WO2001034753A1

WO2001034753A1 - Detergent composition

Info

Publication number: WO2001034753A1
Application number: PCT/US2000/030526
Authority: WO
Inventors: Rodolfo Gilberto Rios-Diaz; Patricia Sara Berger
Original assignee: The Procter & Gamble Company
Priority date: 1999-11-12
Filing date: 2000-11-03
Publication date: 2001-05-17
Also published as: MXPA02004784A; MA25690A1; CN1390249A; BR0015488A; EP1228181A1; AU1585801A

Abstract

Detergent compositions consisting of a sensory enhancing ingredient and conventional detergent ingredients. The sensory enhancing ingredient can be delivered as an add-on to the finished product via spray drying, or in crystal form or alternatively it can be included as an encapsulated particle. If delivered as an encapsulated particle the particle may or may not also contain perfume(s).

Description

DETERGENT COMPOSITION

FIELD OF THE INVENTION

The present invention relates to detergent compositions comprising sensory enhancing ingredients The sensory enhancing ingredients provide improved sensory perceptions including improved mildness, and a feeling of freshness and coolness on the skin especially when used in granular detergents for handwash operations

BACKGROUND OF THE INVENTION Detergent compositions in the form of synthetic detergent granules and liquids are used in may areas throughout the world for purposes of laundering soiled clothes In areas in which mechanical washing machines are not prevalent, laundering soiled clothes generally entails some sort of handwashing operation Such geographic areas use detergent compositions in granular, paste, gel, or bar form In operations involving hand laundering, the hands and arms of the user are typically exposed to the aqueous wash solutions in which the detergent composition is contained Repeated exposure to wash solutions during handwashing operations can lead to skin irritation which can eventually lead to skin lesions, itching, burning, cracking or other skin damage Many attempts have been made by formulators of handwash laundry detergents to alleviate the detrimental effects of hand laundering operations on the arms and hands of users of such detergent products It is therefore desirable to have a laundry detergent composition suitable for handwash operations which exhibits mildness toward the skin of users while maintaining cleaning performance

In the area of handwash detergents it is also desirable to formulate a detergent composition that improves the overall experience of the consumer during the handwash process by providing pleasant sensory signals These sensory signals provide improved skin feel and include sensations such as coolness or freshness on the skin However, many ingredients that provide such a sensory signal have the drawback of imparting a disagreeable odor to the wash solution

Accordingly, it would be desirable to have a laundry detergent composition suitable for handwashing operations that exhibits superior cleaning performance while imparting a mild feel to the hands and arms of users Additionally, it is also desirable to provide formulations that improve the experience of consumers throughout the handwash process by delivering sensory enhancing ingredients into the wash solution without imparting a disagreeable odor or negatively impacting cleaning performance

There has been a continuing search for methods and compositions which will effectively and efficiently deliver mildness yet maintain superior cleaning Current compositions focus solely on the clinical mildness of the compositions to skin of the hands and arms However, the various solutions now existing in the art fail to address the need to signal the resulting mildness to the consumer in an easily perceivable manner Additionally, current formulations do not address the importance of creating an improved skin feel during the handwashing process The present invention relates to detergent compositions that signal mildness to the consumer during the wash and thereby significantly improve consumer acceptance of such compositions The present invention also relates to detergent compositions that improve the consumers' overall experience through the handwash process

By the present invention it has now been discovered that by adding sensory enhancing ingredients to detergent compositions containing conventional surfactant systems, the resulting compositions are perceived to be milder than compositions without the sensory enhancing ingredient These compositions also impart a freshness and coolness to the wash solution and consumers' skin during the wash Additionally, the sensory enhancing ingredients do not have a detrimental impact on the cleaning performance ofthe compositions

The present invention solves the long-standing need for a simple, effective, hand wash detergent composition which delivers superior cleaning and provides a mild and fresh skin feel during and after the wash

