol may be commercially available for example from Aldrich, eugenol may be commercially available for example from Sigma, Systems - Bioindustries (SBI) Manheimer Inc.
Typically, the antimicrobial essential oil or active thereof or mixture thereof is present in the composition at a level of at least 0.003% by weight of the total composition, preferably from 0.006% to 10%, more preferably from 0.1 % to 8%
and most preferably of from 0.03% to 3%.
It has now been found that combining said antimicrobial essential oil or an active thereof or a mixture thereof with a peroxygen bleach, in a composition, delivers not only excellent immediate disinfecting properties to the surfaces treated with said composition, but also long lasting disinfecting properties. Indeed, it is speculated that peroxygen bleach and said essential oilslactives adsorb on a surface having been treated with said composition and thus reduce or even prevent the contamination of microorganisms over time, typically up to 48 hours after the surface has been treated with said composition, thereby delivering long lasting disinfection. In other words, it is speculated that a microfilm of said active ingredients is deposited on the surface treated with said compositions allowing protection against microorganisms recontamination overtime. Advantageously, this long lasting disinfection benefits is obtained with the compositions of the present invention comprising peroxygen bleach and antimicrobial essential oilslactives even when used under highly diluted conditions, i.e., up to dilution levels of from 1:100 (composition:water}.
Excellent long lasting disinfection is obtained by treating a surface with a composition comprising a peroxygen bleach and an antimicrobial essential oil or active thereof as described herein, on a variety of microorganisms, e.g., the growth of Gram positive bacteria like Staphylococcus aureus, and Gram negative bacteria like Pseudomonas aeroginosa as well as of fungi tike Candida albicans is reduced or even prevented on a surface having been treated with said composition.
Long lasting disinfection properties of the compositions herein may be measured by the bactericidal activity of said compositions. A test method suitable to evaluate the long lasting bactericidal activity of a composition may be as follow:
First, the surfaces (e.g. glass) to be tested are respectively treated with either a composition according to the present invention or a reference composition, e.g., a negative control composed of pure water (for example by spraying the composition directly on the surface or first spraying the composition on a sponge used to clean the surface or when the composition herein is executed in the form of wipe by wiping the surface therewith). After a variable time frame (e.g. 24 hours) each surface is respectively inoculated with bacteria (106-7cfu/slide) cultured in for example TSB (Tryptone Soya Broth) and left typically from a few seconds to 2 hours before evaluating the remaining living bacteria. Then living bacteria (if any) are recovered from the surface {by touching TSA +
neutraliser plates and by re-suspending the bacteria into the neutralisation broth and plating them on agar) and incubated at appropriate temperature, e.g. 37°C to let them grow typically over night. Finally, a visual grading of the living bacteria is made by comparing side by side the cultures and/or dilutions thereof (e.g. 10-2 or 10-1 ) resulting from the surfaces treated with the compositions according to the present invention and the reference composition.
The combination of ingredients according to the present invention, i.e., a peroxygen bleach and an antimicrobiai essential oil and/or active thereof, may be formulated in a composition being either in a solid, pasty or liquid form. In the case where the compositions according to the present invention are formulated as solids, they will be mixed with an appropriate solvent, typically water, before use. In liquid form, the compositions are preferably but not necessarily formulated as aqueous compositions. Liquid compositions are preferred herein for convenience of use.
In a preferred embodiment the liquid compositions according to the present invention are aqueous compositions typically comprising from 50% to 99% by weight of the total composition of water, preferably from 70% to 99% and more preferably from 80% to 99%. These aqueous compositions preferably have a pH
as is of not more than 12.0, more preferably from 1 to 10, and most preferably from 2 to 9. The pH of the compositions can be adjusted by using organic or inorganic acids, or alkalinising agents.
Optional ingredients In a preferred embodiment of the present invention, as effective long lasting disinfection is provided with the combination of ingredients of the present invention the compositions comprising said combination do not require the addition of other antimicrobial compounds. However, in particular embodiments of the present invention, depending on the end use desired with said compositions they may further comprise, as optional ingredients, other antimicrobial compounds that further contribute to the antimicrobial/antibacterial activity of the compositions according to the present invention. Such antimicrobial ingredients include parabens like ethyl paraben, propyl paraben, methyl paraben, glutaraldehyde or mixtures thereof.
The compositions herein may further comprise a variety of other optional ingredients such as surfactants, chelants, solvents, builders, stabilisers, bleach activators, soil suspenders, dye transfer agents, brighteners, perfumes, anti dusting agents, enzymes, dispersant, dye transfer inhibitors, pigments, perfumes, radical scavengers, pH buffers, dyes or mixtures thereof.
The compositions according to the present invention may comprise any surfactant known to those skilled in the art including nonionic, anionic, cationic, amphoteric and/or zwitterionic surfactants. Said surfactants are suitable as they contribute to the cleaning performance of the compositions herein.
Typically, the compositions according to the present invention comprise up to 50%
by weight of the total composition of a surfactant, or mixtures thereof, preferably from 0.3 % to 30 % and more preferably from 0.4 % to 25 %.
Particularly suitable anionic surfactants for use herein include water-soluble salts or acids of the formula ROS03M wherein R is preferably a Cg-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cg-C20 alkyl component, more preferably a Cg-C16 alkyl or hydroxyalkyl, and M is H or a ration, e.g., an alkali metal ration {e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium rations and quaternary ammonium rations, such as tetramethyl-ammonium and dimethyl piperdinium rations and quaternary ammonium rations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Other suitable anionic surfactants for use herein include alkyl-Biphenyl-ether-sulphonates and alkyl-carboxylates. Other anionic surfactants can include salts {including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C20 linear alkylbenzenesulfonates, Cg-C22 primary or secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as 16 methyl ester sulfonates; aryl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin suffonates, alkyl phosphates, isethionates such as the aryl isethionates, N-aryl taurates, alkyl succinamates ahd sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C1g monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cg-C14 diesters), aryl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkyipolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH20)kCH2C00-M+ wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming ration. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" {Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al.
at Column 23, line 58 through Column 29, line 23.
Preferred anionic surfactants for use herein are the C8-C16 alkyl sulfonates, C16 alkyl sulfates, C8-C16 alkyl alkoxylated sulfates (e.g., C8-C16 alkyl ethoxylated sulfates), and mixtures thereof. Such anionic surfactants are preferred herein as it has been found that they contribute to the disinfecting properties of a disinfecting composition herein. For example, C8-C16 alkyl sulfate acts by disorganizing the bacteria cell membrane, inhibiting enzymatic activities, interrupting the cellular transport and/or denaturing cellular proteins.
Indeed, it is speculated that the improved disinfecting performance further associated with the addition of an anionic surfactant, especially a C8-C16 alkyl sulfonate, a C8-C16 alkyl sulfate and/or a C8-C16 alkyl alkoxylated sulfate, in a composition according to the present invention, is likely due to multiple mode of attack of said surfactant against the bacteria.
