MXPA98007736A - Detergent compositions that comprise composite of profragan - Google Patents

Abstract

The present invention is directed to a detergent composition containing a compound of propragrance selected from the group consisting of an acetal, a ketal, or mixtures thereof, wherein at least one of an aldheido ketone or main alchol of the acetal or ketal of "pro-fragrance" is a fragrance compound, the compound of profragrance having a ClogP of at least about 4, wherein the detergent composition has a pH of at least 7.1 when measured in a 1% solution in distilled water at 20 ° C. , as well as a deters agent

Description

DETERGENT COMPOSITIONS THAT COMPRISE COMPOUND OF PRQFRAGRANCE FIELD OF THE INVENTION The present invention relates to a detergent composition comprising a compound of acetone or ketal pro-fragance.

BACKGROUND PE t? IIWENCXQN Most consumers have expected perfumed laundry products »and that fabrics that have been washed also have a pleasant fragrance. It is also desired by consumers that washed fabrics keep the fragrance pleasant over time. The perfume additives can make the laundry compositions aesthetically more pleasing to the consumer and, in some cases, the perfume imparts a pleasant fragrance to the fabrics treated therewith. However, the amount of perfume carried from a detergent solution to the surface of a fabric is often marginal and does not last long on the surface thereof. Furthermore, some perfume release systems are not stable under alkaline conditions, such as in detergent compositions and laundry detergent solutions. Similarly, fragrance materials are often very expensive. Thus, its inefficient use in detergents and the ineffective cleaning of detergents to the surface of the fabric usually results in a high cost for both consumers and manufacturers of detergents. Therefore »the industry continues to look for a more efficient and effective perfume release in laundry products. Acétals and ketals have been known in perfumery for a long time. See Steffen Arctander »" Perfume and Flavor Chemicals. " Arctander, N.J .. 1969. Most of these are methyl and ethyl types and their molecular weights can vary widely. for example, the Arctander summary numbers 6, 11, 210, S51, 689 »1697, 1702, 2480 and 2478. However, the known acetals and ketals are generally not suitable for use in laundry products. For the number 2478 »which is d citronelil acetal of fen lacetaldehyde» molecular weight 414.7 »Arctander reports" ... and it is not an exaggeration to say that this acetal is practically abandoned and obsolete in today's perfumery ". For the number 2480, which is digeranil acetal of fentaltaldehyde »Arctander reports" the material of the title does not offer substantial advantages or type of unique aroma "and nowadays can be considered of little more than academic interest". The latter material was still commercially available in 1992 as ROSETAL A (Catalog »IFF). Vehicle mechanisms for the release of perfume, such as by encapsulation, are also known in the art. See »for example, the Patent of E.U.A. 5, 188,753, issued February 23, 1993. Early efforts to delay the release of perfumes in detergents included the use of certain organometallic compounds, such as t-tanate or zirconate esters. See U.S. Pat. 3,849,326, issued November 19, 1974, and the U.S. Patent. 3,923,700. Issued December 2, 1975. Limited amounts of titanium or zirconium can be used as catalysts to synthesize pro-perfume materials. Personal care compositions are also known, such as deodorant sticks, comprising fragrances "activated for the body". The term apparently refers to the previously known tendency of materials such as acetals derived from perfume alcohols to be hydrolyzed under acid pH conditions thereby releasing the fragrance. See »for example» the patent of E.U.A. 5,378,468, issued on January 3, 1995, and the patent of E.U.A. 3,932,520, issued January 13, 1976. Potential profragrance materials for use in such personal care compositions include particular acetals and ketals, exemplified by vanillin acetal of propylene glycol. The exemplified materials are apparently rather hydrophobic derivatives of alcohol or short chain diol of fragrance aldehydes, and after hydrolysis, release 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 and similar deodorant sticks, and compositions containing potential fragrance materials are applied directly to the substrate (ie, the skin); therefore »deposition problems resulting from dilution, rinsing» etc. »associated with the laundry procedure are not a problem. The factors that affect the substantivity of fragrance materials on fabrics are described in Estcher et al. JAOCS »71p. 31-40 (1994). Laundry detergents are used in dilute aqueous form and contain numerous detergent adjuvants. such as synthetic detergents, detergency builders, enzymes and the like »which are capable of forming micelles» or of solubilizing the pro-fragrance. In addition »the washing process includes rinsing and» sometimes »drying with stirring machines after washing. Rinsing tends to remove the profraganc material to deposited useful. The drying with mixing machines further exacerbates the problem of releasing adequate residual fragrance towards the surface of the textile fabrics. Based on the foregoing »there is a need for a detergent composition having a propragance compound with improved dispersibility in aqueous solutions» particularly detergent solutions, improved deposition on the fabric surface in the washing solution »and improved retention on the surface washed during rinsing. None of the existing techniques provide all the advantages and benefits of the present invention.

BRIEF DESCRIPTION OF THE -tNVE CIQN The present invention is directed to a detergent composition comprising a compound of pro-fragrance selected from the group consisting of an acetal, a ketal, and mixtures thereof, wherein at least one of an aldehyde, ketone or acetal main alcohol or cetal of pro ragancia. is a fragrance compound, the compound of pro-fragrance 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, as well as a detersive surfactant. These and other features, aspects and advantages of the present invention will become better understood after reading the following description as well as the attached remarks.