SUMMARY OF THE INVENTION The present invention relates to detergent compositions comprising from 0 01% to 1 0% by weight of the total composition, of a sensory enhancing ingredient, preferably 0 01%) to 0 5% by weight of the total composition, most preferably 0 01 % to 0 1% by weight of the total composition and from about 99 0% to about 99 99%, preferably from about 99.50% to 99 99%, and most preferably 99 90%o to about 99 99% of conventional laundry ingredients selected from the group consisting of surfactants, builders, chelants, brighteners, bleaching ingredients, photobleaches, enzymes, soil release polymers, dye transfer inhibitors, fillers, perfumes and mixtures thereof

All percentages, ratios, and proportions herein are on a weight basis unless otherwise indicated All documents cited are hereby incorporated by reference in their entirety DETAILED DESCRIPTION OF THE INVENTION

The present invention provides detergent compositions useful in handwashing operations which provide an especially desirable and noticeable skin-feel, attributable to the addition of a sensory enhancing ingredient The enhanced sensory effects include coolness, freshness, and a mild feeling on the skin of consumers during and after use Sensory enhancing ingredient

A sensory enhancing ingredient is an ingredient that when added to a detergent composition creates a physiological sensation of freshness and coolness on the skin ofthe hands and arms when the detergent composition is dissolved in the wash water While not wishing to be bound by theory, it is believed that the sensory enhancing ingredients enhance the perception of coolness on the nerve's endings ofthe skin by binding with calcium (Ca) ions and reducing their transport through the cellular membrane A low level of Ca ions increases the frequency of discharge ofthe neurons sensible to cold, and as a consequence creates a cooling sensation

It is also believed that the addition of sensory enhancing ingredients to detergent compositions, leads to slight variations in the rheological properties such as viscosity, surface tension and density, of the wash solution prepared from the detergent composition, improving the feel ofthe wash solution on the skin throughout the handwash process

The best known natural compound which has a physiological cooling effect is menthol However, the typically strong peppermint odor is not generally accepted by consumers in laundry or dish detergent applications It has been found that ketals of the formula

in which R¹ represents a C₂-C₆-alkylene radical having at least 1, but not more than 3, hydroxyl group(s), preferably 1 hydroxyl group, and either R² and R independently of one another represent Ci-Cio alkyl which is optionally substituted by 1 to 3 radicals selected from the group comprising hydroyl, amino and halogen (such as fluorine, chlorine, bromine or iodine), C₅-C₇ cycloalkyl, preferably cyclohexyl, C₆-Cι₂ aryl, preferably phenyl, with the proviso that the total of the C atoms of R² and R^λ is not less than 3, or R² and R^ together represent an alkylene radical which, together with the carbon atom which carries the radicals R² and R³, forms a 5-7 membered ring, it being possible for this alkylene radical, in turn to be substituted by Cj-C₆ alkyl groups Preferred radicals R² and R³ comprise methyl, isopropyl and tert. -butyl. The length of the radicals R and R influences the effect of the compounds. Shorter radicals lead to an immediate, short effect, while longer radicals lead to a delayed, but prolonged effect.

Preferred radicals R^! are 1,2-and 1,3-alkylene radicals which, together with the two oxygen atoms and with the carbon atom to which the two oxygen atoms are attached, form a dioxolane or dioxane ring.

Preferred compounds I in which R² and R' together represent an alkylene radical are those ofthe formula:

in which R to R independently of one another denote hydrogen or Ci-C_f, alkyl, preferably hydrogen or Cι-C alkyl, and m and n independently of one another denote zero or 1. Preferred compounds of the formula la are those in which the total of m+n is 1, i.e. ketals of an optionally substituted cyclohexanone. Preferred substituents, of which there may be present, in particular, 1 to 3, are methyl, isopropyl and tert. -butyl.

