FIELD OF THE INVENTION

[0001] The present invention relates generally to malodor counteracting compositions, and more particularly to compositions including 3-benzyl-tetrahydropyran, which are capable of masking or counteracting malodors arising from odor-causing bacteria, such as Moraxella osloensis (Gram negative) and Staphylococcus aureus (Gram positive).

BACKGROUND OF THE INVENTION

[0002] Fabric products brought into direct contact with human skin, including underclothes, towels, handkerchiefs and the like, have a potential to absorb or attach sweat containing sebum, corneous substances and the like. These fabric products have a propensity to produce a “wet-and-dirty-dustcloth-malodor” or an “acidic or sweaty odor” characteristic once they are damp. This phenomena has been observed where after washing, the laundered fabric products are left untouched in a damp place such as the inside of a laundering machine tub for a long time, or if insufficiently dried. Moreover, for laundered fabric product having been air dried indoors, the malodor readily appears once the product has been wetted with rain or sweat. This malodor is generally called a“damp-dry malodor.”

[0003] Interestingly, the damp-dry malodor of some previously laundered fabric products can be temporarily eliminated by sufficiently drying the fabric products after laundry. However, the damp-dry malodor may reoccur at the time of use or when the fabric products become damp (e.g., from sweat, rain or the like). This can even occur from dry, laundered fabric products from which no damp-dry malodor is sensed.

[0004] This reoccurring damp-dry malodor may be produced not only in a case where fabric products are dried indoors, but also in a case where a dryer or a washing machine having a low temperature drying function is used, and even in the case of fabric products that have been dried outdoors, if the fabric products become damp. The reoccurring damp-dry malodor can also appear when fabric products are stored in a wardrobe or the like for a long time.

[0005] Prior work reported in JP5767831 (B2) (Patent 1 ) and Kubota et al.“Moraxella Species Are Primarily Responsible for Generating Malodor in Laundry,” Appl. Environ. Microbiol., 2012, 73:3317-3324, reveal that microorganisms such as Moraxella osloensis, as well as Staphylococcus aureus in combination with sebum, sweat, or soil in laundry, which remain even after washing, give rise to compounds that create the damp-dry malodor. Accordingly, Patent 1 discloses that inhibiting or eliminating these microorganisms with a spray-on alcohol solution comprising various damp-dry odor control agents possessing ketone, lactone, or ester functionality is one way of combating this problem.

[0006] In view of the foregoing, there is a need for new compositions and methods for deodorizing, inhibiting, or eliminating the damp-dry malodor.

SUMMARY OF THE INVENTION

[0007] The present invention is premised on the realization that an effective concentration of 3-benzyl-tetrahydropyran in a medium is capable of deodorizing, inhibiting, or eliminating a damp-dry malodor in a substrate. [0008] Thus, in accordance with an embodiment of the present invention, a method for counteracting or masking malodor in laundry articles is provided. The method comprises providing a laundry composition comprising 3-benzyl-tetrahydropyran; combining the laundry composition with a liquid medium for contacting the laundry articles, and contacting the laundry articles with the liquid medium comprising the laundry composition. The concentration of 3-benzyl-tetrahydropyran in the liquid medium is at least 15 ppm based on the total mass of the laundry composition.

[0009] In accordance with another embodiment of the present invention, a laundry composition for counteracting or masking malodor in laundry articles is provided. The composition comprises 3-benzyl-tetrahydropyran; and a detersive surfactant or a fabric softener active, wherein the detersive surfactant is selected from the group consisting of an anionic surfactant, a non-ionic surfactant, and combinations thereof; and wherein the fabric softener active is selected from the group consisting of a silicon polymer or compound, a cationic ammonium or imidazolinium polymer or compound, and a combination thereof.

[0010] The objects and advantages of the present invention will be further appreciated in light of the following detailed description and examples.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The accompanying drawing, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with a general description of the invention given above, and the detailed description given below, serve to explain the invention. It will be appreciated that for purposes of clarity and where deemed appropriate, reference numerals have been repeated in the figures to indicate corresponding features.

