WO1998056889A1 - Compositions de nettoyage des aliments renfermant de la cyclodextrine - Google Patents
Compositions de nettoyage des aliments renfermant de la cyclodextrine Download PDFInfo
- Publication number
- WO1998056889A1 WO1998056889A1 PCT/US1998/012159 US9812159W WO9856889A1 WO 1998056889 A1 WO1998056889 A1 WO 1998056889A1 US 9812159 W US9812159 W US 9812159W WO 9856889 A1 WO9856889 A1 WO 9856889A1
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- WO
- WIPO (PCT)
- Prior art keywords
- composition
- cyclodextrin
- optionally
- food
- weight
- Prior art date
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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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/06—Processes in which the treating agent is dispersed in a gas, e.g. aerosols
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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
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/046—Aerosols; Foams
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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
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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
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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
- A61K8/35—Ketones, e.g. benzophenone
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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
- A61K8/37—Esters of carboxylic acids
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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
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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
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/738—Cyclodextrins
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- A—HUMAN NECESSITIES
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- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/90—Block copolymers
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- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/925—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of animal origin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/14—Disinfection, sterilisation or deodorisation of air using sprayed or atomised substances including air-liquid contact processes
- A61L9/145—Disinfection, sterilisation or deodorisation of air using sprayed or atomised substances including air-liquid contact processes air-liquid contact processes, e.g. scrubbing
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
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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
- C11D1/008—Polymeric surface-active agents
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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
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/046—Insoluble free body dispenser
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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
- C11D3/0068—Deodorant 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
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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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
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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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3738—Alkoxylated silicones
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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
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
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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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- 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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- 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
- C11D3/502—Protected perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/005—Compositions containing perfumes; Compositions containing deodorants
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
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Definitions
- the present invention relates to stable, preferably clear, aqueous food cleaning compositions, articles of manufacture, and/or method of use, comprising: solubilized, uncomplexed cyclodextrin; cyclodextrin compatible surfactant; optionally, cyclodextrin compatible antimicrobial active; optionally, hydrophilic perfume providing improved acceptance; or mixtures thereof.
- cyclodextrin compatible means that the cyclodextrin and the other material, or active, do not substantially interact so as to eliminate the ability of cyclodextrin to absorb odor and other undesirable organic molecules, or the desired effect of the material or active.
- the food cleaning composition is designed to remove and/or eliminate undesirable materials, such as soil, organic residue materials such as pesticides, odors caused by a broad spectrum of organic odoriferous materials, on food products and/or food contacting surfaces, such as produce, fruits and vegetables, meat, poultry, fish and other seafoods, food preparing surfaces and/or equipment, such as cutting board, countertop, pots and pans, food containers, and the like.
- undesirable materials such as soil, organic residue materials such as pesticides, odors caused by a broad spectrum of organic odoriferous materials
- food products and/or food contacting surfaces such as produce, fruits and vegetables, meat, poultry, fish and other seafoods, food preparing surfaces and/or equipment, such as cutting board, countertop, pots and pans, food containers, and the like.
- the food cleaning composition preferably remain shelf stable for a substantial period of time.
- Typical examples of such chemical residues are Azinphos- methyl (insecticide for apples, peaches), Benomyl (fungicide for apples, peaches, tomatoes, cucumbers, broccoli, beans), Captan (fungicide for apples, peaches, cucumbers), Chorothalonil (fungicide for tomatoes, carrots, beans, cucumbers, broccoli) Chlorpropham (sprouting inhibitor for potatoes), Dicloran (fungicide for peaches), diphenyl amine (screw worm repellant and post harvest fungicide for apples), Folpet (fungicide for tomatoes), Iprodione (fungicide for peaches, grapes), Linuron (herbicide for carrots), Permethrin (insecticide for lettuce), thiabendazole (fungicide and nematocide for bananas, potatoes, apples) and Vinclozolin (fungicide for grapes, strawberries).
- Azinphos- methyl insecticide for apples, peaches
- Benomyl fungicide for apples, peaches, tomatoes, cucumbers, broccoli
- dishwashing products are not specifically intended for such use, inasmuch as they are usually designed to provide high, persistent suds which makes them inconvenient to remove from the fruits or vegetables which have been washed therewith.
- Uncooked food such as meat, poultry, fish and other seafoods can have particular odor, especially when they are stored and/or frozen for some time and are not fresh.
- Other food especially condiments such as garlic, onion, curry, can leave a noticeable and undesirable odor on food preparing surfaces such as cutting boards and wooden spoons, which are very difficult to remove.
- Liquid solutions are convenient for the user, since they can be applied directly to soiled fruits, vegetables, and other food and food contacting surfaces, followed by rinsing in tap water.
- the present invention relates to stable, preferably clear, aqueous food cleaning and odor absorbing compositions, articles of manufacture and/or method for use.
- the clarity of the liquids connotes cleanliness to the user and is thus highly desirable.
- the compositions are sprayed onto food products and surfaces, with optional scrubbing, and rinsed off, to remove unwanted residues and/or to restore their freshness by reducing the unwanted off-odor.
- Low sudsing is an important attribute so that removal of the solution by rinsing is achieved quickly and easily. It is also advantageous if such compositions are provided in the form of concentrates, which can be diluted by the consumer before use and/or applied to the fruits, vegetables and other food as a direct spray-on.
- Uncomplexed cyclodextrin molecules which are made up of varying numbers of glucose units can absorb many organic materials, such as the chemical residues and off-odor molecules listed hereinabove to improve their removability. While cyclodextrin is an effective absorbing active for organic molecules, some small molecules are not sufficiently absorbed by the cyclodextrin molecules because the cavity of the cyclodextrin molecule may be too large to adequately hold the smaller organic molecule. If a small sized organic odor molecule is not sufficiently absorbed into the cyclodextrin cavity, a substantial amount of malodor can remain.
- low molecular weight polyols can be added to the composition to enhance the formation of cyclodextrin inclusion complexes.
- optional water soluble metal salts can be added to complex with some nitrogen-containing and sulfur-containing malodor molecules.
- compositions contain a cyclodextrin compatible and food approved surfactant to provide the cleaning performance and to improve the removal of dirt and other undesirable materials.
- compositions can optionally provide a "scent signal" in the form of a pleasant odor, such as a fruity odor, which signals the removal of the malodor and/or other undesirable materials. It is desirable to provide further improvements such as a cyclodextrin compatible and food compatible antimicrobial active that provides substantial reduction of microorganisms that cause, e.g., odor, infections, etc., which exist on food and/or food preparation surfaces. It is more preferable that the food cleaning compositions of the present invention contain both a antibacterial active and a surfactant, with both being cyclodextrin compatible and food compatible.
- cyclodextrin can be an organic nutrient for certain microorganisms, especially when in aqueous compositions, it is preferable to include a water-soluble and food compatible antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth, to increase storage stability of clear, aqueous food cleaning and odor-absorbing solutions containing water-soluble cyclodextrin, when the composition does not contain an antimicrobial material as described hereinbelow.
- a cyclodextrin-compatible active is one which does not substantially form a complex with cyclodextrin in the composition, at the usage concentration, so that an effective amount of both the free, uncomplexed active and free, uncomplexed cyclodextrin are available for their intended use.
- the materials incorporated in the food cleaning compositions of the present invention to be food compatible, e.g., suitable for direct or indirect food contact use and/or may be approved as GRAS, prior sanctioned, or subject to GRAS approval via a GRAS petition, for example, a new chemical developed for this invention, and/or toxicologically acceptable to humans under usage conditions.
- Materials added to foods may be categorized as one of several types: (1) direct food additives; (2) indirect food additives; (3) GRAS ingredients (generally recognized as safe) either as direct or indirect food substances; (4) GRAS affirmed, a chemical which may be considered for GRAS classification after experts review adequate technical support data for the GRAS petition; and (5) prior sanctioned, a food ingredient of known food use and granted approval with respect to use of the substance in food prior to September 1958, by the FDA, or USDA.
- Food additives include substances the intended use of which results or may reasonably be expected to result, directly or indirectly, either in their becoming a component of food or otherwise affecting the characteristics of food.
- a material used in the production of food containers and/or packaging materials is subject to the definition if it may become an ingredient in the food, or to affect the characteristics, directly or indirectly, of the food in the container or package.
- direct food additive are those materials which are added directly to foods to achieve a desirable or intended purpose.
- Indirect food additives are those which are added to food containers and/or packages, and which may result in the food simply because of contact of the container/package with the food.
- Indirect food additives may include: (1) adhesives and components of coatings; (2) paper and paperboard components; (3) adjuvants, such as those used in the manufacture of foamed plastics, and sanitizers.
- Sanitizers used in food applications are many and may consists of, but are not limited to: (1) aqueous hypochlorite (K, Na or Ca salts); (2) aqueous solution of dichloroisocyanuric acid, trichloroisocyanuric acid, or the sodium or potassium salts of these acids, with or without the bromides of potassium, sodium, or calcium; (3) anionic surfactant solutions such as dodecylbenzene sulfonic acid, and/or sodium lauryl sulfate; or mixtures of these together or with other anionic surfactants as allowed under FDA regulations; (4) aqueous fatty acid solutions containing decanoic acid, octanoic acid, lactic acid and other ingredients; (5) aqueous solutions comprised of
- Direct GRAS ingredients shall be used under current good manufacturing practice which includes that a direct human food ingredient be of appropriate food grade; that it be prepared and handled as a food ingredient, and that the quantity of the ingredient added to food does not exceed the amount reasonably required to accomplish the intended physical, nutritional, or other technical effect in the food item.
- Indirect GRAS ingredients are those which may be used in the container, packaging and/or wrapper, and which may migrate into the food items because of their close proximity to the food.
- Indirect GRAS ingredients shall be used under current good manufacturing practice which includes that an indirect human food ingredient be of appropriate purity; and that the quantity of the ingredient added to food container, packaging, wrapper, etc. does not exceed the amount reasonably required to accomplish the intended physical, nutritional, or other technical effect in the food-contact item.
- the present invention relates to a stable, preferably clear, preferably aqueous, food cleaning composition, preferably for use on food and food contacting surfaces, such as food preparing equipment and/or food containers, comprising:
- cyclodextrin compatible surfactant that preferably provides a surface tension of from about 20 dyne/cm to about 60 dyne/cm, preferably from about 20 dyne/cm to about 45 dyne/cm (with concentrated compositions having a level of from about 0.1% to about
- an effective amount, to kill, or reduce the growth of microbes, of cyclodextrin compatible and water soluble antimicrobial active preferably from about 0.001% to about 0.8%, more preferably from about 0.002% to about 0.3%, even more preferably from about 0.003%) to about 0.2%, by weight of the usage composition (with concentrated compositions having a level of from about 0.003% to about 2%, preferably from about 0.01% to about 1.2%, more preferably from about 0.1% to about 0.8%, by weight of the concentrated solution, of cyclodextrin-compatible and water soluble antimicrobial active); (D).
- an effective amount of sequestrant/builder to improve cleaning preferably from about 0.0005% to about 3%, more preferably from about 0.005% to about 0.5%, and even more preferably from about 0.01% to about 0.2%, by weight of the usage composition;
- an effective amount to improve acceptance of the composition typically from about 0.003% to about 0.5%, preferably from about 0.01% to about 0.3%, more preferably from about 0.05% to about 0.2%, by weight of the usage composition of hydrophilic perfume, containing at least about 50%, preferably at least about 60%, more preferably at least about 60%, even more preferably at least about 70%, and yet more preferably at least about 80%, by weight of the perfume of perfume ingredients that have a ClogP of less than about 3.5 and optionally, a minor amount of perfume ingredients selected from the group consisting of ambrox, bacdanol, benzyl salicylate, butyl anthranilate, cetalox, damascenone, alpha- damascone, gamma-dodecalactone, ebanol, herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-ionone, alpha-isomethylionone,
- (F) optionally, but preferably, from about 0.01% to about 3%, more preferably from about 0.05% to about 1%, and even more preferably from about 0.1% to about 0.5%, by weight of the usage composition of low molecular weight polyol;
- (G). optionally, from about 0.001% to about 0.3%, preferably from about
- chelator e.g., aminocarboxylate chelator
- H e.g., aminocarboxylate chelator
- I optionally, but preferably, an effective of metallic salt, preferably from about 0.1%) to about 10%, more preferably from about 0.2% to about
- adjunct odor-controlling ingredients preferably selected from the group consisting of alkali carbonate and bicarbonate salts, low molecular weight water soluble ionic polymers, and mixtures thereof; and preferably present at a level of from about 0.005% to about 5%, more preferably from about 0.01% to about 3%, and even more preferably from about 0.1% to about 2%, by weight of the usage composition; and (M). aqueous carrier, said composition containing at least one of (B) and (C), and preferably containing only ingredients which are food compatible.
- the present invention also relates to concentrated compositions, wherein the level of cyclodextrin is from about 3% to about 20%, more preferably from about 5% to about 10%), by weight of the composition which are diluted to form compositions with the usage concentrations of cyclodextrin of, e.g., from about 0.1%) to about 5%o, by weight of the diluted composition, as given hereinabove, which are to the "usage conditions".
