WO1997034989A1 - Detergent compositions comprising pro-fragrance compound - Google Patents
Detergent compositions comprising pro-fragrance compound Download PDFInfo
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- WO1997034989A1 WO1997034989A1 PCT/US1997/005372 US9705372W WO9734989A1 WO 1997034989 A1 WO1997034989 A1 WO 1997034989A1 US 9705372 W US9705372 W US 9705372W WO 9734989 A1 WO9734989 A1 WO 9734989A1
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- detergent composition
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/507—Compounds releasing perfumes by thermal or chemical activation
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
Definitions
- the present invention relates to a detergent composition
- a detergent composition comprising an acetal or a ketal pro-fragrance compound.
- Acetals and ketals have long been known in perfumery. See Steffen Arctander, "Perfume and Flavor Chemicals," Arctander, N.J., 1969. The majority of these are methyl and ethyl types, and molecular weights may range widely. See, for exampie, Arctander abstract numbers 6, 11 , 210, 651 , 689, 1697, 1702, 2480, 2478. However, the known acetals and ketals are generally not desirable for use in laundry products. For 2478, which is phenylacetaldehyde dicitronellyl acetal, molecular weight 414.7, Arctander reports " ...
- compositions such as deodorant sticks, comprising "body- activated" fragrances are also known.
- the term apparently refers to the previously known tendency of materials such as acetals derived from perfume alcohols to hydrolyze under acidic pH conditions thereby releasing fragrance. See, for example, U.S. Patent 5,378,468, issued Jan. 3, 1995 and U.S. Patent 3,932,520, issued January 13, 1976.
- Potential fragrance materials for use in such personal care compositions include particular acetals and ketals, exemplified by propylene glycol vanillin acetal.
- the materials exemplified apparently are rather hydrophilic short chain alcohol or diol derivatives of fragrance aldehydes and upon hydrolysis, deliver one mole of the aldehyde per mole of the potential fragrance material.
- This development is designed to be incorporated with a personal care product vehicle, resulting in clear deodorant sticks and the like, and the compositions containing the potential fragrance materials are applied directly to the substrate (i.e. skin); therefore, the deposition problems resulting from the dilution, rinsing, etc., associated with the laundry process are not at issue.
- Laundry detergents are used in dilute aqueous form and contain numerous detergent adjuncts such as synthetic detergents, builders, enzymes and the like which are capable of micellizing, or solubilizing the pro-fragrance. Further, the laundry process includes rinsing, and sometimes drying with tumbling machines after washing. The rinsing tends to remove the useful pro- fragrance material deposited. The tumble-drying further exacerbates the problem of delivering adequate residual fragrance to textile fabric surfaces.
- the present invention is directed to a detergent composition
- a detergent composition comprising a pro-fragrance compound selected from the group consisting of an acetal, a ketal, and mixtures thereof, wherein at least one of a parent aldehyde, ketone, or alcohol of the pro-fragrance acetal or ketal is a fragrance compound, the pro- fragrance compound having a CLogP of less than about 4, wherein the detergent composition has a pH of at least 7.1 when measured as a 1 % solution in distilled- water at 20°C, and a detersive surfactant.
- a detergent composition of the present invention comprises a pro- fragrance compound including acetals, ketals, or mixtures thereof, provided that compounds from which they are formed comprise at least one fragrance compound.
- pro-fragrance compound means a compound which may or may not be odoriferous in itself but which, upon hydrolysis; produces a desirable odor which is characteristic of one or more of its hydrolysis products. This term includes mixtures of pro-fragrance compounds and further encompasses the term “pro-perfume.”
- Acetals and ketals can be considered as derivable from aldehydes or ketones in combination with alcohols. These aldehydes, ketones and alcohols are herein termed “parents” or “parent compounds” of the acetal or ketal. At least one parent of any of the instant acetals or ketals is a fragrance compound.
- the pro-fragrance compound of this invention has a CLogP of less than about 4, wherein the CLogP is the logarithm to base 10 of the Octanol Water Partition Coefficient of the pro-fragrance compound.
- the pro-fragrances having the CLogP of less than about 4 give good dispersibility in the aqueous solution. Without being bound by theory, it is believed that the CLogP, as described herein, can be lower when the number of alkoxy moiety included in the pro- fragrance compound is increased.
- pro-fragrances can further be characterized as having a molecular weight of at least about 170 and a half-life of less than 60 minutes when measured at pH 0 by the Hydrolysis Half-life (t-1/2) Test as described herein.
- the pro-fragrance compounds of the present invention are stable under pH conditions encountered in the formulation and storage of detergent products which have a pH of from about 7.1 to about 13, and during solution-use of such products. Due to hydrophilicity and high degree of heteroatom inco ⁇ oration, these pro-fragrance compounds give reasonably good deposition from a laundering solution onto fabrics.
