US0092.60817B2
(12) United States Patent (10) Patent No.: US 9.260,817 B2 Williams et al. (45) Date of Patent: *Feb. 16, 2016
(54) FRESHENING COMPOSITIONS A61L 9/14: D06M 13/005; D06M 15/61; COMPRISING MALODOR BINDING D06M 13/192: D06M 13/203: D06M 13/127; POLYMERS AND MALODOR D06M 13/148: D06M 13/256: D06M 13/402; COUNTERACTANTS D06M 23/06: D06M23/02: D06M 16/00 (75) Inventors: Kristin Rhedrick Williams, West USPC ...... 424/400, 76.1, 76.21 Chester, OH (US); Carla Jean Colina, See application file for complete search history. Cincinnati, OH (US); Cahit Eylem, West Chester, OH (US); Lon Montgomery (56) References Cited Gray, Florence, KY (US); Shih-Chuan U.S. PATENT DOCUMENTS Liou, Cincinnati, OH (US); Christine Marie Readnour, Fort Mitchell, KY 5,578,563 A 11/1996 Trinh et al. (US); Ricky Ah-Man Woo, Hamilton, 6,001,342 A 12/1999 Forestier et al. OH (US) (Continued) (73) Assignee: The Procter & Gamble Company, FOREIGN PATENT DOCUMENTS Cincinnati, OH (US) JP WO 82O1993 6, 1982 (*) Notice: Subject to any disclaimer, the term of this JP O3146.064 6, 1991 patent is extended or adjusted under 35 (Continued) U.S.C. 154(b) by 474 days. OTHER PUBLICATIONS This patent is Subject to a terminal dis “Methyl dihydrojasmonate’ CASEN 24851-98-7: http://www. claimer. chemicalbook.com/CASEN 24.851-98-7.htm. (21) Appl. No.: 12/562,534 (Continued) (22) Filed: Sep. 18, 2009 Primary Examiner — Sean Basquill (65) Prior Publication Data Assistant Examiner — Miriam A Levin (74) Attorney, Agent, or Firm — Abbey A. Lopez; Amy I. US 2011 FOOTO181A1 Mar. 24, 2011 Ahn-Roll (51) Int. Cl. A6IL 9/01 (2006.01) (57) ABSTRACT D06M I3/00 (2006.01) Freshening compositions comprising a malodor binding (Continued) polymer, a malodor counteractant comprising at least one aliphatic aldehyde, and an aqueous carrier, wherein the com (52) U.S. Cl. position is essentially free of any material that would soil or CPC ...... D06M 13/005 (2013.01); A61L 2/22 stain fabric; and methods thereof are provided. In some (2013.01); A61L 9/01 (2013.01); A61L 9/14 embodiments, the malodor binding polymer comprises a (2013.01); homopolymeric polyethylenimine having a molecular weight (Continued) of about 1,000 to about 2,000,000. Such freshening compo sitions may be used to reduce malodor and/or microbes on (58) Field of Classification Search inanimate Surfaces or in the air. CPC. A61 L9/012: A61 L 2202/26: A61 L 2209/13; A61L 2209/21: A61L 2/22: A61L 9/01; 15 Claims, 2 Drawing Sheets
Anti-ficrobia benefit of PE on Staphylococcus, P. Erabilis, P.Aer. A. Nigermed
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US 9,260.817 B2 Page 2
(51) Int. Cl. FOREIGN PATENT DOCUMENTS A6IL 2/22 (2006.01) f JP 2006149892 6, 2006 A6IL 9/14 (2006.01) JP 2007215831 8, 2007 D06M 3/27 (2006.01) JP 2007 332130 A 12/2007 D06M 13/148 (2006.01) W8 w883. A 1758. D06M 3/92 (2006.01) D06M I3/2O3 (2006.01) OTHER PUBLICATIONS D06M I3/256 (2006.01) “(+)-Jasmonic acid, methyl ester (cis)-Compound Summary (CID D06M 3/402 (2006.01) 6427970); http://pubchem.ncbi.nlm.gov/summary/summary. D06M 5/6 (2006.01) cgi?=6427970&ncount=14.* "Methyl phenyl carbinyl acetate Compound Summary (CID D06M 23/02 (2006.01) 62341)”; http://pubchem.ncbi.nih.gov/summary/summary. D06M 23/06 (2006.01) cgi?cid=62341&n&ncount=41.* (52) U.S. Cl “Santol pentenol” rw 1032011; http://www.goodscentscompany.
CPC.------D06M 13/127(2013.01):.UT): D06M 13/148 “Polysantol”SIRISE 107898-54-4: http://www.guidechem.com/dictionary/ (2013.01): D06M 13/192 (2013.01): D06M 107898-54-4.html. 13/203 (2013.01): D06M 13/256 (2013.01); “Tetrahydropyran-ChemSpider ID 8554”: http://www.chemspider. (2013.01):D06M 13/402D06M 23/02(2013.01): (2013.01): D06M D06M 15/61 sistialists,al al y104,921; Shi, ttp://www.thegoodscentScompany. thegood 20, ( 2010.61E30.01): ((61301. .01): Chempoint,In data TWO BASF, Lupasolhtml Polyethyleneimine Retrieved from A61 L 2209/13 (2013.01); A61 L 2209/21 internet
U.S. Patent Feb. 16, 2016 Sheet 2 of 2 US 9,260,817 B2
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uotonpe. So seeds US 9,260,817 B2 1. 2 FRESHENING COMPOSITIONS FIG. 2 is a bar graph showing microbe reduction with a COMPRISING MALODOR BINDING freshening composition according to the present invention POLYMERS AND MALODOR containing a malodor binding polymer in comparison to a COUNTERACTANTS freshening composition lacking such malodor binding poly C. FIELD OF THE INVENTION DETAILED DESCRIPTION OF THE INVENTION The present invention relates to freshening compositions comprising a malodor binding polymer, malodor counterac The freshening composition of the present invention is tants comprising at least one aliphatic aldehyde, and an aque 10 designed to deliver genuine malodor reduction and not func ous carrier, and methods thereof. tion merely by using perfume to cover up or mask odors. The freshening composition reduces malodor in the air or on BACKGROUND OF THE INVENTION inanimate surfaces, for example, fabrics that are contami nated with environmental odors such as food and tobacco Freshening products for reducing or masking malodors on 15 odors, or wetted with perspiration. The freshening composi fabrics and in air are currently available and are described in tion may also reduce microbes on inanimate Surfaces or in air. the patent literature. The Procter & Gamble Company sells The freshening composition may also act as a barrier to pre fabric and air freshening products under the FEBREZER) vent malodors from adhering to or penetrating an inanimate brand name. These products typically contain perfume, solu Surface. bilizer, cyclodextrin, and an aqueous carrier. S.C. Johnson A genuine malodor reduction provides a sensory and ana sells products such as Glade(R) Fabric and Air Odor Eliminator lytically measurable (e.g. gas chromatograph) malodor and Oust(R) Surface Disinfectant and Air Sanitizer. Reckitt reduction. Thus, if the freshening composition delivers a Benckiser sells products such as Lysol R Disinfectant Spray. genuine malodor reduction, the freshening composition will Certain freshening compositions do not effectively neutral neutralize malodors in the air and/or on fabrics. “Neutralize” ize a broad range of malodors on fabrics and in the air. 25 or “neutralization” as used herein means chemically reacting Further, certain freshening compositions may cause fabrics to with malodor components (e.g. the reaction of primary turn yellow or brown under natural light and/or make fabric amines with aldehydes to formimines, reductive alkylation of Susceptible to Soiling, particularly products that contain cer amines, protonation and deprotonation of amines, polymer tain types or amounts of aldehydes and/or Surfactants. ization or de-polymerization); or Suppressing the Volatility of There remains a need for improved freshening composi 30 malodorous components such that other parts of the compo tions that neutralize a broad range of malodors, including sition may react (e.g. acid-base neutralization); or physically malodors caused by microbes, and that provide a hedonic entrapping odorous molecules such that they are not re-re benefit, while avoiding Soiling and staining of fabrics that leased into the air (e.g. cyclodextrin inclusion complexes as may be contacted by the freshening composition. described herein). 