Suitable nonionic surfactants for use herein are fatty alcohol ethoxylates and/or propoxylates which are commercially available with a variety of fatty alcohol chain lengths and a variety of ethoxyiation degrees. Indeed, the HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation.
Surfactant catalogues are available which list a number of surfactants, including nonionics, together with their respective HLB values.
Particularly suitable for use herein as nonionic surfactants are hydrophobic nonionic surfactants having an HLB {hydrophilic-lipophilic balance) below 16, preferably below 15 and more preferably below 14. Those hydrophobic nonionic surfactants have been found to provide good grease cutting properties.
Preferred hydrophobic nonionic surfactants for use in the compositions according to the present invention are surfactants having an HLB below 16 and being according to the formula RO-(C2H40)n{C3H60)mH, wherein R is a Cg to C22 alkyl chain or a Cg to C2g alkyl benzene chain, and wherein n+m is from 0 10 to 20 and n is from 0 to 15 and m is from 0 to 20, preferably n+m is from 1 to 15 and, n and m are from 0.5 to 15, more preferably n+m is from 1 to 10 and, n and m are from 0 to 10. The preferred R chains for use herein are the Cg to C22 alkyl chains. Accordingly, suitable hydrophobic nonionic surfactants for use herein are Dobanol R 91-2.5 (HLB= 8.1; R is a mixture of C9 and C11 alkyl chains, n is 2.5 and m is 0), or Lutensol R T03 (HLB=8; R is a C13 alkyl chains, n is 3 and m is 0), or Lutensol R A03 (HLB=8; R is a mixture of C13 and C15 alkyl chains, n is 3 and m is 0), or Tergitol R 25L3 (HLB= 7.7; R is in the range of C12 to C15 alkyl chain length, n is 3 and m is 0), or Dobanol R 23-3 (HLB=8.1; R is a mixture of C12 and C13 alkyl chains, n is 3 and m is 0), or Dobanol R 23-2 (HLB=fi.2; R is a mixture of C12 and C13 alkyl chains, n is 2 and m is 0), or Dobanol R 45-7 (HLB=11.6; R is a mixture of C14 and C15 alkyl chains, n is 7 and m is 0) Dobanol R 23-6.5 (HLB=11.9; R is a mixture of C12 and C13 alkyl chains, n is 6.5 and m is 0), or Dobanol R 25-7 (HLB=12; R is a mixture of C12 and C15 alkyl chains, n is 7 and m is 0), or Dobanol R 91-5 (HLB=11.6; R is a mixture of Cg and C11 alkyl chains, n is 5 and m is 0), or Dobanol R 91-6 (HLB=12.5 ; R is a mixture of Cg and C11 alkyl chains, n is 6 and m is 0), or Dobanol R 91-8 (HLB=13.7 ; R is a mixture of Cg and C11 alkyl chains, n is 8 and m is 0), Dobanol R 91-10 (HLB=14.2 ; R is a mixture of Cg to C11 alkyl chains, n is 10 and m is 0), or mixtures thereof. Preferred herein are Dobanol R 91-2.5 , or Lutensol R T03, or Lutensol R A03, or Tergitol R 25L3, or Dobanol R 23-3, or Dobanol R 23-2, or mixtures thereof. These DobanolR
surfactants are commercially available from SHELL. These LutensolR
surfactants are commercially avaitabte from BASF and these Tergitol R
surfactants are commercially available from UNION CARBIDE.
Other suitable surfactants also include C6-C20 conventional soaps (alkali metal salt of a C6-C20 fatty acid, preferably sodium salts).
Suitable amphoteric surfactants for use herein include amine oxides having the following formula R1R2R3N0 wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chains of from 1 to 30 carbon atoms. Preferred amine oxide surfactants to be used according to the present invention are amine oxides having the following formula R1 R2R3N0 wherein R1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups. R1 may be a saturated substituted or unsubstituted linear or branched hydrocarbon chain.
Suitable amine oxides for use herein are for instance natural blend C8-C10 amine oxides as well as C12-C16 amine oxides commercially available from Hoechst.
Suitable zwitterionic surfactants for use herein contain both cationic and anionic hydrophilic groups on the same molecule at a relatively wide range of pH's.
The typical cationic group is a quaternary ammonium group, although other positively charged groups like phosphonium, imidazolium and sulfonium groups can be used. The typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used. A
generic formula for some zwitterionic surfactants to be used herein is R1-N+(R2)(R3)R4X_ wherein R1 is a hydrophobic group; R2 and R3 are each C1-C4 alkyl, hydroxy alkyl or other substituted alkyl group which can also be joined to form ring structures with the N; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is preferably a carboxylate or sulfonate group. Preferred hydrophobic groups are alkyl groups containing from 1 to 24, preferably less than 18, more preferably less than 16 carbon atoms. The hydrophobic group can contain unsaturation and/or substituents and/or linking groups such as aryl groups, amido groups, ester groups and the like. In general, the simple alkyl groups are preferred for cost and stability reasons.
Highly preferred zwitterionic surfactants include betaine and sulphobetaine surfactants, derivatives thereof or mixtures thereof. Said betaine or sulphobetaine surfactants are preferred herein as they help disinfection by increasing the permeability of the bacterial cell wall, thus allowing other active ingredients to enter the cell.
Furthermore, due to the mild action profile of said betaine or sulphobetaine surfactants, they are particularly suitable for the cleaning of delicate surfaces, e.g., delicate laundry or surfaces in contact with food and/or babies. Betaine and sulphobetaine surfactants are also extremely mild to the skin and/or surfaces to be treated.
Suitable betaine and sulphobetaine surfactants for use herein are the betaine/sulphobetaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values. Some common examples of these detergents are described in U.S. Pat. Nos.
2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
Preferred betaine and sulphobetaine surfactants herein are according to the formula I
R1 - N+ - (CH2)n - Y-I
wherein R1 is a hydrocarbon chain containing from 1 to 24 carbon atoms, preferably from 8 to 18, more preferably from 12 to 14, wherein R2 and R3 are hydrocarbon chains containing from 1 to 3 carbon atoms, preferably 1 carbon atom, wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is 1, Y is selected from the group consisting of carboxyl and sulfonyl radicals and wherein the sum of R1, R2 and R3 hydrocarbon chains is from 14 to 24 carbon atoms, or mixtures thereof.
Examples of particularly suitable betaine surfactants include C12-C18 alkyl dimethyl betaine such as coconut-betaine and C10-C16 alkyl dimethyl betaine such as laurylbetaine. Coconutbetaine is commercially available from Seppic under the trade name of Amonyl 265~. Laurylbetaine is commercially available from Albright & Wilson under the trade name Empigen BB/L~.
