EP0774980A1 - Composition for reducing malodor impression on inanimate surfaces - Google Patents

Composition for reducing malodor impression on inanimate surfaces

Info

Publication number
EP0774980A1
EP0774980A1 EP95928814A EP95928814A EP0774980A1 EP 0774980 A1 EP0774980 A1 EP 0774980A1 EP 95928814 A EP95928814 A EP 95928814A EP 95928814 A EP95928814 A EP 95928814A EP 0774980 A1 EP0774980 A1 EP 0774980A1
Authority
EP
European Patent Office
Prior art keywords
cyclodextrin
composition
beta
weight
cyclodextrins
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP95928814A
Other languages
German (de)
French (fr)
Inventor
Toan Trinh
Jerome Paul Cappel
Philip Anthony Geis
Judith Ann Hollingshead
Mark Lee Mccarty
Donald Marion Swartley
Errol Hoffman Wahl
Susan Schmaedecke Zwerdling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/369,845 external-priority patent/US5939060A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP10180555A priority Critical patent/EP2311502A1/en
Priority to EP02009422A priority patent/EP1232761A1/en
Priority to EP00870010A priority patent/EP1002549A1/en
Priority to DE29522186U priority patent/DE29522186U1/en
Publication of EP0774980A1 publication Critical patent/EP0774980A1/en
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • A61L9/14—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
    • 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
    • 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
    • A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
    • A61L2209/20—Method-related aspects
    • A61L2209/22—Treatment by sorption, e.g. absorption, adsorption, chemisorption, scrubbing, wet cleaning

