MXPA06009802A - Oil containing starch granules for delivering benefit-additives to a substrate - Google Patents

Abstract

An oil containing starch granule is provided comprising:(a) a starch to form an effective matrix for said granule;(b) a perfume oil comprising ingredients having a calculated Clog P of at least 3, said Clog P being the calculated octanol to water partition coefficient, said perfume oil being capable of providing a benefit-additive to a substrate upon contact therewith, said substrate being selected from the group consisting of fabrics, hard surfaces, hair and skin;and (c) an effective amount of a defined organic compound for inhibiting the migration of said oil to the surface of said starch granule.

Description

STARCH GRANULES CONTAINING OIL TO DELIVER ADDITIVES OF BENEFIT TO A SUBSTRATE This invention relates to an oil containing starch granule comprising a starch which forms a matrix for said granule, a perfume oil and a compound of a defined structure to inhibit the migration of the oil to the surface of the starch granule. More particularly, this invention relates to a starch granule containing oil including a defined perfume oil which is capable of delivering a beneficial additive to substrates such as fabrics, hard surfaces, hair and skin, contact of the starch granule with such substrate.

Background of the Invention The addition of the perfume to a liquid detergent composition to impart a pleasing aroma or fragrance to such a detergent composition is well known in the art. The presence of the perfume provides an aesthetic benefit to the consumer with the use of the detergent composition and generally serves as a sign of freshness and cleanliness for washed fabrics which contain a pleasing fragrance. However, despite the improved aroma of the detergent composition itself, relatively little of the perfume fragrance is imparted to fabrics during washing. Primarily, this is because the perfume ingredients in the liquid composition are rapidly dispersed and diluted during washing, in the various aqueous rinse and rinse waters. Consequently, only a relatively limited amount of the perfume is available for contact. of the fabrics during washing, the main part of the perfume being drained from the washing machine with the washing solution. There still exists, therefore, a need in the art to improve the effectiveness of the delivery of perfume from a detergent composition to the washed fabrics and to improve the duration of such fragrance on the fabrics.

Similarly, there is a need in the art to effectively deliver oils other than perfume fragrance as beneficial additives to substrates such as hard surfaces, hair and skin so that the duration of such oils on the substrate is improved. significantly in relation to conventional means to provide such a beneficial additive to the substrate. : Synthesis of the Invention The present invention provides a starch granule containing oil comprising: (a) a starch, such starch being present in an amount to form an effective matrix for said granule; (b) a perfume oil comprising ingredients having a calculated log P of at least 3, said calculated log P is the calculated octanol to water partition coefficient, said perfume oil being capable of providing an additive-benefit to a substrate with contact therewith, said substrate being selected from the group consisting of fabrics, hard surfaces, skin and hair; Y (c) an effective amount of an organic compound to inhibit the migration of said oil to the surface of said starch granule, said compound being represented by the following structure: (1) where Ri and R2 are each independently ,.

H o: (a) a C 1 -C 22 alkylenecarboxy moiety having the formula: - (CH 2) e 3 wherein R 3 is -NHCOR; o -OCOR; or -NR5COR; and wherein R4 and R5 are each independently an alkyl or alkenyl Ca-C22; and e is an integer from 1 to 22; or (b) a linear or branched C? -C22 alkyl; or (c) a linear or branched C? -C22 alkenyl; or (d) a substituted or unsubstituted C2-C22 alkyleneoxy; or (e) an alkyleneoxy substituted alkyl or n? substituted C3-C22; or (f) a substituted or unsubstituted C6-C22 aryloxy; or (g) a substituted or unsubstituted C7-C22 alkylenearyl; or (h) a substituted or unsubstituted C7-C22 alkylene oxidearyl; or (i) a C7-C22 oxyalkylenearyl; o =, (j) an anionic unit having the formula: (CH2) and R6 wherein R6 is -S03M, -OS03M, -P03M, -OP03M, Cl or mixtures thereof, wherein M is hydrogen, or one or more salt-forming cations sufficient to sat the charge balance, or mixtures thereof; and is an integer from 1 to about 22; or (k) a mixture comprising at least two of (a) to (j); Y q is an integer from 0 to about 22; m is an integer from 0 to about 22; Q is (CH2) m or (CH2CHR70); R7 is independently hydrogen, methyl, ethyl, propyl or benzyl; B is H or OH; and Y is CRa. or N.