[0012] FIG. 1 is a plot of ammonia concentration in headspace of a sample over time for samples with or without 3-benzyl-tetrahydropyran;

[0013] FIG. 2 is a plot of trimethylamine concentration in headspace of a sample over time for samples with or without 3-benzyl-tetrahydropyran;

[0014] FIG. 3 is a plot of methyl mercaptan concentration in headspace of a sample over time for samples with or without 3-benzyl-tetrahydropyran;

[0015] FIG. 4 is a plot of diacetyl concentration in headspace of a sample over time for samples with or without 3-benzyl-tetrahydropyran;

[0016] FIGS. 5A and 5B are plots of sensory scores for a 10 ppm (w/w) isovaleric acid sample and a 5 ppm nonenal sample, respectively, with 0.0x, 0.5x, 1 .0x, 2.0x, and 3. Ox ppm of 3-benzyl-tetrahydropyran; and

[0017] FIGS. 6A and 6B are plots of gas chromatography analysis of isovaleric acid and nonenal concentration in the headspace of the 0.0x and 3.0x samples used in FIGS. 5A and 5B, respectively.

DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention relates in general to the field of fragrances, and more particularly to malodor counteracting compositions including 3-benzyl-tetrahydropyran, which are capable of masking or counteracting malodors arising from odor-causing bacteria, such as Moraxella osloensis (Gram negative) and Staphylococcus aureus (Gram positive). [0019] In accordance with an embodiment of the present invention, a laundry composition for counteracting or masking malodor in laundry articles is provided. The composition comprises 3-benzyl-tetrahydropyran formulated in a laundry product, such as laundry washing powders, laundry washing liquids, or fabric softener compositions. As reported in W02006/021663, the malodor counteracting agent of the present invention (i.e. , 3-benzyl-tetrahydropyran) is fragrant, and is described as geranium, woody, phenolic, lactonic, and having a natural rhubarb note with a green astringent woody aspect, suitable for use in a fragrance composition or in perfumery. 3-benzyl- tetrahydropyran is marketed under the French registered tradename BETAHYDRANE by V. MANE FILS.

[0020] In accordance with another embodiment of the present invention, a method for counteracting or masking malodor in laundry articles is provided. The method comprises providing a laundry composition comprising 3-benzyl-tetrahydropyran; combining the laundry composition with a liquid medium for contacting the laundry articles, and contacting the laundry articles with the liquid medium comprising the laundry composition. The concentration of 3-benzyl-tetrahydropyran in the liquid medium is at least 15 ppm based on the total mass of the laundry composition.

[0021] As used herein,“laundry product” includes laundry washing powders, laundry washing liquids, or fabric softener compositions.

[0022] As used herein, the term "fragrant" denotes a compound that gives off an odor.

[0023] As used herein, the term“perfumery” denotes not only perfumery in the usual sense of the term, but also other fields in which the odor of products is important. These may be perfumery compositions in the usual sense of the term, such as fragrancing bases and concentrates, eaux de Cologne, eaux de toilette, fragrances and similar products.

[0024] The amount of the 3-benzyl-tetrahydropyran incorporated into a perfumery composition will vary according to the nature of the composition, the desired fragrant effect, and the nature of the other fragrant or non-fragrant compounds that may be present, as well as the washing and rinsing and may be readily determined by a person skilled in the art, given that it may vary within a very wide range, from 0.1 % to 99% by weight, in particular 0.1% to 50% by weight and especially 0.1 % to 30% by weight.