Other specific zwitterionic surfactants have the generic formulas:
R1-C{O)-N(R2)-(C(R3)2)n-N{R2)2{+)-(C(R3)2)n-S03(-) or R1-C(O)-N(R2)-(C(R3)2)n-N(R2)2(+)-(C{R3)2)n-COO{-) wherein each R1 is a hydrocarbon, e.g. an alkyl group containing from 8 up to 20, preferably up to 18, more preferably up to 16 carbon atoms, each R2 is either a hydrogen (when attached to the amido nitrogen), short chain alkyl or substituted alkyl containing from one to 4 carbon atoms, preferably groups selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, preferably methyl, each R3 is selected from the group consisting of hydrogen and hydroxy groups and each n is a number from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R3)2) moiety. The R1 groups can be branched andlor unsaturated. The R2 groups can also be connected to form ring structures. A
surfactant of this type is a C10-C14 fatty acylamidopropylene(hydroxypropylene)sulfobetaine that is available from the Sherex Company under the trade name "Varion CAS sulfobetaine"~.
The compositions herein may further comprise a chelating agent as a preferred optional ingredient. Suitable chelating agents may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, aminophosphonate chelating agents, substituted heteroaromatic chelating agents, amino carboxylate chelating agents, other carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, biodegradable chelating agents like ethylene diamine N,N'- disuccinic acid, or mixtures thereof.
Suitable phosphonate chelating agents to be used herein include etidronic acid ('!-hydroxyethylene-diphosphonic acid (HEDP)), and/or alkali metal ethane 1-hydroxydiphosphonates.
Suitable amino phosphonate chelating agents to be used herein include amino alkylene poly (alkylene phosphonates), nitrilotris(methylene)triphosphonates, ethylene diamine tetra methylene phosphonates, and/or diethylene triamine penta methylene phosphonates. Preferred aminophosphonate chelating agents to be used herein are diethylene triamine yenta methylene phosphonates.
These phosphonate/amino phosphonate chelating agents may be present either in their acid form or as salts of different rations on some or all of their acid functionalities. Such phosphonate/amino phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST~.
Substituted heteroaromatic chelating agents to be used herein include hydroxypiridine-N-oxide or a derivative thereof.
Suitable hydroxy pyridine N-oxides and derivatives thereof to be used according to the present invention are according to the following formula:
I H
wherein X is nitrogen, Y is one of the following groups oxygen, -CHO, -OH, -(CH2)n-COOH, wherein n is an integer of from 0 to 20, preferably of from 0 to and more preferably is 0, and wherein Y is preferably oxygen. Accordingly particularly preferred hydroxy pyridine N-oxides and derivatives thereof to be used herein is 2-hydroxy pyridine N-oxide. Hydroxy pyridine N-oxides and derivatives thereof may be commercially available from Sigma.
Polyfunctionaliy-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US
patent 4, 10 704, 233, November 3, 1987 to Hartman and Perkins. Ethylenediamine N,N'-disuccinic acid is, for instance, commercially available under the tradename ssEDDSO from Palmer Research Laboratories. Ethylene diamine N,N'- disuccinic acid is particularly suitable to be used in the compositions of the present invention.
Suitable amino carboxylate chelating agents useful herein include ethylene 15 diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentoacetate (DTPA), N-hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetraproprionates, triethyienetetraaminehexa-acetates, ethanoldiglycines, propylene diamine tetracetic acid {PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms. Particularly suitable to be used herein are diethylene triamine yenta acetic acid (DTPA), propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS~ and methyl glycine di-acetic acid (MGDA).
Further carboxylate chelating agents to be used herein includes malonic acid, salicylic acid, glycine, aspartic acid, glutamic acid, or mixtures thereof.
Typically, the compositions according to the present invention comprise up to 5%
by weight of the total composition of a chelating agent, or mixtures thereof, preferably from 0.01 % to 3% by weight and more preferably from 0.01 % to 1.5%.
The compositions herein may comprise a radical scavenger as another optional ingredient. Suitable radical scavengers for use herein include the well-known substituted mono and di hydroxy benzenes and derivatives thereof, alkyl- and aryl carboxylates and mixtures thereof. Preferred radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), p-hydroxy-toluene, hydroquinone (HQ), di-tert-butyl hydroquinone (DTBHQ), mono-tert-butyl hydroquinone {MTBHQ), tert-butyl-hydroxy anysole {BHA), p-hydroxy-anysol, benzoic acid, 2,5-dihydroxy benzoic acid, 2,5-dihydroxyterephtalic acid, toluic acid, catechol, t-butyl catechol, 4-allyl-catechol, 4-acetyl catechol, 2-methoxy-phenol, 2-ethoxy-phenol, 2-methoxy-4-(2-propenyl)phenol, 3,4-dihydroxy benzaldehyde, 2,3-dihydroxy benzaldehyde, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, tert-butyl-hydroxy-anyline, p-hydroxy anyline as well as n-propyl-gallate.
Highly preferred for use herein are di-tert-butyl hydroxy toluene, which is for example commercially available from SHELL under the trade name IONOL CP~ and/or tert-butyl-hydroxy anysoie. These radical scavengers further contribute to the stability of the peroxygen bleach-containing compositions herein.
Typically, the compositions according to the present invention comprise up to 5%
by weight of the total composition of a radical scavenger, or mixtures thereof, preferably from 0.002% to 1.5% by weight and more preferably from 0.002% to 1 %.
The compositions herein may comprise as a preferred optional ingredient a solvent or mixtures thereof. When used, solvents will, advantageously, give an enhanced cleaning to the compositions herein. Suitable solvents for incorporation in the compositions according to the present invention include propylene glycol derivatives such as n-butoxypropanol or n-butoxypropoxypropanol, water-soluble CARBITOLO solvents or water-soluble CELLOSOLVE~ solvents. Water-soluble CARBITOLO solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl. A preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol.
Water-soluble CELLOSOLVE~ solvents are compounds of the 2-alkoxyethoxyethanol class, with 2-butoxyethoxyethanol being preferred. Other suitable solvents are benzyl alcohol, methanol, ethanol, isopropyl alcohol and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol and mixture thereof.
Preferred solvents for use herein are n-butoxypropoxypropanol, butyl carbitol~, benzyl alcohol, isopropanol and mixtures thereof. Most preferred solvents for use herein are butyl carbitol~, benzyl alcohol and/or isopropanol.
The solvents may typically be present within the compositions according to the invention at a level up to 15% by weight, preferably from 2% to 7% by weight of - the composition.
In the embodiment of the present invention wherein the compositions are formulated in the alkaline pH range, typically from 7.5 to 12, the compositions according to the present invention may further comprise a pH buffer or a mixture thereof, i.e. a system composed of a compound or a combination of compounds, whose pH changes only slightly when a strong acid or base is added.
Suitable pH buffers for use herein include borate pH buffer, phosphonate, silicate and mixtures thereof. Suitable borate pH buffers for use herein include alkali metal salts of borates and alkyl borates and mixtures thereof. Suitable borate pH
buffers to be used herein are alkali metal salts of borate, metaborate, tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride and/or alkyl borate containing from 1 to 12 carbon atoms, and preferably from 1 to 4. Suitable alkyl borate includes methyl borate, ethyl borate and propyl borate. Particularly preferred herein are the alkali metal salts of metaborate (e.g. sodium metaborate), tetraborate (e.g., sodium tetraborate decahydrate) or mixtures thereof.