The ketals of the formula 1 can be prepared by known processes. For example, ketal 1 will generally be prepared by acid-catalyzed reaction of the ketone on which ketal 1 is based and not less than the equivalent amount of aliphatic C3-C6 alcohol having not less than 3 and not more than 5 preferably 3, hydroxyl groups. In general, the ketone on which ketal 1 is based and not less than 05 mol equivalents, but, as a rule a 1.2 to 4 fold preferably 1.5 to 3 fold excess of this amount of the C3-C6 alcohol having 3 to 5 hydroxyl groups will be used. A more detailed description of the method of making ketals useful in the present invention can be found in US Patent No. 5,266,592 issued November 30, 1993 to Haarmann & Reimer GmbH, herein incorporated by reference.

Sensory enhancing ingredients suitable for use in the present invention include but are not limited to menthol, methyl lactate, methoneglycerine acetal, cyclohexanol, 5- methyl-2-(l-methylethenyl)-,l,2 propanedio, 3-[5-methyl-2-(l- methylethyl)cyclohexyl]axy-, N,2,3-trimethyl, 2-isopropyl butanamide, and N-ethyl-p- menthan-3-carboxamide. Most preferred is methyl lactate commercially available as Frescolat^®ML Cryst from Haarmann & Reimer.

When included in detergent compositions, these sensory enhancing ingredients deliver to a person who places his skin into a wash solution containing the detergent composition, a sensory signal that connotes less roughness, itching and irritation and therefore mildness They also impart a feeling of coolness and freshness to the consumer Methods of Incorporation

The sensory enhancing ingredients described herein are incorporated into detergent compositions by various methods including but not limited to spraying on the finished detergent granule, in crystal form as an admix, encapsulated alone in a water soluble starch matrix, or encapsulated in combination with a perfume in a water soluble starch matrix The amount of sensory enhancing ingredient added to detergent compositions is from 0 01%) to 1 0%) by weight of the total composition, preferably 0 01 % to 0 5% by weight of the total composition, and most preferably 0 01%> to 0 1%> by weight of the total composition regardless ofthe method of incorporation

The sensory enhancing ingredient can be sprayed onto the finished detergent granules separately or in conjunction with a perfume using conventional spray-on technology well known in the industry

The sensory enhancing ingredient can be added in crystallized form to the detergent as an admix After drying and conditioning of the base detergent granule, admixes are dispersed from dry addition systems onto the base granule

The sensory enhancing ingredient can be added to a detergent composition as a particle encapsulated in a water soluble starch material The process of encapsulation is the same whether encapsulated alone or in combination with a perfume

Starches suitable for use as the encapsulating matrix in the present invention include hydrolyzed starch, acid thinned starch, stai ch esters of long chain hydrocarbons, starch acetates, starch octenyl succinate, and mixtures thereof

The term "hydrolyzed starch¹' refers to oligosacchaπde-type materials that are typically obtained by acid and/or enzymatic hydrolysis of starches, preferably corn starch Suitable hydrolyzed starches for inclusion in the present invention include maltodextπns and corn syrup solids The hydrolyzed starches for inclusion with the mixture of starch esters have a Dextrose Equivalent (DE) values of from about 10 to about 36 DE The DE value is a measure of the reducing equivalence of the hydrolyzed starch referenced to dextrose and expressed as a percent (on a dry basis) The higher the DE value, the more reducing sugars present A method for determining DE values can be found in Standard Analytical Methods of the Member Companies of Corn Industries Research Foundation, 6th ed Corn Refineries Association, Inc Washington, DC 1980, D-52

Starch esters having a degree of substitution in the range of from about 0 01% to about 10 0% may be used to encapsulate the perfume oils of the present invention The hydrocarbon part of the modifying ester should be from a C₅ to Cι₆ carbon chain Preferably, octenylsuccinate (OS AN) substituted waxy corn starches of various types such as 1) waxy starch acid thinned and OSAN substituted, 2) blend of corn syrup solids waxy starch, OSAN substituted, and dextrinized, 3) waxy starch' OSAN substituted and dextrinized, 4) blend of corn syrup solids or maltodextrins with waxy starch acid thinned OSAN substituted, and then cooked and spray dried, 5) waxy starch acid thinned and OSAN substituted then cooked and spray dried, and 6) the high and low viscosities of the above modifications (based on the level of acid treatment) can also be used in the present invention