- the pro-fragrance compounds are subject to hydrolysis when the pH is reduced, they hydrolyze to release their component fragrance compounds when the fabrics (or other surface) upon which they have been deposited are exposed even to reduced pH such as is present in rinse water, air and humidity.
- a reduction in pH should be at least about 0.1 , preferably at least about 0.5 units.
- the pH is reduced by at least about 0.5 units to a pH of about 7.5 or less, more preferably about 6.9 or less.
- the solution in which the fabric (or other surface) is washed is alkaline.
- the preferred pro-fragrance compounds of this invention can be cyclic or acyclic (including mixtures of both cyclic and acyclic) having at least 3 oxygens more preferably, the cyclic pro-fragrance compound having at least two alkoxylate moiety and the acyclic pro-fragrance compound having at least 4 alkoxylate moiety.
- Preferred acetals and ketals herein are those derived from a fragrance or non-fragrance alcohol, particularly C6-C20 (preferably C ⁇
- a fragrance or non-fragrance alcohol particularly C6-C20 (preferably C ⁇
- parent alcohols of the present invention have at least one alkoxy moiety. Due to increasing the member of alkoxy moiety as described above, the pro-fragrances having the CLogP of less than about 4 give good dispersibility in detergent solution.
- the preferred parent alcohols can include the alkoxylates of detergent alcohols, mono-alkyl ethers of short-chain polyalkoxylates, polyols including those which are alkoxylated with 1 to 30 groups of ethylene oxide or propylene oxide.
- acetals and ketals are included within the invention.
- Many fragrant aldehydes, ketones, and alcohols which are suitable parents for the present acetals and ketals are known to the art. See, for example, Arctander's compilation referenced hereinabove for fragrant parents. These will be also obtainable commercially from perfume houses such as IFF, Firmenich, Takasago, H&R, Givaudan-Roure, Dragoco, Aldrich, Quest, and others.
- the pro-fragrances of the present invention include an acetal.
- the acetal can be used to deliver fragrance aldehydes, fragrance alcohols, or both, preferably to deliver fragrance aldehydes derived from parent aldehydes.
- Acetals suitable in the present invention include the following structure:
- X and Y are derived from a starting alcohol and R-
- X and Y in the above general structure which can be either fragrant alcohols or non-fragrant alcohols includes variable alkoxy moieties.
- X and Y can be the same or different allowing the delivery of more than one type of fragrant alcohol.
- the alcohols are non-fragrant alcohols, it is preferred that they are C6-C20 alcohols, especially fatty alcohols, which may optionally be modified by ethoxylation or propoxylation.
- X and Y can be simple alcohols containing a single OH group, or can be polyols containing 2 or more OH groups, more preferably, diols.
- alcohols can be saturated, unsaturated, linear or branched, alkyl, alkenyl, alkylaryl, alkylalkoxylate derivatives with one or more alcohol groups.
- the alcohols may contain additional functionality such as amines, amides, ethers, or esters as a part of their structure.
- the acetal of the present invention can be cyclic or acyclic, and may contain one or more acetal groups through derivatizing one or more aldehydes.
- the terms cyclic and acyclic in this context refers to the presence or absence of a covalent bond connecting moieties X and Y of the acetal.
- X and Y of the cyclic acetals form a ring structure and have at least two alkoxylate moieties.
- the preferred acyclic acetals having at least four alkoxylate moieties incorporate linear alcohols.
- the cyclic acetals are derived from polyols.
- Preferred polyols include those which are alkoxylated with 1 to 30 units of ethylene oxide or propylene oxide.
- Nonlimiting examples of the polyols include sorbitol, glucose, sucrose, and other saccharides.
- the acyclic acetals are derived from mono-alcohols.
- Preferred mono- alcohols containing a single OH group can include the alkoxylates of detergent alcohols and mono-alkyl ethers of short-chain polyalkoxylates.
- the mono-alkyl ethers of short-chain polyalkoxylates include C1-C5 alkyl moiety.
- Nonlimiting examples of the parents alcohols include ethyl alcohol, propyl alcohol, butyl alcohol, lauryl alcohol, and myristyl alcohol.
- Rl and the H of the above general structure are derived from a starting aldehyde.
- both fragrant and non-fragrant aldehydes incorporated into the instant acetals can be aliphatic, allyiic or benzylic.
- the aldehydes can be saturated, unsaturated, linear, branched, or cyclic.
- the structures can include alkyl, alkenyl, or aryl moieties, as well as additional functional groups such as alcohols, amines, amides, esters, or ethers.
- acetals herein will be derived from parent aldehydes having molecular weight above about 80.