In alternate embodiments of the invention, the compound which is used to inhibit the migration of said oil to the surface of the starch granule is represented by the amide amide compound digraso of the formula (2) or a quaternary ammonium compound which corresponds to formula (3) as follows: (2) Ri-C 11-T - (CH 2) m- (CH 2) n T-CII-R; R3 wherein Ri and R2, independently, represent aliphatic hydrocarbon groups C1 to C30, R3 represents (CH2CH20) pH, CH3 or H; T represents NH; n is an integer from 1 to 5; m is an integer from 1 to 5 and p is an integer from 1 to 10. (3J wherein R and R2 are each independently, H or: (a) a C 1 -C 22 alkylenecarboxy moiety having the formula: - (CH2) eR3 wherein R3 is -NHCOR; or -OCOR4; or -NR5COR; and wherein R and R5 are each independently a C? -C22 alkyl or alkenyl; and e is an integer from 1 to 22; or (b) linear or branched C C-C22 alkyl; or (c) a linear or branched C? -C22 alkenyl; or (d) a substituted or unsubstituted alkyleneoxy C2-C22; or (e) a substituted or unsubstituted C3-C22 alkyleneoxy; or i (f) a substituted or unsubstituted aryloxy Cd-C22; or (g) a substituted or unsubstituted alkylenearyl C7-C22; or (h) C7-C22 substituted or unsubstituted alkylene oxidearyl; or (i) C-C22 oxyalkylenearyl; or (j) an anionic unit having the formula; (CH2) and R6 wherein R6 is -S03M, -OS03M, -P03M, -OP03M, Cl or mixtures thereof, wherein M is hydrogen, or one or more salt-forming cations sufficient to sat the charge balance, or mixtures thereof; Re can also be chloride; and is an integer from 1 to about 22; Y (k) a mixture comprising at least two of (a) to (j); Y q is an integer from 0 to about 22; m is an integer from 0 to about 22; Q is (CH2) m or (CH2CHR70); R7 is independently hydrogen, methyl, ethyl, propyl or benzyl; and mixtures thereof; B is H or OH; and Y is N; Rs is H or C? -C4 alkyl; Z ~ is a counter anion, and preferably chloride, or methyl sulfate.

In accordance with the method aspect of the invention there is provided a method for washing fabrics comprising the step of contacting such fabrics with an aqueous solution containing an effective amount of an oil-containing starch granule of the invention.

A method is also provided for preparing a starch granule containing oil comprising the steps of: i: (a) providing a dispersion of starch in water to form a starch solution; (b) melting an effective amount of an organic compound such as an amido amine comprising bis (alkyl amidoethyl) -2-polyethoxy amine to form a melt of amidoamine; (c) adding a fragrance oil to the organic compound melt or to the amidoamine melt of step (b) to form a solution of the organic compound or amidoamine in a fragrance oil, said fragrance oil comprising the ingredients having a log P calculated from at least 3, said log P calculated being the octanol division coefficient to water calculated; (d) adding the solution from step (c) to the starch solution of step (a); (e) homogenizing the resulting solution by mixing it to form a uniform homogenous mixture; Y (f) spraying said homogeneous mixture to form a starch granule containing oil.

The oils useful for the present invention can be any oil that is a liquid of between about 10 ° C and 90 ° C and is capable of providing an additive-benefit to the fabrics, hard surfaces, hair or skin. For laundry applications the preferred oils are perfumes, the term "perfume" is used herein to refer to odoriferous materials which are capable of providing a pleasing fragrance to fabrics, and encompasses the conventional materials commonly used in the compositions detergents to counteract a bad odor in such compositions and / or provide a pleasing fragrance thereto. The perfumes are preferably in the liquid state at room temperature, even when solid perfumes are also useful.