Modified starches having emulsifying and emulsion stabilizing capacity such as starch octenyl succinates have the ability to entrap the sensory enhancing ingredient in the emulsion due to the hydrophobic character of the starch modifying agent The sensory enhancing ingredient remains trapped in the modified starch until dissolved in the wash solution, due to thermodynamic factors i e , hydrophobic interactions and stabilization of the emulsion because of steric hindrance Manufacture of Starch Encapsulated Sensory Enhancing Ingredients

One suitable process for encapsulation of sensory enhancing ingredients is by spray drying of an emulsion of the sensory enhancing ingredient and a starch First a starch is dissolved in water by agitating the mixture with an impeller rotating at 500 RPM for about 20 minutes The starch is left to sit overnight for deareation and complete dispersion to yield a 33wt%> aqueous solution of starch Alternatively, a pre-prepared liquid starch solution with a low level of biocide and/or defoamer can be used The sensory enhancing ingredient is added to the vortex of the starch solution, and agitated at 300 RPM for 10 minutes The resultant emulsion is then ultrasonically mixed for 2-4 minutes Alternate techniques for obtaining submicron emulsion droplet size are well known in the industry and can be employed here The sensory enhancing ingredient droplet size is preferably <1 micrometer The emulsion is then spray dried by conventional spray drying methods using a co-current or counter-current tower and atomized through a spinning disk with co- current or counter-current airflow for drying The emulsion is dried using an inlet air temperature of 185-200°C, and an outlet air temperature of 95-1 15°C. Following drying a flow aid such as Sipernat D10 can be added at about 1 0%> Optional Detersive Ingredients

As a preferred embodiment, the conventional detergent ingredients are selected from typical detergent composition components such as detersive surfactants and detersive builders Optionally, the detergent ingredients can include one or more other detersive adjuncts or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition Usual detersive adjuncts of detergent compositions include the ingredients set forth in U S Pat No. 3,936,537, Baskerville et al and in Great Britain Patent Application No 9705617 0, Trinh et al., published September 24, 1997 Such adjuncts are included in detergent compositions at their conventional art-established levels of use, generally from 0% to about 80% of the detergent ingredients, preferably from about 0.5%) to about 20% and can include color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, solvents, solubilizing agents, chelating agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, fabric softening components, static control agents, bleaching agents, bleaching activators, bleach stabilizers, etc Surfactants

The laundry detergent compositions of the present invention may optionally comprise a non mid-chain branched alkyl sulfate or non-mid chain branched aryl sulphonate surfactant Depending upon the embodiment of the present invention one or more categories of surfactants may be chosen by the formulator Preferred categories of surfactants are selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof Within each category of surfactant, more than one type of surfactant of surfactant can be selected For example, preferably the solid (i e granular) and viscous semi-solid (i e gelatinous, pastes, etc ) systems of the present invention, surfactant is preferably present to the extent of from about 0 1%) to 60 %, preferably to about 30% by weight of the composition

Nonlimiting examples of surfactants useful herein include a) Cπ-Cis alkyl benzene sulfonates (LAS), b) C1 -C20 primary, branched-chain and random alkyl sulfates (AS), c) C10-C₁ secondary (2,3) alkyl sulfates having the formula

OSO₃ ^" M⁺ OSO ^" M⁺

I I ^"