- the present invention also relates to the food cleaning compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of food surfaces with said compositions containing uncomplexed cyclodextrin and other optional ingredients at a level that is effective.
- Said compositions and/or article of manufacture are preferably in association with instructions to use said compositions and product at an effective level to remove undesirable materials from food and/or food preparation surfaces.
- the present invention also relates to methods of using said food cleaning composition, either alone, or incorporated into a spray dispenser, to remove and/or eliminate undesirable materials, such as soil, pesticides, odors caused by a broad spectrum of organic odoriferous materials, from food products, such as produce, fruits and vegetables, meat, poultry, fish and other seafoods, and/or food preparing surfaces, such as cutting board, countertop, pots and pans, food containers, and the like.
- undesirable materials such as soil, pesticides, odors caused by a broad spectrum of organic odoriferous materials
- the present invention relates to a stable, preferably clear, aqueous food cleaning composition, preferably for use on food and food contacting surfaces, such as food preparing equipment and/or food containers, comprising: (A). an effective amount to remove organic residue materials and/or absorb malodors, typically from about 0.01% to about 20% by weight of the composition, with concentrated compositions which are meant to be diluted containing from about 3% to about 20%, preferably from about 5% to about 10% by weight of the composition, and, for more dilute "usage conditions" compositions, a range of from about 0.01%) to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.5% to about 2%, by weight of the usage composition, of solubilized, uncomplexed cyclodextrin;
- cyclodextrin compatible surfactant that preferably provides a surface tension of from about 20 dyne/cm to about 60 dyne/cm, preferably from about 20 dyne/cm to about 45 dyne/cm (with concentrated compositions having a level of from about 0.1% to about
- an effective amount of sequestrant/builder to improve cleaning preferably from about 0.0005% to about 3%, more preferably from about 0.005% to about 0.5%, and even more preferably from about 0.01% to about 0.2%, by weight of the usage composition;
- (E). optionally, but preferably, an effective amount to improve acceptance of the composition, typically from about 0.003% to about 0.5%), preferably from about 0.01% to about 0.3%, more preferably from about 0.05% to about 0.2%, by weight of the usage composition of hydrophilic perfume, containing at least about 50%, preferably at least about 60%, more preferably at least about 60%, even more preferably at least about 70%, and yet more preferably at least about 80%, by weight of the perfume of perfume ingredients that have a ClogP of less than about 3.5 and optionally, a minor amount of perfume ingredients selected from the group consisting of ambrox, bacdanol, benzyl salicylate, butyl anthranilate, cetalox, damascenone, alpha- damascone, gamma-dodecalactone, ebanol, herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-ionone, alpha-isomethylion
- (F) optionally, but preferably, from about 0.01%o to about 3%>, more preferably from about 0.05% to about 1%, and even more preferably from about 0.1% to about 0.5%, by weight of the usage composition of low molecular weight polyol;
- the usage composition of chelator e.g., aminocarboxylate chelator; (H). optionally, from about 0.01% to about 2%, preferably from about 0.05% to about 1%, more preferably from about 0.1% to about 0.5%, by weight of the usage composition of antifoaming agent; (I). optionally, but preferably, an effective of metallic salt, preferably from about 0.1%) to about 10%>, more preferably from about 0.2% to about
- adjunct odor-controlling ingredients preferably selected from the group consisting of alkali carbonate and bicarbonate salts, low molecular weight water soluble ionic polymers, and mixtures thereof; and preferably present at a level of from about 0.005%) to about 5%, more preferably from about 0.01% to about 3% ⁇ , and even more preferably from about 0.1% to about 2%, by weight of the usage composition; and (M).
- aqueous carrier said composition containing at least one of (B) and (C), and containing, essentially, only ingredients which are food compatible, and/or preferably having a pH of more than about 3, more preferably more than about 3.5, said composition optionally being packaged in a container that is capable of dispensing said composition as either 1) small droplets having a weight average diameter of from about 10 ⁇ m to about 120 ⁇ m. and/or 2) a foam, said container optionally being part of an article of manufacture which also comprises non-manually operated spray means, and/or said composition being packaged in association with instructions to use it to clean and/or deodorize food and/or food contact surfaces.
- the present invention also relates to concentrated compositions, wherein the level of cyclodextrin is from about 3%o to about 20%, preferably from about 4% to about 15%, more preferably from about 5% to about 10%, by weight of the concentrated composition.
- the concentrated composition is typically diluted to form usage compositions, with the usage concentration of, e.g., from about 0.1% to about 5%, by weight of the usage composition, as given hereinabove. Specific levels of other optional ingredients in the concentrated composition can readily be determined from the desired usage composition and the desired degree of concentration.
- cyclodextrin includes any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives and/or mixtures thereof.
- the alpha-cyclodextrin consists of six glucose units
- the beta-cyclodextrin consists of seven glucose units
- the gamma-cyclodextrin consists of eight glucose units arranged in donut-shaped rings.
- the specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structures with hollow interiors of specific volumes.
- the "lining" of each internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms; therefore, this surface is fairly hydrophobic.
- the unique shape and physical-chemical properties of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity.
- cyclodextrins and especially mixtures of cyclodextrins with different size cavities, can be used to improve removal of such undesirable materials and odors by forming more water soluble complexes.
- the undesirable odorous materials can be degradation products of food, caused by oxidation and/or bacterial degradation, or the residual odor of the food itself, such as condiments and spices, that remains and lingers on food preparing surfaces.
- the complexation between cyclodextrin and organic materials occurs rapidly in the presence of water.
- the cavities within the cyclodextrin in the solution of the present invention should remain essentially unfilled (the cyclodextrin remains uncomplexed) while in solution, in order to allow the cyclodextrin to absorb various undesirable organic molecules when the solution is applied to a food surface.
- Non-derivatised (normal) beta-cyclodextrin can be present at a level up to its solubility limit of about 1.85% (about 1.85g in 100 grams of water) at room temperature.
- Beta-cyclodextrin is a GRAS affirmed material, and is preferred in the compositions of the present invention.
- Beta-cyclodextrin is not preferred in compositions which call for a level of cyclodextrin higher than its water solubility limit.
- the food cleaning composition of the present invention is clear.
- clear as defined herein means transparent or translucent, preferably transparent, as in “water clear,” when observed through a layer having a thickness of less than about 10 cm.
- the cyclodextrins used in the present invention are highly water- soluble such as, alpha-cyclodextrin and/or derivatives thereof, gamma-cyclodextrin and/or derivatives thereof, derivatised beta-cyclodextrins, and/or mixtures thereof.
- the derivatives of cyclodextrin consist mainly of molecules wherein some of the OH groups are converted to OR groups.
- Cyclodextrin derivatives include, e.g., those with short chain alkyl groups such as methylated cyclodextrins, and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those with hydroxyalkyl substituted groups, such as hydroxypropyl cyclodextrins and/or hydroxyethyl cyclodextrins, wherein R is a -CH 2 -CH(OH)-CH 3 or a "CH2CH 2 -OH group; branched cyclodextrins such as maltose-bonded cyclodextrins; cationic cyclodextrins such as those containing 2-hydroxy-3-(dimethylamino)propyl ether, wherein R is CH2 ⁇ CH(OH)-CH2-N(CH3)2 which is cationic at low pH; quaternary ammonium, e.g., 2-hydroxy-3
- Highly water-soluble cyclodextrins are those having water solubility of at least about 10 g in 100 ml of water at room temperature, preferably at least about 20 g in 100 ml of water, more preferably at least about 25 g in 100 ml of water at room temperature.
- the availability of solubilized, uncomplexed cyclodextrins is essential for effective and efficient odor control performance. Solubilized, water-soluble cyclodextrin can exhibit more efficient removal of undesirable materials.
- Examples of preferred water-soluble cyclodextrin derivatives suitable for use herein are hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin.
- Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from about 1 to about 14, more preferably from about 1.5 to about 7, wherein the total number of OR groups per cyclodextrin is defined as the degree of substitution.
- Methylated cyclodextrin derivatives typically have a degree of substitution of from about 1 to about 18, preferably from about 3 to about 16.
- a known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl- ⁇ -cyclodextrin, commonly known as DIMEB, in which each glucose unit has about 2 methyl groups with a degree of substitution of about 14.
- DIMEB heptakis-2,6-di-O-methyl- ⁇ -cyclodextrin
- a preferred, more commercially available, methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin, commonly known as RAMEB, having different degrees of substitution, normally of about 12.6.
- RAMEB is more preferred than DIMEB, since DIMEB affects the surface activity of the preferred surfactants more than RAMEB.
- the preferred cyclodextrins are available, e.g., from Cerestar USA, Inc. and Wacker Chemicals (USA), Inc.
- cyclodextrins absorb odors more broadly by complexing with a wider range of odoriferous molecules having a wider range of molecular sizes.
- the cyclodextrins is alpha-cyclodextrin and its derivatives thereof, gamma-cyclodextrin and its derivatives thereof, and/or derivatised beta-cyclodextrin, more preferably a mixture of alpha-cyclodextrin, or an alpha-cyclodextrin derivative, and derivatised beta-cyclodextrin, even more preferably a mixture of derivatised alpha-cyclodextrin and derivatised beta-cyclodextrin, most preferably a mixture of hydroxypropyl alpha- cyclodextrin and hydroxypropyl beta-cyclodextrin, and/or a mixture of methylated alpha-cyclodextrin
- the composition is preferably used as a spray. It is preferable that the usage compositions of the present invention contain low levels of cyclodextrin for efficiency and removal reasons. Preferably, the solution used to treat the surface under usage conditions is virtually not discernible after rinsing. Typical levels of cyclodextrin in usage compositions for usage conditions are from about 0.01% to about 5%, preferably from about 0J%> to about 4%, more preferably from about 0.5% to about 2% by weight of the composition. Compositions with higher concentrations are not needed in use. The presence of the surfactant can improve spreading and therefore coverage.
- Concentrated compositions can be used in order to deliver a less expensive product.
- a concentrated product i.e., when the level of cyclodextrin used is from about 3% to about 20%, more preferably from about 5%> to about 10%, by weight of the concentrated composition, it is preferable to dilute the concentrated composition before treating surfaces.
- the concentrated cyclodextrin composition is diluted with about 50% to about 6000%), more preferably with about 75% to about 2000%, most preferably with about 100% to about 1000% by weight of the concentrated composition of water.
- the resulting diluted compositions have usage concentrations of cyclodextrin as discussed hereinbefore, e.g., of from about 0.1% to about 5%, by weight of the diluted composition.
- B CYCLODEXTRIN-COMPATIBLE SURFACTANT
- the cyclodextrin-compatible surfactant B provides improved spreading and soil removal performance, as well as the cleaning of other undesirable materials from the food surfaces, food preparing surfaces and/or food containers, and the like. Furthermore, the composition containing a cyclodextrin-compatible surfactant can penetrate hydrophobic, oily soil better for improved pesticide removal and malodor control. For concentrated compositions, the surfactant facilitates the dispersion of many actives such as antimicrobial actives and perfumes in the concentrated aqueous compositions.
- the preferred surfactants are those which are food compatible.
- the surfactant for use in providing the required low surface tension in the composition of the present invention should be cyclodextrin-compatible, that is it should not substantially form a complex with the cyclodextrin so as to diminish performance of the cyclodextrin and/or the surfactant. Complex formation diminishes both the ability of the cyclodextrin to absorb undesirable organic materials and the ability of the surfactant to lower the surface tension of the aqueous composition.
- Suitable cyclodextrin-compatible surfactants can be readily identified by the absence of effect of cyclodextrin on the surface tension provided by the surfactant. This is achieved by determining the surface tension (in dyne/cm 2 ) of aqueous solutions of the surfactant in the presence and in the absence of about 1%> of a specific cyclodextrin in the solutions.
- the aqueous solutions contain surfactant at concentrations of approximately 0.5%, 0.1%, 0.01%, and 0.005%).
- the cyclodextrin can affect the surface activity of a surfactant by elevating the surface tension of the surfactant solution.
- the surface tension at a given concentration in water differs by more than about 10% from the surface tension of the same surfactant in the 1%> solution of the cyclodextrin, that is an indication of a strong interaction between the surfactant and the cyclodextrin.
- the preferred surfactants herein should have a surface tension in an aqueous solution that is different (lower) by less than about 10%), preferably less than about 5%, and more preferably less than about 1% from that of the same concentration solution containing 1% cyclodextrin.
- Nonlimiting examples of cyclodextrin-compatible nonionic surfactants include block copolymers of ethylene oxide and propylene oxide.
- Suitable block polyoxyethylene-polyoxypropylene polymeric surfactants that are compatible with most cyclodextrins, include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as the initial reactive hydrogen compound.
- Polymeric compounds made from a sequential ethoxylation and propoxylation of initial compounds with a single reactive hydrogen atom, such as C]2-18 aliphatic alcohols are not generally compatible with the cyclodextrin.