35 I. Freshening Composition SUMMARY OF THE INVENTION The freshening composition for reducing malodor com prises a malodor binding polymer, a malodor counteractant The present invention relates to a freshening composition comprising at least one aliphatic aldehyde, and an aqueous for reducing malodor. In one embodiment, the freshening carrier, wherein said composition is essentially free of mate composition for reducing malodor comprises an effective 40 rials that soil or stain fabric. The total amount of surfactants amount of a malodor binding polymer, a malodor counterac (e.g. solubilizer, wetting agent) in the freshening composition tant comprising at least one aliphatic aldehyde; an aqueous is from 0% to 3% or no more than 3%, alternatively from 0% carrier; wherein said composition is essentially free of any to 1% or no more than 1%, alternatively from 0% to 0.9% or material that would soil or stain fabric. In another embodi no more than 0.9%, alternatively from 0% to 0.7 or no more ment, the freshening composition comprises a homopoly 45 than 0.7%, alternatively from 0% to 0.5% or no more than meric polyethyleneimine having a molecular weight of 1,000 0.5%, alternatively from 0% to 0.3% or no more than 0.3%, to 2,000,000; at least one aliphatic aldehyde; a glycol; a by weight of the composition. Compositions with higher dicarboxylic acid to provide a pH of about 3 to about 8; about concentrations can make fabrics Susceptible to Soiling and/or 90% to about 99.5% of an aqueous carrier; wherein said leave unacceptable visible stains on fabrics as the solution composition is essentially free of any material that would soil 50 evaporates. or stain fabric. A. Malodor Binding Polymer The present invention also relates to methods of reducing The freshening composition of the present invention malodor comprising the steps of providing a freshening com includes a malodor binding polymer. A malodor binding position comprising an effective amount of a malodor binding polymer is polymer having an available functional group (e.g. polymer, a malodor counteractant comprising at least one 55 amine) that has the affinity to neutralize malodor compo aliphatic aldehyde, an aqueous carrier, wherein said compo nents. Monomers having an available function group with an sition is essentially free of any material that would soil or affinity to neutralize malodor components are also contem stain fabric; and dispersing an effective amount of said fresh plated. In the case of amine based compounds, the amine will ening composition on an inanimate surface or in the air. have an affinity for aldehyde malodors. The amine may react 60 with aldehyde malodors and form a new compound. Such as BRIEF DESCRIPTION OF THE DRAWINGS an aminol, imine, or enamine which is not odorous. A malodor binding polymer may include amine based FIG. 1 is a bar graph showing the reduction of aldehydic compounds, Such as monoamines, amino acids, polyethyl malodors evaporating off fabrics treated with freshening eneimine polymers (PEIs), modified PEIs, substituted PEIs: compositions according to the present invention containing a 65 acrylic acid polymers, such as polyacrylate co-polymer (e.g. malodor binding polymer in comparison to a freshening com AcumerTM 9000 from Rohm & Haas), polyacrylic acid poly position lacking Such malodor binding polymer. mers (e.g. AcusolTM from Rohm & Haas), and modified acry US 9,260,817 B2 3 4 late copolymers (e.g. AculynTM from Rohm & Haas); and Triethylenetetramine, diethylenetriamine, tetraethylene modified methacrylate copolymers (e.g. HydroSalTM from pentamine; Salvona Technologies); or mixtures thereof. Bis-aminopropylpiperazine; 1. Amine Based Compounds amino substituted polyvinylalcohol with a MW ranging In some embodiments, the malodor binding polymer is an 5 from 400-300,000 Daltons; amine based compound with a molecular weight greater than polyoxyethylene bisamine available from e.g. Sigma; 100 Daltons and at least 10% of its amine groups are primary polyoxyethylene bis6-aminohexyl available from e.g. amines. In one embodiment, the amine-based compound will Sigma; be a polyamine with a molecular weight greater than 150 N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or 10 branched (TPTA); Daltons and 15% to 80% of its amine groups are primary N,N'-bis-(3-aminopropyl)ethylenediamine; amines. In another embodiment, the malodor binding poly bis(amino alkyl)alkyl diamine, linear or branched; and mer is an amine-based compound with a molecular weight 1,4-bis-(3-aminopropyl)piperazine (BNPP). greater than 1000 Daltons and from 0% to about 10% or less d. Polyamino Acids than 10% of its amine groups are primary amines. 15 Suitable amine based compounds include polyamino A general structure for a primary amine compound useful acids. Polyamino acids are made up of amino acids or chemi in this invention is as follows: cally modified amino acids. The amino acids may be selected from cysteine, histidine, isoleucine, tyrosine, tryptophane, leucine, lysine, glutamic acid, glutamine, glycine, alanine, wherein B is a carrier material, and n is an index of value of at aspartic acid, arginine, asparagine, phenylalanine, proline, least 1. Suitable B carriers include both inorganic and organic serine, histidine, threonine, methionine, Valine, and mixtures carrier moieties. By “inorganic carrier, it is meant a carrier thereof. Amino acid derivatives may be tyrosine ethylate, which is comprised of non- or Substantially non-carbon based glycine methylate, tryptophane ethylate, or mixtures thereof. backbones. homopolymers of amino acids; hydroxyamines; polyamino Compounds containing a secondary amine group have a 25 acids; or mixtures thereof. structure similar to the above with the exception that the In chemically modified amino acids, the amine or acidic compound comprises one or more —NH-groups as well as function of the amino acid has reacted with a chemical —NH groups. The amine compounds of this general type reagent. This is often done to protect these chemical amine may be relatively viscous materials. and acid functions of the amino acid in a Subsequent reaction Exemplary amine based compounds are those selected 30 or to give special properties to the amino acids, like improved from monoamines, aminoaryl derivatives, polyamines and solubility. Examples of such chemical modifications are ben derivatives thereof, polyamino acids and copolymers thereof, Zyloxycarbonyl, aminobutyric acid, butyl ester, and pyro glucamines, dendrimers, PEIS, Substituted amines and glutamic acid. More examples of common modifications of amides monoamines, or mixtures thereof. amino acids and Small amino acid fragments can be found in a. Monoamines 35 the Bachem, 1996, Peptides and Biochemicals Catalog. Monoamines may be utilized in the present invention. Non One polyamino acid is polylysine, alternatively polyl limiting examples of Suitable monoamines for use in the ysines or polyamino acids where more than 50% of the amino present invention include, but are not limited to, primary acids are lysine, since the primary amine function in the side amines that also contain hydroxy and/or alkoxy functional chain of the lysine is the most reactive amine of all amino groups, such as the 2-hydroxyamines and/or 3-hy 40 acids. One polyamino acid has a molecular weight of 500 to droxyamines; primary or secondary amines that also contain 10,000,000, alternatively between 2000 and 25,000. a functional group that enhances deposition of the monoam The polyamino acid can be cross linked. The cross linking ine compared to monoamines that lack that functional group, can be obtained for example by condensation of the amine especially when the monoamine is interacting with the benefit group in the side chain of the amino acid like lysine with the agent. Primary monoamines may also be used herein in com 45 carboxyl function on the amino acid or with protein cross bination with secondary monoamines. However, Sufficient linkers like PEG derivatives. The cross linked polyamino levels of the primary monoamine must be used to provide at acids still need to have free primary and/or secondary amino least 10% of the total amine groups within such combinations groups left for neutralization. Cross linked polyamino acid as primary amine groups. has a molecular weight of 20,000 to 10,000,000; alternatively b. Aminoaryl Derivatives 50 between 200,000 and 2,000,000. Exemplary aminoaryl derivatives are the amino-benzene The polyamino acid or the amino acid can be co-polymer derivatives including the alkyl esters of 4-amino benzoate ized with other reagents like for instance with acids, amides, compounds, ethyl-4-amino benzoate, phenylethyl-4-ami acyl chlorides, aminocaproic acid, adipic acid, ethylhexanoic nobenzoate, phenyl-4-aminobenzoate, 4-amino-N'-(3-ami acid, caprolactam, or mixtures thereof. The molar ratio used nopropyl)-benzamide, or mixtures thereof. 