- Nonlimiting examples of the fragrant parent aldehydes include but are not limited by the following examples: hydratropaldehyde, p-t-bucinal, FloralozoneTM, phenylpropanal, anisaldehyde, cymal, cyclamal, triplal, helional, hexylcinnamic aldehyde, vanillin, ethyl vanillin, citral, ethyl citral, citronellal, methyl octyl acetaldehyde, methyl nonyl acetaldehyde, octanal, decanal, dodecanal, lauric aldehyde, chrysanthal, isosyslocitral, melonal, f
- pro-fragrance acetal compounds are nonlimitingly illustrated by the following:
- acyclic acetals which is derived from cyclal c and tripropylene glycol.
- suitable acetals herein are cyclic acetals derived from the reaction of fragrance aldehydes with polyhydroxyglucosides, including the polyhydroxyamides.
- suitable polyhydroxy amides include the C12-C18 N-methylglucamides. See WO 9,206,154.
- Other sugar-derived acetal or ketal parent compounds herein include the N-alkoxy polyhydroxy fatty acid amides, such as C-jo-C ⁇ N-(3-methoxypropyl) glucamide.
- the pro-fragrance compound of the present invention includes a ketal.
- the ketal can be used to deliver a fragrance ketone.
- the discussion for the ketals herein can be constructed using structural principles analogous to those used in discussing acetals supra.
- Ketals suitable in the present invention include the following structure:
- X and Y are derived from alcohols or polyols and R2 and R3 are derived from the parent ketone, and can be the same or different.
- X and Y for ketals in the above general structure can be either fragrant alcohols or non-fragrant alcohols including variable alkoxy moieties.
- the parent alcohols for the ketals can include, but are not limited to, those described as the parent alcohols of the acetals in the section of acetals.
- alcohols can be saturated, unsaturated, linear or branched, alkyl, alkenyl, alkylaryl, alkylalkoxylate derivatives with one or more alcohol groups.
- the parent alcohols may contain additional functionality such as amines, amides, ethers, or esters as a part of their structure.
- both fragrant and non-fragrant ketones can be aliphatic, allyiic or benzylic.
- the ketones can be saturated, unsaturated, linear, branched, or cyclic, preferably including alkyl, alkenyl, or aryl moieties as well as other functional groups including amides, amines, ethers, or esters.
- Nonlimiting examples of the parent ketones include, for example, irone alpha, a/p ⁇ a-ionone, oefa-ionone, gfamma-methyl ionone, methyl fcet ⁇ -naphthyl ketone, c/s-jasmone, damascenone, a/p ⁇ a-damascenone, benzyiacetone, methyl dihydrojasmonate, methyl amyl ketone, methyl heptyl ketone, methyl hexyl ketone, methyl nonyl ketone, carvone, cassione, menthone, and geranylacetone.
- ketones include diketones, e.g. 2,4-pentadione.
- the non-fragrant ketone can contain one or more ketone functional groups and such groups can be further derivatized so that the ketal is polymeric. While polyketals are included herein, they are less preferred than mono- and di-ketals. Monoketals are most preferred.
- pro-fragrance ketal compounds are nonlimitingly illustrated by the following:
- acyclic ketals which is derived from a/p ⁇ a-ionone and tripropylene glycol.
- Variations of the present invention include laundry detergents which incorporate acetals or ketals wherein the parent alcohol is a polymer such as polyvinyl alcohol, starch or synthetic copolymers incorporating tri- or polyhydric alcohols as monomers.
- the pro-fragrance compound herein can be used at widely ranging levels.
- a pro-fragrance acetal, ketal or mixture thereof is formulated in the present detergent compositions at levels in the general range about 0.0001% to about
- a pro-fragrance compound can be used as the sole fragrance compound of the present detergent compositions, or in combination with other pro- fragrances and/or in combination with other fragrance materials, extenders, fixatives, diluents and the like.
- inco ⁇ oration of the pro-fragrance material into a waxy substance, such as a fatty triglyceride may further improve storage stability of the present pro-fragrance compounds in granular laundry detergents, especially those comprising bleaches.
- hydrophobic liquid extenders, diluents or fixatives can be used to form an emulsion wherein the pro-fragrance compound is further stabilized by separating it from the aqueous phase.
- Nonlimiting examples of such stabilizing materials include dipropylene glycol, diethyl phthalate and acetyl triethyl citrate.
- hydrophobic perfumery ingredients which can be used to stabilize the pro-fragrance material
- detergency ingredients which also have a perfume stabilizing effect and can be formulated with the pro-fragrance material.
- Such ingredients include fatty acid amines, low foaming waxy nonionic materials commonly used in automatic dishwashing detergents, and the like.