- Certain of the block polymer surfactant compounds designated Pluronic® and Tetronic® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are readily available.
- Nonlimiting examples of cyclodextrin-compatible surfactants of this type include:
- Pluronic Surfactants with the general formula H(EO) n (PO) m (EO) n H, wherein EO is an ethylene oxide group, PO is a propylene oxide group, and n and m are numbers that indicate the average number of the groups in the surfactants.
- Typical examples of cyclodextrin-compatible Pluronic surfactants are:
- Typical examples of cyclodextrin-compatible Tetronic surfactants are:
- a preferred class of cyclodextrin-compatible nonionic surfactants are the polyalkyleneoxide polysiloxanes having a dimethyl polysiloxane hydrophobic moiety and one or more hydrophilic polyalkylene side chains and have the general formula:
- R 1 (CH 3 ) 2 SiO— [(CH 3 ) 2 SiO] a — [(CH 3 )(R')SiO] b — Si(CH 3 ) 2 — R 1 wherein a + b are from about 1 to about 50, preferably from about 3 to about 30 , more preferably from about 10 to about 25, and each R is the same or different and is selected from the group consisting of methyl and a poly(ethyleneoxide/propyleneoxide) copolymer group having the general formula
- R-2 with at least one R being a poly(ethyleneoxide/propyleneoxide) copolymer group, and wherein n is 3 or 4, preferably 3, total c (for all polyalkyleneoxy side groups) has a value of from 1 to about 100, preferably from about 6 to about 100, total d is from 0 to about 14, preferably from 0 to about 3, and more preferably d is 0, total c+d has a value of from about 5 to about 150, preferably from about 9 to about 100 and each R-2 is the same or different and is selected from the group consisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group, preferably hydrogen and methyl group
- Silwet® surfactants which are available OSi Specialties, Inc , Danbury, Connecticut Representative Silwet surfactants are as follows
- the molecular weight of the polyalkyleneoxy group (R') is less than or equal to about 10,000
- the molecular weight of the polyalkyleneoxy group is less than or equal to about 8,000, and most preferably ranges from about 300 to about 5,000
- the values of c and d can be those numbers which provide molecular weights within these ranges
- the number of ethyleneoxy units (-C2H4O) in the polyether chain (R*) must be sufficient to render the polyalkyleneoxide polysiloxane water dispersible or water soluble
- Preferred Silwet surfactants are L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof
- polyalkyleneoxide polysiloxanes of the present invention can be prepared according to the procedure set forth in U.S. Pat. No. 3,299,1 12, incorporated herein by reference.
- polyalkyleneoxide polysiloxanes of the surfactant blend of the present invention are readily prepared by an addition reaction between a hydrosiloxane (i.e., a siloxane containing silicon-bonded hydrogen) and an alkenyl ether (e.g., a vinyl, allyl, or methallyl ether) of an alkoxy or hydroxy end-blocked polyalkylene oxide).
- a hydrosiloxane i.e., a siloxane containing silicon-bonded hydrogen
- an alkenyl ether e.g., a vinyl, allyl, or methallyl ether
- reaction conditions employed in addition reactions of this type are well known in the art and in general involve heating the reactants (e.g., at a temperature of from about 85° C. to 1 10° C.) in the presence of a platinum catalyst (e.g., chloroplatinic acid) and a solvent (e.g., toluene).
- a platinum catalyst e.g., chloroplatinic acid
- a solvent e.g., toluene
- cyclodextrin-compatible anionic surfactants are the alkyldiphenyl oxide disulfonate, having the general formula:
- R is an alkyl group.
- examples of this type of surfactants are available from the Dow Chemical Company under the trade name Dowfax® wherein R is a linear or branched C 6 -C 16 alkyl group.
- An example of these cyclodextrin-compatible anionic surfactant is Dowfax 3B2 with R being approximately a linear CJ Q group.
- These anionic surfactants are preferably not used when the antimicrobial active or preservative, etc., is cationic to minimize the interaction with the cationic actives, since the effect of both surfactant and cationic active are diminished.
- the surfactants above are either weakly interactive with cyclodextrin (less than 5% elevation in surface tension, or non-interactive (less than 1% elevation in surface tension).
- Normal surfactants like sodium dodecyl sulfate and dodecanolpoly(6)ethoxylate are strongly interactive, with more than a 10% elevation in surface tension in the presence of a typical cyclodextrin like hydroxypropylbeta- cyclodextrin and methylated beta-cyclodextrin.
- Typical levels of cyclodextrin-compatible surfactants in usage compositions are from about 0.01% to about 4%, preferably from about 0.03%> to about 2%, more preferably from about 0.05% to about 1%>, by weight of the composition.
- Typical levels of cyclodextrin-compatible surfactants in concentrated compositions are from about 0.1% to about 8%, preferably from about 0.2% to about 4%, more preferably from about 0.3%> to about 3%>, by weight of the concentrated composition.
- the solubilized, water-soluble antimicrobial active, C is useful in providing protection against organisms that become attached to food, food preparation surfaces and/or food containers.
- the antimicrobial should be cyclodextrin compatible, e.g., not substantially forming complexes with the cyclodextrin in the food cleaning composition.
- the free, uncomplexed antimicrobial, e.g., antibacterial, active provides an optimum antibacterial performance.
- the preferred antibacterials are those which are food compatible, e.g., suitable for direct or indirect food contact use and/or may be approved as GRAS, prior sanctioned, or subject to GRAS approval via a GRAS petition, for example, a new chemical developed for this invention.
- Sanitization of food and food preparation and/or contact surfaces can be achieved by the compositions of the present invention containing antimicrobial materials, e.g., antibacterial halogenated compounds, quaternary compounds, and phenolic compounds.
- Some of the more robust cyclodextrin-compatible antimicrobial halogenated compounds which can function as disinfectants/sanitizers as well as finish product preservatives (vide infra), and are useful in the compositions of the present invention can include lJ'-hexamethylene bis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, and its salts, e.g., with hydrochloric, acetic and gluconic acids.
- the digluconate salt is highly water-soluble, about 70% in water, and the diacetate salt has a solubility of about 1.8% in water.
- chlorhexidine When used as a sanitizer in the present invention it is typically present at a level of from about 0.001% to about 0.4%, preferably from about 0.002% to about 0.3%, and more preferably from about 0.05% to about 0.2%, by weight of the usage composition. In some cases, a level of from about 1% to about 2% may be needed for virucidal activity.
- Other useful biguanide compounds include Cosmoci® CQ®, Vantocil® IB, including poly (hexamethylene biguanide) hydrochloride.
- Other useful cationic antimicrobial agents include the bis-biguanide alkanes.
- Usable water soluble salts of the above are chlorides, bromides, sulfates, alkyl sulfonates such as methyl sulfonate and ethyl sulfonate, phenylsulfonates such as p-methylphenyl sulfonates, nitrates, acetates, gluconates, and the like.
- Suitable bis biguanide compounds are chlorhexidine; l,6-bis-(2- ethylhexylbiguanidohexane)dihydrochloride; 1 ,6-di-(N ] ,N j '-phenyldiguanido- 5,N5')-hexane tetrahydrochloride; l,6-di-(N] ,N ⁇ '-phenyl-N],N]'-methyldiguanido- N5,N5')-hexane dihydrochloride; l,6-di(N ⁇ ,N ⁇ '-o-chlorophenyldiguanido-N5,N5')- hexane dihydrochloride; l,6-di(N],Nj'-2,6-dichlorophenyldiguanido-N5,N5')hexane dihydrochloride; l,6-di[N ⁇ ,
- omega. omega.:, omega. 'di(N ⁇ , N] '-p-chlorophenyldiguanido-N5,N5')m- xylene dihydrochloride; lJ2-di(Nj ,N ⁇ '-p-chlorophenyldiguanido-N5,N5') dodecane dihydrochloride; 1 , 10-di(N ] ,N ⁇ '-phenyldiguanido-N5,N5')-decane tetrahydrochloride; 1 , 12-di(N ⁇ ,N ⁇ '-phenyldiguanido-N5,N5') dodecane tetrahydrochloride; 1 ,6-di(N ⁇ ,N j '-o-chlorophenyldiguanidoJs ⁇ , ⁇ ') hexane dihydrochloride; 1 ,6-di(N i ,
- Preferred antimicrobials from this group are l,6-di-(N ⁇ ,N]'-phenyldiguanido-N5,N5')-hexane tetrahydrochloride; 1,6- di(N ⁇ ,N ⁇ '-o-chlorophenyldiguanido-N5,N5')-hexane dihydrochloride; l,6-di(N ] ,N ⁇ '- 2,6-dichlorophenyldiguanido-N5,N5')hexane dihydrochloride; 1 ,6-di(N ⁇ ,N ⁇ '-2,4- dichlorophenyldiguanido-N5,N5')hexane tetrahydrochloride; 1, 6-di[N],N ⁇ '-.
- omega omega 'di(N], N ⁇ '-p-chlorophenyldiguanido-N5,N5')m- xylene dihydrochloride; lJ2-di(N ⁇ ,N]'-p-chlorophenyldiguanido-N5,N5') dodecane dihydrochloride; 1 ,6-di(N ⁇ ,N j '-o-chlorophenyldiguanido-N5,N5') hexane dihydrochloride; 1 ,6-di(N ] ,N j '-p-chlorophenyldiguanido-N5,N5')-hexane tetrahydrochloride; and mixtures thereof
- the bis biguanide of choice is chlorhexidine its salts, e g , digluconate, dihydrochloride, diacetate, and mixtures thereof
- Quaternary Compounds A wide range of quaternary compounds can also be used as antimicrobial actives, in conjunction with the preferred surfactants
- useful quaternary compounds include' (1) benzalkonium chlorides and/or substituted benzalkonium chlorides such as commercially available Barquat® (available from Lonza), Maquat® (available from Mason), Variquat® (available from Witco/Sherex), and Hyamine® (available from Lonza), (2) dialkyl quaternary such as Bardac® products of Lonza, (3) N-(3-chloroallyl) hexaminium chlorides such as Dowicide® and Dowicil® available from Dow, (4) benzethonium chloride such as Hyamine® 1622 from Rohm & Haas, (5) methylbenzethonium chloride represented by Hyamine® 10X supplied by Rohm & Haas, (6) cetylpyridinium chloride such as Cepacol chloride available from of Merrell Labs Typical
- the surfactants when added to the antimicrobials tend to provide improved antimicrobial action This is especially true for the siloxane surfactants, and especially when the siloxane surfactants are combined with the chlorhexidine antimicrobial actives
- the preferred sequestrant and/or builder herein is polyphosphate salt or organic polycarboxylic salt, e.g., sodium and/or potassium citrate, and/or sodium and/or potassium ethylenediaminetetraacetate, which are standard items of commerce and are or may be approved as GRAS.
- organic polycarboxylic acids especially those that are or may be approved as GRAS, such as citric, tartaric, malic, etc. acids, can also be used.
- a preferred version of polyphosphate is an anhydrous Fast Dissolving STPP manufactured by the FMC corporation.
- phosphates such as sodium hexametaphosphate can also be used, and phosphates are useful to maintain the clarity of dilute solutions made from hard water.
- the sequestrant/builder is present at a level of from about 0.0005% to about 3%>, preferably from about 0.005% to about 0.5%, and more preferably from about 0.01% to about 0.2%, by weight of the dilute composition. Sequestrant/builders can help maintain the efficacy of the formulas in the presence of hardness. Additionally, other buffer/builders may be used. Potassium/sodium carbonate and/or versions of potassium/sodium ortho-phosphate are convenient and may provide additional pH control. (E). PERFUME
- the food cleaning composition of the present invention can also optionally provide a "scent signal" in the form of a pleasant odor which signals the removal of undesirable materials from food and/or food contacting surfaces.
- a scent signal in the form of a pleasant odor which signals the removal of undesirable materials from food and/or food contacting surfaces.
- Any type of food compatible perfume can be incorporated into the composition of the present invention.
- One preferred type are perfume compositions that provide various fruity odors.
- the scent signal is designed to provide a fleeting perfume scent, and is not designed to be overwhelming or to be used as an odor masking ingredient.
- perfume is added as a scent signal, it is added only at very low levels, e.g., from about 0% to about 0.5%, preferably from about 0.003% to about 0.3%, more preferably from about 0.005% to about 0.2%, by weight of the usage composition.
- Perfume can also be added as a more intense odor in product and on surfaces. When stronger levels of perfume are preferred, relatively higher levels of perfume can be added. It is essential, however, that the perfume be added at a level wherein even if all of the perfume in the composition were to complex with the cyclodextrin molecules, there will still be an effective level of uncomplexed cyclodextrin molecules present in the solution to provide adequate removal of undesirable materials and/or odor control.
- perfume is typically present at a level wherein less than about 90% of the cyclodextrin complexes with the perfume, preferably less than about 50% of the cyclodextrin complexes with the perfume, more preferably, less than about 30% of the cyclodextrin complexes with the perfume, and most preferably, less than about 10% of the cyclodextrin complexes with the perfume.