Boron salts like sodium metaborate and sodium tetraborate are commercially available from Borax and Societa Chimica Larderelio under the trade name sodium metaborate~ and Borax~.
Typically, the compositions according to the present invention may comprise up to 15% by weight of the total composition of a pH buffer, or mixtures thereof, preferably from 0.01 % to 10%, more preferably from 0.01 % to 5% and most preferably from 0.1 % to 3%.
Packaging form of the compositions:
The compositions herein may be packaged in a variety of suitable detergent packaging known to those skilled in the art. The liquid compositions herein may desirably be packaged in manually operated spray-type dispensing containers, which are usually made of synthetic organic polymeric plastic materials, and preferably in a trigger spray dispenser or pump spray dispenser. Said spray-type dispensers allow to uniformly applied to a relatively large area of a surface to be treated the liquid disinfecting compositions of the present invention. Such spray-type dispensers are particularly suitable to treat vertical surfaces.
Suitable spray-type dispensers to be used according to the present invention include manually operated foam trigger-type dispensers sold for example by Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are disclosed, for instance, in US-4,701,311 to Dunnining et al.
and US-4,64fi,973 and US-4,538,745 both to Focarracci. Particularly preferred to be used herein are spray-type dispensers such as T 8500~ or T 8900~
commercially available from Continental Spray International or T 8100~
commercially available from Canyon, Northern Ireland. in such a dispenser the liquid composition is divided in fine liquid droplets resulting in a spray that is directed onto the surface to be treated. Indeed, in such a spray-type dispenser the composition contained in the body of said dispenser is directed through the spray-type dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism. More particularly, in said spray-type dispenser head the composition is forced against an obstacle, e.g. a grid or a cone or the like, thereby providing shocks to help atomise the liquid composition, i.e. to help the formation of liquid droplets.
The compositions of the present invention may also be executed in the form of wipes. By "wipes", it is meant herein disposable towels, e.g. paper towels, impregnated with a liquid composition according to the present invention.
Preferably said wipes are packaged in a plastic box. The advantage of this execution is a faster usage of a disinfecting composition by the user, this even outside the house, i.e. there is no need to pour the liquid compositions according to the present invention on the surfaces to be treated and to dry it out with a cloth. In other words, wipes allow immediate and long lasting disinfection of the surfaces in one step.
The compositions according to the present invention are used to treat a surface thereby delivering long lasting disinfection to said surface. By "treat", it is meant herein applying the composition to the surface in its neat (in the preferred embodiment herein wherein the composition is liquid) or diluted form.
By "diluted form", it is meant herein that the compositions to be used, being either in a liquid or a solid form, is diluted by the user typically with water up to 100 times their weight of water, preferably into 80 to 40 times their weight of water and more preferably 60 to 40, before being applied to the surface to treat.
By "surface", it is meant herein any surface including animate surface like human skin, mouth, teeth, and inanimate surfaces. Inanimate surfaces include, but are not limited to, hard-surfaces typically found in houses like kitchens, bathrooms, or in car interiors, e.g., tiles, walls, floors, chrome, glass, smooth vinyl, any plastic, plastified wood, table top, sinks, cooker tops, dishes, sanitary fittings such as sinks, showers, shower curtains, wash basins, WCs and the like, as well as fabrics including clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like, and carpets.
Inanimate surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
The present invention will be further illustrated by the following examples.
Examples The following compositions were made by mixing the listed ingredients in the listed proportions (weight % unless otherwise specified).
Compositions I II III IV V VI
by weight 5 Hydrogen peroxide 7.0 2.0 1.0 2.0 4.0 3.0 Thyme oil - 0.05 - -- 0.5 -Clove oil 0.5 - -- 0.05 - 0.1 Geranium oil - 0.07 - - - -Eucalyptus oil 0.2 - 0.02 0.01 - 0.2 10 Geraniol - -- 0.5 - 0.5 0.1 Alkyl sulphate 4 3 10 1 4 0.5 DETPMP 0.1 0.15 0.15 0.1 0.15 0.2 Water and minors --- --- ---up to 100%----- -H2S04 up to pH 4 Compositions VII Vlll IX X XI XII
by weight Hydrogen peroxide7.0 2.0 5.0 1.0 4.0 1.5 Thyme oil - 0.4 -- -- 0.5 --Clove oil 0.5 - -- 0.2 -- 0.1 Geranium oil - 0.2 -- -- - --Eucalyptus oil 0.2 - 0.2 0.2 - 0.2 Geraniol - - 0.15 - 0.005 0.1 Betaine 1.5 0.1 - 0.03 - 0.1 Amine oxide 3 1.2 1.0 1 - 1.0 Alkyl sulphate - - 1.5 - 4 -HEDP 0.1 - -- 0.02 - 0.1 BHT - -- 0.1 -- - 0.05 DTPA 0.1 -- 0.15 0.1 0.15 -DETPMP - 0.15 -- -- -- 0.2 Tetraborate - -- 0.8 - - 1.0 Water and minors ---------up to 100%-- --------HEDP is 1-hydroxyethylene-diphosphonic acid DETPMP is diethyfene triamine penta methylene phosphonate DTPA is diethylene triamine pentacetate Alkyl sulfate is a C10 alkyl sulphate Betaine is coco alkyldimethyl betaine available from Albright 8 Wilson under the trade name of Empigen BBIL~.
Amine oxide is N-decyldimethyl amine oxide The compositions of the examples above are according to the present invention, they may be used neat or diluted, e.g., at a dilution level of 1:50 or of 1:25 (composition:water), to provide effective long lasting disinfecting performance on the surface treated.
surfactants are commercially available from SHELL. These LutensolR
surfactants are commercially avaitabte from BASF and these Tergitol R
surfactants are commercially available from UNION CARBIDE.
Other suitable surfactants also include C6-C20 conventional soaps (alkali metal salt of a C6-C20 fatty acid, preferably sodium salts).
Suitable amphoteric surfactants for use herein include amine oxides having the following formula R1R2R3N0 wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chains of from 1 to 30 carbon atoms. Preferred amine oxide surfactants to be used according to the present invention are amine oxides having the following formula R1 R2R3N0 wherein R1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups. R1 may be a saturated substituted or unsubstituted linear or branched hydrocarbon chain.
Suitable amine oxides for use herein are for instance natural blend C8-C10 amine oxides as well as C12-C16 amine oxides commercially available from Hoechst.
Suitable zwitterionic surfactants for use herein contain both cationic and anionic hydrophilic groups on the same molecule at a relatively wide range of pH's.