- pro-fragrances are used along with other fragrance materials in detergent compositions herein, it is preferred that the pro-fragrance be added separately from the other fragrance materials. Synthesis of pro-fragrances
- Acetals and ketals can be prepared by the acid-catalyzed reaction of an aldehyde or ketone with an alcohol (or diol), using conventional acid catalysis such as HCl or p-toluenesulfonic acid, or supported sulfonic acid catalysts e.g., AMBERLYST 15TM See Meskens, F., Synthesis, (7) 501 (1981) and Meskens, F., Jannsen Chim Acta (1) 10 (1983). Many aldehyde, ketone and alcohols useful in the synthesis of acetal and ketal pro-fragrances of the present invention are sensitive to strong acid conditions and can undergo undesirable side reactions. See Bunton, CA. et al, J. Org.
- the detergent composition of the present invention includes a detersive surfactant in addition to the pro-fragrance compound(s).
- the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-Ci2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxylates), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
- the C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154.
- sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C-jQ-Ci ⁇ N-(3-methoxypropyl) glucamide.
- 8 glucamides can be used for low sudsing.
- C-JO- C20 conventional soaps may also be used; however, synthetic detergents are preferred. If high sudsing is desired, the branched-chain C-jo-Ci ⁇ soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. See also U.S. Patent 3,664,961 , issued May 23, 1972.
- compositions incorporating only synthetic detergents have a detergent level of from about 0.5% to about 50%.
- Compositions containing soap preferably comprise from about 10% to about 90% soap.
- the detergent compositions herein preferably, have a pH of from about 7.1 to about 13, more typically from about 7.5 to about 9.5 for liquid detergents and from about 8 to about 12 for granular detergents when measured at 1% concentration of the distilled water at 20°C. Test Methods
- the pro-fragrances of the invention are characterized by their octanol/water partition coefficient P.
- the octanol/water partition coefficient of a pro-fragrance is the ratio between its equilibrium concentration in octanol and in water. Since the partition coefficients of the pro-fragrance compounds are large, they are more conveniently given in the form of their logarithm to the base 10, logP.
- CLogP The "calculated logP” (CLogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J.B. Taylor and CA. Ramsden, Eds., p. 295, Pergamon Press, 1990). The fragment approach is based on the chemical structure of a compound and takes into account the numbers and type of atoms, the atom connectivity, and chemical bonding.
- the CLogP values which are the most reliable and widely used estimates for this physicochemical property, are preferably instead of the experimental logP values in the selection of pro- fragrances. Determination of Hydrolysis Half-life (t-1/2)
- Hydrolysis half-life is the measurement used to determine the ease with which the pro-fragrance compound undergoes acid hydrolysis and thereby releases its fragrance component(s) upon exposure to acid conditions.
- the pro- fragrance compounds of the invention have a half-life of less than 60 minutes, under the described hydrolysis conditions at pH 0.
- pro-fragrances of the invention have a half-life at pH 2 of less than 60 minutes.
- the more reactive pro-fragrances that is, those with half-life at pH 2 of less than one minute, are most suitable, although those having a half-life of less than 60 minutes at pH 0 are also useful.
- pro-fragrances having a half-life of less than 60 minutes at pH 0, and half-life greater than one minute at pH 2 should preferably be used.
- Hydrolysis half-life is determined by UV/V spectroscopy in a 90/10 dioxane/water system at 30OC by following the appearance of the carbonyl absorbance. Because of the hydrophobicity of the pro-fragrance compounds of the invention, a high dioxane water ratio is needed to ensure solubility of the pro- fragrance.
- the pH of the water used is achieved by using aqueous HCl.
- the concentration of the pro-fragrance in the dioxane water system can be adjusted to achieve convenient, measurable absorbance changes.
- Pro-fragrance is weighed out in a 10ml volumetric flask using an analytical balance (Mettler AE 200) Precision is 1/10 mg. The weighed material is dissolved in about 8ml dioxane. Both the dioxane solution of pro-fragrance and aqueous acid solution prepared as described supra are pre-heated in their separate containers to a temperature of 30 + 0.25°C by means of a water-bath. 1.000ml of aqueous acid solution is added to the pro-fragrance solution by means of an Eppendorf pipetter. This is followed by diluting to the 10ml mark with dioxane. Hydrolysis time is measured, starting upon addition of the acid.
- the pro-fragrance solution is mixed for 30 seconds by shaking, and the solution is transferred to a quartz cuvette.
- the absorbance of the pro-fragrance solution (At) is followed at a regular series of time intervals, and the cuvette is kept in the water-bath at the above-indicated temperature between measurements.
- Initial absorbance (Ao) measurements are carried out using an equal concentration of pro-fragrance in a 90/10 v/v dioxane - deionized water solution, and final absorbance (Af) measurements are taken using the hydrolyzed pro-fragrance solution after the hydrolysis is complete.
- the wavelength at which the hydrolysis is followed is chosen at the wavelength of the absorbance maximum of the parent aldehyde or ketone.
- Reaction half-lifes are determined using conventional procedures.