DETAILED DESCRIPTION OF THE INVENTION While the specification concludes with remarks that particularly point out and claim the invention differently, it is thought that the present invention will be better understood from the following description of the preferred modalities. All percentages and relationships used below are by weight of the total composition "unless otherwise indicated. All measurements referred to herein are made at 25 ° C "unless otherwise specified. All percentages, ratios and levels of ingredients referred to herein are based on the actual amount of the ingredient, and do not include solvents, fillers or other materials with which the ingredient may be combined as a commercially available product "unless otherwise indicated another thing. All publications »issued patent applications and patents referred to herein are incorporated herein by reference in their entirety. The citation of any reference is not an admission with respect to any determination as to its availability as a prior art for the claimed invention. As used herein "comprising" means that other steps and other components may be added that do not affect the final result. This term encompasses the terms "consisting of" and "consisting essentially of".

PR0FRA6ANCIAS A detergent composition of the present invention comprises a pro-fragrance compound which includes acetals. ketals or mixtures thereof, provided that the compounds of which they are formed comprise at least one fragrance compound. As used herein, "pro-fragrance" compound means a compound that may or may not be odoriferous in itself but which, after hydrolysis, produces a desirable aroma that is characteristic of one or more of its hydrolysis products. This term includes mixtures of compounds of profragance, and also encompasses the term "properfume". Acetals and ketals can be considered as derivatives of aldehydes or ketones in combination with alcohols. These aldehydes, ketones and alcohols are referred to herein as "major" or "major compounds" of the acetal or ketal. At least one main compound of any of the present 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 base 10 logarithm of the octanol / water separation coefficient of the profragrance compound. The progragances that the CLogP has of less than approximately 4, give good dispersability in the aqueous solution. Without being limited by theory, it is thought that CLogP, as described herein, may be less when the number of alkoxy moieties included in the pro-fragrance compound is increased. These 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 O by the hydrolysis half-life test (t-1/2) as describes in the present. The pro-fragrance compounds of the present invention are stable under pH conditions found in the formulation and storage of detergent products having a pH of about 7.1 to about 13., and during the use in solution of said products. Due to the hydrophilic character and the high degree of incorporation of heteroatoms, these propragance compounds have reasonably good deposition of a fabric washing solution. Because the propragance compounds are subject to hydrolysis when the pH is reduced, they hydrolyze to release their fragrance compounds when the fabrics (or other surface) on which they have been deposited are exposed even at reduced pH, such as which is present in the rinse water, air or humidity. Said reduction in pH must be at least about O.l, preferably at least about 0.5 units. Preferably, the pH is reduced by at least about 0.5 units at a pH of about 7.5 or less, more preferably about S. 9 or less. Preferably, 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 acrylics (including mixtures of cyclic and acyclic compounds), most preferably having at least 3 oxygens, the cyclic pro-fragrance compound having at least 2 alkoxylate moieties and the compound of pro-fragrance. acrylic co having at least 4 alkoxylate portions. Preferred acetals and ketals herein are those derived from a fragrance or non-fragrance alcohol, particularly linear or branched, saturated or unsaturated aliphatic alcohols of Cß-Cß (preferably C 1 -Cao, more preferably C alco? Alcohols). -C ß). commonly referred to as detergent alcohols, and a fragrant saturated aldehyde of β or more. or fragrance ketones. Preferably, the main alcohols of the present invention have at least one alkoxy moiety. Because the number of members of the alkoxy portion increases as described above, the pro-fragrances having a CLogP of less than about 4 give good dispersibility in the detergent solution. The preferred major alcohols may include the alkoxylates of detergent alcohols, "monoalkyl ethers of short-chain polyalkoxylates" and polyols including those which are alkoxylated with 1 to 30 groups of oxide of ethylene or propylene oxide. More generally, a wide range of acetals and ketals are included within the invention. Many aldehydes »fragrant ketones and alcohols which are suitable main compounds for the acetals and ketals herein are known in the art, see for example the Arctander compilation referred to above for fragrant main compounds. These will also be commercially available from perfume houses such as IFF »Firmenich» TaKasago. H & R »Givaudan-Roure» Dragoco »Aldrich» Quest »and others.