[0025] 3-benzyl-tetrahydropyran may be used as sole fragrant agent or, as is common in perfumery, it may be in a mixture with one or more other fragrant compounds, that a person skilled in the art is capable of selecting as a function of the desired effect. There are no particular restrictions on the fragrance(s) that can be used in combination with 3-benzyl-tetrahydrofuran. The additional fragrant agent(s) may be other fragrant agents known to those skilled in the art. Exemplary fragrants include, but are not limited to, hydrocarbon perfume, alcohol perfume, ether perfume, aldehyde perfume, ketone perfume, ester perfume, lactone perfume, or cyclic ketone perfume, etc. The content of the 3-benzyl-tetrahydropyran-containing perfume ingredient in the laundry composition is not particularly limited, and is preferably from 0.01 % to 10% by mass, more preferably from 0.01 % to 5.0% by mass, particularly preferably from 0.02% to 2.0% by mass.

[0026] The 3-benzyl-tetrahydropyran-containing perfumery composition may be used neat or it may be incorporated into or onto an inert support material or a material that may contain other active ingredients of the finished composition. A wide variety of support materials may be used, including, for example, polar solvents, oils, greases, finely divided solids, cyclodextrins, maltodextrins, gums, resins and any other support material known for such compositions. The 3-benzyl-tetrahydropyran-containing perfumery composition may be encapsulated.

[0027] Laundry washing powders generally comprise 5-30% by weight of anionic surfactants e.g. alkylbenzenesulphonates, fatty acid soaps, alcohol sulphates or alpha- olefin sulphonates; 1 -10% of non-ionic surfactants such as polyethoxylated alcohols; 0- 5% of lather boosters such as alkanolamides; 35-60% of inorganic builders/fillers such as sodium tripolyphosphate, zeolites, sodium carbonate, sodium sulphate or sodium silicate; 0-15% of bleaching agents such as sodium perborate and bleach precursors such as tetraacetylethylenediamine; up to 15% of additional adjuncts such as optical brightening agents, chelating agents, anti-redeposition agents, enzymes, dyes and perfume; and 2-15% of water.

[0028] Laundry washing liquids generally comprise 5-40% by weight of anionic surfactants, e.g. fatty acid soaps or alkylbenzenesulphonates; 1 -20% of non-ionic surfactants, e.g. (poly)ethoxylated alcohols and alkanolamides; 0-30% of builders/sequestrants, e.g. sodium tripolyphosphate, tetrapotassium pyrophosphate, soda ash and silicates; 0-15% of alcohols/coupling agents, e.g. ethanol, glycerol and sodium xylenesulphonate; 1 -5% of additional adjuncts such as anti-redeposition agents, optical brighteners, enzymes, fabric conditioning agents, dyes and perfume; and 40-

60% of water. [0029] Fabric conditioners generally comprise 4-50% by weight of cationic actives e.g. quaternary ammonium or imidazoline derivatives, and additionally 0-5% of other lubricants such as lanolin or fatty acids; 0.5-5% of additional adjuncts such as preservatives, dyes, pH control agents, co-solvents, opacifiers, electrolytes and perfume; 49.5-95.5% of water.

[0030] In any of the foregoing compositions, 3-benzyl-tetrahydropyran is present in the laundry composition a sufficient quantity that, when diluted with a liquid medium (e.g., water) used for washing or treating the laundry articles, provides a deodorant effect to damp-dry malodor. For example, upon dilution the laundry composition may include 15 ppm, 20 ppm, 25 ppm, 30 ppm, or more, which is effective toward masking various malodors, including nitrogen-based (e.g., ammonia, trialkylamines such as trimethylamine, indole, nicotine, pyridine) or sulfur-based (e.g., methylmercaptan, hydrogen sulfide, thioglycolate), as well as fatty acid-based (e.g., isovaleric acid, carpylic acid, terpenoid, ester, aldehydes) malodors. Accordingly, the laundry composition used for washing or treating the laundry articles may include 40 ppm, 50 ppm, 75 ppm, 100 ppm, 160 ppm, 200 ppm, 250 ppm, 300 ppm, 320 ppm, 400 ppm, or in a range between any two of the foregoing.