- the observed first-order rate constant (k 0DS ) is determined by slope of the line provided by plotting the following function vs time (min):
- Half-life as defined herein is the time required for half of the pro-fragrance to be hydrolyzed, and is determined from the observed rate constant (k 0DS ) by the following function:
- the detergent composition of the present invention may further include one or more additional detergent ingredients, commonly used in detergent products, such as materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., conventional perfumes, colorants, dyes, etc.).
- additional detergent ingredients are known to those of skill in the art. The following are illustrative examples of other detergent ingredients.
- Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
- the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
- the compositions will typically comprise at least about 1% builder.
- Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder.
- Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder.
- Lower or higher levels of builder are not meant to be excluded.
- Inorganic or detergent builders include, but are not limited to phosphate builders such as, the alkali metal, ammonium and alkanoiammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, and phytic acid, and non- phosphorous builders such as silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
- Non-phosphate builders are required in some locales.
- Organic builders suitable for use herein include polycarboxyiate builders such as disclosed in U.S. Patent 3,308,067, issued Mar. 7, 1967; 4,144,226, issued Mar. 13, 1979 and 4,246,495, issued Mar. 27, 1979. Soil Release Agents
- Soil Release agents are desirably used in laundry detergents of the instant invention. Suitable soil release agents include those of U.S. Patent 4,968,451 ,
- ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and
- oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. Patent 4,702,857, issued Oct. 27, 1987, for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. Patent 4,877,896, issued Oct.
- compositions herein can contain other ingredients such as enzymes, bleaches, fabric softening agents, dye transfer inhibitors, suds suppressors, and chelating agents, all well known within the art.
- Formulation with Detergents With or Without Conventional Perfumery Materials While the pro-fragrances of the present invention can be used alone and simply mixed with essential detergent ingredient, most notably surfactant, they can also be desirably combined into three-part formulations which combine (a) a non-fragrance detergent base comprising one or more synthetic detergents, (b) one or more pro-fragrance acetals or ketals in accordance with the invention and (c) a fully-formulated fragrance. The latter provides desirable in-package and in- use (wash-time) fragrance, while the pro-fragrance provides a long-term fragrance to the laundered textile fabrics.
- the fully-formulated fragrance can be prepared using numerous known odorant ingredients of natural or synthetic origin.
- the range of the natural raw substances can embrace not only readily-volatile, but also moderately-volatile and slightly-volatile components and that of the synthetics can include representatives from practically all classes of fragrant substances, as will be evident from the following illustrative compilation: natural products, such as tree moss absolute, basil oil, citrus fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil, alcohols, such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, aldehydes, such as citral, HelionalTM, alpha- hexyl-cinnamaldehyde, hydroxycitron
- any conventional fragrant acetal or ketal known in the art can be added to the present composition as an optional component of the conventionally formulated perfume (c).
- Such conventional fragrant acetals and ketals include the well- known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those comprising phenylethyl moieties, or more recently developed specialties such as those described in a U.S. Patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-lndanes, see U.S. Patent 5,084,440, issued Jan. 28, 1992, assigned to Givaudan Co ⁇ .
- Detergents in accordance with the present invention may further, optionally, if desired, contain other known compounds having the capability to enhance substantivity of a fragrance.
- Such compounds include, but are not limited to, the aluminum alkoxides such as isobutylaluminium diferanylate as disclosed in U.S. Patent 4,055,634, issued Oct. 25, 1977; or the known titanate and zirconate esters or oligoesters of fragrant materials such as those disclosed in U.S. Patent 3,947,574, issued March 30, 1976 and U.S. Patent 3,779,932, issued Dec. 18, 1973.
- organoaluminium, organotitanium or organozinc derivatives When using such organoaluminium, organotitanium or organozinc derivatives, they may be incorporated into the detergent compositions of the present invention described herein at their art-known levels. Methods of Use In its method aspect, the present invention can be described as: A method of delivering residual fragrance to a washed surface which comprises the steps of
- a detergent composition comprising a pro-fragrance compound selected from the group consisting of an acetal, a ketal, and mixtures thereof, wherein the pro-fragrance compound having a CLogP of less than about 4 and a detersive surfactant, wherein said detergent composition has a pH of at least 7.1 when measured as a 1% solution in distilled -water at 20°C;
- detergent compositions shown below can be prepared by any conventional method well known in the art.
- a suitable method and formulation are as follows:
- a 200 ml single necked, round bottom flask is prepared.
- a 4.09g portion of P.T. Bucinal (20 mmol), 60ml of benzene, 22.5g of Neodol 23-6.5 (50 mmol), and 0.2g of para-toluene sulfonic acid monohydrate (1 mmol, 5 mol%) is added.
- the vessel is fitted with a Dean-Stark trap and condenser, and is heated to reflux. The reaction is continued until an equivalent of water is collected in the Dean-Stark trap. Upon cooling, the reaction mixture is washed several times with saturated sodium carbonate and water followed by drying with sodium sulfate.