The typical cationic group is a quaternary ammonium group, although other positively charged groups like phosphonium, imidazolium and sulfonium groups can be used. The typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used. A
generic formula for some zwitterionic surfactants to be used herein is R1-N+(R2)(R3)R4X_ wherein R1 is a hydrophobic group; R2 and R3 are each C1-C4 alkyl, hydroxy alkyl or other substituted alkyl group which can also be joined to form ring structures with the N; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is preferably a carboxylate or sulfonate group. Preferred hydrophobic groups are alkyl groups containing from 1 to 24, preferably less than 18, more preferably less than 16 carbon atoms. The hydrophobic group can contain unsaturation and/or substituents and/or linking groups such as aryl groups, amido groups, ester groups and the like. In general, the simple alkyl groups are preferred for cost and stability reasons.
Highly preferred zwitterionic surfactants include betaine and sulphobetaine surfactants, derivatives thereof or mixtures thereof. Said betaine or sulphobetaine surfactants are preferred herein as they help disinfection by increasing the permeability of the bacterial cell wall, thus allowing other active ingredients to enter the cell.
Furthermore, due to the mild action profile of said betaine or sulphobetaine surfactants, they are particularly suitable for the cleaning of delicate surfaces, e.g., delicate laundry or surfaces in contact with food and/or babies. Betaine and sulphobetaine surfactants are also extremely mild to the skin and/or surfaces to be treated.
Suitable betaine and sulphobetaine surfactants for use herein are the betaine/sulphobetaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values. Some common examples of these detergents are described in U.S. Pat. Nos.
2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
Preferred betaine and sulphobetaine surfactants herein are according to the formula I
R1 - N+ - (CH2)n - Y-I
wherein R1 is a hydrocarbon chain containing from 1 to 24 carbon atoms, preferably from 8 to 18, more preferably from 12 to 14, wherein R2 and R3 are hydrocarbon chains containing from 1 to 3 carbon atoms, preferably 1 carbon atom, wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is 1, Y is selected from the group consisting of carboxyl and sulfonyl radicals and wherein the sum of R1, R2 and R3 hydrocarbon chains is from 14 to 24 carbon atoms, or mixtures thereof.
Examples of particularly suitable betaine surfactants include C12-C18 alkyl dimethyl betaine such as coconut-betaine and C10-C16 alkyl dimethyl betaine such as laurylbetaine. Coconutbetaine is commercially available from Seppic under the trade name of Amonyl 265~. Laurylbetaine is commercially available from Albright & Wilson under the trade name Empigen BB/L~.
Other specific zwitterionic surfactants have the generic formulas:
R1-C{O)-N(R2)-(C(R3)2)n-N{R2)2{+)-(C(R3)2)n-S03(-) or R1-C(O)-N(R2)-(C(R3)2)n-N(R2)2(+)-(C{R3)2)n-COO{-) wherein each R1 is a hydrocarbon, e.g. an alkyl group containing from 8 up to 20, preferably up to 18, more preferably up to 16 carbon atoms, each R2 is either a hydrogen (when attached to the amido nitrogen), short chain alkyl or substituted alkyl containing from one to 4 carbon atoms, preferably groups selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, preferably methyl, each R3 is selected from the group consisting of hydrogen and hydroxy groups and each n is a number from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R3)2) moiety. The R1 groups can be branched andlor unsaturated. The R2 groups can also be connected to form ring structures. A
surfactant of this type is a C10-C14 fatty acylamidopropylene(hydroxypropylene)sulfobetaine that is available from the Sherex Company under the trade name "Varion CAS sulfobetaine"~.
The compositions herein may further comprise a chelating agent as a preferred optional ingredient. Suitable chelating agents may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, aminophosphonate chelating agents, substituted heteroaromatic chelating agents, amino carboxylate chelating agents, other carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, biodegradable chelating agents like ethylene diamine N,N'- disuccinic acid, or mixtures thereof.
Suitable phosphonate chelating agents to be used herein include etidronic acid ('!-hydroxyethylene-diphosphonic acid (HEDP)), and/or alkali metal ethane 1-hydroxydiphosphonates.
Suitable amino phosphonate chelating agents to be used herein include amino alkylene poly (alkylene phosphonates), nitrilotris(methylene)triphosphonates, ethylene diamine tetra methylene phosphonates, and/or diethylene triamine penta methylene phosphonates. Preferred aminophosphonate chelating agents to be used herein are diethylene triamine yenta methylene phosphonates.
These phosphonate/amino phosphonate chelating agents may be present either in their acid form or as salts of different rations on some or all of their acid functionalities. Such phosphonate/amino phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST~.
Substituted heteroaromatic chelating agents to be used herein include hydroxypiridine-N-oxide or a derivative thereof.
Suitable hydroxy pyridine N-oxides and derivatives thereof to be used according to the present invention are according to the following formula:
I H
wherein X is nitrogen, Y is one of the following groups oxygen, -CHO, -OH, -(CH2)n-COOH, wherein n is an integer of from 0 to 20, preferably of from 0 to and more preferably is 0, and wherein Y is preferably oxygen. Accordingly particularly preferred hydroxy pyridine N-oxides and derivatives thereof to be used herein is 2-hydroxy pyridine N-oxide. Hydroxy pyridine N-oxides and derivatives thereof may be commercially available from Sigma.
Polyfunctionaliy-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US
patent 4, 10 704, 233, November 3, 1987 to Hartman and Perkins. Ethylenediamine N,N'-disuccinic acid is, for instance, commercially available under the tradename ssEDDSO from Palmer Research Laboratories. Ethylene diamine N,N'- disuccinic acid is particularly suitable to be used in the compositions of the present invention.
Suitable amino carboxylate chelating agents useful herein include ethylene 15 diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentoacetate (DTPA), N-hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetraproprionates, triethyienetetraaminehexa-acetates, ethanoldiglycines, propylene diamine tetracetic acid {PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms. Particularly suitable to be used herein are diethylene triamine yenta acetic acid (DTPA), propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS~ and methyl glycine di-acetic acid (MGDA).
Further carboxylate chelating agents to be used herein includes malonic acid, salicylic acid, glycine, aspartic acid, glutamic acid, or mixtures thereof.
Typically, the compositions according to the present invention comprise up to 5%
by weight of the total composition of a chelating agent, or mixtures thereof, preferably from 0.01 % to 3% by weight and more preferably from 0.01 % to 1.5%.
The compositions herein may comprise a radical scavenger as another optional ingredient. Suitable radical scavengers for use herein include the well-known substituted mono and di hydroxy benzenes and derivatives thereof, alkyl- and aryl carboxylates and mixtures thereof. Preferred radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), p-hydroxy-toluene, hydroquinone (HQ), di-tert-butyl hydroquinone (DTBHQ), mono-tert-butyl hydroquinone {MTBHQ), tert-butyl-hydroxy anysole {BHA), p-hydroxy-anysol, benzoic acid, 2,5-dihydroxy benzoic acid, 2,5-dihydroxyterephtalic acid, toluic acid, catechol, t-butyl catechol, 4-allyl-catechol, 4-acetyl catechol, 2-methoxy-phenol, 2-ethoxy-phenol, 2-methoxy-4-(2-propenyl)phenol, 3,4-dihydroxy benzaldehyde, 2,3-dihydroxy benzaldehyde, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, tert-butyl-hydroxy-anyline, p-hydroxy anyline as well as n-propyl-gallate.