CH₃(CH₂)χ(CH)CH₃ or CH₃(CH2)_V(CH)CH₂CH3

wherein x and (y + 1) are integers of at least about 7, preferably at least about 9, said surfactants disclosed in U S. 3,234,258 Morris, issued February 8, 1966; U.S 5,075,041 Lutz, issued December 24, 1991 , U.S 5,349, 101 Lutz et al., issued September 20, 1994, and U S 5,389,277 Prieto, issued February 14, 1995 each incorporated herein by reference, d) C10-C18 alkyl alkoxy sulfates (AE_XS) wherein preferably x is from 1-7, e) C]o-Ci8 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units, f) C12-C18 alkyl ethoxylates, Cβ-Cn alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units, C₁₂-Cι« alcohol and C₆- C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers inter aha Pluronic* ex BASF which are disclosed in U S 3,929,678 Laughlin et al , issued December 30, 1975, incorporated herein by reference, g) Alkylpolysacchaπdes as disclosed in U S 4,565,647 Llenado, issued January 26, 1986, incorporated herein by reference, h) Polyhydroxy fatty acid amides having the formula

wherein R' is C5-C3 _] alkyl, R° is selected from the group consisting of hydrogen, C _] -C4 alkyl, C_] -C4 hydroxyalkyl, Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof, preferred alkoxy is ethoxy or propoxy, and mixtures thereof, preferred Q is derived from a reducing sugar in a reductive animation reaction, more preferably Q is a glycityl moiety, Q is more preferably selected from the group consisting of -CH2(CHOH)_nCH2OH, - CH(CH₂OH)(CHOH)_n.₁CH₂OH, -CH₂(CHOH)2-(CHOR')(CHOH)CH₂OH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic or aliphatic monosacchaπde, which are described in U S 5,489,393 Connor et al , issued February 6, 1996, and U S 5,45,982 Murch et al , issued October 3, 1995, both incorporated herein by reference Detergency Builders

The handwashing detergent composition may also include a detergent builder to assist in controlling mineral hardness and to enhance the removal of particulate soils Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tπpolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosihcates However, non-phosphate builders are required in some locations Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so- called "underbuilt" situation that may occur with zeolite or layered silicate builders Examples of silicate builders are the alkali metal silicates, particularly those having a SιO Na₂O ratio in the range 1 6 1 to 3 2 1 and layered silicates, such as the layered sodium silicates described in U S Patent 4,664,839, issued May 12, 1987 to H P Rieck NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6") Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum NaSKS-6 has the delta-Na₂Sιθ5 morphology form of layered silicate It can be prepared by methods such as those described in German DE-A- 3,417,649 and DE-A-3,742,043 SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSι_xθ2χ+] yH O wherein M is sodium or hydrogen, x is a number from 1 9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1, as the alpha, beta and gamma forms As noted above, the delta-Na2Sιθ5 (NaSKS-6 form) is most preferred for use herein Other silicates may also be useful such as for example magnesium silicate, which can serve as a crisping agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No 2,321 ,001 published on November 15, 1973

Aluminosilicate builders are useful in the present invention Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations Aluminosilicate builders include those having the empirical formula M_z(zAlO₂)_y] xH₂O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1 0 to about 0 5, and x is an integer from about 15 to about 264

Useful aluminosilicate ion exchange materials are commercially available These aluminosihcates can be crystalline or amorphous in structure and can be naturally- occurring aluminosi cates or synthetically derived A method for producing aluminosilicate ion exchange materials is disclosed in U S Patent 3,985,669, Krummel, et al, issued October 12, 1976 Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Na₁₂[(AlO₂)₁₂(SιO₂)₁₂] xH₂O wherein x is from about 20 to about 30, especially about 27 This material is known as Zeolite A Dehydrated zeolites (x = 0 - 10) may also be used herein Preferably, the aluminosilicate has a particle size of about 0 1-10 microns in diameter

Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred

Included among the polycarboxylate builders are a variety of categories of useful materials One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U S Patent 3, 128,287, issued April 7, 1964, and Lamberti et al, U S Patent 3,635,830, issued January 18, 1972 See also "TMS/TDS" builders of U S Patent 4,663,071 , issued to Bush et al, on May 5, 1987 Suitable ether polycarboxylates also include cyclic compounds, particularly alicyc c compounds, such as those described in U S Patents 3,923,679, 3,835, 163, 4, 158,635, 4, 120,874 and 4, 102,903

Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 , 3, 5-tπhydroxy benzene-2, 4, 6-tπsulphonιc acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitπlotπacetic acid, as well as polycarboxylates such as mellitic acid, succimc acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5- tπcarboxyhc acid, carboxymethyloxysuccinic acid, and soluble salts thereof

Citrate builders, e g , citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for liquid detergent formulations due to their availability from renewable resources and their biodegradability Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders Oxydisuccinates are also especially useful in such compositions and combinations

Also suitable in the detergent compositions of the present invention are the 3,3- dιcarboxy-4-oxa-l,6-hexanedιoates and the related compounds disclosed in U S Patent 4,566,984, Bush, issued January 28, 1986 Useful succimc acid builders include the C5- C_2Q alkyl and alkenyl succimc acids and salts thereof A particularly preferred compound of this type is dodecenylsuccinic acid Specific examples of succinate builders include laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690 5/0,200,263, published November 5, 1986

Other suitable polycarboxylates are disclosed in U S Patent 4, 144,226, Crutchfield et al, issued March 13, 1979 and in U S Patent 3,308,067, Diehl, issued March 7, 1967 See also Diehl U S Patent 3,723,322

Fatty acids, e g , C]₂-C_] g monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator

In situations where phosphorus-based builders can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used Phosphonate builders such as ethane- 1 -hydroxy- 1 , 1 - diphosphonate and other known phosphonates (see, for example, U S Patents 3,159,581 , 3,213,030, 3,422,021, 3,400, 148 and 3,422, 137) can also be used Adjunct Ingredients

The compositions herein can optionally include one or more other detergent adjunct materials or other 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 , perfumes, colorants, dyes, etc ) The following are illustrative examples of such adjunct materials

Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof Other types of enzymes may also be included They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases

Enzyme Stabilizers - The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used ) Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species see Severson, U S 4,537,706

Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5%o to about 20%, of the detergent composition, especially for fabric laundering If present, the amount of bleach activators will typically be from about 0 1 % to about 60%, more typically from about 0 5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator Mixtures of bleaching agents can also be used

Polymeric Soil Release Agent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention Polymeric soil release agents are characterized by having both hydrophihc segments, to hydrophi ze the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophihc segments This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures

Chelating Agents - The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates

Clay Soil Removal/Anti-redeposition Agents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties Granular detergent compositions which contain these compounds typically contain from about 0 01% to about 10 0% by weight of the water-soluble ethoxylates amines, liquid detergent compositions typically contain about 0 01% to about 5%

Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from about 0 1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition

Bπghtener - Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0 05% to about 1 2%, by weight, into the detergent compositions herein Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazo ne, coumaπn, carboxy c acid, mefhinecyanines, dιbenzothιophene-5,5-dιoxιde, azoles, 5- and 6-membered-πng heterocycles, and other miscellaneous agents Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M Zahradnik, Published by John Wiley & Sons, New York (1982)

Dye Transfer Inhibiting Agents - The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process Generally, such dye transfer inhibiting agents include polyvinyl pyrro done polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrohdone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof If used, these agents typically comprise from about 0 01%> to about 10%> by weight of the composition, preferably from about 0 01% to about 5%, and more preferably from about 0 05% to about 2%

Other Ingredients - A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc If desired, soluble magnesium salts such as MgCl , MgSOzi, and the like, can be added at levels of, typically, 0 l%>-2%, to provide additional suds and to enhance grease removal performance

Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function

Liquid detergent compositions can contain water and other solvents as carriers Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable Monohydπc alcohols are preferred for solubihzing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e g , 1,3-propanedιol, ethylene glycol, glycerine, and 1,2- propanediol) can also be used The compositions may contain from 5% to 90%, typically 10%) to 50%) of such carriers

The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6 5 and about 1 1, preferably between about 7 and 10 Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc , and are well known to those skilled in the art Detergent Compositions

The sensory enhancing agent disclosed herein are useful in a wide range of detergent compositions including but not limited to granular detergents, gels, detergent bars, liquid detergents and dishwashing detergents