Definitions

  • the present invention relates to aqueous, preferably clear, compositions, articles of manufacture and/or method of use, for reducing malodor impression, comprising low levels of perfumes; optionally, but preferably, water-soluble cyclodextrin; optionally, but preferably, water-soluble metallic salt; and optionally, but preferably, a solubilizing aid.
  • the compositions are designed to reduce malodor on inanimate surfaces, especially, clothes, e.g., those that have been stored for a long period of time, that are contaminated with environmental odors such as food odors, tobacco odors, and that are wetted with perspiration.
  • the composition is used to restore and/or maintain freshness by reducing malodor without the need for washing or dry cleaning.
  • the present invention relates to aqueous, preferably clear, compositions, articles of manufacture, and or method for use, as a freshening composition.
  • the compositions are sprayed onto fabrics, particularly clothes, to restore their freshness by reducing malodor impression, without washing or dry cleaning.
  • Fabrics treated with some preferred compositions of the present invention also release extra fragrance upon rewetting, such as when the wearer perspires.
  • the freshening compositions of the present invention are designed to extend the wear of fabrics between washing or dry cleaning. Fabrics treated with some preferred freshening compositions of the present invention will stay fresher longer, and receive extra freshening effect via perfume release when it is most needed, that is upon fabric rewetting.
  • Odor masking is the intentional concealment of one odor by the addition of another.
  • the preference to the masking perfume is varied greatly, depending on the application, e.g., underarm odor masking, fabric odor masking, bathroom odor masking, etc.
  • the art teaches the use of perfume as an odor masking device in combination with alcohol in order to solubilize the perfume. It has now been discovered that perfumes with a Clog P of less than 3 do not need alcohol in order to be solubilized and perfumes with a Clog P of greater than 3 can be solubilized with a solubilizing aid.
  • the present invention relates to an aqueous composition for reducing malodor impression, comprising: (A) from about 0.01% to about 1%, by weight of the composition, of perfume;
  • (B) optionally, but preferably, from about 0.1% to about 5%, by weight of the composition of, water-soluble cyclodextrin;
  • (C) optionally, but preferably, from about 0.1% to about 10%, by weight of the composition, of water-soluble metallic salt;
  • composition aqueous carrier; and wherein said composition is essentially free of any material that would soil or stain fabric and wherein said composition contains less than about 5%, by weight of the composition of low molecular weight monohydric alcohols.
  • the composition can be incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of articles and/or surfaces with the composition to reduce malodor at a level that is effective, yet is not discernible when dried on the surface.
  • the present invention relates to an aqueous composition for reducing malodor impression, comprising:
  • (B) optionally, but preferably, from about 0.1% to about 5%, by weight of the composition of, water-soluble cyclodextrin;
  • composition optionally, but preferably, from about 0.1% to about 10%, by weight of the composition, of water-soluble metallic salt;
  • D optionally, but preferably, from about 0% to about 3%, by weight of the composition, of solubilizing aid; and
  • E aqueous carrier; and wherein said composition is essentially free of any material that would soil or stain fabric and wherein said composition contains less than about 5%, by weight of the composition of low molecular weight monohydric alcohols.
  • the perfume selected for use in the fabric freshening composition of the present invention contains ingredients with odor characteristics which are preferred in order to provide a fresh impression on the surface to which the composition is directed, preferably those which provide a fresh impression for fabrics.
  • at least about 25%, more preferably at least about 50%, most preferably at least about 75%, by weight of the perfume is composed of fragrance material selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohols having molecular weights from about 90 to about 240; aliphatic ketones having molecular weights from about 150 to about 260; aromatic ketones having molecular weights from about 150 to about 270; aromatic and aliphatic lactones having molecular weights from about 130 to about 290; aliphatic aldehydes having molecular weights from about 140 to about 200; aromatic aldehydes having molecular weights from about 90 to about 230; aliphatic and aromatic ethers having mole
  • fragrance material selected from the group consisting of:
  • a perfume containing perfume ingredients which are not too hydrophobic.
  • the less hydrophobic perfume ingredients are more soluble in water, and are more available in the freshening composition.
  • the degree of hydrophobicity of a perfume ingredient can be correlated with its octanol/water partitioning coefficient P.
  • the octanol/water partitioning coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water.
  • a perfume ingredient with a greater partitioning coefficient P is more hydrophobic.
  • a perfume ingredient with a smaller partitioning coefficient P is more hydrophilic.
  • the preferred perfume ingredients of this invention have an octanol/water partitioning coefficient P of about 1,000 or smaller. Since the partitioning 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.
  • 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 Clog P 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.
  • hydrophilic perfume when hydrophilic perfume is desired, at least about 25% by weight of the perfume, more preferably about 50%, most preferably about 75%, is composed of perfume ingredients having a Clog P of about 3 or smaller.
  • the freshening composition contains an effective amount of perfume to provide the freshening fragrance to fabrics when first sprayed, some lingering fragrance in-wear, and some extra fragrance to be released upon fabric rewetting.
  • Effective level of perfume is from about 0.01% to about 1%, more preferably from about 0.01% to about 0.5%, most preferably from about 0.015% to about 0.3%, by weight of the composition.
  • the perfume to cyclodextrin weight ratio is typically from about 3: 100 to about 100: 100, preferably from about 4:100 to about 50: 100, more preferably from about 5: 100 to about 40: 100, even more preferably from about 5: 100 to about 25: 100, most preferably from about 1 :8 to about 1 :4.
  • solubilized, water-soluble, uncomplexed cyclodextrin can be added to the composition of the present invention.
  • 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, and the gamma-cyclodextrin consists of eight glucose units arranged in a donut-shaped ring.
  • the specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structure with a hollow interior of a specific volume.
  • the "lining" of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly hydrophobic.
  • the unique shape and physical-chemical property 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. Many perfume molecules can fit into the cavity.
  • Non-derivatised (normal) beta-cyclodextrin can be used although it is not preferred due to its low solubility.
  • the aqueous solution becomes cloudy and is not clear, as preferred by the present invention.
  • the odor absorbing solution of the present invention is clear.
  • the term “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 derivatives thereof, gamma-cyclodextrin and 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 aikyl 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 "CH2-CH(OH)-CH3 or a -CH2CH2-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-(tri
  • 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.
  • 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 DJ EB, in which each glucose unit has about 2 methyl groups with a degree of substitution of about 14.
  • a preferred, more commercially available methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin having a degree of substitution of about 12.6.
  • the preferred cyclodextrins are available, e.g., from American Maize-Products Company and Wacker Chemicals (USA), Inc. It is also preferable to use a mixture of cyclodextrins. Such mixtures can complex with a wider range of perfume molecules having a wider range of molecular sizes.
  • cyclodextrins is alpha-cyclodextrin and its derivatives thereof, gamma-cyclodextrin and its derivatives thereof, and/or derivatised beta-cyclodextrin, and mixtures thereof.
  • Cyclodextrin molecules are known for their ability to form complexes with perfume ingredients and have typically been taught as a perfume carrier.
  • the prior art teaches the use of drier-added fabric softener sheets containing high levels of cyclodextrin/perfume complexes wherein the fabrics treated with this solid cyclodextrin complex release perfume when the fabrics are rewetted.
  • the art also teaches that cyclodextrin/perfume complexes used in aqueous rinse-added fabric softener compositions must be protected, e.g., with a hydrophobic wax coating so the cyclodextrin/perfume complexes will not decompose due to the presence of water. See U.S. Pat.
  • the composition is preferably used as a spray. It is preferable that the composition of the present invention contain low levels of cyclodextrin so that a visible stain does not appear on the fabric at normal usage levels. Preferably, the solution is not discernible when dry. Typical levels of cyclodextrin are from about 0.1% to about 5%, preferably from about 0.2% to about 4%, more preferably from about 0.3% to about 3%, most preferably from about 0.4% to about 2%, by weight of the composition. Compositions with higher concentrations can leave unacceptable visible stains on fabrics as the solution evaporates off of the fabric. This is especially a problem on thin, colored, synthetic fabrics.
  • the fabric be treated at a level of less than about 5 mg of cyclodextrin per mg of fabric, more preferably less than about 2 mg of cyclodextrin per mg of fabric.
  • Concentrated compositions can also be used in order to provide a less expensive product.
  • a concentration i.e., when the level of cyclodextrin used is from about 3% to about 5%, it is preferable to dilute the composition before treating fabrics in order to avoid staining.
  • the cyclodextrin is diluted with about 50% to about 2000%, more preferably with about 60% to about 1000%, most preferably with about 75% to about 500%, by weight of the composition, of water.
  • metallic salt preferably water-soluble zinc salts
  • a water-soluble metallic salt can be used as an odor control agent.
  • a water-soluble metallic salt can be present in the freshening composition of the present invention to absorb amine and sulfur-containing compounds. Furthermore, they usually do not contribute an odor of their own.
  • the water-soluble metallic salts are selected from the group consisting of copper salts, zinc salts, and mixtures thereof.
  • the preferred zinc salts have been used most often for their 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., incorporated herein by reference.
  • U.S. Pat. No. 3,172,817, issued to Leupold, et al. discloses deodorizing compositions containing slightly water-soluble salts of an acyl-acetone with a polyvalent metal, including copper and zinc salts. Said patents are incorporated herein by reference.
  • prefe ed water-soluble zinc salts are zinc chloride, zinc gluconate, zinc lactate, zinc maleate, zinc salicylate, zinc sulfate, etc.
  • Highly-ionized and soluble zinc salts such as zinc chloride, provide the best source of zinc ions.
  • preferred copper salts are copper chloride and copper gluconate.
  • Preferred metallic salts are zinc chloride and copper chloride.
  • Metallic salts are added to the composition of the present invention typically at a level of from about 0.1% to about 10%, preferably from about 0.2% to about 7%, more preferably from about 0.3% to about 5%, by weight of the composition.
  • the freshening composition of the present invention can optionally, but preferably, contain a solubilizing aid to solubilize any excess hydrophobic organic materials, especially the perfume, and also optional ingredients which can be added to the composition, ' e.g., insect repelling agent, antioxidant, etc., that are not readily soluble in the composition, to form a clear solution.
  • a suitable solubilizing aid is surfactant, preferably no-foaming or low-foaming surfactant.
  • Suitable surfactants are nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, preferably nonionic surfactants and cationic surfactants, and mixtures thereof.
  • Anionic surfactants are not preferred, because they can form water-insoluble salts with the metal ions of the preferred metallic salts of this composition.
  • Suitable surfactants can be emulsifiers and/or detersive surfactants. Mixtures of emulsifiers and detersive surfactants are also preferred.
  • a surfactant containing one, or more, alkyl group it is preferred that it contain relatively short alkyl chains of from about 5 to about 14 carbon atoms.
  • Typical nonionic surfactants are polyethylene glycol-polypropylene glycol block copolymers, such as Pluronic® and Pluronic R® surfactants from BASF; Tetronic® and Tetronic R® surfactants from BASF, ethoxylated branched aliphatic diols, such as Surfynol® surfactants from Air Products; ethoxylated alkyl phenols, such as Igepal® surfactants from Rh ⁇ ne-Pou enc; ethoxylated aliphatic alcohols and carboxylic acids; polyethylene glycol diesters of fatty acids; and mixtures thereof.
  • Pluronic® and Pluronic R® surfactants from BASF
  • Tetronic® and Tetronic R® surfactants from BASF ethoxylated branched aliphatic diols, such as Surfynol® surfactants from Air Products
  • ethoxylated alkyl phenols such as Igepal® sur
  • said solubilizing aid is a nonionic surfactant selected from the group consisting of fatty acid esters of ethoxylated sorbitans. More preferably said solubilizing aid is selected from the group consisting of mixtures of laurate esters of sorbitol and sorbitol anhydrides; mixtures of stearate esters of sorbitol and sorbitol anhydrides; and mixtures of oleate esters of sorbitol and sorbitol anhydrides.
  • said solubilizing aid is selected from the group consisting of Polysorbate 20, which is a mixture of laurate esters of sorbitol and sorbitol anhydrides consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; Polysorbate 60 which is a mixture of stearate esters of sorbitol and sorbitol anhydride, consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; Polysorbate 80 which is a mixture of oleate esters of sorbitol and sorbitol anhydrides, consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; and mixtures thereof.
  • Polysorbate 20 is a mixture of laurate esters of sorbitol and sorbitol anhydrides consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide
  • Polysorbate 60 which is a mixture of stearate esters of sorbito
  • said solubilizing aid is Polysorbate 60.
  • Preferred cationic surfactants are di(Cg-Ci2 alkyl)di(Cl-C2 alkyl)ammonium halides, alkylbenzyldimethylammonium halides, amine oxides, and mixtures thereof.
  • Preferred amphoteric surfactants are the betaines. It is preferred that the surfactant have good wetting properties.
  • surfactants that have the hydrophilic groups between hydrophobic chains, such as, Pluronic R surfactants, Surfynol surfactants, polyethylene glycol diesters of fatty acids, fatty acid esters of ethoxylated sorbitans, di(Cg-Ci2 alkyl)di(Cl-C2 alkyl)ammonium halides, and mixtures thereof; surfactants that have hydrophilic groups situated at the extremities of the hydrophobic chain, such as Pluronic surfactants; and mixtures thereof. Mixtures of these surfactants and other types of surfactants are also preferred to form no-foaming or low-foaming solubilizing agents.
  • Polyalkylene glycol can be used as defoaming agent in combination with the solubilizing agents.
  • a solubilizing aid is used in the composition of the present invention, more specifically when fatty acid esters of ethoxylated sorbitans are used as the solubilizing aid, it is preferable to use the process of high shear milling in order aid in the incorporation of excess hydrophobic organic material.
  • solubilizing aids disclosed in the present invention can be used in any type of composition where excess hydrophobic organic material, particularly perfume, separates out of solution and needs assistance to be incorporated into the composition.
  • solubilizing agent When the solubilizing agent is present, it is typically present at a level of from about 0.02% to about 3%, by weight of the composition, more preferably from about 0.05% to about 1%, by weight of the composition, most preferably from about 0.1% to about 0.3%, by weight of the composition.
  • Aqueous solutions are preferred in the present invention for the reduction of malodor impression.
  • the preferred aqueous carrier of the present invention is water.
  • the water which is used can be distilled, deionized, or tap water.
  • Water containing a small amount of low molecular weight monohydric alcohols, e.g., ethanol, methanol, and isopropanol, or polyols, such as ethylene glycol and propylene glycol, can also be useful.
  • the volatile low molecular weight monohydric alcohols such as ethanol and/or isopropanol should be limited since these volatile organic compounds will contribute both to flammability problems and environmental pollution problems.
  • the level of monohydric alcohol be less than about 5%, preferably less than about 3%, more preferably less than about 1%, by weight of the composition.
  • Adjuvants can be optionally added to the freshening composition herein for their known purposes.
  • adjuvants include, but are not limited to, preservatives, defoaming agents, antifoaming agents, bacteriocides, fungicides, antistatic agents, insect and moth repelling agents, colorants, especially bluing agents, antioxidants, and mixtures thereof.
  • solubilized, water-soluble preservatives can be added to the present invention.
  • Preservatives are especially preferred when cyclodextrin is added to the composition of the present invention because cyclodextrin molecules are made up of varying numbers of glucose units which can make them a prime breeding ground for 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 resulting 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 thuringiensis (cereus group) and Bacillus sphaericus: and fungi, e.g.. Aspergi lus ustus.
  • Bacillus sphaericus is one of the most numerous members of Bacillus species in soils.
  • Aspergillus ustus 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 aqueous solutions. It is preferable to use 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.
  • Antimicrobial preservatives useful in the present invention can be 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 perfume molecules for the cyclodextrin cavities, thus rendering the complexed preservatives much less effective.
  • 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., 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 is included in the present invention it 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, but not sufficient enough to contribute to the odor absorbing performance of the composition.
  • the preservative is not 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 composition.
  • the preservative can be any organic preservative material which will not cause damage to fabric appearance, e.g., discoloration, coloration, bleaching.
  • Preferred water-soluble preservatives include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary compounds, dehydroacetic acid, phenyl and phenoxy compounds, and mixtures thereof.
  • Non-limiting examples of the preferred water-soluble preservatives for use in the present invention include a mixture of about 77% 5-chloro-2-methyl-4-isothia- zolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available as a 1.5% aqueous solution under the trade name Kathon® CG by Rohm and Haas Co.; 5-bromo-5-nitro-l,3-dioxane, available under the trade name Bronidox L® from Henkel; 2-bromo-2-nitropropane-l,3-diol, available under the trade name Bronopol® from Inolex; 1 , l'-hexamethylene bis(5-(p- chlorophenyl)biguanide), commonly known as chlorhexidine, and its salts, e.g., with acetic and digluconic acids; a 95:5 mixture of l,3-bis(hydroxymethyl)-5,5-di
  • aqueous compositions of the present invention should have a pH greater than about 3.0, preferably greater than about 4.0, more preferably greater than about 4.5.
  • the preservative can be used at an effective amount, as defined hereinabove.
  • the preservative can be used at a level which provides an antimicrobial effect on the treated fabrics.
  • the composition of the present invention can optionally contain an effective amount of antistatic agent to provide the treated clothes with in-wear static.
  • Preferred antistatic agents are those that are water soluble in at least effective amount, such that the composition remains a clear solution.
  • antistatic agents are onoalkyl cationic quaternary ammonium compounds, e.g., mono(C]o-C]4 alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride, available under the trade name Dehyquart E® from Henkel, and ethyl bis(polyethoxy ethanol) alkylammoniu ethylsulfate, available under the trade name Variquat 66® from Witco Co ., polyethylene glycols, polymeric quaternary ammonium salts, such as polymers conforming to the general formula:
  • a no foaming, or low foaming, agent is used, to avoid foam formation during fabric treatment.
  • polyethoxylated agents such as polyethylene glycol or Variquat 66® are not used when alpha-cyclodextrin is used.
  • the polyethoxylate groups have a strong affinity to, and readily complex with, alpha-cyclodextrin which in turn deplete the uncomplexed cyclodextrin available for the perfume.
  • an antistatic agent it is typically present at a level of from about
  • the composition of the present invention can optionally contain an effective amount of insect and/or moth repelling agents.
  • Typical insect and moth repelling agents are pheromones, such as anti-aggregation pheromones, and other natural and/or synthetic ingredients.
  • Preferred insect and moth repellent agents useful in the composition of the present invention are perfume ingredients, such as citronellol, citranellal, citral, linalool, cedar extract, geranium oil, sandalwood oil, 2- (diethylphenoxy)ethanol, 1-dodecene, etc.
  • Other examples of insect and/or moth repellents useful in the composition of the present invention are disclosed in U.S. Pat.
  • Colorants and dyes can be optionally added to the odor absorbing compositions for visual appeal and performance impression. When colorants are used, they are used at extremely low levels to avoid fabric staining.
  • Preferred colorants for use in the present compositions are highly water-soluble dyes, e.g., Liquitint® dyes available from Milliken Chemical Co.
  • Non-limiting examples of suitable dyes are, Liquitint Blue HP®, Liquitint Blue 65®, Liquitint Patent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow 8949-43®, Liquitint Green HMC®, Liquitint Yellow II®, and mixtures thereof, preferably Liquitint Blue HP®, Liquitint Blue 65®, Liquitint Patent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow 8949-43®, and mixtures thereof.
  • composition of the present invention can also be used in an article of manufacture comprising said composition plus a spray dispenser.
  • the article of manufacture herein comprises a spray dispenser.
  • the composition for reducing malodor impression is placed into a spray dispenser in order to be distributed onto the fabric.
  • Said spray dispenser is any of the manually activated means for producing a spray of liquid droplets as is known in the art, e.g. trigger-type, pump-type, non-aerosol self-pressurized, and aerosol-type spray means.
  • the spray dispenser herein does not include those that will substantially foam the clear, aqueous composition. It is preferred that at least about 80%, more preferably, at least about 90% of the droplets have a particle size of larger than about 30 ⁇ m
  • 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 110 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 odor absorbing 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 odor-absorbing 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.
  • aerosol propellants e.g., gaseous hydrocarbons such as isobutane, and mixed halogenated hydrocarbons
  • Halogenated hydrocarbon propellants such as chlorofluoro hydrocarbons have been alleged to contribute to environmental problems.
  • Hydrocarbon propellants can form complexes with the cyclodextrin molecules thereby reducing the availability of uncomplexed cyclodextrin molecules for odor absorption.
  • Preferred propellants are compressed air, nitrogen, inert gases, carbon dioxide, etc.
  • 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 odor-absorbing fluid 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. 5,111,971, 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 odor absorbing composition from the propellant (preferably compressed air or nitrogen), as disclosed in U.S. Pat. No. 4,260,110, issued April 7, 1981, and incorporated herein by reference. Such a dispenser is available from EP Spray Systems, East Hanover, New Jersey.
  • 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 odor-absorbing composition to be dispensed.
  • the pump mechanism comprises a pump chamber of substantially fixed volume, having an opening at the inner end thereof.
  • 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 odor-absorbing composition, and preferably it does not include those that will foam the odor-absorbing composition.
  • the trigger-spray dispenser herein is typically one which acts upon a discrete amount of the odor- absorbing 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 For the piston type trigger sprayers, 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 For the piston spray dispenser, as the trigger is released, the spring acts on the piston to return it to its original position.
  • the bellows spray dispenser 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.), St. Peters, Missouri; Berry Plastics Corp., Evansville, Indiana — distributor of Guala® sprayers; or Seaquest Dispensing, Cary, Illinois.
  • the preferred trigger sprayers are the blue inserted Guala® sprayer, available from Berry Plastics Corp., or the Calmar TS800-1A sprayers, available from Calmar Inc., because of the fine uniform spray characteristics, spray volume, and pattern size.
  • 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. Preferably, 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.
  • composition for reducing malodor impression herein can be used by distributing, e.g., by placing the aqueous solution into a dispensing means, preferably a spray dispenser and spraying an effective amount onto the desired surface or article.
  • An effective amount as defined herein means an amount sufficient to absorb odor to the point that it is not discernible by the human sense of smell yet not so much as to saturate or create a pool of liquid on said article or surface and so that when dry there is no visual deposit readily discernible. Distribution can be achieved by using a spray device, a roller, a pad, etc.
  • the present invention does not encompass distributing the solution on to shiny surfaces including, e.g., chrome, glass, smooth vinyl, leather, shiny plastic, shiny wood, etc. It is preferable not to distribute the solution onto shiny surfaces because spotting and filming can more readily occur on the surfaces. Furthermore, the solution is not for use on human skin, especially when an antimicrobial preservative is present in the composition because skin irritation can occur.
  • the present invention encompasses the method of spraying an effective amount of the composition for reducing malodor onto household surfaces.
  • household surfaces are selected from the group consisting of countertops, cabinets, walls, floors, bathroom surfaces and kitchen surfaces.
  • the present invention encompasses the method of spraying a mist of an effective amount of the composition for reducing malodor onto fabric and/or fabric articles.
  • said fabric and/or fabric articles include, but are not limited to, clothes, curtains, drapes, upholstered furniture, carpeting, bed linens, bath linens, tablecloths, sleeping bags, tents, car interior, e.g., car carpet, fabric car seats, etc.
  • the present invention encompasses the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto and into shoes wherein said shoes are not sprayed to saturation.
  • the present invention encompasses the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto shower curtains.
  • the present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto and/or into garbage cans and/or recycling bins.
  • the present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression into the air to absorb malodor.
  • the present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression into and/or onto major household appliances including but not limited to: refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers etc., to absorb malodor.
  • the present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto cat litter, pet bedding and pet houses to absorb malodor.
  • the present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto household pets to absorb malodor.
  • Perfume compositions that are used herein are as follows:
  • Perfume D is composed of about 65%, by weight, of ingredients having a Clog P of about 3 or smaller.
  • Perfume E is composed of about 70%, by weight, of ingredients having a Clog P of about 3 or smaller.
  • Examples I and II The ingredients of Examples I and II are mixed and dissolved into clear solutions.
  • Example III The ingredients of Example III are mixed and dissolved into clear solutions.
  • Example IV The ingredients of Example IV are mixed and dissolved into clear solutions. Hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin are obtained as a mixture with an average degree of substitution of about 4.9, from the hydroxypolylation reaction of a mixture of alpha-cyclodextrin and beta-cyclodextrin. Propylene glycol is a minor by-product (about 6%) of the same reaction.
  • Example V Example VI
  • Example VI the hydroxypropyl beta-cyclodextrin and hydroxypropyl gamma-cyclodextrin are obtained as a mixture with an average degree of substitution of about 3.8, from the hydroxypolylation reaction of a mixture of beta-cyclodextrin and gamma-cyclodextrin.
  • Example XI and XII are mixed and dissolved into clear solutions.
  • the zinc chloride of Examples XIII and XIV is added to distilled water. Kathon CG is added to this mixture with mixing. The pH is adjusted to about 4.0 with HCl. The cyclodextrin is dissolved into the solution with mixing. Perfume is added and milled into the solution using a high shear mixer. Solubilizing aid is then added while high shear mixing continues.
  • Example IV The composition of Example IV is sprayed onto clothing using a blue inserted Guala® trigger sprayer, available from Berry Plastics Corp. and allowed to evaporate off of the clothing.
  • Example VII The composition of Example VII is sprayed onto a kitchen countertop using blue inserted Guala® trigger sprayer, available from Berry Plastics Corp., and wiped off with a paper towel.
  • Example X The composition of Example X is sprayed onto clothes using a cylindrical Euromist II® pump sprayer available from Seaquest Dispensing, and allowed to evaporate off of the clothing.
  • compositions of Examples XIII and XIV are sprayed onto clothes using a blue inserted Guala® trigger sprayer, available from Berry Plastics Corp, and allowed to evaporate off of the clothing.