Highly preferred for use herein are di-tert-butyl hydroxy toluene, which is for example commercially available from SHELL under the trade name IONOL CP~ and/or tert-butyl-hydroxy anysoie. These radical scavengers further contribute to the stability of the peroxygen bleach-containing compositions herein.
Typically, the compositions according to the present invention comprise up to 5%
by weight of the total composition of a radical scavenger, or mixtures thereof, preferably from 0.002% to 1.5% by weight and more preferably from 0.002% to 1 %.
The compositions herein may comprise as a preferred optional ingredient a solvent or mixtures thereof. When used, solvents will, advantageously, give an enhanced cleaning to the compositions herein. Suitable solvents for incorporation in the compositions according to the present invention include propylene glycol derivatives such as n-butoxypropanol or n-butoxypropoxypropanol, water-soluble CARBITOLO solvents or water-soluble CELLOSOLVE~ solvents. Water-soluble CARBITOLO solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl. A preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol.
Water-soluble CELLOSOLVE~ solvents are compounds of the 2-alkoxyethoxyethanol class, with 2-butoxyethoxyethanol being preferred. Other suitable solvents are benzyl alcohol, methanol, ethanol, isopropyl alcohol and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol and mixture thereof.
Preferred solvents for use herein are n-butoxypropoxypropanol, butyl carbitol~, benzyl alcohol, isopropanol and mixtures thereof. Most preferred solvents for use herein are butyl carbitol~, benzyl alcohol and/or isopropanol.
The solvents may typically be present within the compositions according to the invention at a level up to 15% by weight, preferably from 2% to 7% by weight of - the composition.
In the embodiment of the present invention wherein the compositions are formulated in the alkaline pH range, typically from 7.5 to 12, the compositions according to the present invention may further comprise a pH buffer or a mixture thereof, i.e. a system composed of a compound or a combination of compounds, whose pH changes only slightly when a strong acid or base is added.
Suitable pH buffers for use herein include borate pH buffer, phosphonate, silicate and mixtures thereof. Suitable borate pH buffers for use herein include alkali metal salts of borates and alkyl borates and mixtures thereof. Suitable borate pH
buffers to be used herein are alkali metal salts of borate, metaborate, tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride and/or alkyl borate containing from 1 to 12 carbon atoms, and preferably from 1 to 4. Suitable alkyl borate includes methyl borate, ethyl borate and propyl borate. Particularly preferred herein are the alkali metal salts of metaborate (e.g. sodium metaborate), tetraborate (e.g., sodium tetraborate decahydrate) or mixtures thereof.
Boron salts like sodium metaborate and sodium tetraborate are commercially available from Borax and Societa Chimica Larderelio under the trade name sodium metaborate~ and Borax~.
Typically, the compositions according to the present invention may comprise up to 15% by weight of the total composition of a pH buffer, or mixtures thereof, preferably from 0.01 % to 10%, more preferably from 0.01 % to 5% and most preferably from 0.1 % to 3%.
Packaging form of the compositions:
The compositions herein may be packaged in a variety of suitable detergent packaging known to those skilled in the art. The liquid compositions herein may desirably be packaged in manually operated spray-type dispensing containers, which are usually made of synthetic organic polymeric plastic materials, and preferably in a trigger spray dispenser or pump spray dispenser. Said spray-type dispensers allow to uniformly applied to a relatively large area of a surface to be treated the liquid disinfecting compositions of the present invention. Such spray-type dispensers are particularly suitable to treat vertical surfaces.
Suitable spray-type dispensers to be used according to the present invention include manually operated foam trigger-type dispensers sold for example by Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are disclosed, for instance, in US-4,701,311 to Dunnining et al.
and US-4,64fi,973 and US-4,538,745 both to Focarracci. Particularly preferred to be used herein are spray-type dispensers such as T 8500~ or T 8900~
commercially available from Continental Spray International or T 8100~
commercially available from Canyon, Northern Ireland. in such a dispenser the liquid composition is divided in fine liquid droplets resulting in a spray that is directed onto the surface to be treated. Indeed, in such a spray-type dispenser the composition contained in the body of said dispenser is directed through the spray-type dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism. More particularly, in said spray-type dispenser head the composition is forced against an obstacle, e.g. a grid or a cone or the like, thereby providing shocks to help atomise the liquid composition, i.e. to help the formation of liquid droplets.
The compositions of the present invention may also be executed in the form of wipes. By "wipes", it is meant herein disposable towels, e.g. paper towels, impregnated with a liquid composition according to the present invention.
Preferably said wipes are packaged in a plastic box. The advantage of this execution is a faster usage of a disinfecting composition by the user, this even outside the house, i.e. there is no need to pour the liquid compositions according to the present invention on the surfaces to be treated and to dry it out with a cloth. In other words, wipes allow immediate and long lasting disinfection of the surfaces in one step.
The compositions according to the present invention are used to treat a surface thereby delivering long lasting disinfection to said surface. By "treat", it is meant herein applying the composition to the surface in its neat (in the preferred embodiment herein wherein the composition is liquid) or diluted form.
By "diluted form", it is meant herein that the compositions to be used, being either in a liquid or a solid form, is diluted by the user typically with water up to 100 times their weight of water, preferably into 80 to 40 times their weight of water and more preferably 60 to 40, before being applied to the surface to treat.
By "surface", it is meant herein any surface including animate surface like human skin, mouth, teeth, and inanimate surfaces. Inanimate surfaces include, but are not limited to, hard-surfaces typically found in houses like kitchens, bathrooms, or in car interiors, e.g., tiles, walls, floors, chrome, glass, smooth vinyl, any plastic, plastified wood, table top, sinks, cooker tops, dishes, sanitary fittings such as sinks, showers, shower curtains, wash basins, WCs and the like, as well as fabrics including clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like, and carpets.
Inanimate surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
The present invention will be further illustrated by the following examples.
Examples The following compositions were made by mixing the listed ingredients in the listed proportions (weight % unless otherwise specified).