55 in these copolymers ranges from 1:1 (reagent/amino acid c. Polyamines (lysine)) to 1:20, alternatively from 1:1 to 1:10. The Examples of Suitable amino functional polymers contain polyamino acid like polylysine can be unethoxylated or par ing at least one primary amine group for the purposes of the tially ethoxylated so long as the requisite amount of primary present invention are: amine remains in the polymer. Polyvinylamine with a MW of 300-2.10E6 Daltons (e.g. 60 e. Dendrimers Lupamine series 1500, 4500, 5000, 9000 available from Also useful amine based compounds are polypropylen BASF); imine dendrimers and the commercially available Starburst(R) Polyvinylamine alkoxylated with a MW of >600 Daltons polyamidoamines (PAMAM) dendrimers, generation and a degree of ethoxylation of at least 0.5; G0-G10 from Dendritech and the dendrimers Astromols(R), Polyvinylamine vinylalcohol-molar ratio 2:1, polyviny 65 generation 1-5 from DSM being DiAminoButane Poly Amine laminevinylformamide-molar ratio 1:2 and polyvinylamine DAB (PA)x dendrimers with X=2"x4 and n being generally vinylformamide-molar ratio 2:1; comprised between 0 and 4. US 9,260,817 B2 5 6 f. PEIS PR 1815 (MW 2000), or Epomin SP-103, Epomin SP-110, In one embodiment, the malodor binding polymer is a PEI. Epomin SP-003, Epomin SP-006, Epomin SP-012, Epomin It has been Surprisingly discovered that amine based poly SP-018, Epomin SP-200, or partially alkoxylated polyethyl mers at a pH of about 4 to about 8, alternatively above 5 to eneimine, like polyethyleneimine 80% ethoxylated from Ald about 8, alternatively 7 can neutralize amine based odors. rich. In one embodiment, the freshening composition con PEIs have the following general formula: tains Lupasol WF (MW 25,000). Also suitable amine based compounds for use in the fresh Homopolymeric PEIs are branched, spherical polyamines ening composition are modified PEIS, partially alkylated with a well defined ratio of primary, secondary and tertiary polyethylene polymers, PEIs with hydroxyl groups, 1,5-pen amine functions. They are best described in the following 10 tanediamine, 1.6-hexanediamine, 1.3 pentanediamine, partial structural formula: 3-dimethylpropanediamine, 1.2-cyclohexanediamine, 1.3- bis(aminomethyl)cyclohexane, tripropylenetetraamine, bis (3-aminopropyl)piperazine, dipropylenetriamine, tris(2-ami noethylamine), tetraethylenepentamine, 15 bishexamethylenetriamine, bis(3-aminopropyl) 1..6-hexam H ethylenediamine, 3,3'-diamino-N-methyldipropylamine, 2-methyl-1,5-pentanediamine, N.N.N',N'-tetra(2-aminoet s --- hyl)ethylenediamine, N.N.N',N'-tetra(3-aminopropyl)-1,4- butanediamine, pentaethylhexamine, 1,3-diamino-2-propyl tert-butylether, isophorondiamine, 4,4'- diaminodicyclohylmethane, N-methyl-N-(3-aminopropyl) ethanolamine, spermine, spermidine, 1-piperazineethaneamine, 2-(bis(2-aminoethyl)amino)etha 25 nol, ethoxylated N-(tallowalkyl)trimethylene diamines, poly HN oxy(methyl-1,2-ethanediyl). C-(2-aminomethyl H ethoxy)-(C.A.S No. 9046-10-0); polyoxy(methyl-1,2- l r ethanediyl). C.-hydro-)-(E)-(2-aminomethylethoxy)-, ether 1S-N-1 ns with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (C.A.S. 30 No. 39423-51-3); commercially available under the trade name Jeffamines T403, D-230, D-400, D-2000: 2,2'2"-tri aminotriethylamine: 2,2'-diamino-diethylamine; 3,3'-di NH2 amino-dipropylamine, 1.3 bis aminoethyl-cyclohexane commercially available from Mitsubishi, and the C12 Ster The chemical structure of homopolymeric PEIs follows a 35 namines commercially available from Clariant like the C12 simple principle: one amine function—two carbons. Sternamin (propylenamine), with n=%. The freshening composition may comprise a homopoly In one embodiment, the malodor binding polymer may be meric polyethylenimine having a molecular weight of about used in an effective amount to provide a reduction of 800 to about 2,000,000, alternatively about 1,000 to about microbes on fabric and/or in the air. When using a malodor 2,000,000, alternatively about 1,200 to about 25,000, alter 40 binding polymer, an effective amount reduces microbes by at natively about 1,300 to about 25,000, alternatively about least 1 log difference as compared to a composition lacking 2,000 to about 25,000, alternatively about 10,000 to about the malodor binding polymer. This difference is then attrib 2,000,000, alternatively about 25,000 to about 2,000,000, uted to the use of the malodor binding polymer and not the alternatively about 25,000. The freshening composition may inherent variability in the microbial species. comprise a homopolymeric polyethylenimine having 15% to 45 Suitable levels of malodor binding polymer are from about 80% primary amino groups. Exemplary homopolymeric PEIs 0.01% to about 2%, alternatively from about 0.01% to about include those that are commercially available under the trade 1%, alternatively about 0.01% to about 0.8%, alternatively name LUPASOL(R) from BASF. Lupasol products are usually about 0.01% to about 0.6%, alternatively about 0.01% to obtained through polymerization of the ethylenimine mono about 0.1%, alternatively about 0.01% to about 0.07%, alter mer. The ethylenimine monomer has totally reacted in the 50 natively about 0.07%, by weight of the freshening composi polymer matrix. Suitable LUPASOL(R) products include tion. Compositions with higher amount of malodor binding LUPASOL(R) FG (MW 800; 42% primary amines), G20wf polymer may make fabrics susceptible to Soiling and/or leave (MW 1300; 40% primary amines), PR8515 (MW 2000; 40% unacceptable visible stains on fabrics as the solution evapo primary amines), WF (MW 25,000; 36% primary amines), rates off of the fabric. FC (MW 800), G20 (MW 1300; 40% primary amines), G35 55 B. Malodor Counteractants (MW 2000; 38% primary amines), G100 (MW 2-0005000; The freshening composition may utilize one or more mal 37% primary amines), HF (MW 25,000; 36% primary odor counteractants. Malodor counteractants may include amines), P (MW 750,000; 37% primary amines), PS (MW components which lower the vapor pressure of odorous com 750,000; 37% primary amines), SK (MW 2,000,000), SNA pounds, Solubilize malodor compounds, physically entrap (MW 1,000,000). Technical information the LUPASOL(R) 60 odors (e.g. flocculate or encapsulate), physically bind odors, products can be found in “Lupasol Types’, BASF, Care or physically repel odors from binding to inanimate Surfaces. Chemicals & Formulators, September 2010. The molecular For example, aliphatic aldehydes react with amine odors, weight of LUPASOL(R) products are recorded as an average Such as fish and cigarette odors. When used in combination molar mass in g/mol (GPC, BASF method). with the malodor binding polymer, the freshening composi In some embodiments, the freshening composition com 65 tion may neutralizeabroader range of malodor causing mate prises Lupasol HF or WF (MW 25,000), P (MW 750,000), PS rials which, in turn, further reduces malodors in the air or on (MW 750,000), SK (MW 2,000,000), G20wfv (MW 1300) or inanimate Surfaces. US 9,260,817 B2 7 8 1. Aliphatic Aldehydes 0.02% to about 0.06%, alternatively about 0.06%, by weight In one embodiment, the freshening composition comprises of the freshening composition. a perfume mixture having one or more fabric-safe, non-yel In addition to aliphatic aldehydes, the freshening compo lowing aliphatic aldehydes. Certain types of aldehydes that sition may also include perfume materials for their scent predominately comprise a straight chain aliphatic backbone experience including enones, ketones, ionones including ion will not discolor fabrics, unlike products that utilize types of one alpha, ionone beta, ionone gamma methyl, or mixtures aldehydes that contain multiple double bonds and benzene thereof. Suitable perfume materials are discussed in U.S. Pat. rings. The following table illustrates the selection of alde No. 5,714,137. The freshening composition may contain an hydes to avoid fabric yellowing. effective amount of perfume to provide the freshening fra 10 grance when first sprayed, some lingering fragrance, and Some extra fragrance to be released upon fabric rewetting. It Fadometer Test on treated Fabric may be desirable for the aliphatic aldehydes to have virtually (0.75 grams of product are pipetted onto a 4 inch x 4 inch (10 cm x 10 cm) no negative impact on the desired perfume character. Swatch which is then subjected to 5 hours Certain malodor counteractants may be odoriferous and of exposure to simulated Sunlight using a 15 negatively impact the overall character of the fragrance. In SUNTEST CPS+ model Fadometer Supplied by Atlas, Chicago, Illinois, this case, a perfume/malodor counteractant premix is formed AldehydeSolution Tested USA. such that the perfume raw materials used are selected to neutralize any odor of the malodor counteractants. This odor Control- untreated fabric No yellowing neutralized premix can then be added to a parent perfume Swatch 1000 ppm amylic cinnamic Yellowish brown mixture without affecting the character of the parent fra aldehyde (aromatic) grance. This permits the malodor counteractants to be used 1000 ppm citronellal Yellowish brown broadly with a large variety of fragrance types. (aromatic) The following are non-limiting examples of perfume for 1000 ppm citral aldehyde No yellowing mulations that include fabric-safe malodor counteractants. (aliphatic) 25 1000 ppm lauric aldehyde No yellowing (1) Pine (aliphatic)
Examples of suitable aliphatic aldehydes are R COH Material Name Amount where R is saturated C, to Clinear and/or branched with no 30 Rosemary 1O.OO Spike Lavender 1O.OO more than two double bonds. Examples of suitable aliphatic Lavandin Grosso S.OO aldehydes are bourgeonal, citral, citronellyl oxyacetalde Spruce (conf-manh) S.OO hyde, cymal, decyl aldehyde, helional, hexyl cinnamic alde Camphor Gum S.OO hyde, lauric aldehyde, ligustral, lyral, melonal, methyl dihy Melonal O.30 dro jasmonate, methyl nonyl acetaldehyde, methyl phenyl 35 Eucalyptol 1S.OO Iso Menthone 1S.OO carbinyl acetate, nonylaldehyde, octylaldehyde, Oxane, P. Iso BornylAcetate 21.70 T. bucinal, polysantol, rhubafuran, tripal, or mixtures Ionone Beta 8.OO thereof. Iso E Super S.OO In one embodiment, the freshening composition includes 1OOOO at least one aliphatic aldehyde selected from the group con 40 sisting of bourgeonal, citral, citronellyl oxyacetaldehyde, cymal, decyl aldehyde, helional, hexyl cinnamic aldehyde, (2) OZonic lauric aldehyde, ligustral, lyral, melonal, methyl dihydro jasmonate, methyl nonyl acetaldehyde, methyl phenyl carbinyl acetate, nonyl aldehyde, 2.6-nonadien-1-al, octyl 45 Material Name Amount aldehyde, oxane, P.T. bucinal, polysantol, rhubafuran. Xi Aldehyde 8.OO tripal, and mixtures thereof. 2'6 Nonadienol 10% In Dpg S.OO In another embodiment, the freshening composition Helional 13.00 includes at least one aliphatic aldehyde selected from the Hydroxycitronellal 11...SO Calone 1951 O.SO group consisting of burgeonal, cymal, hexyl cinnamic alde 50 2'6-Nonadien-1-al/10% In Dpg S.OO hyde, Immethyl dihydro jasmonate, methylnonyl acetalde Lyral 2O.OO hyde, P.T. bucinal, and mixtures therof. Melonal 1.OO In addition to the aforementioned aliphatic aldehydes, any Iso Menthone 1O.OO Floralozone 1O.OO one or more of the following materials may be added to the at Bourgeonal 1O.OO least one aliphatic aldehyde: methyl dihydro jasmonate (an 55 Delta Muscenone 962191 1.OO ester), methyl phenyl carbinyl acetate (an ester), oxane (a Habanolide 100% S.OO tetrahydropyran), polysantol (an alcohol), and rhubafuran (a tetrahydropyran), and mixtures thereof. For purposes of the 100.00 present invention, methyl dihydro jasmonate, methyl phenyl carbinyl acetate, oxane, polysantol, and rhubafuran are 60 (3) Fruity referred to as aliphatic aldehydes rather than referring to each of these materials individually. The aliphatic aldehydes may be present in an amount from Material Name Amount about 0.001% to about 10%, alternatively from about 0.001% Fruitate S.OO to about 5%, alternatively from about 0.01% to about 1%, 65 Orange Terpenes 13.00 alternatively from about 0.02% to about 1%, alternatively Ethyl Acetoacetate 3.00 from about 0.02% to about 0.5%, alternatively from about US 9,260,817 B2 9 10 -continued ening composition of the present invention. Some polyols, e.g., dipropylene glycol, are also useful to facilitate the solu Material Name Amount bilization of some perfume ingredients in the composition of 26 Nonadienol 10% In Dpg 1.00 the present invention. Ethyl Acetate 3.00 The glycol used in the freshening composition of the Benzaldehyde 2.00 present invention may be glycerine, ethylene glycol, propy PrenylAcetate 8.00 Benzyl Acetate 1S.OO lene glycol, dipropylene glycol, polyethylene glycol, propy 2' 6-Nonadien-1-al/10% In Dpg 1.00 lene glycol methyl ether, propylene glycol phenyl ether, pro Ethyl-2-methyl Butyrate 8.00 pylene glycol methyl ether acetate, propylene glycol n-butyl AmylAcetate 3.00 10 Cis 3 HexenylAcetate 3.00 ether, dipropylene glycol n-butyl ether, dipropylene glycol Methyl Dihydro Jasmonate 10.00 n-propyl ether, ethylene glycol phenyl ether, diethylene gly Ligustral S.OO coln-butyl ether, dipropylene glycol n-butyl ether, diethylene Melonal 1.00 Ethyl 2 Methyl Pentanoate 8.00 glycol monobutyl ether, dipropylene glycol methyl ether, Hexyl Acetate 8.00 15 tripropylene glycol methyl ether, tripropylene glycol n-butyl Habanolide 100% 3.00 ether, other glycol ethers, or mixtures thereof. In one embodi ment, the glycol used is ethylene glycol, propylene glycol, or 100.00 mixtures thereof. In another embodiment, the glycol used is diethylene glycol. (4) Citrus Typically, the low molecular weight polyol is added to the composition of the present invention at a level of from about 0.01% to about 5%, by weight of the composition, alterna Material Name Amount tively from about 0.05% to about 1%, alternatively from Orange Terpenes 2O.OO about 0.1% to about 0.5%, by weight of the composition. Lemon Terpenes X5 Fold 2O.OO 25 Compositions with higher concentrations may make fabrics Lime Oil Cf-8-1285-1 (conf.