A égal The pro-fragrances of the present invention include an acetal. The acetal can be used to release fragrance aldehydes »fragrance alcohols or both» preferably to liberate fragrance aldehydes derived from major aldehydes. Suitable acetals in the present invention include the following structure: where X and Y are derived from a starting alcohol »and R? and H are derived from a starting aldehyde. X and Y in general foregoing structure which may be fragrant alcohols or non-fragrant alcohols include variable alkoxy moieties. X and Y can be the same or different »allowing the release of more than one type of fragrant alcohol. When the alcohols are non-fragrant alcohols, it is preferred that they be C ^ -C ^ alcohols, especially fatty alcohols, which optionally can be modified by ethoxylation or propoxylation. X and Y can be simple alcohols containing an individual OH group, or they can be polyols containing two or more OH groups. more preferably, diols. In general, the alcohols can be alkyl-alkenyl derivatives. alkylaryl »saturated alkylalkoxylate» unsaturated »linear or branched» with one or more alcohol groups. The alcohols may contain additional functionality, such as amines »amides» ethers or esters, as part of their structure. Preferably, the acetal of the present invention may be cyclic or acyclic, and may contain one or more acetal groups by derivatization of one or more aldehydes. The terms cyclic and acyclic in this context refer to the presence or absence of a covalent bond linking the X and Y portions of the acetal. X and Y of the cyclic acetals form a ring structure and have at least two alkoxylate portions. Preferred acrylic acids 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. Non-limiting examples of the polyols include sorbitol »glucose, sucrose and other saccharides. The acetic acids are derived from monoalcohols. Preferred monoalcohols containing an individual OH group may include the alkoxylates of detergent alcohols and monoalkyl ethers of short chain polyalkoxides. Preferably, the monoalkyl ethers of short-chain polyalkoxylates include the alkyl portion of C ^ -C ,,,. Non-limiting examples of the main alcohols include ethyl alcohol, propyl alcohol. butyl alcohol »alcohol laup'l co and myristyl alcohol. R and H of the above general structure are derived from a starting aldehyde. In general, the fragrant and non-fragrant aldehydes incorporated in the present acids may be aliphatic, alkylated and benzylic. The aldehydes can be saturated, unsaturated, linear, branched or cyclic. The structures may include alkyl, alkenyl or aryl portions, as well as other functional groups such as alcohols, amines, amides, esters or ethers. Preferably, the acetals herein will be derived from major aldehydes having a molecular weight greater than about 80. Many fragrant aldehydes and alcohols are known in the art which are suitable master compounds for the present acetals and ketals. see »for example» the Arctander compilation referred to above for fragrant main compounds. Non-limiting examples of the fragrant principal aldehydes include but are not limited to the following examples: hydratropaldehyde »pt-bucinal» fToral ozone ,,,, »phenyl Ipropanal» anisaldehyde »cyhal» triplal »helional» aldehyde hexy Icinamic »vanillin, ethyl vanillin, citral, ethyl citral» citronellal, methyl octyl acetaldehyde, methyl nonyl acetaldehyde »octanal, decanal, dodecanal, lauric aldehyde. crisantal. isosisloc tral. melonal trans-4-decenal. adoxal hydroxy-citronellal. and isohexe il cyclohexe il carboxyaldehyde. The preferred preferred pro-fragrance acetal compounds are illustrated in non-limiting manner by the following: which is derived from P.T. Buc nal and tr propi lengl col Preferred as well: which is derived from cycla! c and tripropylene glycol. Some specific examples of acyclic acetals useful herein include: which is derived from P.T. Bucinal and Neodol S-25. Y which is derived from P.T. Bucinal and methyl ether of PEG-300. Additional entity. Suitable acetals of the present invention are cyclic acetals derived from the reaction of fragrance aldehydes with polyhydroxy glycosides, including polyhydroxides. Typical examples of suitable polyhydroxy idas include IM-me and Igluca das C? -C m. see WO 9,206,154. Other major acetal or ketal compounds derived from sugar herein include the N-alkoxy polyhydroxy fatty acid esters such as N- (3-methoxypropyl 1) gluca ida of C 10 -C x β.

Cetals The pro-fragrance compound of the present invention includes a ketal. The ketal can be used to liberate a fragrance ketone. The description of the ketals herein can be constructed using structural principles analogous to those used in describing the acetals above. The ketals suitable in the present invention include the following structure: R3 R "-C-X *" I Y wherein X and Y are derived from alcohols or polyols, and R ^ and R3 are derived from the main ketone and may be the same or different. As noted earlier in defining the acetals, X and Y for the ketals in the above general structure may be fragrant alcohols or non-fragrant alcohols that include varying alkoxy moieties. The major alcohols for the ketals may include, but are not limited to, those described as the main alcohols of the acetals in the acetals section. In general, the alcohols may be saturated, unsaturated, linear or branched alkyl, alkenyl, alkylaryl and alkylalkoxylate derivatives with one or more alcohol groups. The major alcohols may contain other functionalities such as amines, amides, ethers or esters, as part of their structure. R 'and Ra of the above general structure are derived from the main ketone. In general, fragrant and non-fragrant ketones can be phthalate, allylic or benzyl. Ketones may be saturated, unsaturated »linear» branched or cyclic, preferably including alkyl, alkenyl or aryl, as well as other functional groups including amides, amines, ethers or esters. Non-limiting examples of the major ketones include, for example, alpha i roña »alpha-ionone, beta-ionone» gamma-1-ionone »methyl beta-naphthyl ketone, cis-jas ona, ascenone, alpha-damascenone» benc lacetona , dihydrojas methyl onate »methyl amyl ketone» metí! heptyl ketone »methyl hexyl ketone» methyl nonyl ketone »carvone» almost ona »intona and gerani lacetona. Other suitable ketones include diketones, for example. 2 »4-pentadione. The non-aromatic ketone may contain one or more ketone functional groups, and said groups may be further derivatized, so that the ketal is polymeric. While the police are included in the present. they are less preferred than mono- and di-ketals. Monocetals are most preferred. Preferred specific preferred ketal compounds are illustrated in non-limiting manner by the following: which is derived from alpha-ionone and tripropi lengl icol. Some specific examples of acyclic ketals useful herein include: which is derived from 2-octane and Neodol 6-25. Y which is derived from 2-octanone and methyl ether of PEG-300. Variations of the present invention include laundry detergents incorporating acetals or ketals, wherein the main alcohol is a polymer such as polyvinyl alcohol, synthetic starch or copolymers incorporating tri- or polyhydric alcohols as monomers. The pro-fragrance compound herein can be used at widely varying levels. Thus »an acetal or cetal of profragance» or mixture thereof, is formulated in the present detergent compositions at levels in the general scale of from about 0.0001% to about 10% more preferably from about 0.0001 to 5% and more preferably still from about 0.01% to about 1%. . A pro-fragrance compound can be used as the unique fragrance compound of the present detergent compositions, or in combination with other pro-fragrances and / or in combination with other fragrance materials, extensors, fixatives, diluents, and the like. For example, the incorporation of the propragance material into a waxy substance, such as a fatty triglyceride "may further improve the storage stability of the present pro-fragrance compounds in laundry granular detergents" especially those comprising bleach. In the liquid or gel forms of the detergent compositions »extenders» hydrophobic liquid 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. Non-limiting examples of said stabilizing materials include dipropylene glycol. diethyl phthalate and acetyl triethyl citrate. In the same way as there are hydrophobic perfumery ingredients which can be used to stabilize the propragance material, there are also detergent ingredients which also have a perfume setting effect and which can be formulated with the propragance material. Such ingredients include fatty acid amines »low-foam non-ionic waxy materials commonly used in automatic dishwashing detergents and the like. In general, in the cases where the pro-fragrances are used together with other fragrance materials in the detergent compositions herein, it is preferred that the 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 , for example, AMBERLYST ÍS1"" *. See MesKens, F., Synthesis, (7) 501 (1981) and Meskens, F., Jannsen Chi Acta (1) 10 (1983). Many aldehydes »ketones and alcohols useful in the synthesis of acetal and ketal pro-fragances of the present invention are sensitive to strong acid conditions» and may suffer from inconvenient side reactions, see Bunton »C.A-, et al., J. Org. Chem. (44), 3238 »(1978)» and Cort. O. and others »J. Org. Chem. (51). 1310 (1986). It is also known that the acetals of unsaturated alpha-beta-1 aldehydes can undergo migration of the double bond under the inadequate selection of the acid catalyst, see Meskens. F. »Synthes s. (7) 501 »(19B1). and Lu »T.-J and others» J. Org. Chem. (60). 2931 »(1995). For acid sensitive materials »acid catalysts with pKa values between 3 and 4 are the most convenient to minimize the migration of the double bond» while maintaining the reactivity necessary to produce the acetal (or ketal). For example »in the synthesis of digeranil decanal» p-toluenesulfonic acid (p ß = 1) causes inconvenient side reactions with geraniol. Citric acid (pKßX = 3.1 »p, 55 = 4.8, pK, 3 = 6.4) can be used to form the acetal without side reactions.