Abstract

The present invention relates to an aqueous composition for reducing malodor impression. The composition comprises from about 0.01 % to about 1 %, by weight of the composition, of perfume. Optionally, but preferably, the composition comprises from about 0.1 % to about 5 %, by weight of the composition of, water-soluble cyclodextrin, from about 0.1 % to about 10 %, by weight of the composition, of water-soluble metallic salt, from about 0 % to about 3 %, by weight of the composition, of solubilizing aid. The composition is essentially free of any material that would soil or stain fabric and contains less than about 5 %, by weight of the composition of low molecular weight monohydric alcohols.

Description

COMPOSITION FOR REDUCING MALODOR IMPRESSION ON INANIMATE SURFACES
TECHNICAL FIELD
The present invention relates to aqueous, preferably clear, compositions, articles of manufacture and/or method of use, for reducing malodor impression, comprising low levels of perfumes; optionally, but preferably, water-soluble cyclodextrin; optionally, but preferably, water-soluble metallic salt; and optionally, but preferably, a solubilizing aid. Preferably, the compositions are designed to reduce malodor on inanimate surfaces, especially, clothes, e.g., those that have been stored for a long period of time, that are contaminated with environmental odors such as food odors, tobacco odors, and that are wetted with perspiration. Preferably the composition is used to restore and/or maintain freshness by reducing malodor without the need for washing or dry cleaning.
BACKGROUND OF THE INVENTION The present invention relates to aqueous, preferably clear, compositions, articles of manufacture, and or method for use, as a freshening composition. Preferably, the compositions are sprayed onto fabrics, particularly clothes, to restore their freshness by reducing malodor impression, without washing or dry cleaning. Fabrics treated with some preferred compositions of the present invention also release extra fragrance upon rewetting, such as when the wearer perspires. The freshening compositions of the present invention are designed to extend the wear of fabrics between washing or dry cleaning. Fabrics treated with some preferred freshening compositions of the present invention will stay fresher longer, and receive extra freshening effect via perfume release when it is most needed, that is upon fabric rewetting.
Odor masking is the intentional concealment of one odor by the addition of another. The preference to the masking perfume is varied greatly, depending on the application, e.g., underarm odor masking, fabric odor masking, bathroom odor masking, etc. The art teaches the use of perfume as an odor masking device in combination with alcohol in order to solubilize the perfume. It has now been discovered that perfumes with a Clog P of less than 3 do not need alcohol in order to be solubilized and perfumes with a Clog P of greater than 3 can be solubilized with a solubilizing aid.
SUMMARY OF THE INVENTION The present invention relates to an aqueous composition for reducing malodor impression, comprising: (A) from about 0.01% to about 1%, by weight of the composition, of perfume;
(B) optionally, but preferably, from about 0.1% to about 5%, by weight of the composition of, water-soluble cyclodextrin;
(C) optionally, but preferably, from about 0.1% to about 10%, by weight of the composition, of water-soluble metallic salt;
(D) optionally, but preferably, from about 0% to about 3%, by weight of the composition, of solubilizing aid; and
(E) aqueous carrier; and wherein said composition is essentially free of any material that would soil or stain fabric and wherein said composition contains less than about 5%, by weight of the composition of low molecular weight monohydric alcohols.
The composition can be incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of articles and/or surfaces with the composition to reduce malodor at a level that is effective, yet is not discernible when dried on the surface.
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous composition for reducing malodor impression, comprising:
(A) from about 0.01% to about 1%, by weight of the composition, of perfume;
(B) optionally, but preferably, from about 0.1% to about 5%, by weight of the composition of, water-soluble cyclodextrin;
(C) optionally, but preferably, from about 0.1% to about 10%, by weight of the composition, of water-soluble metallic salt; (D) optionally, but preferably, from about 0% to about 3%, by weight of the composition, of solubilizing aid; and (E) aqueous carrier; and wherein said composition is essentially free of any material that would soil or stain fabric and wherein said composition contains less than about 5%, by weight of the composition of low molecular weight monohydric alcohols.
I. COMPOSITION (A) PERFUME
The perfume selected for use in the fabric freshening composition of the present invention contains ingredients with odor characteristics which are preferred in order to provide a fresh impression on the surface to which the composition is directed, preferably those which provide a fresh impression for fabrics. Preferably, at least about 25%, more preferably at least about 50%, most preferably at least about 75%, by weight of the perfume is composed of fragrance material selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohols having molecular weights from about 90 to about 240; aliphatic ketones having molecular weights from about 150 to about 260; aromatic ketones having molecular weights from about 150 to about 270; aromatic and aliphatic lactones having molecular weights from about 130 to about 290; aliphatic aldehydes having molecular weights from about 140 to about 200; aromatic aldehydes having molecular weights from about 90 to about 230; aliphatic and aromatic ethers having molecular weights from about 150 to about 270; and condensation products of aldehydes and amines having molecular weights from about 180 to about 320; and essentially free from nitromusks and halogenated fragrance materials.
More preferably, at least about 25%, more preferably .at least about 50%, most preferably at least about 75%, by weight of the perfume is composed of fragrance material selected from the group consisting of:
Common Name Chemical Type Chemical Name Approx. M.W. adoxal aliphatic aldehyde 2,6, lO-trimethyl-9-undecen-l-al 210 allyl amyl glycolate ester allyl amyl glycolate 182 allyl cyclohexane propionate ester allyl-3-cyclohexyl propionate 1% amyl acetate ester 3 -methyl- 1-butanol acetate 130 amyl salicylate ester amyl salicylate 208 anisic aldehyde aromatic aldehyde 4-methoxy benzaldehyde 136 aurantiol schiff base condensation product of methyl 305 anthranilate and hydroxycitronellal bacdanol aliphatic alcohol 2-ethyl-4-(2,2,3-trimethyl-3- 208 cvclopenten- 1 -y l)-2-buten- 1 -ol benzaldehvde aromatic aldehvde benzaldehyde 106 benzophenone aromatic ketone benzophenone 182 benzyl acetate ester benzyl acetate 150 benzyl salicylate ester benzyl salicylate 228 beta damascene aliphatic ketone 1 -(2,6,6-trimethyl- 1 -cyclo-hexen- 192 l-yl)-2-buten-l-one beta gamma hexanol alcohol 3-hexen-l-ol 100 buccoxime aliphatic ketone l.S-dimethyl-oxime bicyclo[3,2,l] 167 octan-8-one cedrol alcohol octahydro-3 ,6,8,8-tetramethyl- 222 lH-3A,7-methanoazulen-6-ol cetalox ether dodecahydro-3 A,6,6,9 A- 236 tetramethylnaphtho[2, lB]-furan cis-3-hexenyl acetate ester cis-3-hexenyl acetate 142 cis-3-hexenyl salicylate ester beta, gamma-hexenyl salicylate 220 citronellol alcohol 3,7-dimethyl-ό-octenol 156 citronellyl nitrile nitrile geranyl nitrile 151 clove stem oil natural coumahn lactone coumarin 146 cyclohexyl salicylate ester cyclohexyl salicylate 220 cymal aromatic aldehyde 2-methyl-3-<para iso propyl 190 phenyl)propionaldehyde decyl aldehyde aliphatic aldehyde decyl aldehyde 156 delta damascene aliphatic ketone l-(2,6,6-trimethyl-3-cyclo-hexen- 192 l-yl)-2-buten-l-one dihydromyrcenol alcohol 3-methylene-7-methyl octan-7-ol 156 dimethyl benzyl carbinyl ester dimethyl benzyl carbinyl acetate 192 acetate ethyl vanillin aromatic aldehyde ethyl vanillin 166 ethyl-2-methyl butyrate ester ethyl-2-methyl butyrate 130 ethylene brassylate macrocyclic ethylene tridecan-l,13-dioate 270 lactone eucalyptoi aliphatic epoxide 1 ,8-epoxy-para-menthane 154 eugenol alcohol 4-allyl-2-methoxy phenol 164 exaltolide macrocyclic cyclopentadecanolide 240 lactone lor acetate ester dihydro-nor-cyclopentadienyl 190 acetate florhvdral aromatic aldehvde 3-(3-isopropylphenvl) butanal 190 frutene ester dihydro-nor-cyclopentadienyl 206 propionate galaxolide ether 1,3,4,6,7,8-hexahydro- 258 4,6,6,7,8,8- hexamethylcyclopenta-gamma-2- benzopyrane gamma decalactone lactone 4-N-hepty-4-hydroxybutanoic 170 acid lactone gamma dodecalactone lactone 4-N-octyl-4-hydroxy-butanoic 198 acid lactone geraniol alcohol 3 ,7-dimethyl-2,6-octadien- l-ol 154 geranyl acetate ester 3,7-dimethyl-2,6-octadien- 1 -yl 196 acetate geranyl nitrile ester 3,7-diemthyl-2.6-octadienenitrile 149 helional aromatic aldehyde alpha-methyl-3,4, 192 (methylenedioxy) hydrocinnamaldehyde heliotropin aromatic aldehyde heliotropin 150 hexyl acetate ester hexyl acteate 144 hexyl cinnamic aldehyde aromatic aldehyde alpha-n-hexyl cinnamic aldehyde 216 hexyl salicylate ester hexyl salicylate 222 hydroxyambran aliphatic alcohol 2-cyclododecyl-propanol 226 hydroxycitronellal aliphatic aldehdye hydroxycitronellal 172 ionone alpha aliphatic ketone 4-<2,6,6-trimethyl-l- 192 cyclohexenyl- 1 -yl)-3-buten-2-one ionone beta aliphatic ketone 4-{2,6,6-trimethyl-l -cyclohexen- 192 1 -yl)-3-butene-2-one ionone gamma methyl aliphatic ketone 4-(2,6,6-trimethyl-2-cyclohexyl- 206 1 -yl)-3-methyI-3 -buten-2-one iso E super aliphatic ketone 7-acetyl-l,2,3,4,5,6,7,8- 234 octahydro-1, l,6,7,tetramethyl naphthalene iso eugenol ether 2-methoxy-4-{l-propcnyl) phenol 164 isojasmone aliphatic ketone 2-methyl-3-(2-pentenyl)-2- 166 cyclopenten-1-one koavone aliphatic aldehyde acetyi di-isoamylene 182 lauric aldehyde aliphatic aldehyde lauric aldehyde 184 lavandin natural lavender natural lemon CP natural major component d-limonene d-limonene orange terpenes alkene 1 -methy 1-4-iso-propenyl- 1 - 136 cvclohexene linalool alcohol 3-hydroxy-3 ,7-dimethy I- 1 ,6- 154 octadiene linalyl acetate ester 3-hydroxy-3,7-dimethyl-l,6- 196 octadiene acetate lrg 201 ester 2,4-dihydroxy-3,6-dimethyl 1% benzoic acid methyl ester lyral aliphatic aldehyde 4-{4-hydroxy-4-methyl-pentyl) 3- 210 cylcohexene- 1 -carboxaldehyde majantol aliphatic alcohol 2,2-dimethyl-3-(3-methylphenyl)- 178 propanol mayol alcohol 4-(l -methy lethyl) cyclohexane 156 methanol methyl anthranilate aromatic amine methyl-2-aminobenzoate 151 methyl beta naphthyl ketone aromatic ketone methyl beta naphthyl ketone 170 methyl cedrylone aliphatic ketone methyl cedrenyl ketone 246 methyl chavicol ester 1 -methyloxy-4,2-propen- 148 1-yl benzene methyl dihydro jasmonate aliphatic ketone methyl dihydro jasmonate 226 methyl nonyl acetaldehyde aliphatic aldehyde methyl nonyl acetaldehyde 184 musk -ndanone aromatic ketone 4-acetyl-6-tert butyl- 1,1 -dimethyl 244 indane nerol alcohol 2-cis-3,7-dimethyl-2,6-octadien- 154 l-ol nonalactone lactone 4-hydroxynonanoic acid, lactone 156 norlimbanol aliphatic alcohol H2,2,6-trimethyl-cyclohexyl)-3- 226 hexanol orange CP natural major component d-limonene
P. T. bucinal aromatic aldehyde 2-methyl-3(para tert butylphenyl) 204 propionaldehyde para hydroxy phenyl butanone aromatic ketone para hydroxy phenyl butanone 164 patchouli natural 1 phenyl acetaldehyde aromatic aldehyde 1 -oxo-2-phenylethane 120 phenyl acetaldehyde dimethyl aromatic aldehyde phenyl acetaldehyde dimethyl 166 acetaJ acetal phenyl ethyl acetate ester phenyl ethyl acetate 164 phenyl ethyl alcohol alcohol phenyl ethyl alcohol 122 phenyl ethyl phenyl acetate ester 2-phenyIethyl phenyl acetate 240 phenyl hexanol/phenoxanol alcohol 3-methyl-5-phenylpentanol 178 polysantol aliphatic alcohol 3,3-dimethyl-5-{2,2,3-trimethyl- 221
3-cyclopenten- l-yl)-4-penten-2-ol prenyl acetate ester 2-methylbuten-2-ol-4-acetate 128 rosaphen aromatic alcohol 2-methyl-5-phenyl pentanol 178 sandal wood natural alpha-te inene aliphatic alkane l-methyl-4-iso- 136 propy lcyclohexadiene- 1 , 3 teφineol (alpha terpineol and alcohol para-menth-l-en-8-ol, para- 154 beta teφineol) menth-1-en-l-ol teφinyl acetate ester para-menth-l-en-8-yl acetate 196 tetra hydro linalool aliphtic alcohol 3,7-dimethyl-3-octanol 158 tetrahydromyrcenol aliphatic alcohol 2.6-dimethyl-2-octanol 158 tonalid/musk plus aromatic ketone 7-acetyl- 1,1,3 ,4,4,6-hexamethyl 258 tetralin undecalactone lactone 4-N-heptyl-4-hydroxybutanoic 184 acid lactone undecavertol alcohol 4-methyl-3-decen-5-ol 170 undecyl aldehyde aliphatic aldehyde undecanal 170 undecylenic aldehyde aliphatic aldehyde undecylenic aldehyde 168 vanillin aromatic aldehyde 4-hydroxy-3- 152 methoxybenzaldehyde verdox ester 2-tert-butyl cyclohexyl acetate 198 vertenex ester 4-tert-butyl cyclohexyl acetate 198
and mixtures thereof.
When high initial perfume odor impact on fabrics is desired, it is also preferable to select a perfume containing perfume ingredients which are not too hydrophobic. The less hydrophobic perfume ingredients are more soluble in water, and are more available in the freshening composition. The degree of hydrophobicity of a perfume ingredient can be correlated with its octanol/water partitioning coefficient P. The octanol/water partitioning coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. A perfume ingredient with a greater partitioning coefficient P is more hydrophobic. Conversely, a perfume ingredient with a smaller partitioning coefficient P is more hydrophilic. The preferred perfume ingredients of this invention have an octanol/water partitioning coefficient P of about 1,000 or smaller. Since the partitioning 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.
The logP of many perfume ingredients has been reported; for example, the Pomona 92 database, available from Daylight Chemical Information Systems, Inc. (Daylog CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOG P" program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona 92 database. The "calculated logP" (Clog P) is determined by the fragment approach of Hansch and Leo (cf, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sarnrnens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference). 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 Clog P 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.
When hydrophilic perfume is desired, at least about 25% by weight of the perfume, more preferably about 50%, most preferably about 75%, is composed of perfume ingredients having a Clog P of about 3 or smaller.
Preferably the freshening composition contains an effective amount of perfume to provide the freshening fragrance to fabrics when first sprayed, some lingering fragrance in-wear, and some extra fragrance to be released upon fabric rewetting. Effective level of perfume is from about 0.01% to about 1%, more preferably from about 0.01% to about 0.5%, most preferably from about 0.015% to about 0.3%, by weight of the composition. When cyclodextrin is added to the composition of the present invention, the perfume to cyclodextrin weight ratio is typically from about 3: 100 to about 100: 100, preferably from about 4:100 to about 50: 100, more preferably from about 5: 100 to about 40: 100, even more preferably from about 5: 100 to about 25: 100, most preferably from about 1 :8 to about 1 :4. (B) CYCLODEXTRIN
Optionally, but preferably, solubilized, water-soluble, uncomplexed cyclodextrin can be added to the composition of the present invention. As used herein, the term "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, and the gamma-cyclodextrin consists of eight glucose units arranged in a donut-shaped ring. The specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structure with a hollow interior of a specific volume. The "lining" of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly hydrophobic. The unique shape and physical-chemical property 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. Many perfume molecules can fit into the cavity.
Non-derivatised (normal) beta-cyclodextrin can be used although it is not preferred due to its low solubility. When non-derivatised beta-cyclodextrin is used, the aqueous solution becomes cloudy and is not clear, as preferred by the present invention. Not to be limited by theory, it is believed that some beta-cyclodextrin and/or beta-cyclodextrin/perfume complexes solidify and/or precipitate out producing an undesirable cloudy aqueous solution.
Preferably, the odor absorbing solution of the present invention is clear. The term "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.