The perfume oil of the invention comprises ingredients having a calculated log P of at least 3 wherein the log P calculated is the octanol to calculated water coefficient of exposure. The calculated log P is a parameter indicating the solubility in water or the hydrophobicity of the perfume. The higher the value of log P calculated the more hydrophobic the perfume is. An increase in the coefficient division allows a higher substantivity (a value that lasts longer, which is slowly emitted from the laundered clothing; Sina D. Escher and Esther Oliveros; A Quantitative Study of Factors Influencing Substantivity of Chemicals Fragrance in Washed and Dried Fabrics, Journal of the American Society of Chemicals and Oils volume 71, No. 1, pages 31-40, 1994). A perfume with a calculated log P value of 3 or higher is more effectively deposited on the surface of the fabric (from a laundry product) than a perfume with a value below 3. Thus, the perfume ingredients of the invention they have a calculated log P of about 3 or higher, preferably more than about 3.2 and even more preferably more than about 3.3.

The calculated log P of many perfume ingredients has been reported, for example, that of the database Ponoma92, from Daylight Chemical Information Systems, Inc.

(Daylight CIS) of Irving, California. The values are more conveniently calculated using the calculated log P program also available from Daylight CIS. The program also lists the log P values calculated experimentally when they are available from the Pomona database. The calculated log P (ClogP) is usually determined by the fragment approach on Hansch and Leo (A. Leo, in Medicinal Chemistry) Comprehensive, volume 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ransden, Editors, page 295 Pergamon Press, 1990). This approach is based on the chemical structure of the fragrance ingredient and takes into account the numbers and types of atoms, the atom connection and the chemical bond. The log P values calculated which are the most reliable and widely used estimates estimate this physiochemical property that can be used instead of the experimental calculated log P values useful in the present invention. Additional information regarding the calculated log P and log P values can be found in U.S. Patent No. 5,500,138.

Included among the perfumes contemplated for use herein are materials such as aldehydes, ketones, esters and the like which are conventionally employed to impart a pleasing fragrance to liquid and granular dissuasive compositions. Naturally occurring plant and animal oils are also commonly used as components of perfumes. Thus, perfumes useful for the present invention may have relatively simple compositions or may comprise complete mixtures of natural and synthetic chemical components, all of which are intended to provide a pleasant fragrance or odor when applied to fabrics. The perfumes used in the detergent compositions are generally selected to meet the normal requirements of odor, price stability and commercial availability. The term "fragrance" is often used here to mean a perfume itself, rather than the aroma imparted by such perfume.

Other oils which may be useful here to provide an additive-benefit to one or more of the aforementioned substrates of fabrics, hard surfaces, hair and skin include vitamins such as vitamin E (tocopheryl esters), modified silicone oils and unmodified, surfactants, fabric softeners, fatty alcohols, fatty acids, fatty esters, etc. These oils can be used as such or as a combination of any of the mentioned oils can be used.

Detailed description of the invention The starches which are suitable for the starch granule of the present invention can be made from unprocessed starch or from a modified starch derived from tubers, legumes, cereals and grains, for example corn starch, wheat starch, rice starch. Waxy maize starch, oat starch, cassava starch, waxy barley, waxy corn starch, sweet rice starch, amoica, potato starch, tapioca starch, oat starch, cassava starch and mixtures thereof.

Modified starches suitable for use include hydrolyzed starch and acid thinned starch, long chain hydrocarbon starch esters, starch acetates, octenyl starch succinate and mixtures thereof.

The term "hydrolyzed starch" refers to oligosaccharide type materials such as corn starch, maltodextrin and corn syrup solids.

The organic compound useful for inhibiting the migration of the oil to the surface of the granule is preferably an amidoamine having the following formula: R2 (i) wherein Rx = C12 to C30 alkyl or alkenyl, R2 = R? CONH (CH2) m, R3 = (CH2CH20) pH, CH3 or H, n 1 to 5, m = 1 to 5, and p = 1 to 10.

In a more preferred softening compound of the formula (I) Rx = C16 to C22 alkyl, n = 1 to 3, m 1 to 3, 1 . 5 to 3. 5 , In the aforementioned formulas, Rx and R2 are each, independently, long chain alkyl or alkenyl groups having from 12 to 30 carbon atoms, preferably from 16 to 22 carbon atoms, such as for example dodecyl, dodecenyl , octadecyl, pctadecenyl. Typically, Rx and R2 will be derived from natural oils containing fatty acids or mixtures of fatty acids, such as coconut oil, palm oil, tallow, rapeseed oil and fish oil. The chemically synthesized fatty acids are also usable. Saturated fatty acids or mixtures of fatty acid, and especially hydrogenated tallow acid (H-tallow) (also referred to as hard fat), are preferred. Generally and preferably, Rx and R2 are derivatives of the same fatty acid or of the fatty acid mixture.