Another technique that is used to avoid side reactions when preparing acids and ketals of acid-sensitive material such as geran, is the transacetalization of an acetal or dimethyl ketal with a higher molecular weight alcohol, using a moderate Lewis acid, such as titanium isopropoxide or boron trifluoride etherate as a catalyst.

Detersive surfactants The detergent composition of the present invention includes a detersive surfactant in addition to the pro-fragran compounds. Non-limiting examples of synthetic surfactants useful herein, typically at levels of about 0.5Ji to about 90J4"by weight" include the alkylbenzene sulfonates ("LAS") of C ^ -C ^. conventional and the branched chain and random alkylsulfates ("AS") of CX0-C30 »the secondary alkylsulfates (2.3) of C ± o-C ± m and the formula CH3 (HSÍ) > < (CH (CH3 0S03-M * -) CH3 and CH3 (CHa) and (CH (CHaCH3) OS03-M *). Where xy are integers, and where each of xy (y + 1) is at least about 7, preferably at least about 9%, and M is a cation of solubilization in water, especially sodium, unsaturated sulfates such as oleulfate, Ci0-Cxß alkylalkoxysulfates ("AE- ^ S", especially ethoxysulfates). EO 1-7), alkylalkoxycarboxylates of C10-Cß (especially the ethoxycarboxylates EO 1-5), the glycolic ethers of C-C, the alkyl glycosides of Cxo-C1ß and their polyglycosides sulfates, and sulfonated alpha fatty acid esters of C3.a-C3.m- If desired, conventional non-ionic and amphoteric surfactants, such as the Csg-Cxm alkylatoxones ("AE") including the so-called narrow-chain alkylethoxylates and the α-1-ienoxycoxylates of γ-C ^ jg (especially ethoxylates and ethoxy / mixed propoxylates), betaines and sulfobetaines ("sultaine") s ") of CAa-Cxß, amine oxides of C Q-C m, and the like, can also be included in the overall compositions. It is also possible to use the N-to which one or more fatty acid molecules of C o -Clβ. Typical examples include the N-methylgl ions of C as-C m. See WO 9206 »154. Other surfactants derived from sugars include the N-alkoxy-polyhydroxy fatty acid amides such as N- (3-ethoxypropyl 1) g-C-C-cylideamide. The N-propyl-a N-hexyl glucamides of C x-C mt can be used for low foam formation. Conventional C o-Cao soaps can also be used; however, synthetic detergents are preferred. If high foam formation is desired, can Cxo-C soaps be used? of branched chain. Mixtures of anionic and nonionic surfactants are especially useful. Other useful conventional surfactants are listed "in other common texts, see also U.S. Pat. 3,664,961, issued May 23, 1972.

Preferred compositions that incorporate only synthetic detergents have a detergent level of approximately 0.5% to approximately 50%. Compositions containing soap preferably contain from about 10% to about 90% soap. The detergent compositions herein preferably have a pH of about 7.1 to approximately 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 distilled water to 20%.

HETOPQS P PROOF Calculation of CLogP The pro-fragrances of the invention are characterized by their octanol / water partition coefficient. The octanol / water partition coefficient of a profragance is the ratio between its equilibrium concentration in octanol and in water. Since the partition coefficients of the profragrance compounds are large, they are most conveniently given in the form of their logarithm of base 10, logP. The logP of many compounds has been reported.

For example. the Pomona92 database, available through Daylight Chemical Information Systems. Inc. (Daylight CIS), contains many such values. along with quotes to the original literature. However, the logP values are more conveniently calculated through the "CLOGP" program, also available through Daylight CIS. The program also lists experimental values of logP when they are available in the Pomona92 database. The "calculated logP" (CLogP) is determined by the fragment procedure of Hansch and Leo (see, A. Leo, in Co prehensi and Medicinal Chemistry, Vol. 4. C. Hansch, PG Sammens, JB Taylor and CA Ra sden , Eds., P 295. Pergamon Press, 1990). The fragment procedure is based on the chemical structure of a compound and takes into account the numbers and type of atoms, the connectivity of the atoms and the chemical bond. The CLogP values, which are the most reliable and widely used estimates for this physicochemical property, preferably appear instead of the experimental values of logP in the selection of prefragancias.