Preferably, the cyclodextrins used in the present invention are highly water- soluble such as, alpha-cyclodextrin and derivatives thereof, gamma-cyclodextrin and 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 aikyl 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 "CH2-CH(OH)-CH3 or a -CH2CH2-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-(trimethylammonio)propyl ether chloride groups, wherein R is CH2-CH(OH)-CH2-N+(CH3)3Cl"; anionic cyclodextrins such as carboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrin succinylates; amphoteric cyclodextrins such as carboxymethyl/quaternary ammonium cyclodextrins; cyclodextrins wherein at least one glucopyranose unit has a 3-6-anhydro-cyclomalto structure, e.g., the mono-3-6-anhydrocyclodextrins, as disclosed in "Optimal Performances with Minimal Chemical Modification of Cyclodextrins", F. Diedaini- Pilard and B. Perly, The 7th International Cyclodextrin Symposium Abstracts, April 1994, p. 49, herein incorporated by reference; and mixtures thereof. Other cyclodextrin derivatives are disclosed in U.S. Pat. Nos: 3,426,011, Parmerter et al., issued Feb. 4, 1969; 3,453,257; 3,453,258; 3,453,259; and 3,453,260, all in the names of Parmerter et al., and all issued July 1, 1969; 3,459,731, Gramera et al., issued Aug. 5, 1969; 3,553,191, Parmerter et al., issued Jan. 5, 1971; 3,565,887, Parmerter et al., issued Feb. 23, 1971; 4,535,152, Szejtli et al., issued Aug. 13, 1985; 4,616,008, Hirai et al., issued Oct. 7, 1986; 4,678,598, Ogino et al., issued Jul. 7, 1987; 4,638,058, Brandt et al., issued Jan. 20, 1987; and 4,746,734, Tsuchiyama et al., issued May 24, 1988; all of said patents being incorporated herein by reference. 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. 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-β-cyclodextrin, commonly known as DJ EB, in which each glucose unit has about 2 methyl groups with a degree of substitution of about 14. A preferred, more commercially available methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin having a degree of substitution of about 12.6. The preferred cyclodextrins are available, e.g., from American Maize-Products Company and Wacker Chemicals (USA), Inc. It is also preferable to use a mixture of cyclodextrins. Such mixtures can complex with a wider range of perfume molecules having a wider range of molecular sizes. Preferably at least a portion of the cyclodextrins is alpha-cyclodextrin and its derivatives thereof, gamma-cyclodextrin and its derivatives thereof, and/or derivatised beta-cyclodextrin, and mixtures thereof.
Cyclodextrin molecules are known for their ability to form complexes with perfume ingredients and have typically been taught as a perfume carrier. The prior art teaches the use of drier-added fabric softener sheets containing high levels of cyclodextrin/perfume complexes wherein the fabrics treated with this solid cyclodextrin complex release perfume when the fabrics are rewetted. The art also teaches that cyclodextrin/perfume complexes used in aqueous rinse-added fabric softener compositions must be protected, e.g., with a hydrophobic wax coating so the cyclodextrin/perfume complexes will not decompose due to the presence of water. See U.S. Pat. Nos. 5,102,564 Gardlik et al., issued April 7, 1992; 5,234,610, Gardlik et al., issued August 10, 1993; 5,234,611 Trinh, et al., issued August 10, 1993, all of said patents incorporated herein by reference. It is therefore highly surprising and unexpected to find that fabrics treated with the aqueous compositions of the present invention, which contain low levels of unprotected cyclodextrin, also exhibit perfume release upon rewetting. This phenomenon provides a benefit in that fabrics treated with the composition of the present invention will thus remain fresh longer, via a perfume release, when said fabrics are rewetted, such as when the wearer perspires.
For reducing malodor impression on fabrics, the composition is preferably used as a spray. It is preferable that the composition of the present invention contain low levels of cyclodextrin so that a visible stain does not appear on the fabric at normal usage levels. Preferably, the solution is not discernible when dry. Typical levels of cyclodextrin are from about 0.1% to about 5%, preferably from about 0.2% to about 4%, more preferably from about 0.3% to about 3%, most preferably from about 0.4% to about 2%, by weight of the composition. Compositions with higher concentrations can leave unacceptable visible stains on fabrics as the solution evaporates off of the fabric. This is especially a problem on thin, colored, synthetic fabrics. In order to avoid or minimize the occurrence of fabric staining, it is preferable that the fabric be treated at a level of less than about 5 mg of cyclodextrin per mg of fabric, more preferably less than about 2 mg of cyclodextrin per mg of fabric.
Concentrated compositions can also be used in order to provide a less expensive product. When a concentration is used, i.e., when the level of cyclodextrin used is from about 3% to about 5%, it is preferable to dilute the composition before treating fabrics in order to avoid staining. Preferably the cyclodextrin is diluted with about 50% to about 2000%, more preferably with about 60% to about 1000%, most preferably with about 75% to about 500%, by weight of the composition, of water. (C) METALLIC SALT
Optionally, but preferably, metallic salt, preferably water-soluble zinc salts, can be added to the composition of the present invention. A water-soluble metallic salt can be used as an odor control agent. A water-soluble metallic salt can be present in the freshening composition of the present invention to absorb amine and sulfur-containing compounds. Furthermore, they usually do not contribute an odor of their own. Preferably the water-soluble metallic salts are selected from the group consisting of copper salts, zinc salts, and mixtures thereof.
The preferred zinc salts have been used most often for their 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., incorporated herein by reference. U.S. Pat. No. 3,172,817, issued to Leupold, et al., discloses deodorizing compositions containing slightly water-soluble salts of an acyl-acetone with a polyvalent metal, including copper and zinc salts. Said patents are incorporated herein by reference. Examples of prefe ed water-soluble zinc salts are zinc chloride, zinc gluconate, zinc lactate, zinc maleate, zinc salicylate, zinc sulfate, etc. Highly-ionized and soluble zinc salts such as zinc chloride, provide the best source of zinc ions. Examples of preferred copper salts are copper chloride and copper gluconate. Preferred metallic salts are zinc chloride and copper chloride. Metallic salts are added to the composition of the present invention typically at a level of from about 0.1% to about 10%, preferably from about 0.2% to about 7%, more preferably from about 0.3% to about 5%, by weight of the composition. 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. (D) SOLUBILIZING AID
The freshening composition of the present invention can optionally, but preferably, contain a solubilizing aid to solubilize any excess hydrophobic organic materials, especially the perfume, and also optional ingredients which can be added to the composition,' e.g., insect repelling agent, antioxidant, etc., that are not readily soluble in the composition, to form a clear solution. A suitable solubilizing aid is surfactant, preferably no-foaming or low-foaming surfactant. Suitable surfactants are nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, preferably nonionic surfactants and cationic surfactants, and mixtures thereof. Anionic surfactants are not preferred, because they can form water-insoluble salts with the metal ions of the preferred metallic salts of this composition. Suitable surfactants can be emulsifiers and/or detersive surfactants. Mixtures of emulsifiers and detersive surfactants are also preferred. When a surfactant containing one, or more, alkyl group is used, it is preferred that it contain relatively short alkyl chains of from about 5 to about 14 carbon atoms. Typical nonionic surfactants are polyethylene glycol-polypropylene glycol block copolymers, such as Pluronic® and Pluronic R® surfactants from BASF; Tetronic® and Tetronic R® surfactants from BASF, ethoxylated branched aliphatic diols, such as Surfynol® surfactants from Air Products; ethoxylated alkyl phenols, such as Igepal® surfactants from Rhόne-Pou enc; ethoxylated aliphatic alcohols and carboxylic acids; polyethylene glycol diesters of fatty acids; and mixtures thereof. Preferably, said solubilizing aid is a nonionic surfactant selected from the group consisting of fatty acid esters of ethoxylated sorbitans. More preferably said solubilizing aid is selected from the group consisting of mixtures of laurate esters of sorbitol and sorbitol anhydrides; mixtures of stearate esters of sorbitol and sorbitol anhydrides; and mixtures of oleate esters of sorbitol and sorbitol anhydrides. Even more preferably said solubilizing aid is selected from the group consisting of Polysorbate 20, which is a mixture of laurate esters of sorbitol and sorbitol anhydrides consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; Polysorbate 60 which is a mixture of stearate esters of sorbitol and sorbitol anhydride, consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; Polysorbate 80 which is a mixture of oleate esters of sorbitol and sorbitol anhydrides, consisting predominantly of the monoester, condensed with about 20 moles of ethylene oxide; and mixtures thereof. Most preferably, said solubilizing aid is Polysorbate 60. Preferred cationic surfactants are di(Cg-Ci2 alkyl)di(Cl-C2 alkyl)ammonium halides, alkylbenzyldimethylammonium halides, amine oxides, and mixtures thereof. Preferred amphoteric surfactants are the betaines. It is preferred that the surfactant have good wetting properties. Also preferred are surfactants that have the hydrophilic groups between hydrophobic chains, such as, Pluronic R surfactants, Surfynol surfactants, polyethylene glycol diesters of fatty acids, fatty acid esters of ethoxylated sorbitans, di(Cg-Ci2 alkyl)di(Cl-C2 alkyl)ammonium halides, and mixtures thereof; surfactants that have hydrophilic groups situated at the extremities of the hydrophobic chain, such as Pluronic surfactants; and mixtures thereof. Mixtures of these surfactants and other types of surfactants are also preferred to form no-foaming or low-foaming solubilizing agents. Polyalkylene glycol can be used as defoaming agent in combination with the solubilizing agents. When a solubilizing aid is used in the composition of the present invention, more specifically when fatty acid esters of ethoxylated sorbitans are used as the solubilizing aid, it is preferable to use the process of high shear milling in order aid in the incorporation of excess hydrophobic organic material.
The solubilizing aids disclosed in the present invention, specifically the fatty acid esters of ethoxylated sorbitan, can be used in any type of composition where excess hydrophobic organic material, particularly perfume, separates out of solution and needs assistance to be incorporated into the composition.
When the solubilizing agent is present, it is typically present at a level of from about 0.02% to about 3%, by weight of the composition, more preferably from about 0.05% to about 1%, by weight of the composition, most preferably from about 0.1% to about 0.3%, by weight of the composition. (E) AQUEOUS CARRIER
Aqueous solutions are preferred in the present invention for the reduction of malodor impression. The preferred aqueous carrier of the present invention is water. The water which is used can be distilled, deionized, or tap water. Water containing a small amount of low molecular weight monohydric alcohols, e.g., ethanol, methanol, and isopropanol, or polyols, such as ethylene glycol and propylene glycol, can also be useful. However, the volatile low molecular weight monohydric alcohols such as ethanol and/or isopropanol should be limited since these volatile organic compounds will contribute both to flammability problems and environmental pollution problems. If small amounts of low molecular weight monohydric alcohols are present in the composition of the present invention due to the addition of these alcohols to such things as perfumes and as stabilizers for some preservatives, it is preferably that the level of monohydric alcohol be less than about 5%, preferably less than about 3%, more preferably less than about 1%, by weight of the composition.
It has recently been discovered that water has an unexpected odor controlling effect of its own. It has been discovered that the intensity of the odor generated by some polar, low molecular weight organic amines, acids, and mercaptans is reduced when the odor-contaminated fabrics are treated with an aqueous solution. Not to be bound by theory, it is believed that water solubilizes and depresses the vapor pressure of these polar, low molecular weight organic molecules, thus reducing their odor intensity. (F) OTHER OPTIONAL INGREDIENTS
Adjuvants can be optionally added to the freshening composition herein for their known purposes. Such adjuvants include, but are not limited to, preservatives, defoaming agents, antifoaming agents, bacteriocides, fungicides, antistatic agents, insect and moth repelling agents, colorants, especially bluing agents, antioxidants, and mixtures thereof. (1) Preservative
Optionally, solubilized, water-soluble preservatives can be added to the present invention. Preservatives are especially preferred when cyclodextrin is added to the composition of the present invention because cyclodextrin molecules are made up of varying numbers of glucose units which can make them a prime breeding ground for 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 resulting in an unsightly and/or malodorous solution. Because microbial growth in cyclodextrin solutions is highly objectionable when it occurs, it is preferable to include 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 thuringiensis (cereus group) and Bacillus sphaericus: and fungi, e.g.. Aspergi lus ustus. Bacillus sphaericus is one of the most numerous members of Bacillus species in soils. Aspergillus ustus 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 aqueous solutions. It is preferable to use 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. Antimicrobial preservatives useful in the present invention can be 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 perfume molecules for the cyclodextrin cavities, thus rendering the complexed preservatives much less effective. 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., 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. Therefore, many well known preservatives such as short chain alkyl esters of p-hydroxybenzoic acid, commonly known as parabens; N-(4-chlorophenyl)-N'- (3,4-dichlorophenyl) urea, also known as 3,4,4'-trichlorocarbanilide or triclocarban; 2,4,4'-trichloro-2,-hydroxy diphenyl ether, commonly known as triclosan are not preferred in the present invention since they are relatively ineffective when used in conjunction with cyclodextrin.
The water-soluble antimicrobial preservative is included in the present invention it is included at an effective amount. The term "effective amount" as herein defined means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time, but not sufficient enough to contribute to the odor absorbing performance of the composition. In other words, the preservative is not 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 composition.
The preservative can be any organic preservative material which will not cause damage to fabric appearance, e.g., discoloration, coloration, bleaching. Preferred water-soluble preservatives include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary compounds, dehydroacetic acid, phenyl and phenoxy compounds, and mixtures thereof.
Non-limiting examples of the preferred water-soluble preservatives for use in the present invention include a mixture of about 77% 5-chloro-2-methyl-4-isothia- zolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available as a 1.5% aqueous solution under the trade name Kathon® CG by Rohm and Haas Co.; 5-bromo-5-nitro-l,3-dioxane, available under the trade name Bronidox L® from Henkel; 2-bromo-2-nitropropane-l,3-diol, available under the trade name Bronopol® from Inolex; 1 , l'-hexamethylene bis(5-(p- chlorophenyl)biguanide), commonly known as chlorhexidine, and its salts, e.g., with acetic and digluconic acids; a 95:5 mixture of l,3-bis(hydroxymethyl)-5,5-dimethyl- 2,4-imidazolidinedione and 3-butyl-2-iodopropynyl carbamate, available under the trade name Glydant Plus® from Lonza; N-[l,3-bis(hydroxymethyI)2,5-dioxo-4- imidazolidinyl]-N,N'-bis(hydroxy-methyl) urea, commonly known as diazolidinyl urea, available under the trade name Germall II® from Sutton Laboratories, Inc.; N,N"-methylenebis { N'-[ 1 -(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 115® from Sutton Laboratories, Inc.; polymethoxy bicyclic oxazolidine, available under the trade name Nuosept® C from Hϋls America; formaldehyde; glutaraldehyde; polyaminopropyl biguanide; available under the trade name Cosmocil CQ® from ICI Americas, Inc., or under the trade name Mikrokill® from Brooks, Inc; dehydroacetic acid; and mixtures thereof.
Bacteriostatic effects can sometimes be obtained for aqueous compositions by adjusting the composition pH to an acid pH, e.g., less than about pH 4, preferably less than about pH 3. Low pH for microbial control is not a preferred approach in the present invention because the low pH can cause chemical degradation of the cyclodextrins. Therefore, aqueous compositions of the present invention should have a pH greater than about 3.0, preferably greater than about 4.0, more preferably greater than about 4.5.