In order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope

Examples

Exam le 9. Li uid Dishwashin Detergent

Example 11. Detergent Bar

Ingredient Weiaht %

C , ~ linear alkyl benzene sulfonate 30

Phosphate (as sodium 7 tπpolyphosphate)

Sodium carbonate 25

Sodium pyrophosphate 7

Coconut monoethanolamide 2

Zeolite A (0 1 -10 micron) 5

Carboxymethylcellulose 0 2

(EDDS) 0 4

Polyacrylate (m w 1400) 0 2

Nonanoyloxybenzenesulfonate 5

Sodium percarbonate 5

Brightener . ^{0 2}

Perfume 3 0

Protease 0 3

CaSO₄ 1

MgSO₄ 1

Water 4

Sensory enhancing ingredient 0 5

Frecolat" ML

Filler Balance to

100%

Example 12.

After handwashing a 1 1kg laundry load using a detergent composition without a sensory enhancing ingredient added and subsequently using the same detergent composition containing 0 5%> starch encapsulated Frescolat ML as a sensory enhancing ingredient, 69% of 32 consumer panelists generally preferred the solution with a sensory enhancing ingredient 75%> of panelists preferred it for cleaning and 66%> of panelists preferred it for the skin sensation it provided versus the same detergent compositions without a sensory enhancing ingredient These sensory tests were conducted with a product concentration of 4800ppm in 7L of water at 12gpg hardness These conditions are typical of a handwash system

Claims

What is claimed is:

1 A granular detergent composition comprising

(a) conventional detergent ingredients selected from the group consisting of surfactants, builders, chelants, brighteners, bleaching agents, enzymes, soil release polymers, dye transfer inhibitors, fillers, perfumes and mixtures thereof, and

(b) an effective amount of a sensory enhancing ingredient, which is capable, in a dilution of the granular detergent composition in water, of inducing a cooling effect on human skin placed into or in contact with the dilution

2 A granular detergent composition comprising

(a) from about 99% to about 99 99%, of conventional laundry ingredients selected from the group consisting of surfactants, builders, chelants, brighteners, bleaching agents, photobleaches, enzymes, soil release polymers, dye transfer inhibitors, fillers, perfumes and mixtures thereof, and

(b) from 0 01%) by weight to 1 0% by weight of a sensory enhancing ingredient, which is capable, in a dilution of the granular detergent composition in water, of inducing a cooling effect on human skin placed into or in contact with the dilution

3 A detergent composition according to Claim 1 or Claim 2 wherein the sensory enhancing ingredient is selected from the group consisting of menthol, methyl lactate, methoneglyceπne acetal, cyclohexanol, 5- methyl-2-(l -methylethenyl)-, l,2 propanedio, 3-[5-methyl-2-(l -methylethyl)cyclohexyl]axy-, N,2,3-tπmethyl, 2- lsopropyl butanamide, and N-ethyl-p-menthan-3-carboxamιde

4 A detergent composition according to Claim 3 wherein sensory enhancing ingredient is methyl lactate

5 A detergent composition according to Claim 1 or Claim 2 wherein said sensory enhancing ingredient is encapsulated in a modified starch matrix

6 A detergent composition according to Claim 5 wherein the modified starch used to encapsulate the sensory enhancing ingredient comprises a starch raw material that has been modified by treatment said starch raw material with octenyl-succinic acid anyhydπde

7. A detergent composition according to Claim 1 or Claim 2 wherein said sensory enhancing ingredient is encapsulated, together with a perfume, in a modified starch matrix.

8 A detergent composition according to Claim 7 wherein the modified starch used to encapsulate the sensory enhancing ingredient and perfume, comprises a starch raw material that has been modified by treatment said starch raw material with octenyl- succinic acid anyhydride.

9. A detergent composition according to Claim 1 or Claim 2 wherein said sensory enhancing ingredient is added to the detergent composition in the form of crystals

10 A detergent composition according to Claim 1 or Claim 2 wherein said sensory enhancing ingredient is sprayed onto the finished detergent granule