- 10.00 berie) Susceptible to Soiling and/or leave unacceptable visible stains Grapefruit Phase C-Ref. N*12.245 2O.OO on fabrics as the solution evaporates off of the fabric. The Italian Orange Phase Oil 22.90 weight ratio of low molecular weight polyol to the malodor Delta Muscenone 962191 O.SO binding polymer is from about 500:1 to about 4:1, alterna Oxane O.30 30 Iso Menthone 1.00 tively from about 1:100 to about 25:1, alternatively from Rhubafuran O.30 about 1:50 to about 4:1, alternatively about 4:1. Habanolide 100% S.OO 3. Cyclodextrin 100.00 In some embodiments, the freshening composition may include solubilized, water-soluble, uncomplexed cyclodex 35 trin. As used herein, the term “cyclodextrin” includes any of (5) Floral the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha Material Name Amount cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or 40 their derivatives and/or mixtures thereof. The alpha-cyclo Spike Lavender S.OO Rosemary S.OO dextrin consists of six glucose units, the beta-cyclodextrin Helional 1O.OO consists of seven glucose units, and the gamma-cyclodextrin Hydroxycitronellal 1O.OO consists of eight glucose units arranged in a donut-shaped Benzyl Acetate 9.30 Lyral 2O.OO ring. The specific coupling and conformation of the glucose Ligustral 2.OO 45 units give the cyclodextrins a rigid, conical molecular struc Melonal O.20 ture with a hollow interior of a specific volume. The “lining Eucalyptol 2.OO of the internal cavity is formed by hydrogen atoms and gly Iso Menthone 8.OO Bourgeonal 2O.OO cosidic bridging oxygenatoms, therefore this surface is fairly Undecavertol 3.00 hydrophobic. The unique shape and physical-chemical prop Delta Muscenone 962191 O.SO 50 erty of the cavity enable the cyclodextrin molecules to absorb Habanolide 100% S.OO (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. Many 100.00 perfume molecules can fit into the cavity. Cyclodextrin molecules are described in U.S. Pat. No. In certain cases, fabrics that are laundered will have 55 5,714,137, and U.S. Pat. No. 5,942,217. Suitable levels of residual brighteners deposited from detergents with which cyclodextrin are from about 0.1% to about 5%, alternatively they are washed. Therefore, it may be desirable for the ali from about 0.2% to about 4%, alternatively from about 0.3% phatic aldehydes to be compatible with brighteners so that the to about 3%, alternatively from about 0.4% to about 2%, by freshening composition will not discolor any fabrics with weight of the freshening composition. Freshening composi which it comes into contact. A number of the examples above 60 tions with higher concentrations can make fabrics Susceptible are compatible with brighteners. to Soiling and/or leave unacceptable visible stains on fabrics 2. Low Molecular Weight Polyols as the solution evaporates off of the fabric. The latter is Low molecular weight polyols with relatively high boiling especially a problem on thin, colored, synthetic fabrics. In points, as compared to water, such as ethylene glycol, dieth order to avoid or minimize the occurrence of fabric staining, ylene glycol, triethylene glycol, propylene glycol, dipropy 65 the fabric may be treated at a level of less than about 5 mg of lene glycol, and/or glycerine may be utilized as a malodor cyclodextrin per mg of fabric, alternatively less than about 2 counteractant for improving odor neutralization of the fresh mg of cyclodextrin per mg of fabric. US 9,260,817 B2 11 12 C. Buffering Agent about 0.01% to about 0.05%, by weight of the freshening The freshening composition of the present invention composition. Freshening compositions with higher concen includes a buffering agent which may be a dibasic acid, car trations may make fabrics Susceptible to Soiling and/or leave boxylic acid, or a dicarboxylic acid like maleic acid. The acid unacceptable visible stains on fabrics as the solution evapo may be sterically stable, and used in this composition solely rates off of the fabric. for maintaining the desired pH. The freshening composition E. Antimicrobial Compounds may have a pH from about 3 to about 8, alternatively from The freshening composition of the present invention may about 4 to about 7, alternatively from about 5 to about 8, include an effective amount of a compound for reducing alternatively from about 6 to about 8, alternatively about 6 to microbes in the air or on inanimate surfaces. Antimicrobial about 7, alternatively about 7, alternatively about 6.5. 10 compounds are effective on gram negative and gram positive Carboxylic acids such as citric acid may act as metal ion bacteria and fungi typically found on indoor Surfaces that chelants and can form metallic salts with low water solubility. have contacted human skin or pets Such as couches, pillows, As such, in Some embodiments, the freshening composition is pet bedding, and carpets. Such microbial species include essentially free of citric acids. The buffer can be alkaline, Klebsiella pneumoniae, Staphylococcus aureus, Aspergillus acidic or neutral. 15 niger; Klebsiella pneumoniae, Steptococcus pyogenes, Sal Other Suitable buffering agents for freshening composi monella choleraesuis, Escherichia coli, Trichophyton menta tions of this invention include biological buffering agents. grophytes, and Pseudomonoas aeruginosa. In some embodi Some examples are nitrogen-containing materials, Sulfonic ments, the antimicrobial compounds are also effective on acid buffers like 3-(N-morpholino)propanesulfonic acid viruses such H1-N1, Rhinovirus, Respiratory Syncytial, (MOPS) or N-(2-Acetamido)-2-aminoethanesulfonic acid Poliovirus Type 1, Rotavirus, Influenza A, Herpes simplex (ACES), which have a near neutral 6.2 to 7.5 pKa and provide types 1 & 2, Hepatitis A, and Human Coronavirus. adequate buffering capacity at a neutral pH. Other examples Antimicrobial compounds suitable in the freshening com are amino acids Such as lysine or lower alcohol amines like position of the present invention can be any organic material mono-, di-, and tri-ethanolamine. Other nitrogen-containing which will not cause damage to fabric appearance (e.g., dis buffering agents are tri(hydroxymethyl)amino methane 25 coloration, coloration such as yellowing, bleaching). Water (HOCH2)3CNH3 (TRIS), 2-amino-2-ethyl-1,3-propanediol, soluble antimicrobial compounds include organic Sulfur 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-pro compounds, halogenated compounds, cyclic organic nitrogen panol, disodium glutamate, N-methyl diethanolamide, compounds, low molecular weight aldehydes, quaternary 2-dimethylamino-2-methylpropanol (DMAMP), 1,3-bis compounds, dehydroacetic acid, phenyl and phenoxy com (methylamine)-cyclohexane, 1,3-diamino-propanol N,N'- 30 pounds, or mixtures thereof. tetra-methyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxy In one embodiment, a quaternary compound is used. ethyl)glycine (bicine) and N-tris (hydroxymethyl)methyl Examples of commercially available quaternary compounds glycine (tricine). Mixtures of any of the above are also accept Suitable for use in the freshening composition is Barquat able. available from Lonza Corporation; and didecyl dimethyl The freshening compositions may contain at least about 35 ammonium chloride quat under the trade name Bardac(R) 0%, alternatively at least about 0.001%, alternatively at least 2250 from Lonza Corporation. about 0.01%, by weight of the composition, of a buffering The antimicrobial compound may be present in an amount agent. The composition may also contain no more than about from about 500 ppm to about 7000 ppm, alternatively about 1%, alternatively no more than about 0.75%, alternatively no 1000 ppm to about 5000 ppm, alternatively about 1000 ppm more than about 0.5%, by weight of the composition, of a 40 to about 3000 ppm, alternatively about 1400 ppm to about buffering agent. 