- the solvent is removed in vacuo and unreacted parent aldehyde is removed under bulb-to-bulb distillation at 250°C, 0.2mmHg to yield 19.6g of pale brown oil (80%) identified spectroscopically at the desired material.
- the CLogP of resulting acetal is less than 4.
- a 200 ml single necked, round bottom flask is prepared.
- a 4.09g portion of P.T. Bucinal (20 mmol), 60 ml of benzene, 4.81 g of tripropylene glycol (25 mmol), and 0.2g of para-toluene sulfonic acid monohydrate (1 mmol, 5 mol%) is added.
- the vessel is fitted with a Dean-Stark trap and condenser, and is heated to reflux. The reaction is continued until an equivalent of water is collected in the Dean-Stark trap. Upon cooling, the reaction mixture is washed several times with saturated sodium carbonate and water followed by drying with sodium sulfate.
- the solvent is removed in vacuo and unreacted parent aldehyde is removed under bulb-to-bulb distillation at 250°C, 0.2mmHg to yield 6.1g of pale brown oil (80%) identified spectroscopically at the desired material.
- the CLogP of resulting acetal is less than 4.
- Example 3 [Granular Laundry Composition delivering from Di(Neodol 23-6.5) P.T. Bucinal Acetal]
- a laundry detergent composition is prepared by weighing 98g of laundry detergent according to Example 4 with the exception that perfume and pro- fragrance are not included; admixing to said composition 2g of a perfume of flowery-woody type made up of a mixture of a first premix and a conventional ketal (not in accordance with essential pro-fragrance as defined herein) as follows: First Premix:
- the first perfume premix is modified by adding to it 32 parts by weight of 5a/5b (80:20) wherein 5a is 5-ethylenedioxy-3 oera-H-isolongifolane and 5b is 5- ethylenedioxy-3 a/p/73-H-isolongifolane; these two compounds being conventional perfume ketals not in accordance with the present invention, and their synthesis is described in "CYCLIC ISOLONGIFOLANONE-KETALS - THEIR MANUFACTURE AND THEIR APPLICATION", U.S. Patent 5,426,095, issued June 20, 1995 to Brunke and Schatkowski, assigned to Dragoco.
- Example 2 1.0g of a pro-fragrance according to Example 2 is mixed into the powdered, perfume-free detergent composition. Finally, about 1.5g of the above perfume composition is sprayed onto the mixture of detergent and pro-fragrance, to complete the fragranced, pro-fragranced laundry detergent composition.
- This composition has a floral-woody character and leaves an improved, long-lasting scent on textile fabrics washed therewith.
- the practioner will minimize the molecular weight while still seeking the advantages of the invention, for example by selecting pro-fragrances at-1/2 of less than one minute at pH 0.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Fats And Perfumes (AREA)
- Cosmetics (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9533805A JPH11507415A (en) | 1996-03-22 | 1997-03-21 | Detergent composition containing a profragrance compound |
AU24321/97A AU2432197A (en) | 1996-03-22 | 1997-03-21 | Detergent compositions comprising pro-fragrance compound |
BR9708576A BR9708576A (en) | 1996-03-22 | 1997-03-21 | Detergent compositions comprising profragrating compound |
EP97920026A EP0888442A1 (en) | 1996-03-22 | 1997-03-21 | Detergent compositions comprising pro-fragrance compound |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
USPCT/US96/04060 | 1996-03-22 | ||
PCT/US1996/004060 WO1997034986A1 (en) | 1996-03-22 | 1996-03-22 | Detergent compositions containing fragrance precursors and the fragrance precursors themselves |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997034989A1 true WO1997034989A1 (en) | 1997-09-25 |
Family
ID=22254885
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/005373 WO1997034578A1 (en) | 1996-03-22 | 1997-03-21 | Pro-fragrance compound |
PCT/US1997/005372 WO1997034989A1 (en) | 1996-03-22 | 1997-03-21 | Detergent compositions comprising pro-fragrance compound |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/005373 WO1997034578A1 (en) | 1996-03-22 | 1997-03-21 | Pro-fragrance compound |
Country Status (12)