- the cyclodextrin to perfume weight ratio should be greater than about 8:1, preferably greater than about 10: 1, more preferably greater than about 20: 1, even more preferably greater than 40: 1 and most preferably greater than about 70: 1.
- the perfume is hydrophilic and is composed predominantly of ingredients selected from two groups of ingredients, namely, (a) hydrophilic ingredients having a ClogP of less than about 3.5, more preferably less than about 3.0, and (b) ingredients having significant low detection threshold, and mixtures thereof.
- at least about 50%, preferably at least about 60%, more preferably at least about 70%, and most preferably at least about 80% by weight of the perfume is composed of perfume ingredients of the above groups (a) and (b).
- the cyclodextrin to perfume weight ratio is typically of from about 2:1 to about 200: 1; preferably from about 4: 1 to about 100: 1, more preferably from about 6: 1 to about 50: 1, and even more preferably from about 8: 1 to about 30: 1.
- the hydrophilic perfume ingredients are more soluble in water, have less of a tendency to complex with the cyclodextrins, and are more available in the food cleaning composition than the ingredients of conventional perfumes.
- the hydrophilic perfume ingredients can also be more readily rinsed off and removed from the food and food contacting surfaces, and do not leave a high level of residue on said surfaces which can be hydrophobic surfaces.
- the degree of hydrophobicity of a perfume ingredient can be correlated with its octanol/water partition coefficient P.
- the octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. A perfume ingredient with a greater partition coefficient P is considered to be more hydrophobic.
- a perfume ingredient with a smaller partition coefficient P is considered to be more hydrophilic. Since the partition coefficients of the perfume ingredients normally have high values, they are more conveniently given in the form of their logarithm to the base 10, logP. Thus the preferred perfume hydrophilic perfume ingredients of this invention have logP of about 3.5 or smaller, preferably of about 3.0 or smaller.
- the logP of many perfume ingredients have been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP” program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database.
- the "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p.
- the fragment approach is based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
- the ClogP values which are the most reliable and widely used estimates for this physicochemical property, are used instead of the experimental logP values in the selection of perfume ingredients which are useful in the present invention.
- Non-limiting examples of the more preferred hydrophilic perfume ingredients are allyl amyl glycolate, allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisyl acetate, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, calone, camphor gum, laevo-carveol, d-carvone, laevo-carvone, cinnamic alcohol, cinnamyl acetate, cinnamic alcohol, cinnamyl formate, cinnamyl propionate, cis- jasmone, cis-3-hexenyl acetate, coumarin, cuminic alcohol, cuminic aldehyde, Cyclal C,
- Nonlimiting examples of other preferred hydrophilic perfume ingredients which can be used in perfume compositions of this invention are allyl heptoate, amyl benzoate, anethole, benzophenone, carvacrol, citral, citronellol, citronellyl nitrile, cyclohexyl ethyl acetate, cymal, 4-decenal, dihydro isojasmonate, dihydro myrcenol, ethyl methyl phenyl glycidate, fenchyl acetate, florhydral, gamma-nonalactone, geranyl formate, geranyl nitrile, hexenyl isobutyrate, alpha-ionone, isobornyl acetate, isobutyl benzoate, isononyl alcohol, isomenthol, para-isopropyl phenylacetaldehyde, isopulegol, linalyl
- the preferred perfume compositions used in the present invention contain at least 4 different hydrophilic perfume ingredients, preferably at least 5 different hydrophilic perfume ingredients, more preferably at least 6 different hydrophilic perfume ingredients, and even more preferably at least 7 different hydrophilic perfume ingredients. Most common perfume ingredients which are derived from natural sources are composed of a multitude of components. When each such material is used in the formulation of the preferred perfume compositions of the present invention, it is counted as one single ingredient, for the purpose of defining the invention, (b). Low Odor Detection Threshold Perfume Ingredient
- the odor detection threshold of an odorous material is the lowest vapor concentration of that material which can be olfactorily detected.
- the odor detection threshold and some odor detection threshold values are discussed in, e.g., "Standardized Human Olfactory Thresholds", M. Devos et al, IRL Press at Oxford University Press, 1990, and "Compilation of Odor and Taste Threshold Values Data", F. A. Fazzalari, editor, ASTM Data Series DS 48A, American Society for Testing and Materials, 1978, both of said publications being incorporated by reference.
- perfume ingredients that have low odor detection threshold values can improve perfume odor character, even though they are not as hydrophilic as perfume ingredients of group (a) which are given hereinabove.
- Perfume ingredients that do not belong to group (a) above, but have a significantly low detection threshold, useful in the composition of the present invention are selected from the group consisting of ambrox, bacdanol, benzyl salicylate, butyl anthranilate, cetalox, damascenone, alpha-damascone, gamma-dodecalactone, ebanol, herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-ionone, alpha-isomethylionone, lilial, methyl nonyl ketone, gamma-undecalactone, undecylenic aldehyde, and mixtures thereof.
- These materials are preferably present at low levels in addition to the hydrophilic ingredients of group (a), typically less than about 20%, preferably less than about 15%, more preferably less than about 10%>, by weight of the total perfume compositions of the present invention. However, only low levels are required to provide an effect.
- hydrophilic ingredients of group (a) that have a significantly low detection threshold, and are especially useful in the composition of the present invention.
- these ingredients are allyl amyl glycolate, anethole, benzyl acetone, calone, cinnamic alcohol, coumarin, cyclogalbanate, Cyclal C, cymal, 4- decenal, dihydro isojasmonate, ethyl anthranilate, ethyl-2-methyl butyrate, ethyl methylphenyl glycidate, ethyl vanillin, eugenol, flor acetate, florhydral, fructone, frutene, heliotropin, keone, indole, iso cyclo citral, isoeugenol, lyral, methyl heptine carbonate, linalool, methyl anthranilate, methyl dihydrojasmonate, methyl is
- Low molecular weight polyols with relatively high boiling points, as compared to water, such as ethylene glycol, propylene glycol and/or diethylene glycol are preferred optional ingredients for improving organic residue removal and/or odor control performance of the composition of the present invention.
- ethylene glycol, propylene glycol and/or diethylene glycol are preferred optional ingredients for improving organic residue removal and/or odor control performance of the composition of the present invention.
- the incorporation of a small amount of low molecular weight glycols into the composition of the present invention enhances the formation of the cyclodextrin inclusion complexes with small organic molecules.
- the addition of the glycols is believed to fill up void space in the cyclodextrin cavity that is unable to be filled by some organic residue molecules of relatively smaller sizes.
- the glycol used is glycerine, ethylene glycol, propylene glycol, dipropylene glycol or mixtures thereof, more preferably diethylene glycol and propylene glycol.
- Cyclodextrins prepared by processes that result in a level of such polyols are highly desirable, since they can be used without removal of the polyols.
- polyols e.g., dipropylene glycol
- glycol is added to the composition of the present invention at a level of from about 0 01% to about 3%, by weight of the composition, preferably from about 0 05% to about 1%, more preferably from about 0 1% to about 0.5%>, by weight of the composition
- the preferred weight ratio of low molecular weight polyol to cyclodextrin is from about 2 1 ,000 to about 20 100, more preferably from about 3.1,000 to about 15 100, even more preferably from about 5 1,000 to about 10: 100, and most preferably from about 1 100 to about 7 100 (G).
- OPTIONAL AMINOCARBOXYLATE CHELATORS OPTIONAL AMINOCARBOXYLATE CHELATORS
- Chelators e g , ethylenediaminetetraacetic acid (EDTA), hydroxyethylene- diaminetriacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and their salts, and mixtures thereof, can optionally be used to increase antimicrobial and preservative effectiveness against Gram- negative bacteria, especially Pseudomonas species
- EDTA ethylenediaminetetraacetic acid
- hydroxyethylene- diaminetriacetic acid diethylenetriaminepentaacetic acid
- other aminocarboxylate chelators and mixtures thereof, and their salts, and mixtures thereof, can optionally be used to increase antimicrobial and preservative effectiveness against Gram- negative bacteria, especially Pseudomonas species
- sensitivity to EDTA and other aminocarboxylate chelators is mainly a characteristic of Pseudomonas species, other bacterial species highly susceptible to chelators include Achromobacter. Alcaligenes
- aminocarboxylate chelators can help, e g , maintaining product clarity, protecting fragrance and perfume components, and preventing rancidity and off odors
- aminocarboxylate chelators may not be potent biocides in their own right, they function as potentiators for improving the performance of other antimicrobials/preservatives in the compositions of the present invention
- Aminocarboxylate chelators can potentiate the performance of many of the cationic, anionic, and nonionic antimicrobials/preservatives, phenolic compounds, and isothiazolinones, that are used as antimicrobials/preservatives in the composition of the present invention
- Nonlimiting examples of cationic antimicrobials/ preservatives potentiated by aminocarboxylate chelators in solutions are chlorhexidine salts (including digluconate, diacetate, and dihydrochloride salts), benalkonium chloride, cetrimonium, myristalkonium chloride, cetylpyridinium chloride, lauryl pyridinium chloride, and the like
- the optional chelators are present in the compositions of this invention at levels of, typically, from about 0 01% to about 0 3%, more preferably from about 0.02% to about 0 1%, most preferably from about 0 02% to about 0 05% by weight of the usage compositions to provide antimicrobial efficacy in this invention
- Free, uncomplexed aminocarboxylate chelators are required to potentiate the efficacy of the antimicrobials.
- excess alkaline earth especially calcium and magnesium
- transitional metals iron, manganese, copper, and others
- suds suppressors or antifoamers can be used, especially in the case where a certain surfactant level is desired for wetting and/or efficacy, but the degree of foam generated in the washing of produce is desired to be kept low.
- the amount of suds suppresser can be tailored in conjunction with the type and level of surfactant used.
- Preferred suds suppressors include silicones and their derivatives.
- Preferably food grade suds suppressors are used, with DC-1500 and its derivatives, such as DC-4270 and DC2-4242, from Dow Corning being useful suds suppressors.
- suds suppressor is present at a level of from about 0.01%) to about 2%, preferably from about 0.05% to about 1%, more preferably from about 0.1%) to about 0.5%, by weight of the usage composition.
- an article of manufacture suitable for use by an individual to clean food surfaces and/or food preparation and food contact surfaces, containing a food compatible cleaning solution that is capable of being dispensed with a clearly visible content of foam from said container, the foam preferably remaining visible for at least 3 seconds optionally for at least 1 minute.
- the article can comprises a foaming spray head and is preferably of the trigger-type.
- the food compatible cleaning solution optionally comprises a non-detergent cyclodextrin compatible foam enhancing component, optionally selected from polymeric shear-thinning thickeners, optionally at a level of from about 0.001% to about 1%, preferably from about 0.005% to about 0.5%).
- the polymeric shear thinning thickeners are typically selected from the group consisting of substituted celluloses, modified polysaccharides, and naturally occurring gums, e.g., from about 0.001% to about 1% of xanthan gum.
- the cleaning solution preferably comprises all food compatible ingredients.
- the toxicologically acceptable cleaning solution in one embodiment, comprises:
- the present invention can include metallic salts for added odor absorption and/or antimicrobial benefit for the cyclodextrin solution.
- the metallic salts are selected from the group consisting of copper salts, zinc salts, and mixtures thereof.
- Copper salts have some antimicrobial benefits. Specifically, cupric abietate acts as a fungicide, copper acetate acts as a mildew inhibitor, cupric chloride acts as a fungicide, copper lactate acts as a fungicide, and copper sulfate acts as a germicide. Copper salts also possess some malodor control abilities. See U. S. Pat. No. 3,172,817, Leupold, et al., which discloses deodorizing compositions for treating disposable articles, comprising at least slightly water-soluble salts of acylacetone, including copper salts and zinc salts, all of said patents are incorporated herein by reference.
- the preferred zinc salts possess malodor control abilities. Zinc has been used most often for its ability to ameliorate malodor, e.g., in mouth wash products, as disclosed in U.S. Pat. Nos. 4,325,939, issued Apr. 20, 1982 and 4,469,674, issued Sept. 4, 1983, to N. B. Shah, et al., all of which are incorporated herein by reference. Highly-ionized and soluble zinc salts such as zinc chloride, provide the best source of zinc ions.
- Zinc borate functions as a fungistat and a mildew inhibitor
- zinc caprylate functions as a fungicide
- zinc chloride provides antiseptic and deodorant benefits
- zinc ricinoleate functions as a fungicide
- zinc sulfate heptahydrate functions as a fungicide
- zinc undecylenate functions as a fungistat.
- the metallic salts are water-soluble zinc salts, copper salts or mixtures thereof, and more preferably zinc salts, especially ZnCl2- These salts are preferably present in the present invention primarily to absorb amine and sulfur- containing compounds that have molecular sizes too small to be effectively complexed with the cyclodextrin molecules.
- Low molecular weight sulfur-containing materials e.g., sulfide and mercaptans, are components of many types of food odors, e.g., garlic, onion, cabbage, spoiled meat, etc.