2500 ppm, by weight of the freshening composition. D. Solubilizer F. Preservatives The freshening composition of the present invention may The freshening composition of the present invention may contain a solubilizing aid to Solubilize any excess hydropho include a preservative. The preservative is included in the bic organic materials, particularly any perfume materials, and 45 present invention in an amount Sufficient to prevent spoilage also optional ingredients (e.g., insect repelling agent, antioxi or prevent growth of inadvertently added microorganisms for dant, etc.) which can be added to the composition, that are not a specific period of time, but not sufficient enough to contrib readily soluble in the composition, to form a clear Solution. A ute to the odor neutralizing performance of the freshening Suitable solubilizing aid is a Surfactant, such as a no-foaming composition. In other words, the preservative is not being or low-foaming Surfactant. Suitable Surfactants are nonionic 50 used as the antimicrobial compound to kill microorganisms Surfactants, cationic Surfactants, amphoteric Surfactants, on the Surface onto which the composition is deposited in Zwitterionic Surfactants, and mixtures thereof. order to eliminate odors produced by microorganisms. In some embodiments, the freshening composition con Instead, it is being used to prevent spoilage of the freshening tains nonionic Surfactants, cationic Surfactants, and mixtures composition in order to increase the shelf-life of the compo thereof. In one embodiment, the freshening composition con 55 sition. tains hydrogenated castor oil. One Suitable hydrogenated cas The preservative can be any organic preservative material tor oil that may be used in the present composition is Baso which will not cause damage to fabric appearance, e.g., dis phorTM available from BASF. coloration, coloration, bleaching. Suitable water-soluble pre Compositions containing anionic Surfactants and/or deter servatives include organic sulfur compounds, halogenated gent Surfactants may make fabrics Susceptible to Soiling and/ 60 compounds, cyclic organic nitrogen compounds, low or leave unacceptable visible stains on fabrics as the solution molecular weight aldehydes, parabens, propane diaol mate evaporates off of the fabric. In some embodiments, the fresh rials, isothiazolinones, quaternary compounds, benzoates, ening composition is free of anionic Surfactants and/or deter low molecular weight alcohols, dehydroacetic acid, phenyl gent Surfactants. and phenoxy compounds, or mixtures thereof. When the Solubilizing agent is present, it is typically 65 Non-limiting examples of commercially available water present at a level of from about 0.01% to about 3%, alterna soluble preservatives for use in the present invention include tively from about 0.05% to about 1%, alternatively from a mixture of about 77% 5-chloro-2-methyl-4-isothiazolin-3- US 9,260,817 B2 13 14 one and about 23% 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available as a 1.5% aqueous solution Name Average MW under the trade name Kathon(R) CG by Rohm and Haas Co.: L-7608 600 5-bromo-5-nitro-1,3-dioxane, available under the tradename L-7607 1,000 Bronidox L(R) from Henkel: 2-bromo-2-nitropropane-1,3- L-77 600 L-76OS 6,000 diol, available under the trade name BronopolR) from Inolex: L-76O4 4,000 1,1-hexamethylene bis(5-(p-chlorophenyl)biguanide), com L-76OO 4,000 monly known as chlorhexidine, and its salts, e.g., with acetic L-7657 5,000 and digluconic acids; a 95.5 mixture of 1,3-bis(hydroxym L-76O2 3,000; 10 ethyl)-5,5-dimethyl-2,4-imidazolidinedione and 3-butyl-2- and mixtures thereof, iodopropynyl carbamate, available under the trade name Gly dant Plus(R) from Lonza; N-1,3-bis(hydroxymethyl)2.5- H. Aqueous Carrier dioxo-4-imidazolidinyl-N,N'-bis(hydroxy-methyl) urea, The freshening composition of the present invention may include an aqueous carrier. The aqueous carrier which is used commonly known as diazolidinyl urea, available under the 15 may be distilled, deionized, or tap water. Water may be trade name Germall(R) II from Sutton Laboratories, Inc.; present in any amount for the composition to be an aqueous N,N'-methylenebis {N-1-(hydroxymethyl)-2,5-dioxo-4- Solution. In some embodiments, water may be present in an imidazolidinylurea, commonly known as imidazolidinyl amount of about 85% to 99.5%, alternatively about 90% to urea, available, e.g., under the trade name AbiolR from about 99.5%, alternatively about 92% to about 99.5%, alter 3V-Sigma, Unicide U-130R from Induchem, Germall 115(R) natively about 95%, by weight of said freshening composi from Sutton Laboratories, Inc., polymethoxy bicyclic oxazo tion. Water containing a small amount of low molecular lidine, available under the trade name Nuosept(R) C from Hills weight monohydric alcohols, e.g., ethanol, methanol, and America; formaldehyde; glutaraldehyde; polyaminopropyl isopropanol, or polyols, such as ethylene glycol and propy biguanide, available under the trade name Cosmocil CQR, lene glycol, can also be useful. However, the volatile low from ICI Americas, Inc., or under the trade name Mikrokill R. 25 molecular weight monohydric alcohols such as ethanol and/ from Brooks, Inc; dehydroacetic acid; and benzsiothiazoli or isopropanol should be limited since these volatile organic none available under the trade name KoraloneTMB-119 from compounds will contribute both to flammability problems Rohm and Hass Corporation. and environmental pollution problems. If Small amounts of Suitable levels of preservative are from about 0.0001% to low molecular weight monohydric alcohols are present in the about 0.5%, alternatively from about 0.0002% to about 0.2%, 30 composition of the present invention due to the addition of alternatively from about 0.0003% to about 0.1%, by weight of these alcohols to Such things as perfumes and as stabilizers for the freshening composition. some preservatives, the level of monohydric alcohol may be less than about 6%, alternatively less than about 3%, alterna G. Wetting Agent tively less than about 1%, by weight of the freshening com The freshening composition may include a wetting agent 35 position. that provides a low Surface tension that permits the composi I. Other Optional Ingredients tion to spread readily and more uniformly on hydrophobic Adjuvants can be optionally added to the freshening com surfaces like polyester and nylon. It has been found that the position herein for their known purposes. Such adjuvants aqueous solution, without such a wetting agent will not include, but are not limited to, water soluble metallic salts, spread satisfactorily. The spreading of the composition also 40 antistatic agents, insect and moth repelling agents, colorants, allows it to dry faster, so that the treated material is ready to antioxidants, and mixtures thereof. use Sooner. Furthermore, a composition containing a wetting II. Method of Making agent may penetrate hydrophobic, oily soil better for The freshening composition can be made in any Suitable improved malodor neutralization. A composition containing manner known in the art. All of the ingredients can simply be a wetting agent may also provide improved “in-wear elec 45 mixed together. In certain embodiments, it may be desirable trostatic control. For concentrated compositions, the wetting to make a concentrated mixture of ingredients and dilute by agent facilitates the dispersion of many actives such as anti adding the same to an aqueous carrier before dispersing the microbial actives and perfumes in the concentrated aqueous composition into the air or on an inanimate Surface. In another compositions. embodiment, the malodor binding polymer may be dispersed Nonlimiting examples of wetting agents include block 50 in one vessel containing deionized water and ethanol, and low copolymers of ethylene oxide and propylene oxide. Suitable molecular polyols. To this vessel, then, the buffer is added block polyoxyethylene-polyoxypropylene