[0031] Our recent investigations have revealed that dilute broth solutions of 3- benzyl-tetrahydropyran against Moraxella osloensis (NBRC 1 1 1460) and Staphylococcus aureus (NBRC 13276) demonstrated minimum inhibitory concentration (MIC) values at room temperature of 160 ppm and 320 ppm, respectively. Other ingredients having fragrant and/or antimicrobial properties against Moraxella osloensis and/or Staphylococcus aureus may be used in combination with 3-benzyl- tetrahydropyran. Such ingredients include, but are not limited to, NOREENAL™ (6,8- dimethyl-,(6R)-7-nonenal); beta-ionone (4-(2,6,6-trimethylcyclohex-1 -ene-1 -yl)-but-3- ene-2-one); teatree oil; terpinen-4-ol; thymol; cinnamon leaf oil; petitgrain oil; clove oil; patchouli oil; or combinations thereof. Additionally, other factors such as temperature, pH, identity and concentration of surfactants, etc. can also affect MIC values under the present conditions. For example, in one embodiment a combination of 3-benzyl- tetrahydropyran and a quaternary ammonium and/or imidazoline derivative softening agent provides enhancement of MIC values.

[0032] Thus in accordance with another embodiment of the present invention, the laundry composition used for washing or treating the laundry articles may include an effective concentration of 3-benzyl-tetrahydropyran that is sufficient to inhibit or kill Moraxella osloensis (NBRC 1 1 1460) and Staphylococcus aureus (NBRC 13276) in the liquid medium or on the laundry articles. For example, the concentration of 3-benzyl- tetrahydropyran in the laundry composition may be in a range from about 160 ppm to about 400 ppm.

[0033] EXAMPLES

[0034] EXAMPLE 1 : Deodorant Effect Using Detector Tube

[0035] Samples containing a model malodor system comprising exemplary malodor agents (ammonia 0.005 wt%, trimethylamine 0.003 wt%, and methyl mercaptan 0.001 % from Wako Pure Chemical Industries, Ltd; and diacetyl 1 wt% from V. MANE FILS) diluted in dipropylene glycol (DPG) were prepared and stored in 1 oz. capped, brown glass bottles. Another set of samples containing the exemplary malodor agents (ammonia, trimethylamine, methyl mercaptan, and diacetyl), also diluted in DPG, were prepared and treated with BETAHYDRANE (5 times the concentration of the malodor). Each of the samples was stirred at 20°C. At predetermined lime intervals, headspace gas in the vial bottle was passed through a gas detection tube (manufactured by GASTEC Corporation), and plotted against time. The model numbers of GASTEC tubes were ammonia = No. 3L; trimethylamine = No.180L; methyl mercaptan = No. 70L; and diacetyl = No. 92.

[0036] As shown in FIGS. 1-4, without the addition of BETAHYDRANE™, the gas phase concentrations of ammonia (~50 ppm), trimethylamine (~9.5 ppm), methyl mercaptan (~5.5 ppm), and (~180 ppm) diacetyl remained essentially constant over time. In contrast, the BETAHYDRANE™ treated samples showed substantial reduction in the gas phase concentrations of each of the malodor agents, where the concentrations after 12 minutes were ammonia (~10 ppm, ~80% reduction), trimethylamine (~4.5 ppm, ~50% reduction), methyl mercaptan (~1.2 ppm, ~80% reduction), and diacetyl (75 ppm, ~60% reduction).