Country | Link |
---|---|
EP (3) | EP0888439A1 (en) |
JP (3) | JP3708129B2 (en) |
CN (2) | CN1218392A (en) |
AR (1) | AR006356A1 (en) |
AU (3) | AU5372096A (en) |
BR (3) | BR9612555A (en) |
CA (2) | CA2249411A1 (en) |
CZ (2) | CZ299798A3 (en) |
MX (1) | MXPA98007743A (en) |
TR (2) | TR199801878T2 (en) |
WO (2) | WO1997034578A1 (en) |
ZA (3) | ZA972404B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999021954A1 (en) * | 1997-10-29 | 1999-05-06 | The Procter & Gamble Company | Laundry compositions having reduced malodor and methods for providing the same |
DE102016223412A1 (en) | 2016-11-25 | 2018-05-30 | Henkel Ag & Co. Kgaa | Cyclic ketals as perfume precursors |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA9711272B (en) * | 1996-12-19 | 1998-06-23 | Procter & Gamble | Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity. |
US6013618A (en) * | 1997-04-24 | 2000-01-11 | Procter & Gamble Company | Perfumes having odor longevity benefits |
US6087322A (en) * | 1997-04-24 | 2000-07-11 | The Procter & Gamble Company | Fragrance pro-accords |
WO1999016735A1 (en) * | 1997-09-26 | 1999-04-08 | The Procter & Gamble Company | Method for making acetal compounds |
GB2352179A (en) * | 1999-07-21 | 2001-01-24 | Unilever Plc | Deodorising perfume compositions |
US6165452A (en) * | 1999-07-21 | 2000-12-26 | International Flavors & Frangrances Inc. | Cyclic trimers of aldehydes, organoletpic uses thereof and process for preparing same |
DE19948667A1 (en) * | 1999-10-08 | 2001-04-12 | Henkel Kgaa | Detergent component with double-controlled fragrance release |
US6610646B2 (en) * | 2000-06-01 | 2003-08-26 | The Procter & Gamble Company | Enhanced duration fragrance delivery system having a non-distorted initial fragrance impression |
JP4689106B2 (en) * | 2000-10-13 | 2011-05-25 | 花王株式会社 | Citral acetal |
US6506793B2 (en) | 2000-10-13 | 2003-01-14 | Kao Corporation | Citral acetal |
US8592361B2 (en) * | 2002-11-25 | 2013-11-26 | Colgate-Palmolive Company | Functional fragrance precursor |
JP4926698B2 (en) * | 2004-02-25 | 2012-05-09 | 出光興産株式会社 | Alkyl acetal compound, process for producing the same, and lubricating oil composition |
WO2008155683A1 (en) * | 2007-06-18 | 2008-12-24 | Firmenich Sa | Malodor counteracting compositions and method for their use |
WO2009156278A1 (en) * | 2008-06-27 | 2009-12-30 | Henkel Ag & Co. Kgaa | Polymeric pro-fragrance |
EP2334626A1 (en) * | 2008-09-12 | 2011-06-22 | Firmenich S.A. | Divinyl ether derivatives capable of releasing active aldehydes and ketones and methods of use for perfuming surfaces |
WO2014096063A1 (en) * | 2012-12-18 | 2014-06-26 | Dsm Ip Assets B.V. | (6r,10r)-6,10,14-trimetylpentadecan-2-one prepared from 3,7-dimetyloct-2-enal or 3,7-dimetylocta-2,6-dienal |
JP6231378B2 (en) * | 2012-12-28 | 2017-11-15 | 花王株式会社 | Liquid detergent composition for clothing |
WO2014160820A1 (en) * | 2013-03-28 | 2014-10-02 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine |
JP7232833B2 (en) * | 2017-12-20 | 2023-03-03 | エス エイチ ケルカル アンド カンパニー リミテッド | Acetal with the odor of ethyl vanillin and ethyl vanillin derivatives |
US11667869B2 (en) * | 2018-06-22 | 2023-06-06 | Firmenich Sa | Enol ether pro perfume |
Citations (4)
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US3879425A (en) * | 1972-08-01 | 1975-04-22 | Int Flavors & Fragrances Inc | Ethylene acetal of 3-phenyl-4-pentenal |
JPH02276041A (en) * | 1989-04-15 | 1990-11-09 | Tsumura & Co | Acetals of 3-and 4-(4-hydroxy-4-methyl bentyl)-3-cyclohexane-1-carboxyaldehyde and perfume composition having this compound |
WO1994006441A1 (en) * | 1992-09-22 | 1994-03-31 | The Mennen Company | Composition containing body activated fragrance for contacting the skin and method of use |
US5500138A (en) * | 1994-10-20 | 1996-03-19 | The Procter & Gamble Company | Fabric softener compositions with improved environmental impact |
-
1996
- 1996-03-22 AU AU53720/96A patent/AU5372096A/en not_active Abandoned
- 1996-03-22 MX MXPA98007743A patent/MXPA98007743A/en unknown
- 1996-03-22 JP JP51657597A patent/JP3708129B2/en not_active Expired - Fee Related