- Low molecular weight amines are also components of many food odors, such as fish odor, etc.
- metallic salts When metallic salts are added to the composition of the present invention they are typically present at a level of from about 0.1% to about 10%>, preferably from about 0.2% to about 8%, more preferably from about 0.3% to about 5%> by weight of the usage composition.
- zinc salts When zinc salts are used as the metallic salt, and a clear solution is desired, it is preferable that the pH of the solution is adjusted to less than about 7, more preferably less than about 6, most preferably, less than about 5, in order to keep the solution clear. (J).
- ENZYMES ENZYMES
- Enzymes can be used to remove certain types of soils on food, especially degraded protein materials, glycoproteins, fruit resins, and the like. Enzymes can digest some soil and help both in the removal of the soil and the diffusion and/or penetration of other actives such as cyclodextrin and/or antimicrobial actives, to improve their performance. Proteases and amylases are especially desirable. The activity of commercial enzymes depends very much on the type and purity of the enzyme being considered. Enzymes that are water soluble proteases like pepsin, tripsin, ficin, bromelin, papain, rennin, and mixtures thereof are particularly useful.
- Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, preferably from about 0.001 mg to about 3 mg, more preferably from about 0.002 mg to about 1 mg, of active enzyme per gram of the aqueous compositions.
- the aqueous compositions herein can comprise from about 0.0001% to about 0.5%, preferably from about 0.001% to about 0.3%, more preferably from about 0.005% to about 0.2% by weight of a commercial enzyme preparation.
- Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.0005 to 0J Anson units (AU) of activity per gram of aqueous composition.
- Nonlimiting examples of suitable, commercially available, water soluble proteases are pepsin, tripsin, ficin, bromelin, papain, rennin, and mixtures thereof.
- Papain can be isolated, e.g., from papaya latex, and is available commercially in the purified form of up to, e.g., about 80% protein, or cruder, technical grade of much lower activity.
- Other suitable examples of proteases are the subtilisins which are obtained from particular strains of B. siiblilis and B. licheniforms.
- Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE W .
- proteases suitable for removing protein-based soils include those sold under the trade names ALCALASE* and SAVINASE ® by Novo Industries A S (Denmark) and MAXATASE 110 by International Bio- Synthetics, Inc. (The Netherlands).
- Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985); Protease B (see European Patent Application Serial No.
- Patent 3,600,319 issued August 17, 1971 to Gedge, et al., European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas, and in U.S. Patent 3,519,570. All of the above patents and applications are incorporated herein, at least in pertinent part.
- Enzyme-polyethylene glycol conjugates are also preferred.
- Such polyethylene glycol (PEG) derivatives of enzymes wherein the PEG or alkoxy-PEG moieties are coupled to the protein molecule through, e.g., secondary amine linkages. Suitable derivatization decreases immunogenicity, thus minimizes allergic reactions, while still maintains some enzymatic activity.
- An example of protease-PEG's is PEG-subtilisin Carlsberg from B. lichenniformis coupled to methoxy-PEGs through secondary amine linkage, and is available from Sigma-Aldrich Corp., St. Louis, Missouri. (K). ANTIMICROBIAL PRESERVATIVES
- solubilized, water-soluble, antimicrobial preservative can be added to the composition of the present invention if the antimicrobial material C. is not sufficient, or is not present, because cyclodextrin molecules are made up of varying numbers of glucose units which can be consumed by certain microorganisms, especially when in aqueous compositions.
- This drawback can lead to the problem of storage stability of cyclodextrin solutions for any significant length of time. Contamination by certain microorganisms with subsequent microbial growth can result in an unsightly and/or malodorous solution.
- a solubilized, water-soluble, antimicrobial preservative which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear, aqueous odor-absorbing solution containing water-soluble cyclodextrin.
- Typical microorganisms that can be found in cyclodextrin supplies and whose growth can be found in the presence of cyclodextrin in aqueous cyclodextrin solutions include bacteria, e.g., Bacillus ihuringiensis (cereus group) and Bacillus sphaericus: and fungi, e.g., Asper illus uslus.
- Bacillus sphaericus is one of the most numerous members of Bacillus species in soils.
- Aspergillus vshis is common in grains and flours which are raw materials to produce cyclodextrins.
- Microorganisms such as Escherichia coli and Pseudomonas aeruginosa are found in some water sources, and can be introduced during the preparation of cyclodextrin solutions.
- Other Pseudomonas species such as P. cepacia, are typical microbial contaminants in surfactant manufacturing facilities and may readily contaminate packed finished products. Typical other bacterial contaminants may include Burkholderia. Enterohacter and Gluconobacier species.
- Representative fungal species which may be associated with agricultural soils, crops and in the case of this invention, corn products such as cyclodextrins include Aspergillus. Absidia. Penicillhim. Paecilomyces. and other species.
- a broad spectrum preservative e.g., one that is effective on both bacteria (both gram positive and gram negative) and fungi.
- a limited spectrum preservative e.g., one that is only effective on a single group of microorganisms, e.g., fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary and/or supplementary activity.
- a mixture of broad spectrum preservatives can also be used.
- aminocarboxylate chelators may be used alone or as potentiators in conjunction with other preservatives.
- chelators which include, e.g., ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and their salts, and mixtures thereof, can increase preservative effectiveness against Gram-negative bacteria, especially Pseudomonas species, as disclosed herein before.
- EDTA ethylenediaminetetraacetic acid
- hydroxyethylenediaminetriacetic acid hydroxyethylenediaminetriacetic acid
- diethylenetriaminepentaacetic acid diethylenetriaminepentaacetic acid
- other aminocarboxylate chelators and mixtures thereof, and their salts, and mixtures thereof, can increase preservative effectiveness against Gram-negative bacteria, especially Pseudomonas species, as disclosed herein before.
- Antimicrobial preservatives useful in the present invention include biocidal compounds, i.e., substances that kill microorganisms, or biostatic compounds, i.e., substances that inhibit and/or regulate the growth of microorganisms.
- Preferred antimicrobial preservatives are those that are water-soluble and are effective at low levels because the organic preservatives can form inclusion complexes with the cyclodextrin molecules and compete with the organic residue molecules for the cyclodextrin cavities, thus rendering the cyclodextrins ineffective as organic residue removing and/or odor controlling actives.
- Water-soluble preservatives useful in the present invention are those that have a solubility in water of at least about 0.3 g per 100 ml of water, i.e., greater than about 0.3% at room temperature, preferably greater than about 0.5%> at room temperature. These types of preservatives have a lower affinity to the cyclodextrin cavity, at least in the aqueous phase, and are therefore more available to provide antimicrobial activity.
- Preservatives with a water-solubility of less than about 0.3% and a molecular structure that readily fits into the cyclodextrin cavity have a greater tendency to form inclusion complexes with the cyclodextrin molecules, thus rendering the preservative less effective to control microbes in the cyclodextrin solution.
- the water-soluble antimicrobial preservative in the present invention is included at an effective amount
- effective amount means a level sufficient to prevent spoilage, or prevent growth of inadvertently added microorganisms, for a specific period of time
- the preservative is not necessarily being used to kill microorganisms on the surface onto which the composition is deposited in order to eliminate odors produced by microorganisms Instead, it is preferably being used to prevent spoilage of the cyclodextrin solution in order to increase the shelf-life of the composition
- Preferred levels of preservative are from about 0 0001% to about 0 5%, more preferably from about 0 0002% to about 0 2%, most preferably from about 0 0003% to about 0 1%, by weight of the usage composition
- the cyclodextrin to preservative molar ratio should be greater than about 5 1, preferably greater than about 10 1, more preferably greater than about 50 1, even more preferably greater than about 100 1
- the preservative can be any organic preservative materials which are food compatible, e g , suitable for direct or indirect food contact use or may be petitioned for food use
- Preferred water-soluble preservatives include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary ammonium compounds, dehydroacetic acid, phenyl and phenolic compounds, and mixtures thereof
- Preferred water-soluble preservatives for use in the present invention are organic sulfur compounds
- organic sulfur compounds suitable for use in the present invention are (i) 3-Isothiazolone Compounds
- a preferred preservative is an antimicrobial, organic preservative containing 3-isothiazolone groups having the formula
- Y is an unsubstituted alkyl, alkenyl, or alkynyl group of from about 1 to about 18 carbon atoms, an unsubstituted or substituted cycloalkyl group having from about a 3 to about a 6 carbon ring and up to 12 carbon atoms, an unsubstituted or substituted aralkyl group of up to about 10 carbon atoms, or an unsubstituted or substituted aryl group of up to about 10 carbon atoms;
- Ri is hydrogen, halogen, or a (C1-C4) alkyl group
- R-2 is hydrogen, halogen, or a (C]-C4) alkyl group.
- Y is methyl or ethyl
- R-* and R2 should not both be hydrogen. Salts of these compounds formed by reacting the compound with acids such as hydrochloric, nitric, sulfuric, etc. are also suitable.
- a preferred preservative is a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably a mixture of about 77% 5-chloro-2-methyl-4-isothiazolin-3-one and about 23%o 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available as a 1.5%) aqueous solution under the trade name Kathon 00 CG by Rohm and Haas Company.
- Kathon® When Kathon® is used as the preservative in the present invention it is present at a level of from about 0.0001% to about 0.01%, preferably from about 0.0002% to about 0.005%, more preferably from about 0.0003% to about 0.003%, most preferably from about 0.0004% to about 0.002%, by weight of the composition.
- isothiazolins include l,2-benzisothiazolin-3-one, available under the trade name Proxel® products; and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, available under the trade name Promexal®. Both Proxel and Promexal are available from Zeneca. They have stability over a wide pH range (i.e., 4-12). Neither contain active halogen and are not formaldehyde releasing preservatives. Both Proxel and
- Promexal are effective against typical Gram negative and positive bacteria, fungi and yeasts when used at a level from about 0.001% to about 0.5%, preferably from about
- Sodium Pyrithione Another preferred organic sulfur preservative is sodium pyrithione, with water solubility of about 50% When sodium pyrithione is used as the preservative in the present invention it is typically present at a level of from about 0 0001%) to about
- 0.01% preferably from about 0 0002% to about 0 005%, more preferably from about 0.0003%) to about 0.003%, by weight of the usage composition.
- Preferred preservatives for use in the present invention are halogenated compounds Some non-limiting examples of halogenated compounds suitable for use in the present invention are
- Bronidox L 00 5-bromo-5-nitro- 1,3 -dioxane
- Bronidox L * has a solubility of about 0 46% in water
- Bronidox is typically present at a level of from about 0 0005% to about 0 02%, preferably from about 0 001% to about 0 01%, by weight of the usage composition
- Bronopol has a solubility of about 25% in water
- Bronopol is typically present at a level of from about 0 002%) to about 0.1%), preferably from about 0 005%) to about 0 05%, by weight of the usage composition
- the digluconate salt is highly water-soluble, about 70% in water, and the diacetate salt has a solubility of about 1 8% in water
- chlorohexidine is used as the preservative in the present invention it is typically present
- dibromopropamidine 4,4'- (Trimethylenedioxy)bis-(3-bromobenzamidine) diisethionate, or dibromopropamidine, with water solubility of about 50%, when dibromopropamidine is used as the preservative in the present invention it is typically present at a level of from about 0 0001%. to about 0 05%, preferably from about 0 0005% to about
- Preferred water-soluble preservatives for use in the present invention are cyclic organic nitrogen compounds.
- Some non-limiting examples of cyclic organic nitrogen compounds suitable for use in the present invention are: (i) Imidazolidinedione Compounds
- Preferred preservatives for use in the present invention are imidazolidione compounds.
- imidazolidinedione compounds suitable for use in the present invention are: l,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione, commonly known as dimethyloldimethylhydantoin, or DMDM hydantoin, available as, e.g., Glydant® from Lonza.
- DMDM hydantoin has a water solubility of more than 50% in water, and is mainly effective on bacteria.
- DMDM hydantoin When DMDM hydantoin is used, it is preferable that it be used in combination with a broad spectrum preservative such as Kathon CG®, or formaldehyde.
- a preferred mixture is about a 95:5 DMDM hydantoin to 3-butyl-2-iodopropynylcarbamate mixture, available under the trade name Glydant Plus® from Lonza.
- Glydant Plus® is typically present at a level of from about 0.005%) to about 0.2%) by weight of the usage composition;
- N-[l,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N'- bis(hydroxymethyl) urea commonly known as diazolidinyl urea, available under the trade name Germall II® from Sutton Laboratories, Inc. (Sutton) can be used as the preservative in the present invention.
- Germall II® is typically present at a level of from about 0.01% to about 0.1%) by weight of the usage composition;
- N,N"-methylenebis ⁇ N'-[l-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea ⁇ commonly known as imidazolidinyl urea, available, e.g., under the trade name Abiol® from 3V-Sigma, Unicide U-13® from Induchem, Germall 1 15® from (Sutton) can be used as the preservative in the present invention.