Determination of the half-life of hydrolysis (t-1/2) The average value of hydrolysis is the measurement used to determine the ease with which the compound of pro-fragrance undergoes acid hydrolysis and thus releases its fragrance components. with exposure to acidic 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. Preferably the compounds of the invention have a half-life at pH 2 of less than 60 minutes. For granular detergents »the most reactive pro-fragrances, ie those with a half-life at pH 2 of less than 1 minute, are the most suitable, although those with a half-life of less than 60 minutes at pH O are also useful. For applications with liquid detergents, pro-fragrances having a half-life of less than 60 minutes at pH O and a half-life greater than 1 minute at pH 2 should preferably be used. The half-life of the hydrolysis is determined by UV spectroscopy. / V in a dioxane / water system of 90/10 at 30 ° C following the appearance of the carbonyl absorbency. Due to the hydrophobicity of the pro-fragrance compounds of the invention, a high dioxane / water ratio is needed to ensure the solubility of the pro-fragrance. The pH of the water used is achieved using aqueous HCl. The concentration of the profragance in the oxano / water system can be adjusted to achieve measurable, measurable absorbance changes. All measurements are carried out using a spectrophotometer with Hewlett Packard 8452 A diode array using quartz specimen cells with a path length of 1 cm. The materials used include 1 »4-d-oxane by HPLC of grade 99.9% (Sig a-Aldrich)» volumetric solution of HCl IN (JT Baker) »deionized water filtered with M liQPlus (M ore) with resistivity of 18.2 M Ohm cm. The pH's are measured using a Orion 230 A standard with pH regulators, pH 4 and pH 7. The HCl to IN standard is used directly for pH O conditions. For pH 2 conditions, HCl is diluted to IN with deionized water. The profragrance is measured in a 10 ml volumetric flask using an analytical balance (Mettler AE 200) Precision and is 1/10 mg. The heavy material is dissolved in approximately 8 ml of dioxane. Both the solutions of dioxane of profragance and of aqueous acid solution prepared as described above are preheated in their separate containers at a temperature of 30 ± 0.25 ° C by means of a bath with water. 1000 ml of aqueous acid solution is added to the profraganc solution by means of an Eppendorf pipette. This is followed by dilution to the 10 ml mark with dioxide. The hydrolysis time is measured, starting with the addition of the acid. The profragrance solution is mixed for 30 seconds with stirring and the solution is transferred to a quartz pipette. The absorbance of the profragrance solution (A) is followed in a regular series of time intervals and the pipette is kept in the bath with water at the above indicated temperature between the measurements. The initial absorbance measurements are carried out <; A0) Using an equal concentration of profragance in a solution of dioxane and deionized water with v / v of 90/10 and measurements of final absorbency (A ^ are taken using the hydrolyzed profragrance solution after the hydrolysis is complete. The wavelength at which the hydrolysis is followed is chosen over the wavelength of the maximum absorbency of the aldehyde or ketone of origin.The reaction half-lives are determined using conventional procedures.; kOBß) is determined by the slope of the line provided by plotting the following function with respect to time (in): LnC (A0-A ^) / (A ^ -A ^) 3 where said function is the natural logarithm of the relationship between the difference of absorbance at the initial time (A0) and the final time (A.,) on the difference of absorbance at time t (A ^) and the final time ( TO.,). The half-life as defined herein is the time required for half of the profragancy to hydrolyze and be determined from the constant observed rate (koßß) by the following function: Ln (l / 2) = -Kßß.t -, a Additional Detergent Ingredients In addition to the pro-fragrance compounds described herein, the detergent composition of the present invention may further include one or more additional detergent ingredients commonly used in detergent products, such as materials to assist or enhance cleaning performance. substrate treatment by cleaning or modifying the aesthetics of the detergent composition (for example »conventional perfumes» dyes »dyes, etc.) Such additional ingredients are known to those skilled in the art. The following are illustrative examples of other detergent ingredients.

Detergency builders - Builders may optionally be included in the compositions herein to aid in the control of mineral hardness. Both inorganic and organic builders can be used. Detergency builders are typically used in laundry washing compositions to aid in the removal of particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically contain at least about 1% of the builder. Liquid formulations typically contain from about 5% to about 50%. more typically from about 5% to about 30%. by weight »of the detergency builder. Granular formulations typically contain from about 10% to about 10%. more typically from about 15% to about 50% by weight. of the detergency improver. It is not implied that lower or higher levels of detergent builder are excluded. Inorganic builders include, but are not limited to, phosphate builders such as alkali metal, ammonium or alkali metal polyphosphate salts! ammonium (exemplified by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates and phytic acid, and non-phosphorus builders such as silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and alu-inosites. Phosphate-free detergency builders are required in some locations. Organic builders suitable for use herein include polycarboxylate builders, such as those described in U.S. Pat. 3,308,067, issued March 7, 1967; 4,144,226 »issued on March 13, 1979 and 4,246,495» issued on March 27, 1979.