- 1996-03-22 BR BR9612555A patent/BR9612555A/en unknown
- 1996-03-22 EP EP96910554A patent/EP0888439A1/en not_active Withdrawn
-
1997
- 1997-03-19 ZA ZA9702404A patent/ZA972404B/en unknown
- 1997-03-21 CZ CZ982997A patent/CZ299798A3/en unknown
- 1997-03-21 AU AU24322/97A patent/AU2432297A/en not_active Abandoned
- 1997-03-21 CA CA002249411A patent/CA2249411A1/en not_active Abandoned
- 1997-03-21 CZ CZ983049A patent/CZ304998A3/en unknown
- 1997-03-21 BR BR9708576A patent/BR9708576A/en not_active Application Discontinuation
- 1997-03-21 BR BR9708236A patent/BR9708236A/en unknown
- 1997-03-21 EP EP97920026A patent/EP0888442A1/en not_active Withdrawn
- 1997-03-21 AU AU24321/97A patent/AU2432197A/en not_active Abandoned
- 1997-03-21 CA CA002249269A patent/CA2249269A1/en not_active Abandoned
- 1997-03-21 EP EP97920027A patent/EP0904048A1/en not_active Withdrawn
- 1997-03-21 JP JP9533805A patent/JPH11507415A/en active Pending
- 1997-03-21 JP JP9533806A patent/JPH11507397A/en active Pending
- 1997-03-21 CN CN97194595A patent/CN1218392A/en active Pending
- 1997-03-21 TR TR1998/01878T patent/TR199801878T2/en unknown
- 1997-03-21 WO PCT/US1997/005373 patent/WO1997034578A1/en not_active Application Discontinuation
- 1997-03-21 AR ARP970101159A patent/AR006356A1/en unknown
- 1997-03-21 TR TR1998/01879T patent/TR199801879T2/en unknown
- 1997-03-21 CN CN97194763A patent/CN1219196A/en active Pending
- 1997-03-21 WO PCT/US1997/005372 patent/WO1997034989A1/en not_active Application Discontinuation
- 1997-03-24 ZA ZA9702514A patent/ZA972514B/en unknown
- 1997-03-24 ZA ZA9702512A patent/ZA972512B/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3879425A (en) * | 1972-08-01 | 1975-04-22 | Int Flavors & Fragrances Inc | Ethylene acetal of 3-phenyl-4-pentenal |
JPH02276041A (en) * | 1989-04-15 | 1990-11-09 | Tsumura & Co | Acetals of 3-and 4-(4-hydroxy-4-methyl bentyl)-3-cyclohexane-1-carboxyaldehyde and perfume composition having this compound |
WO1994006441A1 (en) * | 1992-09-22 | 1994-03-31 | The Mennen Company | Composition containing body activated fragrance for contacting the skin and method of use |
US5378468A (en) * | 1992-09-22 | 1995-01-03 | The Mennen Company | Composition containing body activated fragrance for contacting the skin and method of use |
US5500138A (en) * | 1994-10-20 | 1996-03-19 | The Procter & Gamble Company | Fabric softener compositions with improved environmental impact |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 9051, Derwent World Patents Index; Class D23, AN 90-380454, XP002035906 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999021954A1 (en) * | 1997-10-29 | 1999-05-06 | The Procter & Gamble Company | Laundry compositions having reduced malodor and methods for providing the same |
DE102016223412A1 (en) | 2016-11-25 | 2018-05-30 | Henkel Ag & Co. Kgaa | Cyclic ketals as perfume precursors |
WO2018095814A1 (en) | 2016-11-25 | 2018-05-31 | Henkel Ag & Co. Kgaa | Cyclic ketals as fragrance precursor compounds |
US10941156B2 (en) | 2016-11-25 | 2021-03-09 | Henkel Ag & Co. Kgaa | Cyclic ketals as fragrance precursor compounds |
Also Published As
Publication number | Publication date |
---|---|
CN1219196A (en) | 1999-06-09 |
CZ304998A3 (en) | 1999-03-17 |
BR9708236A (en) | 1999-08-03 |
JPH11507415A (en) | 1999-06-29 |
WO1997034578A1 (en) | 1997-09-25 |
JPH11513742A (en) | 1999-11-24 |
EP0888442A1 (en) | 1999-01-07 |
AR006356A1 (en) | 1999-08-25 |
CN1218392A (en) | 1999-06-02 |
BR9708576A (en) | 1999-08-03 |
JP3708129B2 (en) | 2005-10-19 |
CZ299798A3 (en) | 1999-03-17 |
CA2249411A1 (en) | 1997-09-25 |
JPH11507397A (en) | 1999-06-29 |
ZA972512B (en) | 1997-09-25 |
BR9612555A (en) | 1999-07-20 |
EP0904048A1 (en) | 1999-03-31 |
TR199801878T2 (en) | 1998-12-21 |
AU2432297A (en) | 1997-10-10 |
CA2249269A1 (en) | 1997-09-25 |
MXPA98007743A (en) | 2002-07-22 |
TR199801879T2 (en) | 1998-12-21 |
ZA972514B (en) | 1997-09-25 |
EP0888439A1 (en) | 1999-01-07 |
AU5372096A (en) | 1997-10-10 |
ZA972404B (en) | 1997-09-25 |
AU2432197A (en) | 1997-10-10 |
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