As stated above, it is preferable to use the preservative at an effective amount, as defined hereinabove. Optionally however, the preservative can be used at a level which provides an antimicrobial effect on the treated fabrics. (2) Antistatic Agents The composition of the present invention can optionally contain an effective amount of antistatic agent to provide the treated clothes with in-wear static. Preferred antistatic agents are those that are water soluble in at least effective amount, such that the composition remains a clear solution. Examples of these antistatic agents are onoalkyl cationic quaternary ammonium compounds, e.g., mono(C]o-C]4 alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride, available under the trade name Dehyquart E® from Henkel, and ethyl bis(polyethoxy ethanol) alkylammoniu ethylsulfate, available under the trade name Variquat 66® from Witco Co ., polyethylene glycols, polymeric quaternary ammonium salts, such as polymers conforming to the general formula:
-[N(CH3)2-(CH2)3-NH-CO-NH-(CH2)3-N(CH3)2+-CH2CH2OCH2CH2l-x 2+ 2x[Cl"l
available under the trade name Mirapol A- 15® from Rhόne-Poulenc, and
-[N(CH3)2-(CH2)3-NH-CO-(CH2)4-CO-NH-(CH2)3-N(CH3)2-(CH2CH2θCH2CH2l-x + x[CI"],
available under the trade name Mirapol AD-1® from Rhόne-Poulenc, quaternized polyethyleneimines, vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer, available under the trade name Gafquat HS-100® from GAF; triethonium hydrolyzed collagen ethosulfate, available under the trade name Quat-Pro
E® from Maybrook; and mixtures thereof.
It is preferred that a no foaming, or low foaming, agent is used, to avoid foam formation during fabric treatment. It is also preferred that polyethoxylated agents such as polyethylene glycol or Variquat 66® are not used when alpha-cyclodextrin is used. The polyethoxylate groups have a strong affinity to, and readily complex with, alpha-cyclodextrin which in turn deplete the uncomplexed cyclodextrin available for the perfume. When an antistatic agent is used it is typically present at a level of from about
0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.3% to about 3%, by weight of the composition.
(3) Insect and/or Moth Repelling Agent
The composition of the present invention can optionally contain an effective amount of insect and/or moth repelling agents. Typical insect and moth repelling agents are pheromones, such as anti-aggregation pheromones, and other natural and/or synthetic ingredients. Preferred insect and moth repellent agents useful in the composition of the present invention are perfume ingredients, such as citronellol, citranellal, citral, linalool, cedar extract, geranium oil, sandalwood oil, 2- (diethylphenoxy)ethanol, 1-dodecene, etc. Other examples of insect and/or moth repellents useful in the composition of the present invention are disclosed in U.S. Pat.
Nos. 4,449,987, 4,693,890, 4,696,676, 4,933,371, 5,030,660, 5, 196,200, and in "Semio Activity of Flavor and Fragrance Molecules on Various Insect Species", B.D. Mookherjee et al., published in Bioactive Volatile Compounds from Plants. ASC Symposium Series 525, R. Teranishi, R.G. Buttery, and H. Sugisawa, 1993, pp. 35- 48, all of said patents and publications incorporated herein by reference. When an insect and/or moth repellent is used it is typically present at a level of from about 0.005% to about 3%, , by weight of the composition. (4) Colorant
Colorants and dyes, especially bluing agents, can be optionally added to the odor absorbing compositions for visual appeal and performance impression. When colorants are used, they are used at extremely low levels to avoid fabric staining. Preferred colorants for use in the present compositions are highly water-soluble dyes, e.g., Liquitint® dyes available from Milliken Chemical Co. Non-limiting examples of suitable dyes are, Liquitint Blue HP®, Liquitint Blue 65®, Liquitint Patent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow 8949-43®, Liquitint Green HMC®, Liquitint Yellow II®, and mixtures thereof, preferably Liquitint Blue HP®, Liquitint Blue 65®, Liquitint Patent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow 8949-43®, and mixtures thereof.
H. ARTICLE OF MANUFACTURE The composition of the present invention can also be used in an article of manufacture comprising said composition plus a spray dispenser. SPRAY DISPENSER
The article of manufacture herein comprises a spray dispenser. The composition for reducing malodor impression is placed into a spray dispenser in order to be distributed onto the fabric. Said spray dispenser is any of the manually activated means for producing a spray of liquid droplets as is known in the art, e.g. trigger-type, pump-type, non-aerosol self-pressurized, and aerosol-type spray means. The spray dispenser herein does not include those that will substantially foam the clear, aqueous composition. It is preferred that at least about 80%, more preferably, at least about 90% of the droplets have a particle size of larger than about 30μm 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 110 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 odor absorbing 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 odor-absorbing 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. Common aerosol propellants, e.g., gaseous hydrocarbons such as isobutane, and mixed halogenated hydrocarbons, are not preferred. Halogenated hydrocarbon propellants such as chlorofluoro hydrocarbons have been alleged to contribute to environmental problems. Hydrocarbon propellants can form complexes with the cyclodextrin molecules thereby reducing the availability of uncomplexed cyclodextrin molecules for odor absorption. Preferred propellants are compressed air, nitrogen, inert gases, carbon dioxide, etc. A more complete description of commercially available aerosol- spray dispensers appears in U.S. Pat. Nos.: 3,436,772, Stebbins, issued April 8, 1969; and 3,600,325, Kaufman et al., issued .August 17, 1971; both of said references are incorporated herein by reference. Preferably 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 odor-absorbing fluid 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. 5,111,971, 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 odor absorbing composition from the propellant (preferably compressed air or nitrogen), as disclosed in U.S. Pat. No. 4,260,110, issued April 7, 1981, and incorporated herein by reference. Such a dispenser is available from EP Spray Systems, East Hanover, New Jersey.
More preferably, 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 odor-absorbing 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. A more complete disclosure of commercially available dispensing devices appears in: U.S. Pat. Nos.: 4,895,279, Schultz, issued January 23, 1990; 4,735,347, Schultz et al., issued April 5, 1988; and 4,274,560, Carter, issued June 23, 1981; all of said references are herein incorporated by reference.
Most preferably, 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 odor-absorbing composition, and preferably it does not include those that will foam the odor-absorbing composition. The trigger-spray dispenser herein is typically one which acts upon a discrete amount of the odor- absorbing 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. For the piston type trigger sprayers, as the trigger is compressed, it acts on the fluid in the chamber and the spring, increasing the pressure on the fluid. For 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. For the piston spray dispenser, as the trigger is released, the spring acts on the piston to return it to its original position. For the bellows spray dispenser, 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 more complete disclosure of commercially available dispensing devices appears in U.S. Pat. Nos. 4,082,223, Nozawa, issued Apr. 4, 1978; 4,161, 288, McKinney, issued Jul. 17, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984; and 4,819,835, Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr. 19, 1994; all of said references are incorporated herein by reference.
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.), St. Peters, Missouri; Berry Plastics Corp., Evansville, Indiana — distributor of Guala® sprayers; or Seaquest Dispensing, Cary, Illinois.
The preferred trigger sprayers are the blue inserted Guala® sprayer, available from Berry Plastics Corp., or the Calmar TS800-1A sprayers, available from Calmar Inc., because of the fine uniform spray characteristics, spray volume, and pattern size. 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. Preferably, it is made of high density polyethylene or clear polyethylene terephthalate. For smaller four fl-oz. size (about 118 ml), 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.
HI. METHOD OF USE The composition for reducing malodor impression herein can be used by distributing, e.g., by placing the aqueous solution into a dispensing means, preferably a spray dispenser and spraying an effective amount onto the desired surface or article. An effective amount as defined herein means an amount sufficient to absorb odor to the point that it is not discernible by the human sense of smell yet not so much as to saturate or create a pool of liquid on said article or surface and so that when dry there is no visual deposit readily discernible. Distribution can be achieved by using a spray device, a roller, a pad, etc. Preferably, the present invention does not encompass distributing the solution on to shiny surfaces including, e.g., chrome, glass, smooth vinyl, leather, shiny plastic, shiny wood, etc. It is preferable not to distribute the solution onto shiny surfaces because spotting and filming can more readily occur on the surfaces. Furthermore, the solution is not for use on human skin, especially when an antimicrobial preservative is present in the composition because skin irritation can occur.
The present invention encompasses the method of spraying an effective amount of the composition for reducing malodor onto household surfaces. Preferably said household surfaces are selected from the group consisting of countertops, cabinets, walls, floors, bathroom surfaces and kitchen surfaces.
The present invention encompasses the method of spraying a mist of an effective amount of the composition for reducing malodor onto fabric and/or fabric articles. Preferably, said fabric and/or fabric articles include, but are not limited to, clothes, curtains, drapes, upholstered furniture, carpeting, bed linens, bath linens, tablecloths, sleeping bags, tents, car interior, e.g., car carpet, fabric car seats, etc.
The present invention encompasses the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto and into shoes wherein said shoes are not sprayed to saturation. The present invention encompasses the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto shower curtains.
The present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto and/or into garbage cans and/or recycling bins.
The present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression into the air to absorb malodor.
The present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression into and/or onto major household appliances including but not limited to: refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers etc., to absorb malodor.
The present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto cat litter, pet bedding and pet houses to absorb malodor. The present invention relates to the method of spraying a mist of an effective amount of the composition for reducing malodor impression onto household pets to absorb malodor.
All percentages, ratios, and parts herein, in the Specification, Examples, and Claims are by weight and are approximations unless otherwise stated.
The following are non-limiting examples of the instant composition. Perfume compositions that are used herein are as follows:
A B C
Perfume Ingredients Wt.% Wt.% Wt.%
3 ,7-Dimethyl-6-octenol 10 - 5
Benzyl salicylate 5 20 5
Benzyl acetate 10 15 5
Benzophenone 3 5 -
Octahydro-3,6,8,8-tetramethyl-lH-3A,
7-methanoazulen-6-ol 2 - -
3-Methylene-7-methyl octan-7-ol 10 - 5
Dihydro-nor-cyclopentadienyl acetate 5 - 5
1,3,4,6, 7,8-Hexahydro-4,6,6,7,8,8- hexamethyl-cyclopenta- gamma-2-benzopyrane 10 - -
Phenyl ethyl alcohol 15 10 20
3 -Hydroxy-3 , 7-dimethyl- 1 ,6- octadiene acetate 4 - 5
3-Hydroxy-3,7-dimethyl-l,6-octadiene 6 15 5
Methyl dihydro jasmonate 3 10 5
2-Methyl-3(para tert butylphenyl) propionaldehdye 10 15 20
Phenyl ethyl acetate 2 5 1
4-Hydroxy-3 -methoxybenzaldehyde - - 1 para-Menth-l-en-8-ol, para-menth-
1-en-l-ol 5 - 8
Anisic aldehyde - - 2
Coumarin - - 5
2-Methyl-3-(para iso propylphenyl) propionaldehyde - - 3
Total 100 100 100 D E
Perfume Material Wt.% Wt.%
Amyl salicylate 8 - Benzyl acetate 8 8
Benzyl Salicylate - 2
Citronellol 7 27
Dihydromyrcenol 2 -
Eugenol 4 - Flor acetate 8 -
Galaxolide 1 -
Geraniol 5 -
Hexyl cinnamic aldehyde 2 -
Hydroxycitronellal 3 - Lilial 2 -
Linalool 12 13
Linalyl acetate 5 -
Lyral 3 -
Methyl dihydrojasmonate 3 - Nerol 2 -
Phenoxy ethyl propionate - 3
Phenylethyl acetate 5 17
Phenylethyl alcohol 8 17 alpha-Terpineol 5 13 alpha-Terpinene 5 -
Tetrahydromyrcenol 2 -
Total 100 100
Perfume D is composed of about 65%, by weight, of ingredients having a Clog P of about 3 or smaller.
Perfume E is composed of about 70%, by weight, of ingredients having a Clog P of about 3 or smaller.
The following are non-limiting examples of the instant composition.
Example I Example II
Ingredients Wt.% Wt.%
Methylated beta-cyclodextrin 0.2 - Hydroxypropyl beta- cyclodextrin - 0.2
Zinc chloride 1.0 1.0
Perfume A 0.02 -
Perfume B - 0.02
HC1 (a) (a)
Distilled water Balance Balance
(a) To adjust solution pH to about 4.8
Examples I and II The ingredients of Examples I and II are mixed and dissolved into clear solutions.
Example III Example IV
Ingredients Wt.% Wt.% Methylated alpha-cyclodextrin 0.1 -
Methylated beta-cyclodextrin 0.1 -
Hydroxypropyl alpha-cyclodextrin - 0.11
Hydroxypropyl beta-cyclodextrin - 0.29
Propylene glycol - 0.025 Zinc chloride 2.0 1.0
Perfume C 0.03 -
Perfume D - 0.02
HC1 (a) (a)
Distilled water Balance Balance (a) To adjust solution pH to about 4.8
Example HI
The ingredients of Example III are mixed and dissolved into clear solutions.
Example IV
The ingredients of Example IV are mixed and dissolved into clear solutions. Hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin are obtained as a mixture with an average degree of substitution of about 4.9, from the hydroxypolylation reaction of a mixture of alpha-cyclodextrin and beta-cyclodextrin. Propylene glycol is a minor by-product (about 6%) of the same reaction. Example V Example VI
Ingredients Wt.% Wt.%
Methylated beta-cyclodextrin 0.5 -
Hydroxypropyl beta-cyclodextrin - 0.6
Hydroxypropyl gamma-cyclodextrin - 0.3
Zinc chloride 1.0 1.5
Perfume E 0.1 -
Perfume E - 0.15
HC1 (a) (a)
Distilled water Balance Balance
(a) To adjust solution pH to about 4.8
Examples V and VI
The ingredients of Examples V and VI are mixed and dissolved into clear solutions. In Example VI, the hydroxypropyl beta-cyclodextrin and hydroxypropyl gamma-cyclodextrin are obtained as a mixture with an average degree of substitution of about 3.8, from the hydroxypolylation reaction of a mixture of beta-cyclodextrin and gamma-cyclodextrin.
Example VII Example VIII
Ingredients Wt.% wt.%
Methylated beta-cyclodextrin 0.5 -
Hydroxypropyl-beta-cyclodextrin - 0.5
Zinc chloride 1.0 1.0
Perfume E 0.1 0.1
Kathon CG 0.0008 0.0008
HC1 (a) (a)
Distilled water Balance Balance
(a) To adjust solution pH to about 4.8
Examples VII and VIII
The ingredients of Examples VII and VIII are mixed and dissolved into clear solutions.
Example IX Example X
Ingredients Wt.% Wt.%
Methylated beta-cyclodextrin 0.3 -
Hydroxypropyl-beta-cyclodextrin - 0.3 Zinc chloride 1.0 1.0
Perfume D 0.03 0.03
Kathon CG 0.0008 0.0008
Surfynol 4651 0.1 0.1
HC1 (a) (a)
Distilled water Balance Balance
(a) To adjust solution pH to about 4.8
1 Surfynol 465® available from Air Products, has the general structure:
Examples IX and X
The ingredients of Examples IX and X are mixed and dissolved into clear solutions.
Example XI Example XTI
Ingredients Wt.% Wt.%
Methylated beta-cyclodextrin 0.5 -
Hydroxypropyl beta-cyclodextrin - 0.5
ZnSO «7H2O 2.2 2.2
Perfume D 0.03 -
Perfume E - 0.04
Glydant Plus® 0.01 0.01
Distilled Water Balance Balance
Example XI and XII
The ingredients of Example XI and XII are mixed and dissolved into clear solutions.
Example XIII Example XIV
Ingredients Wt. % Wt.%
Methylated beta-cyclodextrin 1.0 -
Hydroxypropyl beta-cyclodextrin - 1.0 Zinc chloride 1.0 1.0
Polysorbate 60 0.07 0.07
Kathon CG 0.0008 0.0008
HCL * *
Perfume 0.07 0.07
Distilled Water Balance Balance
*To adjust pH to about 4.0.
Example XV
The zinc chloride of Examples XIII and XIV is added to distilled water. Kathon CG is added to this mixture with mixing. The pH is adjusted to about 4.0 with HCl. The cyclodextrin is dissolved into the solution with mixing. Perfume is added and milled into the solution using a high shear mixer. Solubilizing aid is then added while high shear mixing continues.
Examples XVI
The composition of Example IV is sprayed onto clothing using a blue inserted Guala® trigger sprayer, available from Berry Plastics Corp. and allowed to evaporate off of the clothing.
Example XVII
The composition of Example VII is sprayed onto a kitchen countertop using blue inserted Guala® trigger sprayer, available from Berry Plastics Corp., and wiped off with a paper towel.
Example X m
The composition of Example X is sprayed onto clothes using a cylindrical Euromist II® pump sprayer available from Seaquest Dispensing, and allowed to evaporate off of the clothing.
Example XTX
The compositions of Examples XIII and XIV are sprayed onto clothes using a blue inserted Guala® trigger sprayer, available from Berry Plastics Corp, and allowed to evaporate off of the clothing.