Soil release agents. The soil release agents are conveniently used in laundry detergents of the present invention. Suitable soil release agents include those of the U.S. Patent. 4,968,451 »November 6, 1990. Such ester oligomers can be prepared by ethoxylating allyl alcohol (b) by reacting the product of (a) with dimethyl terephthalate (" DMT ") and 1,2-propylene glycol. ("PG") in a process of transesterifi cation / ol igignization of two stages and (Or by reacting the product of (b) with sodium metabisulfite in water »the polyesters of terephthalate of 1.2-propylene / polioxyeti wood finished off at its "non-ionic" ends of US Patent 4,711,730, issued December 8, 1987, for example, those produced by transesterification / oligoing of poly ether (ethylene glycol) methyl, DMT , PG and pol i (ethylene glycol) ("PEG"); the oligomeric esters capped at their partially and completely anionic ends, from US Pat. No. 4,721,580, issued January 26, 1988, such as oligomers based on ethylene glycol ("EG"), PG, DMT and Na-3.6-dioxa -8-hydroxyoctanesulfonate; the non-ionic topped block polyester oligomeric compounds of the U.S. Pat. 4,702,857, issued on October 27, 1987, produced for example based on DMT, PEG topped with Me and EG and / or PG, or a combination of DMT, EG and / or PG, PEG topped with Me and Na-dimethyl- 5-sulfoisophthalate; tereftal ato-esters capped at their ends, anionic »especially sulfoaroyl, from the patent of E.U.A. 4,877,896. issued on October 31, 1989, the latter being typical of SRA's useful in products for both laundry and cloth conditioners, one example being an ester composition made of monosodium salt of m-sulfobenzoic acid. PG and DMT which also contain, optionally but preferably »added PG 'for example PEG 3400. Another preferred soil release agent is a sulphonated end-capped type described in US Pat. 5 »415» 807.

Other Ingredients The compositions herein may contain other ingredients such as enzymes, bleaches, fabric softening agents, decolorizing transfer inhibitors, foam suppressors and chelating agents, all well known in the art.

Formulations with detergents with conventional perfumery materials or without them. Although the pro-fragrances of the present invention can be used alone or simply mixed with essential detergent ingredient, very notably surfactant can also be conveniently combined three-part formulations that combine (a) a non-fragrant detergent base containing one or more synthetic detergents (b) one or more acetals or ketals of pro-fragrance according to the invention and (c) a fully formulated fragrance. The latter provides convenient fragrance in the package and in use (wash time), while profragance provides a long-lasting fragrance to washed textile fabrics. The formulation of the detergent compositions of the present invention, the fully formulated fragrance can be prepared using numerous known odorant ingredients of natural or synthetic origin. The variety of natural unprocessed substances can include components that are not only easily volatile "but also moderately volatile and slightly volatile" and that of synthetics can include representatives of virtually all kinds of fragrant substances "as will be evident from the following illustrative compilation: products natural »such as absolute tree moss» basil oil »citrus fruit oils (such as berga oil or» tangerine oil »etc.), absolute mastic, myrtle oil, palmarosa oil» patchouli oil »oil small grain of Paraguay »wormwood oil, alcohols, such as farmesol» geraniol »linalool» nerol »alcohol feni letíl ico. Rodinol cinnamic alcohol, aldehydes such as citral, Helional ™, alpha-hexy-cinnamaldehyde, hydroxy tronelal, Lilia! ™ (p-t-buty 1-alpha-methyl Idihydrocinnamaldehyde). methi lnol i lacetaldehído, ketones, such as aliüonona, alfa-ionona, beta-i onona, isoraldein (iso eti 1-alfa-onona), methylionone, esters, such as l lfenoxiacetato, benci Isal ici lato, c nami Ipropionato, ci tronel i lacetato, citronel iletoxolato, deci lacetato, dimethyl benci Icarbini lacetato, dimeti Ibencilcarb ilbutirato, eti lacetoacetato, etilacet lacetato, hexeni 1 isobutirato, lina! ilacetato, meti Idihidrojas onato »stretch! lacetato »veti eri lacetato» etc., lactones, such as gamma-undecalactone »various components often used in perfumery such as amyl ketone» indole »p-methane-B-thiol-3-one and met-1-eugenol. Likewise, any conventional fragrant acetal or ketal known in the art may be added in 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 -cetals "as well as acetals or ketals based on benzaldehyde. those that contain more recently developed phenylethyl moieties or specialties such as those described in US Pat. entitled "Acetáis and Ketals of Oxo-Tetral nsand Oxo-Indaneses", see the patent of E.U.A. 5.0B4,440, issued on January 28, 1992, is sold to Givaudan Corp. Of course, other synthetic specialties may be included in the perfume compositions for fully formulated detergents. These include enol oxo-tetral ethers and alkyl-substituted oxo-indanes as described in US Pat. 5,332,725, issued July 26, 1994, and the U.S. Patent. 5,264,615 issued on December 9, 1991. It is preferred that the pro-fragrance compound be separately added from conventional fragrances to the detergent compositions of the invention.

Formulation with other compounds for fragrance release for special purposes. The detergents according to the present invention may further contain »optionally» if desired other known compounds which have the ability to enhance the durability of a fragrance. Such compounds include but are not limited to aluminum alkoxides such as isobutyl aluminum isobutyl difluorium as described in U.S. Pat. 4,055,634, issued October 25, 1977; or the known titanate- and cytoseto-esters or -oligosters of fragrant materials such as those described in the U.S. Patent. 3,947,574, issued March 30, 1976 and the U.S. Patent. No. 3,779,932, filed December 18, 1973. When such organoaluminum derivatives are used, organo titanium or zinc organ, these can be incorporated into the detergent compositions of the present invention described herein at their levels known in the art. nét? p-3 axis? 3Q In the aspect of its method, the present invention can be described as: A method for releasing residual fragrance to a washed surface which consists of the steps of: (a) washing said surface in an aqueous solution of a detergent composition containing a 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 per at least 7.1 when measured as a 1% solution in distilled water at 20 ° C; (b) subsequently exposing said surface to a pH reduction. E MPLOS The following examples describe and demonstrate to a greater degree embodiments within the scope of the present invention. The examples are given only for the purpose of illustration and are not to be construed as limitations of the present invention, since many variations thereof are possible without departing from the spirit and scope of the invention. The detergent compositions shown below can be prepared by any conventional method well known in the art. A suitable method and formulation are as follows: EXAMPLE Preparation q d? (NeoqO1 23-6.5) -P. T.-bupinal-ac tal by acid catalysis A 200 ml single-neck round bottom flask is prepared. a 4.09 g portion of P.T. Bucinal (20 moles), 60 ml of benzene, 22.5 of Neodol 23-6.5 (50 moles), and 0.2 g of para-toluenesulfonic acid monohydrate (1 mol, 5 mol%). The basin is equipped with a siphon and a Dean-Stark condenser and refluxed. The reaction is continued until an equivalent of water is collected in the Dean-Stark siphon. Immediately after cooling the reaction mixture is washed several times with saturated sodium carbonate and water followed by drying with sodium sulfate. The solvent is removed n vacuo and the aldehyde of unreacted origin is separated by distillation from ampule to ampule at 250 ° C, 0.2 mmHg to yield 19.6 g of pale brown oil (80%) identified spectroscopically with the desired material. The CLogP of the resulting acetate is less than 4.