polymeric Surfac until fully dispersed and visually dissolved. In a separate tants include those based on ethylene glycol, propylene gly vessel, the solubilizer and perfume are mixed until homog col, glycerol, trimethylolpropane and ethylenediamine as the enous. The solution of solubilizer and perfume are then added initial reactive hydrogen compound. Polymeric compounds 55 to the first mixing vessel, and mixed until homogenous. made from a sequential ethoxylation and propoxylation of III. Methods of Use initial compounds with a single reactive hydrogenatom, Such The freshening composition of the present invention can be as Casaliphatic alcohols, are not generally compatible with used by dispersing, e.g., by placing the aqueous solution into the cyclodextrin. Certain of the block polymer surfactant a dispensing means, such as a spray dispenser and spraying an compounds designated Pluronic R and Tetronic R by the 60 effective amount into the air or onto the desired surface or BASF-Wyandotte Corp., Wyandotte, Mich., are readily avail article. An effective amount as defined herein means an able. amount sufficient to neutralize malodor to the point that it is Nonlimiting examples of cyclodextrin-compatible wetting not discernible by the human sense of smell yet not so much agents of this type are described in U.S. Pat. No. 5,714,137 as to Saturate or create a pool of liquid on an article or Surface and include the Sillwet(R) Surfactants available from Momen 65 and so that, when dry, there is no visual deposit readily dis tive Performance Chemical, Albany, N.Y. Exemplary Silwet cernible. Dispersing can be achieved by using a spray device, Surfactants are as follows: a roller, a pad, etc. US 9,260,817 B2 15 16 The present invention encompasses the method of dispers The present invention relates to the method of dispersing a ing an effective amount of the composition for reducing mal mist of an effective amount of the composition for reducing odor onto household surfaces. The household surfaces are malodor impression onto cat litter, pet bedding and pet houses selected from the group consisting of countertops, cabinets, to neutralize malodor. The present invention relates to the method of dispersing a walls, floors, bathroom surfaces, and kitchen Surfaces. 5 mist of an effective amount of the composition for reducing The present invention encompasses the method of dispers malodor impression onto household pets to neutralize mal ing a mist of an effective amount of the composition for odor. reducing malodoronto fabric and/or fabric articles. The fabric EXAMPLES and/or fabric articles include, but are not limited to, clothes, to curtains, drapes, upholstered furniture, carpeting, bed linens, Malodor Reduction bath linens, tablecloths, sleeping bags, tents, car interior, e.g., Table 1 show non-limiting examples of freshening compo car carpet, fabric car seats, etc. sitions according to the present invention. TABLE 1.
V I II III IV (Control) VI VII VIII LUPASOLTMWF O.O7O O.O70 O.O15 O.O3S O O.O3S 0.0525 O.O7 CAS 90O2-98-6 Diethylene 0.175 0.175 O.O70 0.175 0.175 0.175 O.170 0.175 Glycol Perfume mixture O.2102 O488O O.O20 O.236 0.655 0.655 0.655 0.655 comprising (0% (0.012 (0.012 (0.012 (0.012 aliphatic aldehydes) aldehydes) aldehydes) aldehydes) aldehydes) aldehydes Hydroxypropyl O.630 O-630 O.630 O O.630 O.630 O.630 O.630 Beta Cyclo dextrin (CD) BASOPHORTM O O.OSO O.OSO O.OSO O.OSO O.OSO O.OSO O.OSO ELH 60 UNIQUAT TM O OO60 O O.O60 O.O60 O.O60 O.O60 O.O60 2250 BARDACTM O.139 O.100 O O O O O 225OJ SILWETTML- O.1OO O.1OO 0.175 O.100 O.100 O.100 O.100 O.100 7600 Citric Acid O.O4S OO15 O.O15 O.O15 O.O15 O.O15 O.15 O.O15 Maleic Acid O O.OSO O.O60 O.OSO O.OSO O.OSO O.OSO O.OSO CAS 110-1 6-7 ACES O.100 O O O O O O O Sodium O O O O.O2O O.O2O O.O2O O.O2O O.O2O Hydroxide KORALONETM O OO150 O O.O15 O.O15 O.O15 O.O15 O.O15 B-119 Ethanol 3.OOO 3OOO 3.OOO 3.OOO 3.OOO 3.OOO 3.OOO 3.OOO Deionized 95.571 95.347 95.865 96.264 95.318 95.18O 95.095 95.148 Water
Total 100 100 1OO 100 1OO
The present invention encompasses the method of dispers Formulations VI, VII, and VIII in Table 1 are prepared and ing a mist of an effective amount of the composition for compared to Control Formulation V, a composition contain reducing malodor impression onto and into shoes wherein the ing no malodor binding polymer, for their effect on malodor. shoes are not sprayed to saturation. 50 FIG. 1 shows that when including a malodor binding polymer The present invention encompasses the method of dispers in a freshening composition in accordance with the present ing a mist of an effective amount of the composition for invention, aldehydic malodor evaporating off the treated fab reducing malodor impression onto shower curtains. ric decreases. The present invention relates to the method of dispersing a Fabric samples are infused with the malodor of interest. mist of an effective amount of the composition for reducing 55 For grease infusion, place 8 ounces of grease in a Presto TM malodor impression onto and/or into garbage cans and/or electric skillet and cover with the skillet lid. Place the skillet recycling bins. in a 30 gallon metal garbage can. Run the electric cord from the skillet through a 1.5 inch hole in the garbage can. Heat the The present invention relates to the method of dispersing a skillet to 121° C. and allow it to equilibrate for 15 minutes. mist of an effective amount of the composition for reducing go Remove the lid. Suspend 8 inch by 8 inch fabric swatches malodor impression into the air to neutralize malodor. from the metal clips on a carousel in the garbage can lid. The present invention relates to the method of dispersing a Measured from the bottom of the swatches, the distance to the mist of an effective amount of the composition for reducing top of the skillet is 8 inches. Place lid on garbage can and malodor impression into and/or onto major household appli manually turn the carousel 15 rotations per minute for a ances including, but not limited to, refrigerators, freezers, 65 period of 40 minutes. After infusion, spray the swatches with washing machines, automatic dryers, ovens, microwave the respective freshening compositions that are to be tested. ovens, dishwashers, etc., to neutralize malodor. The spray for each Swatch consists of two full strokes of the US 9,260,817 B2 17 18 trigger sprayer bottle. The bottle is held 6 inches away from growth or no growth. Samples are plated and counted to the fabric and the spray is centered on the fabric. Immediately determine mean log 10 reduction. after treatment, cut each Swatch in half, roll, and place each All percentages stated herein are by weight unless other into a 125 mL headspace vial. Seal the vials. Allow the vials wise specified. It should be understood that every maximum to equilibrate for at least 2 hours at 100° C. and then analyze numerical limitation given throughout this specification will by sampling each vial using a PDMS SPME fiberand analyze include every lower numerical limitation, as if such lower by GC/MS. Malodor components, previously identified, are numerical limitations were expressly written herein. Every then tracked through all the samples. Data is compiled of total minimum numerical limitation given throughout this specifi area count of the cumulative area counts of the individual cation will include every higher numerical limitation, as if peaks. 10 Such higher numerical limitations were expressly written herein. Every numerical range given throughout this specifi Microbe Reduction cation will include every narrower numerical range that falls Table 2 show non-limiting examples of freshening compo within Such broader numerical range, as if such narrower sitions according to the present invention. numerical ranges were all expressly written herein. 