[0037] EXAMPLE 2: Deodorant Effect using Sensory and Gas Chromotography

[0038] Samples containing exemplary malodor agents, isovaleric acid (10 ppm), and nonenal (5 ppm) were prepared and stored in capped, brown glass bottles. Samples containing the exemplary malodor agents were treated with BETAHYDRANE™ at O.Ox, 0.5x, 1.0x, 2.0x, and 3.0x the concentration of the respective malodor agents. After two hours, each sample was subjected to sensory evaluation (0-5 scale) and quantitative analysis (GC peak area). Criteria for sensory evaluation was: 0 - No Odor; 1 - Slightly Weak; 2 - Weak; 3 - Easily Detected; 4 - Strong; and 5 - Distinctively Strong. Seven samples were analyzed for this study. [0039] As shown in FIGS. 5A and 5B, a reduction of the sensory value gradually declined over increasing exposure to BETAHYDRANE™. For isovaleric acid (FIG. 5A), the sensory value decreased from an average value of about 4 to an average value of about 2. A similar reduction was observed form nonenal (FIG. 5B). The decrease in sensory values for isovaleric acid and nonenal correlated with the peak area analysis using gas chromatography (GC), as shown in FIGS. 6A and 6B. respectively. GC analysis was performed using Agilent Technologies 7890B GC, with Agilent Technologies 5977A mass spectrometer, using a DB-WAX(J&W) 60mx0.25mmx0.25pm column; 1 μΙ injection volume; injection temperature 240°C; 100:1 split ratio; He carrier gas; 1.2ml/min column flow; and Oven 40 (1 min hold)→85°C (3°C/min)→230°C(10°C/min).

[0040] EXAMPLE 3: Deodorant effect in softener base

[0041] Multiple 30cm x 30cm towel cloths, each treated with 20 ml_ of a model malodor composition distinctive for body odor (ammonia (30 ppm), acetic acid (50 ppm), isovalerate (10 ppm), and nonenal (5 ppm)), were individually rinsed in 3 L of aqueous solution of a softener composition (1 mL) for 10 min, and then air dried over 24 hours. The rinse solutions included a softener composition containing 0.8 wt% of 1) dipropylene glycol (DPG); 2) a fragrance; and a fragrance containing 4,000 ppm BETAHYDRANE™, thus providing 32 ppm BETAHYDRANE™ in the softener composition.

[0042] Criteria for sensory evaluation was based on what degree the 32 ppm BETAHYDRANE fabric softener can counteract the model body odor: None (0%); Not so much (0%); Neither (8%); Fee! slightly (43%); Gan feel (48%). Forty-two samples were analyzed for this study.

[0043] EXAMPLE 5 - Minimum Inhibitory Concentration (MIC)

[0044] Testing was performed to determine the MIC values for 3-benzyl- tetrahydropyran against test bacteria Staphylococcus aureus (NBRC 13276) and Moraxella osloensis (NBRC 1 1 1460). The testing method included preparation of the test broth solutions, where samples of 3-benzyl-tetrahydropyran were dissolved with ethanol, then diluted with water to provide 4.0 wt% solutions (concentration of ethanol was 6.0%). The 2-fold dilutions of this solution were prepared using Mueller Hinton Broth (MHB).

[0045] In order to prepare cell suspensions of the test bacteria, Staphylococcus aureus and Moraxella osloensis were separately cultured on Soybean-Casen Digest Agar for 24 hours at 35°C. After incubation, the respective cultures were suspended in normal (isotonic) saline solution and the resultant solutions contain ~10 ⁴ cells per milliliter. These suspensions were used as the cell suspension for inoculation.

[0046] Transfer of 0.05 ml cell suspensions to 4.95 mL of each test solution, which was subsequently incubated at 35°C. Normal saline solution was used as a control. After incubation, growth of the test bacteria was observed with the naked eye and estimated the MIC. The results of MIC test of the 3-benzyl-tetrahydropyran against Staphylococcus aureus and Moraxella osloensis are shown in Tables 1 and 2. [0047] Table 1 : MIC values for 3-benzyl-tetrahydropyran against Staphylococcus aureus.

[0048] Table 2: MIC values for 3-benzyl-tetrahydropyran against Moraxella osloensis.

[0049] While the present invention was illustrated by the description of one or more embodiments thereof, and while embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. For example, incorporating focusing agents into other sampling devices for other analytical techniques is envisioned. Additional advantages and modification will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative product and method, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept embraced by the following claims.