EWEMPtQ Z Preparation of tri p rop l len col-P.T.-buc al-acetal by acid catalysis A 200 ml round neck »single-neck flask is prepared. A 4.09 g portion of P.T.-Bucinal (20 mmoles) is added. 60 ml of benzene »4.81 g of tripropylene glycol (25 mmol) and 0.2 g of paratoluenesulfonic acid monohydrate (1 mmol, 5 mol%). The vessel is equipped with a siphon and Dean-Stark condenser and heated to reflux. The reaction is continued until an equivalent of water is collected in the Dean-Stark siphon. Immediately after cooling, the reaction mixture is washed several times with saturated sodium carbonate and water followed by drying with sodium sulfate. The solvent __ vacuo is separated and the unreacted aldehyde of origin is separated by distillation from ampule to ampule at 250 ° C. 0.2 mmHg to produce 6.1 g of pale brown oil (80%) identified spectroscopically in the desired material. The CLogP of the resulting acetal is less than 4.

EXAMPLE 3 Granular laundry composition derived from diCododol-23-6.5) -P.T.-bucine1 acetal Profragancy of Example 1 1.0% C11-C13 Dodecylbenzenesulfonate 21.0% Al qui letoxi lato EO 1-8 of C12-C13 1.2% Tripol i sfos ato de sodio 35.0% Zeolite Na 4A 14.0% Sodium silicate in relation of 2.0 2.0% Sodium carbonate 23.4% Enzyme (savinasa ™ and / or lipolasa ™ by Novo 1.4% Carboxi ethylcellulose 0.3% Anionic dirt cleaning agent * 0.3% 0.2% polish S l icon foam suppressor (Dow Corning Corp) 0.2% Perfume ** 0.3% Sodium sulfate 0.5% Rest in humidity up to 100% * A See U.S. 4,968,451 »z Perfume composition of the following formula: Benzyl salicylate 20% Brazil ethylene 20% Gala? -lido (50% solution in benzyl benzoate) 20% Aldehyde hexi linamic 20% Tetra ídro l nalool 20% 100% AX PLO 4 Granular washing detergent derived from di (Neodol-23-6.5) -P.T.-bucina1 Profragancy of Example 1 1.0% Linear docec lbencenesulfonate 21.0% Nonionic surfactant (Neodol 23-6.5 1.2% Sodium tripolyphosphate 35.0% Zeolite Na 4A 14.0% Sodium silicate in relation of 2.0 2.0% Sodium carbonate 23.4% Enzyme (savinasa ™ and / or lipolase ™ by Novo 1.5% Carboxymethylcellulose 0.3% Anionic dirt release agent ** • 0.3% Abr ripper 0.2% Silicone foam suppressor (Dow Corning Corp) 0.2% Perfume * 2 0.3% Sodium sulfate 0.5% Remaining in humidity up to 100% * A See U.S. 4,968,451 * a See * 2 in Example 3 E Efl P 5 Laundry detergent comprising profragance and fully formulated perfume composition having a conventional ketal fragrance component A laundry detergent compost is prepared by weighing 98 g of laundry detergent in accordance with Example 4 except that perfume and profragancy are not included; the addition in admixture to said composition of 2 g of a perfume of the flower and wood type integrated a mixture of a first premix and a conventional ketal (not in accordance with essential profragancy as defined herein) as follows: First premix: Bergamot oil 7.5 g Linalool 4.0 g Phlegitic alcohol 4.0 g Benzyl Acetate 2.0 g Citronelol 0.5 g Hedine ™ (a) 10.0 g Lira! ™ (b) 4.0 g Troxalal hydroxide 2.5 g Rose oxide 1 (c) to 10% in DPG 2.5 g Aldehyde hexi Iciná ico, alpha 7.5 g Indonesian Patchouli Oil 4.0 g Iso E ™ (b) 2.0 g Acetate vetiveril 2.0 g Brahmanol ™ F (c) 2.0 g Benci Isa1 ici lato 2.0 g Cis-3-Hexeni lsal icilato 1.0 g Cedra ber ™ < b) 1.0 g Musk Xylene 1.0 g % Indola in DPG 0.5 g Opoponac extract 0.5 g Extract of 15% oak moss in DPG 5.0 g (a) Firmenich (b) IFF (C) DRAGOCO Total parts by weight of the first premix: 68.0 g The first perfume premix is modified by adding 32 parts by weight of 5a / 5b (80:20 where 5a is 5-eti lendioxy-3-beta-H-isolongifolane and 5b is 5-et lendiox i-Salfa-H-isolongifolano these two conventional perfume compounds are not in accordance with the present invention, and their synthesis is described in "CYCLIC ISOLONGIFOLANONE-KETALS-THEIR MANUFACTURE AND THEIR APPLICATION" US Patent No. 5,426,095, issued July 20, 1995 to Brunke and Shatkowsk, loaned to Dragoco 1.0 g of a pro-fragrance according to Example 2 are mixed into the perfume-free powder detergent composition Finally, approximately 1.5 g of the above perfume composition is sprayed onto the detergent mixture and profragance, to complete the detergent composition for washing clothes with fragrance and profragance.This composition has a character of flower and wood and leaves an improved aroma and of prolonged duration on the textile fabrics washed with the same ma.