15 The dimensions and values disclosed herein are not to be TABLE 2 understood as being strictly limited to the exact numerical IX values recited. Instead, unless otherwise specified, each Such (Control) X dimension is intended to mean both the recited value and a functionally equivalent range Surrounding that value. For LUPASOLTMWF O O.O7 CAS 90O2-98-6 example, a dimension disclosed as “40 mm is intended to Diethylene Glycol O.25 O.25 mean “about 40 mm.” Perfume mixture O.O2 O.O2 Every document cited herein, including any cross refer comprising aliphatic (0.002 aldehydes) (0.002 aldehydes) aldehydes enced or related patent or application, is hereby incorporated Hydroxypropyl Beta CD O.63 O.63 herein by reference in its entirety unless expressly excluded BASOPHORTMELEH 60 O.15 O.15 25 or otherwise limited. The citation of any document is not an UNIQUAT TM 2250 O O admission that it is prior art with respect to any invention BARDAC TM 22SOJ O.S O.S SILWETTML-7600 O.1 O.1 disclosed or claimed herein or that it alone, or in any combi Citric Acid O O nation with any other reference or references, teaches, Sug Maleic Acid O O gests or discloses any such invention. Further, to the extent CAS 110-1 6-7 30 that any meaning or definition of a term in this document ACE O.1 O.1 Sodium Hydroxide O.OO6 O.OO6 conflicts with any meaning or definition of the same term in a KORALONETMB-119 O O document incorporated by reference, the meaning or defini Ethanol 3.OOO 3.OOO tion assigned to that term in this document shall govern. Deionized Water 95.244 95.174 While particular embodiments of the present invention 35 have been illustrated and described, it would be obvious to Total 1OO 100 those skilled in the art that various other changes and modi fications can be made without departing from the spirit and Formulation IX, the control formulation containing no scope of the invention. It is therefore intended to cover in the malodor binding polymer, and Formulation X are compared appended claims all such changes and modifications that are for their effect on microbe reduction. FIG. 2 shows the results 40 within the scope of this invention. of formulations with and without PEIs when tested for non residual fabric sanitizer efficacy against Staphylococcus What is claimed is: aureus (ATCC 6538), Aspergillus niger (ATCC 6275), Pro 1. A freshening composition for reducing malodor com teus mirabilis (ATCC 7002) and Pseudomonas aeruginosa prising: 45 about 0.01% to about 0.07%, by weight of said freshening (ATCC 15442). composition, of a malodor binding polymer, wherein the Formulation efficacy was assessed by employing a North malodor binding polymer is a homopolymeric polyeth American Bactericidal Fabric Spray Test Method that is a yleneimine having a molecular weight of about 25,000 quantitative modification of the AOAC Germicidal Spray Daltons and 15% to 80% primary amino groups: Products Test method (961.02). This method is a recognized 50 a malodor counteractant comprising at least one aliphatic test standard inaccordance to U.S. EPA Pesticide Assessment aldehyde; Guidelines Subdivision G, Series 91-52(b)(1). The refer from about 0.05% to about 1%, by weight of said compo enced AOAC method was applied to fabric surfaces. Fabric sition, of Surfactant; and swatches (1.5 inch, 100% blue oxford cotton) as can be an aqueous carrier; obtained from Testfabrics Inc. were treated with 2 fully 55 wherein said composition is essentially free of any material depressed sprays of trigger sprayer bottle containing the that would soil or stain fabric, respective formulation. A contact time between 10 to 30 wherein said composition comprises a pH of about 6 to minutes at ambient temperature was chosen as a conservative about 8. time estimate for sprayed fabric surfaces, as provided in Sub 2. The composition of claim 1 wherein said at least one division G, Series 91-1(b)(4)(i). Any excess liquid is drained 60 aliphatic aldehyde is present in the amount of about 0.001% off and then transferred to a jar containing 20 ml neutralizer to about 5% by total weight of said composition. and/or growth promoting broth. The jar is mixed by Vortex 3. The composition of claim 2 wherein said at least one ing, followed by Sonication in a Branson Bransonic Ultra aliphatic aldehyde is selected from the group consisting of sonic Sonicator for 5 minutes. Within 30 minutes of neutral bourgeonal, citral, citronellyl oxyacetaldehyde, cymal, decyl ization, the jar is mixed for 2-3 seconds on a Vortex type mixer 65 aldehyde, helional, hexyl cinnamic aldehyde, lauric alde and serially diluted. All the samples were incubated (48+4 hyde, ligustral, lyral, melonal, methyl dihydro jasmonate, hours) under the appropriate conditions and monitored for methyl nonyl acetaldehyde, methyl phenyl carbinyl acetate, US 9,260,817 B2 19 20 nonyl aldehyde, 2" 6-nonadien-1-al, octyl aldehyde, oxane, a dicarboxylic acid to provide a pH of about 6 to about 8: P.T. bucinal, polysantol, rhubafuran, tripal, and mixtures and about 90% to about 99.5%, by weight of said compo thereof. sition, of an aqueous carrier, 4. The composition of claim 1 wherein said at least one wherein said composition is essentially free of any material aliphatic aldehyde is present in the amount of about 0.001% 5 that would soil or stain fabric. to about 1% by total weight of said composition. 12. The aqueous freshening composition of claim 11, 5. The composition of claim 1 wherein said composition wherein the freshening composition reduces malodor on fab further comprises a buffering agent selected from the group rics that are wetted with perspiration. consisting of carboxylic acid, dicarboxcylic acid, N-(2-Ac 13. A freshening composition for reducing malodor com etamido)-2-aminoethanesulfonic acid, and mixtures thereof. 10 prising: 6. The composition of claim 1 wherein said composition about 0.01% to about 0.07%, by weight of said composi further comprises maleic acid. tion, of a malodor binding polymer, wherein the malodor 7. The composition of claim 1 wherein said composition is binding polymer is a homopolymeric polyethylene free of anionic surfactants. imine having a molecular weight of about 25,000 Dal 8. The composition of claim 1 wherein said aqueous carrier 15 tons; is present in an amount of 90% to about 99.5%. about 0.001% to about 5%, by weight of said composition, 9. The freshening composition of claim 1, wherein the of a malodor counteractant comprising at least one ali freshening composition reduces malodor on fabrics that are phatic aldehyde; wetted with perspiration. less than 3%, by weight of said composition, of surfactant; 10. A method of reducing malodor comprising the steps of: and a. providing the freshening composition of claim 1: an aqueous carrier; b. dispersing an effective amount of said freshening com wherein said composition is essentially free of any material position on an inanimate surface or in the air. that would soil or stain fabric, 11. An aqueous freshening composition for reducing mal wherein said composition comprises a pH of about 6 to odor comprising: 25 about 8. a homopolymeric polyethyleneimine having a molecular 14. The composition of claim 13 wherein said aqueous weight of about 25,000 Daltons and 15% to 80% pri carrier is present in an amount of 90% to about 99.5%. mary amino groups: 15. The freshening composition of claim 13, wherein the at least one aliphatic aldehyde; freshening composition reduces malodor on fabrics that are less than 1%, by weight of said composition, of a surfac 30 wetted with perspiration. tant;