R3 represents (CH2CH20) pH, CH3 or H, or mixtures thereof may also be present. When R3 represents the preferred group (CH2CH20) pH, p is a positive number representing the average degree of ethoxylation, and is preferably from 1 to 10, especially 1.5 to 6, and more preferably from about 2 to 4, such as 2.5, n and m are each integers from 1 to 5, preferably 2 to 4, especially 2. Compounds of the formula (I) in which R 3 represents the preferred (CH 2 CH 20) group are widely mentioned herein as ethoxylated amidoamines and the term "Hydroxyethyl" is also used to describe the group (CH2CH20) pH.

The laundry detergent compositions of the invention may contain one of a mixture of surfactants from the group consisting of anionic, nonionic, and cationic surfactants.

Any suitable non-ionic detergent compound can be used as a surfactant in the present laundry detergent compositions, with many members thereof being described in the various annual numbers of Detergents and Emulsifiers, by John W. McCutcheon. Such volumes give chemical formulas and trade names for commercial nonionic detergents sold in the United States of America, and substantially all of those detergents. they can be used in the present compositions. However, it is preferred that such a non-ionic detergent be a condensation product of ethylene oxide and higher fatty alcohol (although when instead of the higher fatty alcohol, higher fatty acids and alkyl [octyl, nonyl and isooctyl] can also be employed. ] phenols The higher fat halves such as the alkyls of such alcohols and the resulting condensation products will normally be linear, from 10 to 18 carbon atoms, preferably from 10 to 16 carbon atoms, more preferably from 12 to 15 carbon atoms and sometimes more preferably from 12 to 14 carbon atoms. Because such fatty alcohols are usually commercially available only as mixtures, the numbers of carbon atoms given are necessarily averages but in some cases the ranges of carbon atom numbers may be real limits for the alcohols employed and for the corresponding alkyl.

The ethylene oxide (EtO) contents of the nonionic detergents will normally be in the range of 3 to 15 moles of ethylene oxide per mole of higher fatty alcohol, although as much as 20 moles of ethylene oxide may be present. Preferably such ethylene oxide content will be from 3 to 10 moles and more preferably will be from 6 to 7 moles, -J for example, 6.5 or 7 moles per mole of higher fatty alcohol (and per mole of non-ionic detergent). As with the higher fatty alcohol, the given polyethoxylate limits are also limits of the averages of the numbers of ethylene oxide groups present in the condensation product. Examples of suitable nonionic detergents include those sold by Shell Chemical Company under the trademark Neodol®, including Neodol 25-7, Neodol 23-6.5 and Neodol 25-3. .J Other useful nonionic detergent compounds include the alkyl polyglycoside and alkylpolysaccharide surfactants which are well known and extensively described in the art.

The detergent composition may contain an alkyl benzene sulfonate anionic surfactant wherein the alkyl radical contains from about 10 to about 16 carbon atoms in a straight or branched chain and preferably from 12 to 15 carbon atoms. Examples of suitable synthetic anionic surfactants are the benzene sulfonates of (C4-C20) alkyl of potassium, particularly the sodium benzene sulfonates of linear alkyl (C? O-C? S) secondary of sodium.

Other suitable anionic detergents which are optionally included in the present liquid detergent compositions are the ethoxylated and sulphated higher fatty alcohols of the formula RO (C2H0) mS03M, wherein R is a fatty alkyl of from 10 to 18 carbon atoms, m is from 2 to 6 (preferably having a value of from 1-5 to 1/2 the number of carbon atoms in R) and M is a solubilizing salt forming cation, such as alkali metal benzene sulfonate, ammonium or of higher alkyl wherein the higher alkyl is from 10 to 15 carbon atoms. The proportion of the ethylene oxide in the polyethoxylated higher alkanol sulfate is generally from 1 to 11 ethylene oxide groups and preferably from 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, with three moles being most preferred , especially when the higher alkanol is 11 to 15 carbon atoms.