- imidazolidinyl urea is typically present at a level of from about 0.05% to about 0.2%), by weight of the usage composition.
- Another preferred water-soluble cyclic organic nitrogen preservative is polymethoxy bicyclic oxazolidine, having the general formula:
- n has a value of from about 0 to about 5, and is available under the trade name Nuosept® C from H ⁇ ls America. When Nuosept® C is used as the preservative, it is typically present at a level of from about 0.005% to about 0.1%, by weight of the usage composition.
- a preferred preservative for use in the present invention is formaldehyde.
- Formaldehyde is a broad spectrum preservative which is normally available as formalin which is a 37% aqueous solution of formaldehyde.
- typical levels are from about 0.003% to about 0.2%, preferably from about 0.008% to about 0.1%. more preferably from about 0.01% to about 0.05%, by weight of the usage composition.
- a preferred preservative for use in the present invention is glutaraldehyde.
- Glutaraldehyde is a water-soluble, broad spectaim preservative commonly available as a 25% or a 50% solution in water.
- glutaraldehyde is typically present at a level of from about 0.005% to about 0.1%, preferably from about 0.01 % to about 0.05%, by weight of the usage composition. (e). Quaternary Compounds
- Preferred preservatives for use in the present invention are cationic and/or quaternary compounds.
- Such compounds include polyaminopropyl biguanide, also known as polyhexamethylene biguanide having the general formula:
- Polyaminopropyl biguanide is a water-soluble, broad spectrum preservative which is available as a 20% aqueous solution available under the trade name Cosmocil CQ® from ICI Americas, Inc , or under the trade name Mikrokill® from Brooks, Inc l-(3-Chlorallyl) -3,5,7-triaza-l-azoniaadamantane chloride, available, e g., under the trade name Dowicil 200 from Dow Chemical, is an effective quaternary ammonium preservative, it is freely soluble in water, however, it has the tendency to discolor (yellow), therefore it is not highly preferred
- quaternary ammonium compounds When quaternary ammonium compounds are used as the preservative in the present invention, they are typically present at a level of from about 0 005%> to about 0 2%, preferably from about 0 01 % to about 0 1 %, by weight of the usage composition (f).
- Dehydroacetic Acid a level of from about 0 005%> to about 0 2%, preferably from about 0 01 % to about 0 1 %, by weight of the usage composition (f).
- a preferred preservative for use in the present invention is dehydroacetic acid
- Dehydroacetic acid is a broad spectrum preservative preferably in the form of a sodium or a potassium salt so that it is water-soluble This preservative acts more as a biostatic preservative than a biocidal preservative
- dehydroacetic acid is typically used at a level of from about 0 005% to about 0 2%>, preferably from about 0 008% to about 0 1%, more preferably from about 0 01% to about 0.05%), by weight of the usage composition (g).
- phenyl and phenolic compounds suitable for use in the present invention are
- benzyl alcohol with a water solubility of about 4%>
- 2- phenylethanol with a water solubility of about 2%
- 2-phenoxyethanol with a water solubility of about 2 67%
- typical effective level of these phenyl and phenoxy alcohol is from about 0 1% to about 0 5%, by weight of the usage composition (h).
- adjunct odor-controlling materials can enhance the capacity of the cyclodextrin to control odors as well as broaden the range of odor types and molecule sizes which can be controlled
- Such materials include, for example, metallic salts, water-soluble cationic and anionic polymers, water-soluble bicarbonate salts, and mixtures thereof.
- water-soluble polymers e.g., water-soluble cationic polymer and water-soluble anionic polymers can be used in the composition of the present invention to provide additional odor control benefits.
- Cationic polymers e.g., polyamines
- Water-soluble cationic polymers e.g., those containing amino functionalities, amido functionalities, and mixtures thereof, are useful in the present invention to control certain acid-type odors.
- Anionic polymers e.g., polyacrylic acid
- Water-soluble anionic polymers e.g., polyacrylic acids and their water-soluble salts are useful in the present invention to control certain amine-type odors.
- Preferred polyacrylic acids and their alkali metal salts have an average molecular weight of less than about 20,000, more preferably less than 5,000.
- Polymers containing sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, and their water-soluble salts, and mixtures thereof, and mixtures with carboxylic acid and carboxylate groups, are also suitable.
- Water-soluble polymers containing both cationic and anionic functionalities are also suitable. Examples of these polymers are given in U.S. Pat. 4,909,986, issued March 20, 1990 to N. Kobayashi and A. Kawazoe, incorporated herein by reference. Another example of water-soluble polymers containing both cationic and anionic functionalities is a copolymer of dimethyldiallyl ammonium chloride and acrylic acid, commercially available under the trade name Merquat 280® from Calgon.
- a water-soluble polymer When a water-soluble polymer is used it is typically present at a level of from about 0.005%) to about 5%, preferably from about 0.01% to about 3%>, more preferably from about 0.1% to about 2%, by weight of the usage composition.
- Soluble Carbonate and/or Bicarbonate Salts Water-soluble alkali metal carbonate and/or bicarbonate salts, such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, sodium carbonate, and mixtures thereof can be added to the composition of the present invention in order to help to control certain acid-type odors, as well as to provide additional sequestrant/builder benefit.
- Preferred salts are sodium carbonate monohydrate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and mixtures thereof.
- these salts are typically present at a level of from about 0.1% to about 5%>, preferably from about 0.2% to about 3%, more preferably from about 0.3%> to about 2%, by weight of the composition.
- incompatible metal salts it is preferably that incompatible metal salts not be present in the invention.
- the composition should be essentially free of zinc and other incompatible metal ions, e.g., Ca, Fe, Ba, etc. which form water-insoluble salts.
- Aqueous solutions are preferred for organic residue removal and/or odor control.
- the dilute aqueous solution provides the maximum separation of cyclodextrin molecules on the food and food contacting surfaces and thereby maximizes the chance that an organic residue, such as a pesticide molecule and/or an odor molecule will interact with a cyclodextrin molecule.
- the preferred carrier of the present invention is water.
- the water which is used can be distilled, deionized, or tap water. Water not only serves as the liquid carrier for the cyclodextrins, but it also facilitates the complexation reaction between the cyclodextrin molecules and any organic residue molecules that are on the food and/or food contacting surfaces when they are treated.
- the carrier in addition to water, can contain a low molecular weight organic solvent that is highly soluble in water such as ethanol.
- Low molecular weight alcohols can help to dissolve water insoluble organic residues such as some pesticide and facilitate the complexation and removal of these undesirable materials by cyclodextrin.
- Low molecular weight alcohols can also help to dissolve the wax that are coated on some food such as apples, and facilitate wax removal by surfactants.
- the optional water soluble low molecular weight solvent can be used at a level of up to about 50%), typically from about 1% to about 20%, preferably from about 2% to about 15%, more preferably from about 5% to about 10%>, by weight of the total composition.
- Factors that need to consider when a high level of solvent is used in the composition are odor, flammability, and environment impact. (O) OTHER OPTIONAL INGREDIENTS
- composition of the present invention can optionally contain other optional ingredients, such as colorants, antioxidants, and mixtures thereof in addition to the cyclodextrin molecules.
- composition of the present invention can also be used in an article of manufacture comprising said composition plus a spray dispenser.
- the most basic article of manufacture comprises uncomplexed cyclodextrin, a carrier, and a spray dispenser.
- Said compositions and/or article of manufacture are preferably in association with instructions to use said compositions and product for cleaning and removal of undesirable materials from food and/or food contacting surfaces.
- the article of manufacture herein comprises a spray dispenser.
- the food cleaning composition is placed into a spray dispenser in order to be distributed onto the food and/or food contacting surfaces
- Said spray dispenser for producing a spray of liquid droplets can be any of the manually activated means as is known in the art, e.g.
- trigger-type, pump-type, non-aerosol self-pressurized, and aerosol-type spray means for dispensing the food cleaning composition to a small amount of food and/or food contacting surfaces in consumer's household, such as produce, fruits and vegetables, meat, poultry, fish and other seafoods, food preparing surfaces and/or equipment, such as cutting board, countertop, pots and pans, food containers, and the like, as well as non-manually operated, powered sprayers for conveniently cleaning large amounts of food and/or large areas of food contacting surfaces, e g., in commercial and/or constitutional settings, such as in supermarkets, restaurants, cafeterias, and the like.
- the spray dispenser herein can include those that will substantially foam the clear, aqueous food cleaning composition
- the spray dispenser can be an aerosol dispenser
- Said aerosol dispenser comprises a container which can be constructed of any of the conventional materials employed in fabricating aerosol containers
- the dispenser must be capable of withstanding internal pressure in the range of from about 20 to about 1 10 p.s i g., more preferably from about 20 to about 70 p s i g
- the one important requirement concerning the dispenser is that it be provided with a valve member which will permit the clear, aqueous food cleaning composition contained in the dispenser to be dispensed in the form of a spray of very fine, or finely divided, particles or droplets.
- the aerosol dispenser utilizes a pressurized sealed container from which the clear, aqueous food cleaning composition is dispensed through a special actuator/valve assembly under pressure
- the aerosol dispenser is pressurized by incorporating therein a gaseous component generally known as a propellant.
- the spray dispenser can be a self-pressurized non-aerosol container having a convoluted liner and an elastomeric sleeve.
- Said self-pressurized dispenser comprises a liner/sleeve assembly containing a thin, flexible radially expandable convoluted plastic liner of from about 0 010 to about 0 020 inch thick, inside an essentially cylindrical elastomeric sleeve The liner/sleeve is capable of holding a substantial quantity of food cleaning composition product and of causing said product to be dispensed
- a more complete description of self-pressurized spray dispensers can be found in U S Pat Nos 5, 1 1 1,971, Winer, issued May 12, 1992, and 5,232, 126, Winer, issued Aug 3, 1993, both of said references are herein incorporated by reference
- Another type of aerosol spray dispenser is one wherein a barrier separates the food cleaning composition from the propellant (preferably compressed air or nitrogen), as disclosed in U S Pat No 4,260J 10, issued April 7,
- the spray dispenser is a non-aerosol, manually activated, pump-spray dispenser
- Said pump-spray dispenser comprises a container and a pump mechanism which securely screws or snaps onto the container
- the container comprises a vessel for containing the aqueous food cleaning composition to be dispensed.
- the pump mechanism comprises a pump chamber of substantially fixed volume, having an opening at the inner end thereof Within the pump chamber is located a pump stem having a piston on the end thereof disposed for reciprocal motion in the pump chamber
- the pump stem has a passageway there through with a dispensing outlet at the outer end of the passageway and an axial inlet port located inwardly thereof.
- the container and the pump mechanism can be constructed of any conventional material employed in fabricating pump-spray dispensers, including, but not limited to' polyethylene, polypropylene, polyethyleneterephthalate; blends of polyethylene, vinyl acetate, and rubber elastomer
- a preferred container is made of clear, e.g., polyethylene terephthalate
- Other materials can include stainless steel
- the spray dispenser is a manually activated trigger-spray dispenser.
- Said trigger-spray dispenser comprises a container and a trigger both of which can be constructed of any of the conventional material employed in fabricating trigger-spray dispensers, including, but not limited to: polyethylene; polypropylene; polyacetal; polycarbonate; polyethyleneterephthalate; polyvinyl chloride; polystyrene; blends of polyethylene, vinyl acetate, and rubber elastomer. Other materials can include stainless steel and glass.
- a preferred container is made of clear, e.g. polyethylene terephthalate.
- the trigger-spray dispenser does not incorporate a propellant gas into the food cleaning composition, and preferably it does not include those that will foam the food cleaning composition.
- the trigger-spray dispenser herein is typically one which acts upon a discrete amount of the food cleaning composition itself, typically by means of a piston or a collapsing bellows that displaces the composition through a nozzle to create a spray of thin liquid.
- Said trigger-spray dispenser typically comprises a pump chamber having either a piston or bellows which is movable through a limited stroke response to the trigger for varying the volume of said pump chamber. This pump chamber or bellows chamber collects and holds the product for dispensing.
- the trigger spray dispenser typically has an outlet check valve for blocking communication and flow of fluid through the nozzle and is responsive to the pressure inside the chamber.
- the trigger As the trigger is compressed, it acts on the fluid in the chamber and the spring, increasing the pressure on the fluid.
- the bellows spray dispenser As the bellows is compressed, the pressure increases on the fluid.
- the increase in fluid pressure in either trigger spray dispenser acts to open the top outlet check valve.
- the top valve allows the product to be forced through the swirl chamber and out the nozzle to form a discharge pattern.
- An adjustable nozzle cap can be used to vary the pattern of the fluid dispensed.
- the spring acts on the piston to return it to its original position.
- the bellows acts as the spring to return to its original position. This action causes a vacuum in the chamber.
- the responding fluid acts to close the outlet valve while opening the inlet valve drawing product up to the chamber from the reservoir.