Claims

1. An aqueous composition for reducing malodor impression, comprising:
(A) from 0.01% to 1%, preferably from 0.01% to 0.5%, more preferably from 0.015% to 0.3%, by weight of the composition, of perfume preferably comprised of perfume ingredients having a Clog P of 3 or smaller, more preferably comprised of perfume ingredients selected from the group consisting of benzaldehyde, benzyl acetate, cis-3- hexenyl acetate, coumarin, dihydromyrcenol, dimethyl benzyl carbinyl acetate, ethyl vanillin, eucalyptol, eugenol, iso eugenol, flor acetate, geraniol, hydroxycitronellal, koavone, linalool, methyl anthranilate, methyl beta naphthyl ketone, methyl dihydro jasmonate, nerol, nonalactone, phenyl ethyl acetate, phenyl ethyl alcohol, alpha teφineol, beta teφineol, vanillin, and mixtures thereof;
(B) aqueous carrier; and wherein said composition is essentially free of any material that would soil or stain fabric and wherein said composition contains less than 5%, by weight of the composition, of low molecular weight monohydric alcohols.
2. The composition of Claim 1 additionally comprising at least one additional ingredient selected from the group consisting of:
A. from 0.1% to 5%, preferably from 0.2% to 4%, more preferably from 0.3% to 3%, by weight of the composition, of solubilized, water- soluble, uncomplexed cyclodextrin, preferably selected from the group consisting of derivatised beta-cyclodextrins, alpha-cyclodextrin and its derivatives, gamma-cyclodextrin and its derivatives, and mixtures thereof, wherein the perfume to cyclodextrin weight ratio is from 3:100 to 100:100, preferably from 4:100 to 50:100, more preferably from 5:100 to 25:100;
B. from 0.1% to 10%, preferably from 0.2% to 7%, by weight of the composition, of water-soluble metallic salts selected from the group consisting of water-soluble zinc salts, water-soluble copper salts, and mixtures thereof, preferably zinc chloride, or zinc gluconate, or zinc lactate, or zinc maleate, or zinc salicylate, or zinc sulfate, or copper chloride, or copper gluconate, or mixtures thereof, more preferably, zinc chloride;
C. from 0% to 3%, preferably from 0.05% to 1%, by weight of the composition, of solubilizing aid, preferably a low foaming surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof; or D. an effective amount, preferably from 0.0001% to 0.5%, more preferably from 0.0002% to 0.2%, and most preferably from 0.0003% to 0.1%, by weight of the composition, of solubilized, water-soluble, antimicrobial preservative having a water solubility of greater than 0.3%, at room temperature.
3. The composition of any of Claims 2-4 wherein said cyclodextrin derivatives are selected from the group consisting of methyl substituted cyclodextrins, ethyl substituted cyclodextrins, hydroxyalkyl substituted cyclodextrins, branched cyclodextrins, cationic cyclodextrins, quaternary ammonium cyclodextrins, anionic cyclodextrins, amphoteric cyclodextrins, cyclodextrins wherein at least one glucopyranose unit has a 3-6-anhydro-cyclomalto structure, and mixtures thereof.
4. The composition of Claim 2 wherein said cyclodextrin is selected from the group consisting of alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl alpha-cyclodextrin, hydroxyethyl beta-cyclodextrin, hydroxypropyl alpha-cyclodextrin, hydroxypropyl beta-cyclodextrin, and mixtures thereof, preferably methylated beta-cyclodextrin, or a mixture of methylated alpha- cyclodextrin and methylated beta-cyclodextrin, or hydroxypropyl beta-cyclodextrin, or a mixture of hydroxypropyl beta-cyclodextrin and hydroxypropyl alpha- cyclodextrin.
5. The composition of Claim 2 wherein said preservative is selected from the group consisting of organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary compounds, phenyl and phenoxy compounds, and mixtures thereof.
6. An article of manufacture, which comprises the composition of each of the above claims and a spray dispenser, preferably selected from the group consisting of aerosol spray dispensers; self pressurized, non-aerosol spray dispensers; pump-spray dispensers; and trigger spray-dispensers, more preferably pump-spray dispensers or trigger spray dispensers wherein said dispenser comprises a container comprising transparent polyethylene terephthalate.
7. The method of treating an inanimate article or surface, to remove malodor, which comprises distributing an effective amount of the composition of any of the Claims 1-5, preferably using the article of manufacture of Claim 6, onto said article or surface, preferably fabric, or household surfaces, or shoes, or garbage cans and recycling bins, or the air, or major household appliances, or cat litter, or pets and pet beds, the fabric and shoes preferably not being sprayed to saturation, more preferably, clothes, or curtains, or drapes, or upholstered furniture, or bed linens, or tents, or sleeping bags, or car seats, or car caφeting and fabric interiors, or countertops, or walls, or floors, or bathroom surfaces, or kitchen surfaces, wherein said composition is virtually not discernible when dried on said article or surface.
EP95928814A 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces Ceased EP0774980A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP10180555A EP2311502A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces
EP02009422A EP1232761A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression
EP00870010A EP1002549A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces
DE29522186U DE29522186U1 (en) 1994-08-12 1995-08-10 Composition for reducing the perception of an unpleasant odor from inanimate surfaces