The most highly preferred water soluble anionic detergent compounds are the ammonium and substituted ammonium salts (such as mono, di and tri ethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium). and magnesium) of the higher alkylbenzene sulfonates, and the higher alkyl sulfates.

Reinforcing materials are essential components of the liquid detergent compositions of the present invention. In particular, from about 2% to about 15% of an alkali metal carbonate, such as sodium carbonate, and preferably from about 3% to about 10% by weight.

A phosphate enhancer, and in particular an alkali metal (sodium) polyphosphate in an amount of from about 5% to about 30%, by weight, is an integral component of the present liquid detergent compositions. The amount of such phosphate enhancer is preferably from about 8% to about 20%.

Examples of suitable phosphorus-containing inorganic builders include water-soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates. Specific examples of inorganic phosphate boosters include sodium and potassium tripolyphosphates, phosphates, and hexametaphosphates.

The aluminiosilicate type zeolite A reinforcer, usually hydrated, can optionally be included in the compositions of the invention. The hydrated zeolites X and Y can also be useful, as it can be the zeolites that occur naturally that can act as detergent builders. Of the various products of zeolite A, zeolite 4A, a type of zeolite molecule in which the pore size is about 4 Angstroms, is frequently preferred. This type of zeolite is well known in the art and the methods for its manufacture are described in the art such as in the patent of the United States of America No. 3,114,603.

The zeolite boosters are generally of the formula: (Na20) x • (Al203) and • (Si02) z • w H20 where x is 1, and is from 0.8 to 1.2 ,; preferably 1, z is from 1.5 to 3.5, preferably 2 or. 3 or about 2, and w is from 0 to 9, preferably 2.5 to 6. The crystalline types of zeolite which may be employed herein include those described in the "Zeolite Molecular Series" by Donald Breck, published in 1974 by John Wiley & Sons, the typical zeolites commercially. available being listed in Table 9.6 to pages 747-749 of the text, such Table being incorporated herein by reference.

The zeolite booster can be a univalent cation exchange zeolite, for example, it must be an aluminosilicate of a univalent cation such as sodium /, potassium, lithium (when practicable) or other alkali metal, or ammonium. A zeolite having an alkali metal cation, especially sodium, is more preferred, as indicated in the formula shown above. The zeolites employed can be characterized as having a can exchange capacity for the calcium ion, which is normally from about 200 to about 400 or more milligram equivalents of calcium carbonate hardness per gram of aluminosilicate, preferably 250. to 350 mg, for example / grams, on an anhydrous zeolite base. A preferred amount of zeolite is from about 8% to about 20%.

Other components may be present in the detergent compositions to improve the properties and in some cases, to act as diluents or fillers. Illustrative of suitable auxiliaries are the enzymes to further improve the cleaning of certain hard dirt from removing from clothing or from hard surfaces. Among the enzymes, proteolytic and amylolytic enzymes are most useful. Other useful auxiliaries are foaming agents, such as lauric myristic diethanolamide, when the foam is desired, and anti-foaming agents, when desired, such as dimethyl silicone fluids. Also useful are polymers, anti-redeposite agents, bleaches, fluorescent brighteners, such as stilbene brighteners, dyes such as dyes and pigments and perfume.

ANALYTICAL METHODS 1. SPME Top Space Analysis Dry Fabric Heated Solid phase microextraction (SPME, Almirall * JR, Furton, KG In Solid Phase Microextraction, A Practical Guide, Scheppers-Wercinski, S., Editors, Marcel Dekker, New York, 1999, pages 203-216) is a technique solvent-free extraction through which the analytes are extracted from a matrix (such as a fabric) inside a polymer or other coated phase on a fumed silica fiber. The SPME is coupled with gas chromatography (GC) for the desorption and analysis of the analytes.

Materials: 1. Gas chromatograph with detection of mass spectra of ion trap and entrance liner SPME 0.75 mm ID.

(Varian GC3800 / Saturn 2000 equipped with an Auto Sampler Combi Pal) Column GC: CP-SIL-8CB-MS, 30 m X 0.25 mm X 0.25 μm. 3. SPME fiber: 100 micron polydimethylsiloxane (Supelco 57300-U (manual) or 57301 (automated). 4. Top-space containers of 10 mL with a folded lid and Septa Varian MLA201000 and MLA200051ML.