- a broad array of trigger sprayers or finger pump sprayers are suitable for use with the compositions of this invention. These are readily available from suppliers such as Calmar, Inc., City of Industry, California; CSI (Continental Sprayers, Inc.),
- the preferred trigger sprayers are the blue inserted Guala sprayer, available from Berry Plastics Corp., or the Calmar TSS00-1A ® , TS1300 ® , and TS-800-2 ® , available from Calmar Inc., because of the fine uniform spray characteristics, spray volume, and pattern size. More preferred are sprayers with precompression features and finer spray characteristics and even distribution, such as Yoshino sprayers from Japan.
- Any suitable bottle or container can be used with the trigger sprayer, the preferred bottle is a 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape to the Cinch bottle.
- It can be made of any materials such as high density polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, glass, or any other material that forms bottles.
- it is made of high density polyethylene or clear polyethylene terephthalate.
- a finger pump can be used with canister or cylindrical bottle.
- the preferred pump for this application is the cylindrical Euromist II from Seaquest Dispensing. More preferred are those with precompression features.
- the article of manufacture herein can also comprise a non-manually operated spray dispenser.
- non-manually operated it is meant that the spray dispenser can be manually activated, but the force required to dispense the food cleaning composition is provided by another, non-manual means.
- Non-manually operated sprayers include, but are not limited to, powered sprayers, air aspirated sprayers, liquid aspirated sprayers, electrostatic sprayers, and nebulizer sprayers.
- the food cleaning composition is placed into a spray dispenser in order to be distributed onto the food and/or food contacting surfaces.
- the non-manually operated spray dispensers are particularly useful to wash and clean a large amount of food and/or a large area of food contacting surfaces, such as in commercial and/or constitutional settings, e.g., in supermarkets, restaurants, cafeterias, and the like
- Powered sprayers include self contained powered pumps that pressurize the aqueous food cleaning composition and dispense it through a nozzle to produce a spray of liquid droplets.
- Powered sprayers are attached directly or remotely through the use of piping/tubing to a reservoir (such as a bottle) to hold the aqueous food cleaning composition
- Powered sprayers may include, but are not limited to, centrifugal or positive displacement designs It is preferred that the powered sprayer be powered by a portable DC electrical current from either disposable batteries (such as commercially available alkaline batteries) or rechargeable battery units (such as commercially available nickel cadmium battery units)
- Powered sprayers may also be powered by standard AC power supply available in most buildings
- the discharge nozzle design can be varied to create specific spray characteristics (such as spray diameter and particle size) It is also possible to have multiple spray nozzles for different spray characteristics
- the nozzle can comprise an adjustable nozzle shroud that would allow the spray characteristics to be altered
- Nonlimiting examples of commercially available powered sprayers are disclosed in U S Pat Nos 4,865,255, Luvisotto, issued Sep 12, 1989 which is incorporated herein by reference Preferred powered sprayers are readily available from suppliers such as Solo, Newport News, Virginia (e g , Solo Spraystar rechargeable sprayer, listed as manual part # US 460 395) and Multi-sprayer Systems, Minneapolis, Minnesota (e g , model Spray 1 )
- Air aspirated sprayers include the classification of sprayers generically known as "air brushes"
- a stream of pressurized air draws up the aqueous food cleaning composition and dispenses it through a nozzle to create a spray of liquid
- the food cleaning composition can be supplied via separate piping/tubing or more commonly is contained in ajar to which the aspirating sprayer is attached
- Air aspirated sprayers are readily available from suppliers such as The Badger Air-Brush Co , Franklin Park, Illinois (e g , model # 155) and Wilton Air Brush Equipment, Woodridge, Illinois (e g , stock # 415-4000, 415-4001, 415- 4100)
- Liquid aspirated sprayers are typical of the variety in widespread use to spray garden chemicals
- the aqueous food cleaning composition is drawn into a fluid stream by means of suction created by a Venturi effect
- the high turbulence serves to mix the aqueous food cleaning composition with the fluid stream (typically water) in order to provide a uniform mixture/concentration It is possible with this method of delivery to dispense the aqueous concentrated food cleaning composition of the present invention and then dilute it to a selected concentration with the delivery stream
- Electrostatic sprayers impart energy to the aqueous food cleaning composition via a high electrical potential. This energy serves to atomize and charge the aqueous food cleaning composition, creating a spray of fine, charged particles. As the charged particles are carried away from the sprayer, their common charge causes them to repel one another. This has two effects before the spray reaches the target. First, it expands the total spray mist. This is especially important when spraying to fairly distant, large areas. The second effect is maintenance of original particle size. Because the particles repel one another, they resist collecting together into large, heavier particles like uncharged particles do. This lessens gravity's influence, and increases the charged particle reaching the target.
- Nonlimiting examples of commercially available electrostatic sprayers appears in U.S. Pat. Nos. 5,222,664, Noakes, issued Jun. 29, 1993; 4,962,885, Coffee, issued Oct. 16, 1990; 2,695,002, Miller, issued Nov. 1954; 5,405,090, Greene, issued Apr. 11, 1995; 4,752,034, Kuhn, issued Jun. 21, 1988; 2,989,241 , Badger, issued Jun. 1961; all of said patents are incorporated herein by reference.
- Electrostatic sprayers are readily available from suppliers such as Tae In Tech Co, South Korea and Spectrum, Houston, Texas.
- Nebulizer sprayers impart energy to the aqueous food cleaning composition via ultrasonic energy supplied via a transducer. This energy results in the aqueous food cleaning composition to be atomized.
- Various types of nebulizers include, but are not limited to, heated, ultrasonic, gas, venturi, and refillable nebulizers.
- Nonlimiting examples of commercially available nebulizer sprayers appears in U.S. Pat. Nos. 3,901,443, Mitsui, issued Aug. 26, 1975; 2,847,248, Schmitt, issued Aug. 1958; 5,51 1,726, Greenspan, issued Apr. 30, 1996; all of said patents are incorporated herein by reference.
- Nebulizer sprayers are readily available from suppliers such as A&D Engineering, Inc., Milpitas, California (e.g., model A&D Un- 231 ultrasonic handy nebulizer) and Amici, Inc , Spring City, Pennsylvania (model swirler nebulizer)
- the preferred article of manufacture herein comprises a non-manually operated sprayer, such as a battery-powered sprayer, containing the aqueous food cleaning composition More preferably the article of manufacture comprises a combination of a non-manually operated sprayer and a separate container of the aqueous food cleaning composition, to be added to the sprayer before use and/or to be separated for filling/refilling
- the separate container can contain a usage composition, or a concentrated composition to be diluted before use, and/or to be used with a diluting sprayer, such as with a liquid aspirated sprayer, as described herein above
- the separate container should have structure that mates with the rest of the sprayer to ensure a solid fit without leakage, even after motion, impact, etc and when handled by inexperienced consumers
- the sprayer desirably can also have an attachment system that is safe and preferably designed to allow for the liquid container to be replaced by another container that is filled E g , the fluid reservoir can be replaced by a filled container This can minimize problems with filling, including minimizing leakage, if the proper mating and sealing means are present on both the sprayer and the container
- the sprayer can contain a shroud to ensure proper alignment and/or to permit the use of thinner walls on the replacement container This minimizes the amount of material to be recycled and/or discarded
- the package sealing or mating system can be a threaded closure (sprayer) which replaces the existing closure on the filled and threaded container
- a gasket is desirably added to provide additional seal security and minimize leakage The gasket can be broken by action of the sprayer closure
- An alternative sealing system can be based on one or more interlocking lugs and channels Such systems are commonly referred to as “bayonet” systems Such systems can be made in a variety of configurations, thus better ensuring that the proper replacement fluid is used
- the locking system can also be one that enables the provision of a "child-proof cap on the refill bottle
- This "lock- and-key" type of system thus provides highly desirable safety features
- the lock and key can be integral to the sealing mechanism.
- the interlocking pieces can be separate from the sealing system.
- the shroud and the container could be designed for compatibility. In this way, the unique design of the container alone could provide the requisite assurance that the proper recharge/refill is used.
- the present invention also relates to methods for removing dirt and other unwanted residues from food, food products, food preparation surfaces and/or food contact surfaces, and to detersive compositions, especially in liquid form, preferably clear compositions, which are especially suitable for practicing said methods.
- the compositions of the present invention typically are applied, e.g., through a trigger-type spray device, directly to soiled food and/or food contact surfaces, optionally with different degree of scaibbing as may be required, and subsequently rinsed off with water.
- fruits and vegetables such as apples, grapes, peaches, potatoes, lettuce, tomatoes, celery, and the like, are sprayed with the liquid compositions of the present invention in a spray device, with light scrubbing as may be required.
- the fruits and vegetables After rinsing in tap water, the fruits and vegetables are cleaner and/or have less organic chemical residues, and are ready for use.
- edible protein food such as meat, poultry, fish and other seafood are sprayed with the compositions of the present invention, slightly scrubbed as needed, and rinsed with tap water to yield foods which are fresher, less odorous and/or less contaminated with microorganisms.
- a cutting board that is used to cut, e.g., fish, seafood, onion, garlic, or other odorous foods, is sprayed with the clear liquid composition of the present invention and scrubbed then rinsed with tap water becomes clean and absent of undesirable smell.
- compositions are typically applied by either a non-manually operated powered spray dispenser, or as dilute solutions in which the produce is dipped.
- the produce is then rinsed to remove the undesirable materials.
- This method is highly desirable for treatment of any produce that is then sealed, e.g., by application of a, e.g., wax, coating.
- the current coating used on apples seals in any pesticide residue on the apple and makes it more difficult to remove.
- the present method improves removal of such pesticides by making them easier to remove. Since pesticides are applied while the produce is still in the field, more complete removal when the produce is picked will improve the produce for the final consumer.
- Some other actives such as some fungicides and sprouting inhibitors and growth regulators are treated after harvest and before packaging, it is desirable to remove them at the point of consumption, e.g., in the consumer's home or at the food preparation areas of restaurants and cafeterias.
- Such large scale cleaning which uses a non-manually operated sprayer to dispense the compositions of the present invention is also very useful for commercial and/or institutional food serving facilities such as restaurants and cafeterias to clean a large amount of fresh fruits and vegetables to serve customers with cleaner and safer food.
- the cyclodextrin solution which contains, e.g., surfactant and/or antimicrobial compound, etc.
- An effective amount means an amount sufficient to remove soils and absorb unwanted materials to the point that consumption by humans is safer and/or more desirable. Distribution can be achieved by using a spray device, a roller, a pad, etc. Soils and other unwanted organic residues can also be removed by dipping the food products or equipment into a bath of the compositions of the present invention.
- the present invention also encompasses the method of spraying an effective amount of cyclodextrin solution onto food preparation surfaces such as countertops, cutting boards, and food containers.
- the present invention relates to the method of spraying a mist of an effective amount of cyclodextrin solution into and/or onto major household appliances including, but not limited to: refrigerators, freezers, ovens, microwave ovens, dishwashers etc., to remove unwanted residues and/or malodor. Unwanted residues can result when, e.g., one sprays the area with consumer products containing chemicals to kill bugs.
- the presence of the surfactant promotes spreading of the solution and the antimicrobial active provides improved odor control as well as antimicrobial action, by minimizing the formation of odors. Both the surfactant and the antimicrobial active provide improved performance and the mixture is especially effective.
- Perfume compositions that are used herein are as follows: Perfume A - Citrus Odor
- compositions are prepared by mixing and dissolving the ingredients in waterto form clear solutions.