EXAMPLE 6 Detergent that has the shape of a bar for laundry that contains profragance Profragancy of Example 1 1.0% Mix of bait soap and coconut soap (80:20) 44.0% Linear Dodecylbenzenesulfonate 12.0% Sodium tripolyphosphate 6.0% Sodium carbonate 8.0% Sodium sulfate 0.5% Talc 9.0% Perfume * - * - 0.2% Rest in humidity up to 100% * See * 2 in Example 3 E E PUQ 7 LIQUID DETERGENT CONTAINING PROPHRAGNANCE Profragancy of Example 1 1.0% Ethoxylated C12-C15 alcohol sulfate • 2.5 sodium 1B.0% Nonionic Surfactant of Neodol 23-9 2.0% Alqui 1-N-methylglucamide of cxst 5.0% Cumen sodium sulfonate 3.0% Citric acid 3.0% Fatty acid (C12-C14) 2.0% Boric acid 3.5% Sodium hydroxide 2.85 Tretraet lén ethoxylated pentaimine 1.2% Dirt release polymer 0.15% 1,2-Propanediol 8.0% Ethanol 3.6% Monoethanolamine 1.1% Secondary ingredients * - * • 1.8% Remains in humidity up to 100% * A Secondary ingredients include rinse aid and enzi as Although the examples and embodiments described herein are illustrative of the invention, those skilled in the art will recognize that variations or modifications in light thereof are completely within the scope of the invention. In one such variation, the practitioner will minimize the molecular weight while still seeking advantages of the invention, for example selecting pro-fragrances to a medium of less than one minute at pH 0.

Claims (13)

NQVEDAP PE INVENCIQN CLAIMS

1. - A detergent composition, characterized in that it contains: (a) a pre-fragrance compound selected from the group consisting of an acetal, ketal and mixtures thereof, wherein at least one aldehyde, a ketone or an alcohol of acetal origin or the profagration ketal is a fragrance compound, composed of profragran that has a CLogP of less than about 4; and (b) a detersive surfactant; wherein the detergent composition has a pH of at least 7.1 when measured in a 1% solution in distilled water at 20 ° C.

2. The detergent composition according to claim 1. further characterized in that the propragran compound has: (a) an elec- tric weight of at least about 170; and < b > a half-life of at least about 60 minutes, when measured at pH 0 using the Medium Life Test (t-1/2) by Hydrolysis.

3. The detergent composition according to claim 2, further characterized in that the detergent composition contains from about 0.001% to about 5% of the compound of propragrance and from about 0.5% to about 90% of the surfactant. deters vo.

4. - The detergent composition according to claim 3 »further characterized in that the CLogP is at least about 3.

5. The detergent composition according to claim 3. further characterized in that the detergent composition is a granular composition having a pH from about 8 to about 12 and because the compound of propragrance has a half-life of at least 1 minute when measured at pH 0.

6. The detergent composition according to claim 3. further characterized in that the detergent composition is a liquid composition and because the compound of profragrance has a half life for at least 60 minutes when measured at pH or and a half-life greater than 1 minute when measured at pH 2.

7. The detergent composition according to claim 3 »Further characterized in that the compound of propragrance has at least 8 oxygens and is selected from the group consisting of cyclic, acyclic compounds and mixtures thereof.

8. The detergent composition according to claim 3, further characterized in that the detersive surfactant contains one or more synthetic surfactants selected from the group consisting of amphoteric non-ionic »anionic» cationic »zwitterionic surfactants and mixtures of the same.

9. - The detergent composition according to claim 7 »further characterized in that the cyclic propragrance compound has at least two alkoxylate portions and in that the alcohol of origin of the acyclic propragrance compound is selected from the group consisting of polyallylated polyols with 1 to 30 groups of ethylene oxide or propylene oxide.

10. The detergent composition according to claim 7 »further characterized in that the compound of acyclic profragrance has at least 4 portions of alkoxylate and in that the alcohol of origin of the compound of acyclic profragrance is selected from the group consisting of alcohol alkoxylates. detergents and monoalkyl ethers of short chain polyalkoxylates and mixtures thereof.

11. The detergent composition according to claim 8 »characterized in that it also contains one or more components selected from the group consisting of detergency builders. dirt-releasing agents, enzymes. bleach fabric softening agents »dye transfer inhibitors, foam suppressors and chelating agents. and similar.

12. A detergent composition, characterized in that it contains: (a) from about 0.001% to about 5% of a compound of profiency selected from the group consisting of an acetal »a ketal and mixtures thereof, wherein at least one of an aldehyde »a ketone or an alcohol of 1-acetal origin or the acetal of propragrance is a fragrance compound, the fragrance compound having a CLogP for less than about 4; (b) from about 0.5% to about 90% of a detersive surfactant; (c) at least about 1% of a detergency builder; wherein the detergent composition has a pH of at least 7.1 when measured in a 1% solution in distilled water at 20 ° C.

13. The detergent composition according to claim 12, characterized in that it also contains one or more components selected from the group consisting of soil cleaning agents, enzymes, bleaches, fabric softening agents, dye transfer inhibitors, suppressants. of foam and chelating agents, and the like.