Method: 1. Using clean dry scissors, cut (3) one gram patches (2 grams for bad odor) from the cotton towel that will be analyzed. 2. Use a glass rod to insert each patch into a 10 mL top space container, being careful to insert enough to avoid damaging the SPME fiber. 3. Cover the containers and allow the equilibrium at room temperature for at least 24 hours. 4. Balance the containers at 50 ° C for at least 30 minutes in a Sampler Auto.

Insert fiber and expose for 25 minutes at 50 ° 6. Inject into a gas chromatograph and desorb for 30 minutes at 250 ° C.

GC conditions: Injector Temperature: 250 ° C Column Flow: 1 mL / min Column Oven: The total run time: 45 minutes, Procedure for undressing for towels For all sample evaluations, 24 Ferry hand towels (86% cotton, 14% polyester) were prepared in a 17 gallon top load washing machine for hot washing (120 ° F), with an extra-large placement, in tap water. Two wash cycles with 100 g of Viva 2 Mexicano free powder detergent fragrance, one washed with water only, the extra rinsing switch was set, it was used for all washes. After the three wash cycles were completed, the towels were dried in an electric clothes dryer, and placed flat for storage. All the cloth ballast used for the tests was processed in the same way as the towels between each use.

Table 1. Base Detergent, Bl: Starch granules The starch / AA granules were prepared using the Capsul starch (commercial product of National Starch). Capsul is an octenyl succinate of dextrinized waxy corn starch. The process of dextrinization to degrade starch is what differentiates Capsul starch from other types of starches. The following procedure was used to prepare the starch / AA granules: Pre-mix 33% Capsul starch in water, at least one day in advance using the GREERCO model No. 1L mixer. Allow the air to settle. Take the required amount of this and add the fragrance oil and the melted amidoamine mixture and homogenize using a Silverson model L4R mixer. Pour this mixture into the Armfield FT80 high-form spray dryer and spray dry at 190 ° C with 0.5 to 1.0 bar of spray pressure.

The composition of starch granules (the amounts shown are the percentages by weight) is as follows (Table 2) used to prepare the compositions shown in Table 4: Table 2. Composition of Starch Granules * Substantive fragrance Dinasty from Internatonal Flavors and Frgances, Inc., containing the following ingredients: Surface Oil Content of Starch Granules / AA and Performance Comparison with Starch / Silica One study indicates that the hydrophobic additive AA significantly reduces the amount of perfume (substantive fragrance Dinasty) on the surface of dried starch capsules from 2.89% (without AA) to 0.24% (Table 3). In contrast to AA, another study reveals that a hydrophobically modified silica (Aerosil R974, the preferred additive of prior art, patent application WO 01/05926) does not reduce the amount of surface oil to the same extent as amidoamine does ( Table 3). Aerosil reduces the amount of surface oil (Dinasty perfume) in the starch granule from 3.09% (without Aerosil) to 2.38% (with Aerosil). The surface oil was measured by extracting the particle encapsulated with hexane at room temperature and atmospheric pressure followed by gas chromatography. Hexane extracts only the fragrance oil on the surface of the particle, not the oil encapsulated within the particle.

Table 3. Quantities of Surface Oil (only substantive fraction) in the Starch Fragrance Granule * The granule consists of [starch Capsul (65%), Fragrance Substantive Dinasty (35%)] ** The granule consists of [starch Capsul (60%), Amidoamine Digrasa (5%), Fragrance Substantive Dinasty (35%)] *** The granule consists of [starch Capsul (64.29%), Aerosil R974 (0.71%), Fragrance Substantive Dinasty (35%)] Table 4. Compositions 1 and 2 Fragrance added later to the base pear Bl * • - The granules contained 35% substantive fragrance Dinasty (or 0.43% in the formula) (Table 2) Fragrance composition shown (Table 2) The above formulas were used under the following conditions: Test conditions: The temperature is 77 ° F, the hardness of water is 50 parts per million, 10 minutes of washing, 5 minutes of rinsing, the washing machines are Maytag machines, wash cycle 3.

The cloth load is 12 towel patches (10 X 10 inches). The patches are prewash to undress before use. After washing, the patches are dried on a clothesline for 1 and 7 days.