- compositions of the above Examples are sprayed onto soiled produce, e.g., fruits and vegetables such as apples, grapes, peaches, potatoes, lettuce, tomatoes, celery, and the like, using a blue inserted Guala® trigger sprayer, available from Berry Plastics Corp , with light scrubbing as may be required
- soiled produce e.g., fruits and vegetables such as apples, grapes, peaches, potatoes, lettuce, tomatoes, celery, and the like
- a blue inserted Guala® trigger sprayer available from Berry Plastics Corp , with light scrubbing as may be required
- the produce is then rinsed in tap water to remove the unwanted materials
- compositions of the above Examples are sprayed onto protein foods such as defrost meat, stored fish and seafood, and the like, that have developed some off odor, using a cylindrical Euromist II® pump sprayer available from Seaquest
- Dispensing with light scrubbing as may be required They are then rinsed in tap water to obtain fresher foods with low off odor
- compositions of Examples I, IV, VIII, and IX are sprayed onto large stainless steel trays that previously are used to marinate chicken quarters, using a rechargeable battery-operated Solo Spraystar sprayer, with scrubbing as may be required The treated trays are then rinsed off in tap water with scrubbing as may be required, let dry, and are ready to be reused
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Abstract
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU79610/98A AU7961098A (en) | 1997-06-09 | 1998-06-09 | Food cleaning compositions containing cyclodextrin |
JP50322399A JP2002504175A (ja) | 1997-06-09 | 1998-06-09 | シクロデキストリンを含有した食品クリーニング組成物 |
HU0100360A HUP0100360A3 (en) | 1997-06-09 | 1998-06-09 | Food cleaning compositions containing cyclodextrin |
EP98930149A EP1124923A1 (fr) | 1997-06-09 | 1998-06-09 | Compositions de nettoyage des aliments renfermant de la cyclodextrine |
CA002293651A CA2293651A1 (fr) | 1997-06-09 | 1998-06-09 | Compositions de nettoyage des aliments renfermant de la cyclodextrine |
KR19997011629A KR20010013619A (ko) | 1997-06-09 | 1998-06-09 | 사이클로덱스트린을 함유하는 식품 세정 조성물 |
BR9810426-8A BR9810426A (pt) | 1997-06-09 | 1998-06-09 | Composições para a limpeza de alimentos contendo ciclodextrina |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US87133997A | 1997-06-09 | 1997-06-09 | |
US87157697A | 1997-06-09 | 1997-06-09 | |
US87104297A | 1997-06-09 | 1997-06-09 | |
US08/871,042 | 1997-06-09 | ||
US08/871,119 US5955093A (en) | 1997-06-09 | 1997-06-09 | Uncomplexed cyclodextrin compositions for odor control |
US08/871,119 | 1997-06-09 | ||
US08/871,339 | 1997-06-09 | ||
US08/871,576 | 1997-06-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998056889A1 true WO1998056889A1 (fr) | 1998-12-17 |
Family
ID=27505958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/012159 WO1998056889A1 (fr) | 1997-06-09 | 1998-06-09 | Compositions de nettoyage des aliments renfermant de la cyclodextrine |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP1124923A1 (fr) |
JP (1) | JP2002504175A (fr) |
KR (1) | KR20010013619A (fr) |
CN (1) | CN1269819A (fr) |
AU (1) | AU7961098A (fr) |
BR (1) | BR9810426A (fr) |
CA (1) | CA2293651A1 (fr) |
HU (1) | HUP0100360A3 (fr) |
ID (1) | ID28183A (fr) |
TR (1) | TR200000439T2 (fr) |
WO (1) | WO1998056889A1 (fr) |
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WO2000030601A1 (fr) * | 1998-11-23 | 2000-06-02 | The Procter & Gamble Company | Compositions de desodorisation et d'assainissement de la peau |
WO2000030600A1 (fr) * | 1998-11-23 | 2000-06-02 | The Procter & Gamble Company | Compositions de desodorisation de la peau |
WO2000030599A1 (fr) * | 1998-11-23 | 2000-06-02 | The Procter & Gamble Company | Compositions de desodorisation et d'assainissement de la peau |
WO2002006437A1 (fr) * | 2000-07-19 | 2002-01-24 | The Procter & Gamble Company | Compositions nettoyantes |
WO2002008373A1 (fr) * | 2000-07-19 | 2002-01-31 | The Procter & Gamble Company | Composition de nettoyage |
US6344218B1 (en) | 1998-11-23 | 2002-02-05 | The Procter & Gamble Company | Skin deodorizing and santizing compositions |
WO2003011350A2 (fr) * | 2001-07-27 | 2003-02-13 | Bausch & Lomb Incorporated | Composition et procede permettant d'inhiber la fixation des desinfectants a base de biguanide par du poly(ethylene) |
WO2003015835A1 (fr) * | 2001-08-17 | 2003-02-27 | Bausch & Lomb Incorporated | Composition et procede d'inhibition de l'assimilation d'agents anti-microbiens a base de biguanide par des hydrogels |
DE102005015328A1 (de) * | 2005-04-01 | 2006-10-05 | Henkel Kgaa | Klares Wasch- und Reinigungsmittel mit Fließgrenze |
WO2008017820A1 (fr) * | 2006-08-05 | 2008-02-14 | Givaudan Nederland Services B.V. | Compositions de parfum |
JP2013116117A (ja) * | 2000-12-15 | 2013-06-13 | Ecolab Inc | 家禽類を処理する際に洗浄する方法及び組成物 |
WO2013148716A3 (fr) * | 2012-03-30 | 2013-12-27 | Robertet, Inc. | Compositions neutralisant les mauvaises odeurs contenant des acides et des cétones alicycliques |
US8632636B1 (en) * | 2006-07-18 | 2014-01-21 | Oral Health Technologies, LLC | Wet wiper articles and methods for cleaning removable dental appliances |
US8741275B2 (en) | 2010-06-04 | 2014-06-03 | Robetet, Inc. | Malodor neutralizing compositions comprising undecylenic acid or citric acid |
US8828917B2 (en) | 2010-08-12 | 2014-09-09 | Segetis, Inc. | Carboxy ester ketal removal compositions, methods of manufacture, and uses thereof |
WO2014151555A1 (fr) * | 2013-03-15 | 2014-09-25 | The Procter & Gamble Company | Compositions de soin personnel |
CN104450225A (zh) * | 2014-11-03 | 2015-03-25 | 唐翊珲 | 一种农药残留清除剂及其制备方法 |
US9156809B2 (en) | 2012-11-29 | 2015-10-13 | Segetis, Inc. | Carboxy ester ketals, methods of manufacture, and uses thereof |
US9200241B2 (en) | 2011-01-27 | 2015-12-01 | Robertet, Inc. | Malodor neutralizing compositions comprising bornyl acetate or isobornyl acetate |
EP2861085A4 (fr) * | 2012-06-12 | 2016-04-13 | Univ Cornell | Nanosystèmes pour la formulation de biocides efficaces à risque minimal |
US9458414B2 (en) | 2012-09-21 | 2016-10-04 | Gfbiochemicals Limited | Cleaning, surfactant, and personal care compositions |
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EP3474907B1 (fr) * | 2016-06-24 | 2020-08-12 | The Procter and Gamble Company | Article absorbant comprenant des complexes de cyclodextrine |
KR102453599B1 (ko) * | 2018-07-16 | 2022-10-17 | (주)덕산테코피아 | 4차 암모늄-시클로덱스트린 또는 그 유도체를 포함하는 포토레지스트 박리액 조성물 |
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- 1998-06-09 CA CA002293651A patent/CA2293651A1/fr not_active Abandoned
- 1998-06-09 BR BR9810426-8A patent/BR9810426A/pt unknown
- 1998-06-09 HU HU0100360A patent/HUP0100360A3/hu unknown
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Cited By (39)
Publication number | Priority date | Publication date | Assignee | Title |
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US6344218B1 (en) | 1998-11-23 | 2002-02-05 | The Procter & Gamble Company | Skin deodorizing and santizing compositions |
WO2000030600A1 (fr) * | 1998-11-23 | 2000-06-02 | The Procter & Gamble Company | Compositions de desodorisation de la peau |
WO2000030599A1 (fr) * | 1998-11-23 | 2000-06-02 | The Procter & Gamble Company | Compositions de desodorisation et d'assainissement de la peau |
WO2000030601A1 (fr) * | 1998-11-23 | 2000-06-02 | The Procter & Gamble Company | Compositions de desodorisation et d'assainissement de la peau |
US6656456B2 (en) | 1998-11-23 | 2003-12-02 | The Procter & Gamble Company | Skin deodorizing compositions |
WO2002008374A1 (fr) * | 2000-07-19 | 2002-01-31 | The Procter & Gamble Company | Composition de nettoyage |
WO2002006437A1 (fr) * | 2000-07-19 | 2002-01-24 | The Procter & Gamble Company | Compositions nettoyantes |
EP1493803A1 (fr) * | 2000-07-19 | 2005-01-05 | The Procter & Gamble Company | Compositions de nettoyage |
WO2002008373A1 (fr) * | 2000-07-19 | 2002-01-31 | The Procter & Gamble Company | Composition de nettoyage |
JP2013116117A (ja) * | 2000-12-15 | 2013-06-13 | Ecolab Inc | 家禽類を処理する際に洗浄する方法及び組成物 |
WO2003011350A2 (fr) * | 2001-07-27 | 2003-02-13 | Bausch & Lomb Incorporated | Composition et procede permettant d'inhiber la fixation des desinfectants a base de biguanide par du poly(ethylene) |
WO2003011350A3 (fr) * | 2001-07-27 | 2003-09-25 | Bausch & Lomb | Composition et procede permettant d'inhiber la fixation des desinfectants a base de biguanide par du poly(ethylene) |
WO2003015835A1 (fr) * | 2001-08-17 | 2003-02-27 | Bausch & Lomb Incorporated | Composition et procede d'inhibition de l'assimilation d'agents anti-microbiens a base de biguanide par des hydrogels |
DE102005015328A1 (de) * | 2005-04-01 | 2006-10-05 | Henkel Kgaa | Klares Wasch- und Reinigungsmittel mit Fließgrenze |
US11957768B2 (en) | 2006-07-18 | 2024-04-16 | Oral Health Technologies, LLC | Wet wiper articles and methods for cleaning removable dental appliances |
US8632636B1 (en) * | 2006-07-18 | 2014-01-21 | Oral Health Technologies, LLC | Wet wiper articles and methods for cleaning removable dental appliances |
US10857075B2 (en) | 2006-07-18 | 2020-12-08 | Oral Health Technologies, LLC | Wet wiper articles and methods for cleaning removable dental appliances |
US9937108B2 (en) | 2006-07-18 | 2018-04-10 | Oral Health Technologies, LLC | Wet wiper articles and methods for cleaning removable dental appliances |
WO2008017820A1 (fr) * | 2006-08-05 | 2008-02-14 | Givaudan Nederland Services B.V. | Compositions de parfum |
US10722607B2 (en) | 2006-08-05 | 2020-07-28 | Givaudan S.A. | Perfume compositions |
US9011829B2 (en) | 2006-08-05 | 2015-04-21 | Givaudan Nederland Services B.V. | Perfume compositions |
US9549886B2 (en) | 2010-05-10 | 2017-01-24 | Gfbiochemicals Limited | Personal care formulations containing alkyl ketal esters and methods of manufacture |
US8741275B2 (en) | 2010-06-04 | 2014-06-03 | Robetet, Inc. | Malodor neutralizing compositions comprising undecylenic acid or citric acid |
US8828917B2 (en) | 2010-08-12 | 2014-09-09 | Segetis, Inc. | Carboxy ester ketal removal compositions, methods of manufacture, and uses thereof |
US9200241B2 (en) | 2011-01-27 | 2015-12-01 | Robertet, Inc. | Malodor neutralizing compositions comprising bornyl acetate or isobornyl acetate |
EP3056247A3 (fr) * | 2012-03-30 | 2016-10-12 | Robertet, Inc. | Compositions de neutralisation des mauvaises odeurs contenant des acides et des cétones alicycliques |
WO2013148716A3 (fr) * | 2012-03-30 | 2013-12-27 | Robertet, Inc. | Compositions neutralisant les mauvaises odeurs contenant des acides et des cétones alicycliques |
US9114180B2 (en) | 2012-03-30 | 2015-08-25 | Robertet, Inc. | Malodor neutralizing compositions containing acids and alicyclic ketones |
EP2861085A4 (fr) * | 2012-06-12 | 2016-04-13 | Univ Cornell | Nanosystèmes pour la formulation de biocides efficaces à risque minimal |
US9458414B2 (en) | 2012-09-21 | 2016-10-04 | Gfbiochemicals Limited | Cleaning, surfactant, and personal care compositions |
US9156809B2 (en) | 2012-11-29 | 2015-10-13 | Segetis, Inc. | Carboxy ester ketals, methods of manufacture, and uses thereof |
US9896645B2 (en) | 2013-03-15 | 2018-02-20 | The Procter & Gamble Company | Personal care compositions |
US10316269B2 (en) | 2013-03-15 | 2019-06-11 | The Procter & Gamble Company | Personal care compositions |
WO2014151171A1 (fr) * | 2013-03-15 | 2014-09-25 | The Procter & Gamble Company | Compositions de soin personnel |
WO2014151555A1 (fr) * | 2013-03-15 | 2014-09-25 | The Procter & Gamble Company | Compositions de soin personnel |
CN105120835A (zh) * | 2013-03-15 | 2015-12-02 | 宝洁公司 | 个人护理组合物 |
CN104450225A (zh) * | 2014-11-03 | 2015-03-25 | 唐翊珲 | 一种农药残留清除剂及其制备方法 |
CN110573053A (zh) * | 2017-06-19 | 2019-12-13 | 松下知识产权经营株式会社 | 餐具清洗机 |
CN110573053B (zh) * | 2017-06-19 | 2022-07-22 | 松下知识产权经营株式会社 | 餐具清洗机 |
Also Published As
Publication number | Publication date |
---|---|
HUP0100360A3 (en) | 2001-12-28 |
EP1124923A1 (fr) | 2001-08-22 |
AU7961098A (en) | 1998-12-30 |
HUP0100360A2 (hu) | 2001-07-30 |
CA2293651A1 (fr) | 1998-12-17 |
KR20010013619A (ko) | 2001-02-26 |
CN1269819A (zh) | 2000-10-11 |
TR200000439T2 (tr) | 2000-11-21 |
BR9810426A (pt) | 2000-09-05 |
ID28183A (id) | 2001-05-10 |
JP2002504175A (ja) | 2002-02-05 |
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