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
US289991 1988-12-21
US28997094A 1994-08-12 1994-08-12
US28973194A 1994-08-12 1994-08-12
US28999194A 1994-08-12 1994-08-12
US289970 1994-08-12
US289731 1994-08-12
US08/369,845 US5939060A (en) 1994-08-12 1995-01-06 Composition for reducing malodor impression on inanimate surfaces
US369845 1995-01-06
PCT/US1995/010210 WO1996004940A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces

Related Child Applications (3)

Application Number Title Priority Date Filing Date
EP02009422A Division EP1232761A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression
EP10180555A Division EP2311502A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces
EP00870010A Division EP1002549A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces

Publications (1)

Publication Number Publication Date
EP0774980A1 true EP0774980A1 (en) 1997-05-28

Family

ID=27501512

Family Applications (3)

Application Number Title Priority Date Filing Date
EP95928814A Ceased EP0774980A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces
EP10180555A Ceased EP2311502A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces
EP00870010A Withdrawn EP1002549A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces

Family Applications After (2)

Application Number Title Priority Date Filing Date
EP10180555A Ceased EP2311502A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces
EP00870010A Withdrawn EP1002549A1 (en) 1994-08-12 1995-08-10 Composition for reducing malodor impression on inanimate surfaces

Country Status (11)

Country Link
EP (3) EP0774980A1 (en)
JP (3) JP3810433B2 (en)
AU (1) AU3242995A (en)
BR (1) BR9508569A (en)
CA (2) CA2330720C (en)
CZ (1) CZ289396B6 (en)
DE (1) DE29522186U1 (en)
MX (1) MX9701122A (en)
PL (1) PL318553A1 (en)
RU (1) RU2149025C1 (en)
WO (1) WO1996004940A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0949006A1 (en) 1998-04-08 1999-10-13 The Procter & Gamble Company A packaged product
EP1059122A1 (en) 1999-06-07 2000-12-13 The Procter & Gamble Company A spray device with flat fan nozzle
EP1133322B1 (en) * 1998-11-25 2003-09-24 The Procter & Gamble Company Improved uncomplexed cyclodextrin compositions for odor control

Families Citing this family (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR9701048A (en) 1994-08-12 1998-12-15 Procter & Gamble Non-complex odor cyclodextrin solutions on inanimate surfaces
US5733535A (en) * 1995-10-25 1998-03-31 The Procter & Gamble Co. Topical compositions containing N-acetylcysteine and odor masking materials
US5911976A (en) * 1996-10-24 1999-06-15 The Procter & Gamble Company Compositions for reducing body odor
US5879666A (en) * 1996-10-24 1999-03-09 The Procter & Gamble Company Methods and compositions for reducing body odor
ID23044A (en) * 1996-10-24 2000-01-13 Procter & Gamble METHODS AND COMPOSITIONS TO REDUCE SMELL BODY
US5882638A (en) * 1996-10-24 1999-03-16 The Proctor & Gamble Company Methods using uncomplexed cyclodextrin solutions for controlling environmental odors
US5874067A (en) * 1996-10-24 1999-02-23 The Procter & Gamble Company Methods for controlling environmental odors on the body
US5897855A (en) * 1996-10-24 1999-04-27 The Procter & Gamble Company Methods and compositions for reducing body odor
US5780020A (en) * 1996-10-28 1998-07-14 The Proctor & Gamble Company Methods and compositions for reducing body odor
US5885599A (en) * 1996-10-28 1999-03-23 The Procter & Gamble Company Methods and compositions for reducing body odors and excess moisture
US6103678A (en) * 1996-11-07 2000-08-15 The Procter & Gamble Company Compositions comprising a perfume and an amino-functional polymer
JP2002514912A (en) * 1996-12-17 2002-05-21 ザ、プロクター、エンド、ギャンブル、カンパニー Animal care system and litter with reduced odor
US6287550B1 (en) 1996-12-17 2001-09-11 The Procter & Gamble Company Animal care system and litter with reduced malodor impression
US6656923B1 (en) 1997-06-09 2003-12-02 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor and wrinkle control
WO1998056337A1 (en) * 1997-06-09 1998-12-17 The Procter & Gamble Company Malodor reducing composition containing amber and musk materials
US5861145A (en) * 1997-06-09 1999-01-19 The Procter & Gamble Company Method of reducing body odor using perfumed, odor absorbing, two phase compositions
US5861144A (en) * 1997-06-09 1999-01-19 The Procter & Gamble Company Perfumed compositions for reducing body odors and excess moisture
US5942214A (en) * 1997-06-09 1999-08-24 The Procter & Gamble Company Methods for controlling environmental odors on the body using compositions comprising uncomplexed cyclodextrins and perfume
US5874070A (en) * 1997-06-09 1999-02-23 The Procter & Gamble Company Compositions for reducing body odor
US5871718A (en) * 1997-06-09 1999-02-16 The Procter & Gamble Company Perfumed two phase compositions for reducing body odor
US6001343A (en) * 1997-06-09 1999-12-14 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor and wrinkle control
JP4459309B2 (en) * 1997-06-09 2010-04-28 ザ、プロクター、エンド、ギャンブル、カンパニー Uncomplexed cyclodextrin composition for odor control
JP4219413B2 (en) * 1997-06-09 2009-02-04 ザ、プロクター、エンド、ギャンブル、カンパニー Uncomplexed cyclodextrin composition for odor and wrinkle control
US5861147A (en) * 1997-06-09 1999-01-19 The Procter & Gamble Company Methods for controlling environmental odors on the body using compositions comprising uncomplexed cyclodextrins and perfume
US5955093A (en) * 1997-06-09 1999-09-21 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US5861143A (en) * 1997-06-09 1999-01-19 The Procter & Gamble Company Methods for reducing body odors and excess moisture
US5861146A (en) * 1997-06-09 1999-01-19 The Procter & Gamble Company Method for reducing body odor
US5897854A (en) * 1997-06-09 1999-04-27 The Procter & Gamble Company Methods for reducing body odor
AU740240B2 (en) * 1998-04-27 2001-11-01 Procter & Gamble Company, The Improved uncomplexed cyclodextrin compositions for odor control
WO1999055814A1 (en) * 1998-04-27 1999-11-04 The Procter & Gamble Company Improved uncomplexed cyclodextrin compositions for odor and wrinkle control
US6528013B1 (en) 1998-04-27 2003-03-04 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor and wrinkle control
BR9815836A (en) * 1998-04-27 2000-12-26 Procter & Gamble Improved decomplexed cyclodextrin compositions for odor control
US6253710B1 (en) 1998-06-24 2001-07-03 The Sherwin-Williams Company Odor control for animal litter
US6358469B1 (en) 1998-12-01 2002-03-19 S. C. Johnson & Son, Inc. Odor eliminating aqueous formulation
DE19859808A1 (en) 1998-12-23 2000-06-29 Henkel Kgaa Multi-phase cleaning agent with lignin sulfonate
DE19859640A1 (en) 1998-12-23 2000-06-29 Henkel Kgaa Detergent for hard surfaces
GB2346900A (en) * 1999-02-18 2000-08-23 Reckitt & Colman Inc Deodorizing compositions for fibrous substrates
EP1161589B1 (en) 1999-03-16 2003-07-23 Kao Corporation Liquid deodorant
US6696395B1 (en) 1999-03-18 2004-02-24 The Procter & Gamble Company Perfumed liquid household cleaning fabric treatment and deodorizing compositions packaged in polyethylene bottles modified to preserve perfume integrity
PE20010060A1 (en) * 1999-03-18 2001-02-22 Procter & Gamble LIQUID SCENTED COMPOSITIONS FOR HOME CLEANING, FABRIC TREATMENT AND DEODORIZATION PACKAGED IN POLYETHYLENE BOTTLES MODIFIED TO PRESERVE THE INTEGRITY OF THE PERFUME
WO2000067714A1 (en) * 1999-05-07 2000-11-16 The Procter & Gamble Company Cosmetic compositions
AU3885099A (en) * 1999-05-07 2000-11-21 Procter & Gamble Company, The Cosmetic compositions
AU3885199A (en) * 1999-05-07 2000-11-21 Procter & Gamble Company, The Cosmetic compositions comprising cyclic oligosaccharide and fragrance
US6764986B1 (en) 1999-07-08 2004-07-20 Procter & Gamble Company Process for producing particles of amine reaction products
US6740713B1 (en) 1999-07-08 2004-05-25 Procter & Gamble Company Process for producing particles of amine reaction products
US6972276B1 (en) 1999-07-09 2005-12-06 Procter & Gamble Company Process for making amine compounds
GB2352179A (en) * 1999-07-21 2001-01-24 Unilever Plc Deodorising perfume compositions
US6893647B1 (en) 2000-05-05 2005-05-17 The Procter & Gamble Company Cosmetic compositions
WO2001087360A2 (en) 2000-05-15 2001-11-22 The Procter & Gamble Company Compositions comprising cyclodextrin derivatives
US20020007055A1 (en) 2000-05-15 2002-01-17 Hirotaka Uchiyama Compositions comprising cyclodextrin
WO2002041927A1 (en) * 2000-11-27 2002-05-30 Zeon Corporation Deodorant, masking agent for ammonia, deodorant for excretion odor, and water-absorbing deodorizing material
DE10149362A1 (en) 2001-10-06 2003-04-30 Beiersdorf Ag Antiperspirant product based on microemulsions
DE10149373A1 (en) * 2001-10-06 2003-04-30 Beiersdorf Ag Antiperspirant product based on microemulsion gels
EP1523543A1 (en) * 2002-07-18 2005-04-20 Quest International Services B.V. Improvements in or relating to perfume compositions
US20040223871A1 (en) * 2003-05-05 2004-11-11 The Procter & Gamble Company Method of freshening air
US20040223943A1 (en) * 2003-05-05 2004-11-11 The Procter & Gamble Company Air freshener
DE10344967B4 (en) * 2003-09-07 2011-07-28 Henkel AG & Co. KGaA, 40589 Alkoxyl group-containing cyclodextrin derivatives; Process for their preparation and their use
EP2088186B1 (en) 2003-12-13 2013-07-31 Henkel AG & Co. KGaA Multi-component thin-to-thick system
DE102007003143A1 (en) 2007-01-16 2008-07-17 Henkel Kgaa New alkaline protease from Bacillus gibsonii and detergents and cleaners containing this novel alkaline protease
DE102007008656A1 (en) 2007-02-20 2008-09-04 Henkel Ag & Co. Kgaa Washing and cleaning composition for cleaning of textiles and hard surfaces and for removal of burned or persistent dirt, comprises urea derivatives, which is sulfonyl urea
DE102007008655A1 (en) 2007-02-20 2008-08-21 Henkel Ag & Co. Kgaa Siderophore-metal complexes as bleach catalysts
DE102007008868A1 (en) 2007-02-21 2008-08-28 Henkel Ag & Co. Kgaa Automatic dishwasher detergent containing a sugar acid amide, e.g. N-octyl-D-gluconamide, useful especially for removing tenacious and-or burnt-on dirt from hard surfaces or textiles
DE102007010785A1 (en) 2007-03-02 2008-09-04 Henkel Ag & Co. Kgaa Use of superoxide dismutases to cleave and/or remove Amadori and/or Maillard products, especially as components of detergent, cosmetic or pharmaceutical products
DE102007017656A1 (en) 2007-04-12 2008-10-16 Henkel Ag & Co. Kgaa Biheteroaryl metal complexes as bleaching catalysts
DE102007017657A1 (en) 2007-04-12 2008-10-16 Henkel Ag & Co. Kgaa Tris / heterocyclyl) metal complexes as bleach catalysts
DE102007017655A1 (en) 2007-04-12 2008-10-16 Henkel Ag & Co. Kgaa Use of acylureas in detergents and cleaners
DE102007017654A1 (en) 2007-04-12 2008-10-16 Henkel Ag & Co. Kgaa Bis (hydroxyquinoline) metal complexes as bleaching catalysts
DE102007036392A1 (en) 2007-07-31 2009-02-05 Henkel Ag & Co. Kgaa Compositions containing perhydrolases and alkylene glycol diacetates
JP5245149B2 (en) * 2007-08-30 2013-07-24 ライオン株式会社 Liquid finish composition for textile products
DE102007049830A1 (en) 2007-10-16 2009-04-23 Henkel Ag & Co. Kgaa New protein variants by circular permutation
DE102007051092A1 (en) 2007-10-24 2009-04-30 Henkel Ag & Co. Kgaa Subtilisin from Becillus pumilus and detergents and cleaners containing this new subtilisin
DE102008000084A1 (en) * 2008-01-17 2009-07-23 Wacker Chemie Ag Aqueous emulsion containing a cyclodextrin derivative, a fragrance and a polysorbate
DE102008053519A1 (en) 2008-02-20 2009-09-03 Henkel Ag & Co. Kgaa Esterified oligomeric or polymeric silicic acid with a surfactant comprising an alkoxy group useful e.g. in washing or cleaning agent and cosmetic products, and for cleaning of textiles and hard surfaces
DE102008014759A1 (en) 2008-03-18 2009-09-24 Henkel Ag & Co. Kgaa Use of imidazolium salts in detergents and cleaners
DE102008027375A1 (en) 2008-06-09 2009-12-10 Henkel Ag & Co. Kgaa Bacitracin-metal complexes as bleaching catalysts
US8178078B2 (en) 2008-06-13 2012-05-15 S.C. Johnson & Son, Inc. Compositions containing a solvated active agent suitable for dispensing as a compressed gas aerosol
JP5700913B2 (en) * 2008-09-30 2015-04-15 小林製薬株式会社 Aromatic composition
DE102009001803A1 (en) 2009-03-24 2010-09-30 Henkel Ag & Co. Kgaa Textile treatment agent, useful e.g. for the finishing of textile fabrics and for removing stains from textile fabrics, comprises polymers with carboxyl groups in a specific concentration and divalent cations in a specific concentration
DE102009001693A1 (en) 2009-03-20 2010-09-23 Henkel Ag & Co. Kgaa 4-aminopyridine derivatives as catalysts for the cleavage of organic esters
ES2568457T3 (en) 2009-03-20 2016-04-29 Henkel Ag & Co. Kgaa Use of polymers with carboxyl groups in combination with divalent cations for the formation of a protective layer
DE102009003027A1 (en) 2009-05-12 2010-12-02 Henkel Ag & Co. Kgaa Probiotic cleaner for hard surfaces
DE102009029060A1 (en) 2009-09-01 2011-03-03 Henkel Ag & Co. Kgaa Agent for the treatment of hard surfaces
CN103124566B (en) * 2010-09-24 2016-11-23 凯杰生物工程（深圳）有限公司 Use counteractant preparation and/or the method processing biological sample
US20120183489A1 (en) 2011-01-14 2012-07-19 Ricky Ah-Man Woo Compositions comprising metallated malodor control polymers
GB2534454B (en) * 2013-05-14 2021-07-07 Lion Corp Liquid treatment composition for textile product
US20150104348A1 (en) * 2013-10-10 2015-04-16 The Iams Company Pet Deodorizing Composition
EP2865739B1 (en) * 2013-10-28 2018-09-19 Symrise AG Use of lactones
WO2016049397A1 (en) * 2014-09-26 2016-03-31 The Procter & Gamble Company Freshening compositions and devices comprising same
DE102014226909A1 (en) 2014-12-23 2016-06-23 Henkel Ag & Co. Kgaa Polymers for surface-modifying cleaners
DE102015212611A1 (en) 2015-07-06 2017-01-12 Henkel Ag & Co. Kgaa Star block comb polymers as bioactive carrier matrices for the drug-eluting semi-permanent coating of surfaces
EP3432856A1 (en) 2016-03-24 2019-01-30 The Procter and Gamble Company Hair care compositions comprising malodor reduction compositions
US20180010071A1 (en) * 2016-07-11 2018-01-11 Scent Control Sciences, LLC Method of eliminating odor
CA3061539A1 (en) 2017-05-05 2018-11-08 Symrise Ag Composition for odour improvement
JP7335131B2 (en) * 2018-11-07 2023-08-29 ザ プロクター アンド ギャンブル カンパニー Low pH fabric care composition
US11781093B2 (en) 2018-11-07 2023-10-10 The Procter & Gamble Company Process for treating a fabric and related compositions
JP6931018B2 (en) * 2019-04-16 2021-09-01 花王株式会社 Spatial spraying method for aerosol-forming fragrance compositions