The detergent composition is 78 gm.

Washing is done by filling the washing machines with water and then adding the water hardness to 50 parts per million by adding a supply solution of > 250,000 parts per million of water. Add the product and stir for 1 minute.

Add the patches, wash for 10 minutes and rinse for 5 'minutes.

After the washing has been completed, pat dry the clothes on a clothesline for 1 to 7 days and cut samples of the fabrics for SPME analysis (1 gm of fabric / SPME container, 4 containers / product).

Table 5. The Total Fragrance Accounts on the Dried Cloth Surface (after day 7) as observed by the Solid Phase Microextraction Method As shown in Table 5, the use of the fragrance granules (composition 2, Table 4) deposits, relatively more fragrance on the fabric surface compared to a control (composition 1, Table 4).

Claims (12)

RE I V I ND I CAC I ONE S

1. A starch granule containing oil comprising: (a) a starch, said starch being present in an amount to form an effective matrix for said granule; (b) a perfume oil comprising ingredients having a calculated log P of at least 3, said log P being the division coefficient of. octanol to calculated water, said perfume oil being able to provide an additive-benefit to a substrate upon contact therewith, said substrate being selected from the group consisting of fabrics, hard surfaces, skin and hair; Y (c) an effective amount of an organic compound to inhibit the migration of said oil to the surface of said starch granule, said compound being represented by the following structure: R2-Y- - (CH2) q- (Q) m B where Rx and R2 are each independently, H or: (a) a C 1 -C 22 alkylenecarboxy moiety having the formula: - (CH2) eR3 wherein R3 is -NHCOR4; or -OCOR4; or - R5COR4; and wherein R4 and R5 are each independently a C? -C22 alkyl or alkenyl; and e is an integer from 1 to 22; or (b) a linear or branched C? -C22 alkyl; or - (c) a linear or branched C? -C22 alkenyl; or (d) a substituted or unsubstituted C2-C22 alkyleneoxy; or (e) a substituted or unsubstituted C3-C22 alkyleneoxy alkyl; or (f) a substituted or unsubstituted C6-C22 aryloxy; or (g) a substituted or unsubstituted C7-C22 alkylenearyl; or (h) a substituted or unsubstituted C7-C22 alkylene oxidearyl; or (i) a C7-C22 oxyalkylenearyl; or (j) an anionic unit that has the formula: (CH2) and R6 wherein R6 is -S03M, -OS03M, -P03M, -OP03M, Cl or mixtures thereof, wherein M is hydrogen, or one or more salt-forming cations sufficient to satisfy the charge balance, or mixtures thereof; and is an integer from 1 to about 22; or (k) a mixture comprising at least two of (a) to (j); Y q is an integer from 0 to about 22; m is an integer from 0 to about 22; Q is (CH2) m or (CH2CHR70); R7 is independently hydrogen, methyl, ethyl, propyl or benzyl; B is H or OH; and Y is CRx or N.

A starch granule containing oil comprising: (a) a starch, said starch forms a matrix for said granule; (b) a perfume oil comprising ingredients having a calculated log P of at least 3, said log P calculated as the octanol division coefficient to water calculated, said perfume oil being capable of providing an additive-benefit to a substrate on contact therewith, said substrate being selected from the group consisting of fabrics, hard surfaces, skin and hair; Y (c) an effective amount of a dike amido amine compound to inhibit the migration of said oil to the surface of said starch granule, said compound being represented by the following structure: R, -C 11 -t- (CH 2) m -N (CH 2) n T-CII R 2 where R x and R 2, independently, represent aliphatic hydrocarbon groups C 12 to C 30, R 3 represents (CH2CH20) pH, CH3 or H; T represents NH; n is an integer from 1 to 5; m is an integer from 1 to 5 and p is an integer from 1 to 10.