Compositions I II III IV V VI
by weight 5 Hydrogen peroxide 7.0 2.0 1.0 2.0 4.0 3.0 Thyme oil - 0.05 - -- 0.5 -Clove oil 0.5 - -- 0.05 - 0.1 Geranium oil - 0.07 - - - -Eucalyptus oil 0.2 - 0.02 0.01 - 0.2 10 Geraniol - -- 0.5 - 0.5 0.1 Alkyl sulphate 4 3 10 1 4 0.5 DETPMP 0.1 0.15 0.15 0.1 0.15 0.2 Water and minors --- --- ---up to 100%----- -H2S04 up to pH 4 Compositions VII Vlll IX X XI XII
by weight Hydrogen peroxide7.0 2.0 5.0 1.0 4.0 1.5 Thyme oil - 0.4 -- -- 0.5 --Clove oil 0.5 - -- 0.2 -- 0.1 Geranium oil - 0.2 -- -- - --Eucalyptus oil 0.2 - 0.2 0.2 - 0.2 Geraniol - - 0.15 - 0.005 0.1 Betaine 1.5 0.1 - 0.03 - 0.1 Amine oxide 3 1.2 1.0 1 - 1.0 Alkyl sulphate - - 1.5 - 4 -HEDP 0.1 - -- 0.02 - 0.1 BHT - -- 0.1 -- - 0.05 DTPA 0.1 -- 0.15 0.1 0.15 -DETPMP - 0.15 -- -- -- 0.2 Tetraborate - -- 0.8 - - 1.0 Water and minors ---------up to 100%-- --------HEDP is 1-hydroxyethylene-diphosphonic acid DETPMP is diethyfene triamine penta methylene phosphonate DTPA is diethylene triamine pentacetate Alkyl sulfate is a C10 alkyl sulphate Betaine is coco alkyldimethyl betaine available from Albright 8 Wilson under the trade name of Empigen BBIL~.
Amine oxide is N-decyldimethyl amine oxide The compositions of the examples above are according to the present invention, they may be used neat or diluted, e.g., at a dilution level of 1:50 or of 1:25 (composition:water), to provide effective long lasting disinfecting performance on the surface treated.
Claims (10)
1. The use, in a composition, of a peroxygen bleach and an antimicrobial essential oil or an active thereof or a mixture thereof, for long lasting disinfection on a surface treated with said composition.
2. The use according to claim 1 wherein said antimicrobial essential oil or an active thereof or a mixture thereof is present in said composition at a level of at least 0.003% by weight of the total composition, preferably from 0.006% to 10%, more preferably from 0.1 % to 8% and most preferably from 0.03% to 3%.
3. The use according to any of the preceding claims wherein said antimicrobial essential oil is selected from the group consisting of thyme oil, lemongrass oil, citrus oil, lemon oil, orange oil, ajowan oil, anise oil, clove oil, aniseed oil, cinnamon oil, geranium oil, rose oil, lavender oil, citronella oil, eucalyptus oil, peppermint oil, mint oil, camphor oil, sandalwood oil, cedar oil, rosmarin oil, pine oil, vervain oil, fleagrass oil, lemongrass oil, ratanhiae oil and mixtures thereof, and preferably is thyme oil, ajowan oil, citronella oil, clove oil, cinnamon oil, geranium oil, eucalyptus oil, peppermint oil, mint oil or a mixture thereof, and/or wherein said active of essential oil is selected from the group consisting of thymol, eugenol, menthol, carvacrol, verbenone, eucalyptol, cedrol, anethol, pinocarvone, geraniol, hinokitiol, berberine, ferulic acid, cinnamic acid, methyl salicylic acid, methyl salicylate, terpineol, limonene and mixtures thereof, and preferably is thymol, eugenol, verbenone, eucalyptol, terpineol, cinnamic acid, methyl salicylic acid, limonene, geraniol or a mixture thereof.
4. The use according to any of the preceding claims wherein said peroxygen bleach or a mixture thereof is present in said composition at a level of at least 0.01 % by weight of the total composition, preferably from 0.1 % to 15%, and more preferably from 1% to 10%.
5. The use according to any of the preceding claims wherein said peroxygen bleach is hydrogen peroxide and/or a water soluble source thereof typically selected from the group consisting of percarbonate, persilicate, persulphate, perborate, peroxyacid, dialkylperoxide, diacylperoxide, preformed percarboxylic acid, organic and inorganic peroxides, organic and inorganic hydroperoxides and mixtures thereof, more preferably is hydrogen peroxide.
6. The use according to any of the preceding claims wherein said composition further comprises a surfactant up to a level of 50% by weight of the total composition, typically selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof.
7. The use according to claim 6 wherein said surfactant is an amphoteric surfactant, preferably an amine oxide and/or a zwitterionic surfactant, preferably a betaine or sulfobetaine surfactant, and/or an anionic surfactant, preferably a C8-C16 alkyl sulfonate, C8-C16 alkyl sulfate and/or C8-C16 alkyl alkoxylated sulfate.
8. The use according to any of the preceding claims wherein said composition further comprises at least an ingredient selected from the group consisting of chelants, solvents, builders, stabilisers, bleach activators, soil suspenders, dye transfer agents, brighteners, perfumes, anti dusting agents, enzymes, dispersant, dye transfer inhibitors, pigments, perfumes, radical scavengers, dyes, and mixtures thereof.
9. The use according to any of the preceding claims wherein said composition is a liquid composition, preferably an aqueous composition having a pH of not more than 12, more preferably from 1 to 10 and most preferably from 2 to 9.
10. The use according to any of the preceding claims wherein said composition further comprises a pH buffer or a mixture thereof, preferably a borate pH
buffer, more preferably an alkali metal salt of borate, metaborate, tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride, or an alkyl borate containing from 1 to 12 carbon atoms, or a mixture thereof, up to a level of 15% by weight of the total composition, preferably from 0.01%
to 10% and more preferably from 0.1% to 3%.