Family Cites Families (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH262916A (en) * 1945-06-28 1949-07-31 Inc Airkem Process for cooling stale air.
US3172817A (en) 1959-09-28 1965-03-09 Schickedanz Ver Papierwerk Method of deodorizing the human body and materials therefor
US3436772A (en) 1966-10-14 1969-04-08 David T Stebbins Method for relaxing wrinkles in fabrics
US3459731A (en) 1966-12-16 1969-08-05 Corn Products Co Cyclodextrin polyethers and their production
US3426011A (en) 1967-02-13 1969-02-04 Corn Products Co Cyclodextrins with anionic properties
US3453257A (en) 1967-02-13 1969-07-01 Corn Products Co Cyclodextrin with cationic properties
US3453258A (en) 1967-02-20 1969-07-01 Corn Products Co Reaction products of cyclodextrin and unsaturated compounds
US3453259A (en) 1967-03-22 1969-07-01 Corn Products Co Cyclodextrin polyol ethers and their oxidation products
US3453260A (en) 1967-03-22 1969-07-01 Corn Products Co Cyclic anhydride esters of cyclodextrin
US3565887A (en) 1968-05-15 1971-02-23 Corn Products Co Unsaturated and long chain esters of cyclodextrin
US3553191A (en) 1968-05-21 1971-01-05 Cpc International Inc Aminoethyl cyclodextrin and method of making same
US3600325A (en) 1968-07-02 1971-08-17 Cpc International Inc Aerosol fabric de-wrinkler
US4082223A (en) 1975-12-06 1978-04-04 Yoshino Kogyosho Co., Ltd. Trigger type spraying device
US4274560A (en) 1976-04-30 1981-06-23 Emson Research Incorporated Atomizing pump dispenser
US4161288A (en) 1976-10-05 1979-07-17 Creative Dispensing Systems, Inc. Fluid dispenser method and apparatus
US4260110A (en) 1977-02-18 1981-04-07 Winfried Werding Spray nozzle, devices containing the same and apparatus for making such devices
EP0032779B1 (en) * 1980-01-21 1983-06-29 Pfw (Nederland) B.V. Novel method for preparation of homogeneous dimethylether-propelled water-based aerosols
US4325939A (en) 1980-09-22 1982-04-20 Richardson-Vicks Inc. Zinc derivatives and their use in dental compositions
US4434917A (en) 1981-05-26 1984-03-06 Yoshino Kogyosho Co., Ltd. Trigger-actuated atomizer
US4469674A (en) 1981-09-03 1984-09-04 Richardson-Vicks Inc. Stable oral compositions containing zinc and fluoride compounds
US4449987A (en) 1981-10-29 1984-05-22 Avon Products, Inc. Fragrant insect repellent composition and combustible candle composition containing same
JPS58124452A (en) * 1982-01-21 1983-07-25 株式会社嶋田環境科学研究所 Deodorant composition
HU191101B (en) 1983-02-14 1987-01-28 Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt,Hu Process for preparing water-soluble cyclodextrin polymers substituted with ionic groups
GB8315880D0 (en) * 1983-06-09 1983-07-13 Rizla Ltd Sprayable germicide materials
EP0147685B1 (en) 1983-12-17 1989-04-26 Hoechst Aktiengesellschaft Beta-cyclodextrin and process for its preparation
US4616008A (en) 1984-05-02 1986-10-07 Takeda Chemical Industries, Ltd. Antibacterial solid composition for oral administration
US4933371A (en) 1984-07-26 1990-06-12 Shirlo, Inc. Controlling ticks and fleas with linalool
JPH0651725B2 (en) 1985-02-28 1994-07-06 メルシャン株式会社 Partially methylated cyclodextrin and method for producing the same
US4735347A (en) 1985-05-28 1988-04-05 Emson Research, Inc. Single puff atomizing pump dispenser
US4678598A (en) 1985-08-06 1987-07-07 Kao Corporation Liquid shampoo composition
FR2599257B1 (en) * 1986-05-29 1989-12-29 Robertet Sa AGENT FOR NEUTRALIZING UNDESIRABLE ODORS FROM EXCRETIONS AND EXCREMENTS FROM ANIMALS.
US4693890A (en) 1986-06-27 1987-09-15 International Flavors & Fragrances Inc. Use of 1-nonen-3-ol for repelling insects
US4696676A (en) 1986-06-27 1987-09-29 International Flavors & Fragrances Inc. Use of 1-nonen-3-ol for repelling insects
EP0254505B1 (en) 1986-07-21 1992-04-22 Yoshino Kogyosho Co., Ltd. Trigger type liquid dispenser
JPS6359962A (en) * 1986-08-29 1988-03-15 大蔵興産株式会社 Malodor removing composition
JPS63164953A (en) * 1986-12-27 1988-07-08 株式会社林原生物化学研究所 Deodorizing composition
US4895279A (en) 1988-07-25 1990-01-23 Emson Research Inc. Flat-top valve member for an atomizing pump dispenser
US5102564A (en) 1989-04-12 1992-04-07 The Procter & Gamble Company Treatment of fabric with perfume/cyclodextrin complexes
DE3907555A1 (en) * 1989-03-09 1990-09-13 Hoechst Ag USE OF MONOTERPEN AS AN AIR IMPROVEMENT
US4938416A (en) * 1989-05-16 1990-07-03 Consoldiated Ceramic Products, Inc. Method of delivering a water-based room air freshener
US5232126A (en) 1989-05-26 1993-08-03 Robert Winer Liner for dispensing container
US5111971A (en) 1989-05-26 1992-05-12 Robert Winer Self-pressurized container having a convoluted liner and an elastomeric sleeve
FR2647348B1 (en) * 1989-05-29 1994-11-04 Robertet Sa AIR FRESHENER COMPOSITIONS CONTAINING AT LEAST TWO ALDEHYDES AND AIR FRESHENER PRODUCTS CONTAINING THE SAME
US5030660A (en) 1989-11-01 1991-07-09 Wisconsin Alumni Research Foundation Insect repellent containing 1-dodecene
US5196200A (en) 1991-04-25 1993-03-23 International Flavors & Fragrances Inc. Bisabolene-containing composition, process for preparing same, organoleptic uses thereof and uses thereof as insect repellent
DE4127451A1 (en) * 1991-08-20 1993-02-25 Sucke Norbert William Dipl Phy Removing smell from article soiled with vomit e.g. baby clothes - by application of neutralising, sterilising and opt. deodorising compsn.
US5234611A (en) 1991-08-28 1993-08-10 The Procter & Gamble Company Fabric softener, preferably liquid, with protected, dryer-activated, cyclodextrin/perfume complex
US5207933A (en) * 1991-08-28 1993-05-04 The Procter & Gamble Company Liquid fabric softener with insoluble particles stably suspended by soil release polymer
US5303867A (en) 1993-06-24 1994-04-19 The Procter & Gamble Company Trigger operated fluid dispensing device
EP0731717B1 (en) * 1993-11-30 2002-07-31 Quest International B.V. Anti-smoke perfumes and compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9604940A1 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0949006A1 (en) 1998-04-08 1999-10-13 The Procter & Gamble Company A packaged product
WO1999051354A1 (en) 1998-04-08 1999-10-14 The Procter & Gamble Company A packaged product
EP1010389A2 (en) 1998-04-08 2000-06-21 The Procter & Gamble Company A process of cleaning carpets and the like
EP1133322B1 (en) * 1998-11-25 2003-09-24 The Procter & Gamble Company Improved uncomplexed cyclodextrin compositions for odor control
EP1059122A1 (en) 1999-06-07 2000-12-13 The Procter & Gamble Company A spray device with flat fan nozzle
WO2000074862A1 (en) 1999-06-07 2000-12-14 The Procter & Gamble Company A spray device with flat fan nozzle

Also Published As

Publication number Publication date
JP3810433B2 (en) 2006-08-16
CA2196702A1 (en) 1996-02-22
EP1002549A1 (en) 2000-05-24
CA2330720A1 (en) 1996-02-22
JPH10503958A (en) 1998-04-14
CZ40197A3 (en) 1997-08-13
CA2330720C (en) 2001-10-02
DE29522186U1 (en) 2000-06-15
WO1996004940A1 (en) 1996-02-22
JP2002069840A (en) 2002-03-08
CZ289396B6 (en) 2002-01-16
RU2149025C1 (en) 2000-05-20
AU3242995A (en) 1996-03-07
BR9508569A (en) 1997-12-23
EP2311502A1 (en) 2011-04-20
JP3964444B2 (en) 2007-08-22
JP2006299501A (en) 2006-11-02
PL318553A1 (en) 1997-06-23
CA2196702C (en) 2001-05-15
MX9701122A (en) 1997-05-31

Similar Documents

Publication Publication Date Title
US5939060A (en) Composition for reducing malodor impression on inanimate surfaces
US6077318A (en) Method of using a composition for reducing malodor impression
US5663134A (en) Composition for reducing malodor impression on inanimate surfaces
CA2196702C (en) Composition for reducing malodor impression on inanimate surfaces
US5578563A (en) Composition for reducing malodor impression on inanimate surfaces
US5668097A (en) Uncomplexed cyclodextrin solutions for odor control on inanimate surfaces
EP0774978B1 (en) Method of treating inanimate surfaces with uncomplexed cyclodextrin solutions for odor control
US5593670A (en) Uncomplexed cyclodextrin solutions for odor control on inanimate surfaces
US5714137A (en) Uncomplexed cyclodextrin solutions for odor control on inanimate surfaces
EP0776220B1 (en) Fabric treating composition containing beta-cyclodextrin
US6682694B2 (en) Uncomplexed cyclodextrin solutions for odor control on inanimate surfaces
US7645746B1 (en) Composition for reducing malodor impression on inanimate surfaces
EP1232761A1 (en) Composition for reducing malodor impression

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970116

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

17Q First examination report despatched

Effective date: 19990203

RIN1 Information on inventor provided before grant (corrected)

Inventor name: ZWERDLING, SUSAN, SCHMAEDECKE

Inventor name: WAHL, ERROL, HOFFMAN

Inventor name: SWARTLEY, DONALD, MARION

Inventor name: MCCARTY, MARK, LEE

Inventor name: HOLLINGSHEAD, JUDITH, ANN

Inventor name: GEIS, PHILIP, ANTHONY

Inventor name: CAPPEL, JEROME, PAUL

Inventor name: TRINH, TOAN

APBN Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2E

APBR Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3E

APAF Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNE

APBT Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9E

APBK Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNE

APBN Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2E

APBR Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3E

APAF Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

APBT Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9E

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20140408