3. A starch granule containing oil comprising: (a) a starch, said starch forms a matrix for said granule; (b) a perfume oil comprising ingredients having a calculated log P of at least 3, said log P calculated as the octanol division coefficient to water calculated, said perfume oil being capable of providing an additive-benefit to a substrate on contact therewith, said substrate being selected from the group consisting of fabrics, hard surfaces, skin and hair; Y (c) an effective amount of quaternary amine compound to inhibit the migration of said oil to the surface of said starch granule, said compound being represented by the following structure: where R and R2 are each independently, H o: [a) a C 1 -C 22 alkylenecarboxy moiety having the formula: - (CH2) eR3 wherein R3 is -NHCOR4; or -OCOR4; or -NR5COR4; and wherein R and R5 are each independently a C? -C22 alkyl or alkenyl; and e is an integer from 1 to 22; or (b) linear or branched C C-C22 alkyl; or (c) a linear or branched C? -C22 alkenyl; or (d) a substituted or unsubstituted alkyleneoxy C2-C22; (e) a substituted or unsubstituted C3-C22 alkyleneoxy alkyl; or [f) a substituted or unsubstituted C5-C22 aryloxy; "- or (g) a substituted or unsubstituted alkylenearyl C7-C22; or (h) substituted or unsubstituted alkylene oxide C7-C22; or (i) C7-C22 oxyalkylenearyl; or (j) an anionic unit having the formula: (CH2) and R6 wherein R6 is -S03M, -OS03M, -P03M, -OP03M, Cl or mixtures thereof, wherein M is hydrogen, or one or more salt-forming cations sufficient to satisfy the charge balance, or mixtures thereof; R6 can also be chloride; and is an integer from 1 to about 22; and (k) a mixture comprising at least two of (a) to (j); Y q is an integer from 0 to about 22; m is an integer from 0 to about 22; Q is (CH2) m or (CH2CHR70); R7 is independently hydrogen, methyl, ethyl, propyl or benzyl; and mixtures thereof; B is H or OH; and Y is N; R8 is H or C? -C4 alkyl; Z- is a counter anion, and preferably chloride, or methyl sulfate.

4. A starch granule containing oil as claimed in clauses 1, 2 or 3, characterized in that said oil comprises a perfume.

5. A method for preparing an oil containing starch granule as claimed in clauses 1, 2 or 3, characterized in that it comprises the steps of: - ' (a) providing a dispersion of starch in water to form a starch solution; (b) melting an effective amount of an organic compound such as an amido amine comprising bis (alkyl amidoethyl) -2-polyethoxy amine to form a melt of amidoamine; (c) adding a fragrance oil to the organic compound melt or amidoamine melt of step (b) to form a solution of the organic compound or amidoamine in a fragrance oil, said fragrance oil comprising * the ingredients having a log P calculated from at least 3, said log P calculated being the octanol division coefficient to water calculated; (d) adding the solution from step (c) to the starch solution of step (a); (e) homogenizing the resulting solution by mixing it to form a uniform homogenous mixture; Y (f) spraying said homogeneous mixture to form the starch granule containing oil.

6. A method as claimed in clause 5, characterized in that said organic compound is a quaternary ammonium compound.

A method for washing fabrics comprising the steps of: (a) forming an aqueous solution containing an effective amount of the starch granule containing oil according to clauses 1, 2 or 3; and (b) contacting the fabrics to be washed with the aqueous solution of (a).

8. A method as claimed in clause 7, characterized in that said oil-containing starch granule comprises a digraso amido amine compound.

9. A method as claimed in clause 7, characterized in that said oil-containing starch granule comprises a quaternary ammonium compound.

10. A laundry detergent composition comprising: (a) a surfactant or mixture of surfactants selected from the group consisting of anionic surfactants, -. nonionic and cationic; Y (b) an effective amount of a starch granule containing oil according to clauses 1, 2 or 3.

11. A laundry detergent composition as claimed in clause 10, characterized in that said oil-containing starch granule comprises a digraso amido amine compound.

12. A laundry detergent composition as claimed in clause 10, characterized in that said oil-containing starch granule comprises a quaternary ammonium compound. SUMMARIZES A starch granule containing oil is provided comprising: (a) a starch to form an effective matrix for said granule; (b) a perfume oil comprising ingredients having a calculated log P of at least 3, said log P calculated to be the calculated octanol to water fractionation coefficient, said perfume oil being capable of providing a benefit-additive to a substrate in contact therewith, said substrate being selected from the group consisting of fabrics, hard surfaces, skin and hair; and (c) an effective amount of an organic compound defined to inhibit the migration of said oil to the surface of said starch granule.