buffer, more preferably an alkali metal salt of borate, metaborate, tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride, or an alkyl borate containing from 1 to 12 carbon atoms, or a mixture thereof, up to a level of 15% by weight of the total composition, preferably from 0.01%
to 10% and more preferably from 0.1% to 3%.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1997/009260 WO1998054279A1 (en) | 1997-05-30 | 1997-05-30 | Disinfecting compositions and processes for disinfecting surfaces |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2293703A1 true CA2293703A1 (en) | 1998-12-03 |
Family
ID=22260986
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002293703A Abandoned CA2293703A1 (en) | 1997-05-30 | 1997-05-30 | Disinfecting compositions and processes for disinfecting surfaces |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0985015A1 (en) |
JP (1) | JP2002502391A (en) |
KR (1) | KR20010013210A (en) |
AU (1) | AU3221497A (en) |
CA (1) | CA2293703A1 (en) |
CO (1) | CO4950548A1 (en) |
IL (1) | IL133187A0 (en) |
MA (1) | MA24556A1 (en) |
PE (1) | PE77199A1 (en) |
SK (1) | SK163899A3 (en) |
TR (1) | TR200000110T2 (en) |
WO (1) | WO1998054279A1 (en) |
ZA (1) | ZA984593B (en) |
Families Citing this family (30)
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DE19838079A1 (en) * | 1998-08-21 | 2000-02-24 | Dragoco Gerberding Co Ag | Fragrance |
GB9902665D0 (en) * | 1999-02-05 | 1999-03-31 | Mandops Uk Ltd | Foliar fertiliser |
US7090916B2 (en) * | 1999-04-30 | 2006-08-15 | Cathm, Llc | Paper product for use in sterilizing an area |
US6325969B1 (en) | 1999-04-30 | 2001-12-04 | James Aamodt | Paper product impregnated with chemical material |
DE19962343A1 (en) | 1999-12-23 | 2001-07-05 | Henkel Ecolab Gmbh & Co Ohg | Disinfectant washing of delicate textiles with peracids |
US20020061282A1 (en) * | 2000-10-11 | 2002-05-23 | Constantine Georgiades | Tooth whitening composition and method employing dicarboxylic acid whitening agent |
JP4600967B2 (en) * | 2001-09-17 | 2010-12-22 | 株式会社カネボウ化粧品 | Antibacterial composition and cosmetics and external preparation for skin |
CA2558266C (en) * | 2004-03-05 | 2017-10-17 | Gen-Probe Incorporated | Reagents, methods and kits for use in deactivating nucleic acids |
JP2008514596A (en) * | 2004-09-24 | 2008-05-08 | ミシガン ステイト ユニバーシティー | Composition without carrier for the treatment of onychomycosis |
JP2006104076A (en) * | 2004-09-30 | 2006-04-20 | Kobayashi Pharmaceut Co Ltd | Composition for nasal foramen |
US7258878B2 (en) | 2004-12-20 | 2007-08-21 | Kimberly-Clark Worldwide, Inc. | Anti-microbial composition and methods of use thereof |
FR2900940B1 (en) * | 2006-05-12 | 2008-07-18 | Univ Montpellier Ii | "MATERIALS BASED ON A FIBROUS, WIRED OR NON-WOVEN FIBER COATED WITH A MATRIX, CONTAINING AT LEAST ONE ANTIMICROBIAL AGENT AND METHOD OF MANUFACTURING" |
WO2009098243A1 (en) | 2008-02-06 | 2009-08-13 | Janssen Pharmaceutica Nv | Combinations of anilinopyrimidines and pyrion compounds |
BRPI0914031B1 (en) | 2008-10-20 | 2023-12-12 | Unilever Ip Holdings B.V. | USE OF A HAND HYGIENE COMPOSITION |
MX2012003563A (en) | 2009-09-24 | 2012-04-30 | Unilever Nv | Disinfecting agent comprising eugenol, terpineol and thymol. |
EP2579718B1 (en) | 2010-06-10 | 2014-10-01 | Janssen Pharmaceutica, N.V. | Combinations of pyrimethanil and monoterpenes |
FR2967553B1 (en) * | 2010-11-24 | 2013-06-28 | Xeda International | NEW PROCESS FOR TREATING PLANT PRODUCTS BEFORE OR AFTER HARVESTING WITH PHOSPHONIC ACID AND ROOT OIL |
BR112013013085B1 (en) | 2010-12-07 | 2018-02-14 | Unilever N.V. | Oral Care Composition, Mouth Rinse, Toothpaste, Toothpaste, Method for Disinfecting Oral Cavity and Use of a Composition |
US9949477B2 (en) | 2010-12-30 | 2018-04-24 | Kimberly-Clark Worldwide, Inc. | Durable antimicrobial composition |
US9693941B2 (en) | 2011-11-03 | 2017-07-04 | Conopco, Inc. | Liquid personal wash composition |
WO2014073731A1 (en) * | 2012-11-09 | 2014-05-15 | (주)크린바이오 | Antifungal composition using natural plant-based oils |
CN103584256B (en) * | 2013-11-26 | 2015-07-22 | 青岛嘉瑞生物技术有限公司 | Natural food preservative prepared by utilizing ulva resource development and preparation method |
CN105052952A (en) * | 2015-08-03 | 2015-11-18 | 佛山市顺德区宝铜金属科技有限公司 | Seed treatment agent |
KR20170021573A (en) | 2015-08-18 | 2017-02-28 | 허진희 | External use sanitizers containing hinoki cypress leaf extract and lemon leaf extract and manufacturing method of the same |
KR102238172B1 (en) * | 2018-12-28 | 2021-04-19 | 주식회사 코드스테리 | Sterilizer for room and medical instruments using dual type plasma platform |
CN114080219B (en) * | 2019-07-05 | 2024-08-20 | 宝洁公司 | Personal care cleansing compositions |
KR102170702B1 (en) | 2019-09-05 | 2020-10-27 | (주)피치켐 | Disinfectant composition including citric acid and catalase |
KR102376979B1 (en) | 2019-12-31 | 2022-03-21 | (주)피치켐 | Disinfectant composition with enhanced antiviral effects |
CN111893000B (en) * | 2020-08-04 | 2022-03-08 | 韶关浪奇有限公司 | Non-phosphorus detergent for dish-washing machine and preparation process thereof |
KR20230087687A (en) | 2021-12-09 | 2023-06-19 | (주)피치켐 | Disinfectact compositions having antiviral effects |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3702983A1 (en) * | 1986-06-09 | 1987-12-10 | Henkel Kgaa | DISINFECTANT AND THEIR USE FOR SKIN AND MUCUS SKIN DISINFECTION |
FR2601850B1 (en) * | 1986-07-25 | 1990-05-04 | Garcin Francoise | ANTISEPTIC COMPOSITION INCORPORATING ESSENTIAL OILS. |
AU1890292A (en) * | 1991-04-19 | 1992-11-17 | Procter & Gamble Company, The | Antimicrobial oral compositions |
-
1997
- 1997-05-30 AU AU32214/97A patent/AU3221497A/en not_active Abandoned
- 1997-05-30 IL IL13318797A patent/IL133187A0/en unknown
- 1997-05-30 JP JP50061499A patent/JP2002502391A/en active Pending
- 1997-05-30 SK SK1638-99A patent/SK163899A3/en unknown
- 1997-05-30 EP EP97927857A patent/EP0985015A1/en not_active Withdrawn
- 1997-05-30 KR KR19997011197A patent/KR20010013210A/en not_active Application Discontinuation
- 1997-05-30 CA CA002293703A patent/CA2293703A1/en not_active Abandoned
- 1997-05-30 TR TR2000/00110T patent/TR200000110T2/en unknown
- 1997-05-30 WO PCT/US1997/009260 patent/WO1998054279A1/en not_active Application Discontinuation
-
1998
- 1998-05-27 MA MA25091A patent/MA24556A1/en unknown
- 1998-05-28 ZA ZA984593A patent/ZA984593B/en unknown
- 1998-05-29 PE PE1998000435A patent/PE77199A1/en not_active Application Discontinuation
- 1998-06-01 CO CO98030689A patent/CO4950548A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
IL133187A0 (en) | 2001-03-19 |
CO4950548A1 (en) | 2000-09-01 |
TR200000110T2 (en) | 2000-08-21 |
EP0985015A1 (en) | 2000-03-15 |
MA24556A1 (en) | 1998-12-31 |
SK163899A3 (en) | 2000-08-14 |
ZA984593B (en) | 1999-03-16 |
WO1998054279A1 (en) | 1998-12-03 |
KR20010013210A (en) | 2001-02-26 |
AU3221497A (en) | 1998-12-30 |
PE77199A1 (en) | 1999-08-25 |
JP2002502391A (en) | 2002-01-22 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |