Patent Description:
Consumer demand has previously created the need for hueing of textile substrates without staining to provide a whitening effect for the treated substrates. The solution to this problem resulted in colored speckles being added to detergents. These colored speckles are visually apparent to the consumer as being lightly colored particles among the non-colored (i.e. white) particles of the actual detergent. However, more recently, there is a demand for the same whitening effect without the visual appearance of colored speckles in the granular detergent. Thus, the need exists for materials for use in laundry care compositions (such as laundry detergent compositions, laundry aids, and fabric care compositions) and other consumer products that are indiscernible in these compositions, yet they provide an equivalent whitening effect to the textile substrates treated therewith without bleeding into the surrounding composition and without staining the substrates that come into contact with the materials.

The occult particles of the present disclosure are ideally suited for providing all of these consumer-desired features to the powdered or granular laundry care compositions (such as laundry detergent compositions, laundry aids, and fabric care compositions). The occult particles provide an aesthetically-pleasing whitening effect to textile substrates treated therewith. They are non-staining to the treated substrates. They also resist bleeding or transferring to the surrounding laundry care composition. Furthermore, the occult particles of the present disclosure provide release of color, or other actives, from the clay carrier and provide desirable color to the wash water. For these reasons, and others that will be described herein, the present occult particles represent a useful advance over the prior art. It is understood that the occult particles of the present disclosure are also ideally suited for providing other consumer-desired features, such as, for example, coloring of wash water and color-change effects.

<CIT> discloses a granule suitable as an additive in a laundry powder composition, and having a particle size distribution such that <NUM> wt% of the particles are less than <NUM> in diameter, the granule comprising <NUM>-<NUM> wt% shading dye solids absorbed into at least <NUM> wt% hydratable salt.

<CIT> relates to a detergent composition comprising <NUM>-<NUM> wt% of colored particles comprising a colored ingredient which is a hueing agent, the colored particle having a Particle Size Distribution of <NUM>-<NUM> and a Hunter color L value of <NUM>-<NUM>.

<CIT> concerns a particle for use in a detergent composition and comprising (i) a coating layer comprising a binder selected from surfactant, surfactant precursor, film-forming polymer, film forming inorganic salt, and mixtures thereof, and (ii) a core being at least partially coated by said coating layer; wherein the particle comprises a hueing dye.

<CIT> describes a particle comprising (a) a specified azo-compound as hueing agent, and (b) clay.

<CIT> discloses a scouring cleanser composition of (<NUM>) <NUM>-<NUM> wt% of anhydrous water insoluble abrasive material having a particle size of <NUM>-<NUM> selected from silica, fedspar, pumic volcanic ash, diatomaceous earth, bentonite, calcium carbonate and talc, and mixtures thereof, (<NUM>) <NUM>-<NUM> wt% of a specified bleaching agent, (<NUM>) <NUM>-<NUM> wt% of a water-soluble organic detergent, and (<NUM>) <NUM>-<NUM> wt% of a coloring agent which is a specified pigmented carrier capable of undergoing color extension on contact with aqueous media.

<CIT> addresses a process for preparing a granular composition for use in a granular detergent product comprising mixing <NUM>-<NUM> wt% of a specified dry particulate coloring material having substantially no particles larger than <NUM>µ with <NUM>-<NUM> wt% of a granular material selected from hydratable salts and detergent compositions having an average particle size of <NUM>-<NUM>; and spraying onto the obtained mixture <NUM>-<NUM> wt% of (a), of water to form agglomerates.

In one aspect, the invention relates to an occult particle, which is a particle comprising:.

In another aspect, the invention relates to a laundry care composition comprising the above occult particle of the invention.

In a further aspect, the invention relates to a process for producing occult particles comprising the following steps:.

The present disclosure relates to non-bleeding and non-staining occult particles for use in granular or powdered laundry care compositions (such as laundry detergent compositions, laundry aids, and fabric care compositions). The particles are characterized in that they hide and/or greatly reduce the appearance of the hueing agent in non-colored (i.e. white) granular powdered detergent. The occult particles of the present invention may also find applications in other consumer products outside powdered or granular detergent compositions, such as laundry detergent compositions, laundry aids, and fabric care compositions. For example, the occult particles may be incorporated into tablets (such as toilet pucks and/or appliance cleaning tablets) or film-encased compositions (such as dishwasher detergents).

The occult particles are comprised of a clay carrier and a coloring agent. Herein, the present disclosure describes an occult particle and a method for making the occult particle which results in release of the coloring agent into wash water while reducing, or even eliminating, color migration or bleed on powdered detergent.

The term "non-staining" as used herein, generally refers to a coloring agent, or a composition that contains such a coloring agent, that may be washed or removed from substrate surfaces (e.g. skin, fabric, wood, concrete) with relatively little effort and without staining the substrate to an appreciable extent.

The term "non-bleeding," as used herein, generally refers to a coloring agent-containing composition that does not substantially color the material surrounding the composition under conditions wherein the material is not intended to be colored. For example, the occult particles of the present invention will generally be considered to be "non-bleeding" if the occult particles fail to substantially color the surrounding powdered detergent in its unused state (i.e. while it remains in the package).

The term "water-insoluble" or "minimally water soluble," as used herein, generally refers to a material whose solubility in water at <NUM> and <NUM> atmosphere of pressure is less than <NUM> grams/<NUM> of water.

The term "water-soluble," as used herein, generally refers to a material whose solubility in water at <NUM> and <NUM> atmosphere of pressure is greater than <NUM> grams/<NUM> of water.

The term "carrier-coloring agent composite" as used herein refers to a material or "carrier" (clay or other, single component or multi-component, powder or granule) that has at least some part of its surface in contact with a color or coloring agent. The color or coloring agent may be absorbed and/or adsorbed to the surface of the carrier.

The term "pure color," as used herein, generally refers to a coloring agent that is free from solvent. The pure color may, however, include salts and other impurities typically found in the coloring agent as a result of its manufacturing process.

The term "cut color," as used herein, generally refers to a coloring agent that contains a certain amount of solvent.

The term "color value" or "CV" or "absorbance value," as used herein, generally refers to a parameter used to quantify the concentration of "pure color" in "cut color".

For example: If an absorbance of approximately <NUM> is recorded (peak or maximum absorbance value within the visible spectrum, i.e. <NUM>-<NUM>) for a <NUM>/L solution of "pure" coloring agent using a <NUM> cuvette, then, the "color value" or "CV" or "absorbance value" of the "pure" coloring agent is defined as <NUM>/<NUM>/L = <NUM>. A 5wt% solution of "pure" coloring agent in solvent ("cut color") will be expected to record a "color value" or "CV" or "absorbance value" of <NUM>.

The term "solvent or solvent system" generally refers to a molecule or a mixture of molecules that can dissolve enough pure color in it to produce a solution having at least <NUM>. 5wt% of pure color and includes mixtures of solvents.

The term "diluent" refers to a molecule of mixture of molecules that is added to the "cut color," prior to application of the "cut color" to the carrier material, and includes mixtures of diluents.

The term "color premix" refers to a mixture of cut color and diluent.

The carrier material is preferably in the form of a powder which is characterized by having a majority of its particles under <NUM> (microns) in size and, in one aspect, under <NUM> in size. The occult particle may be comprised of a majority by weight of the carrier material. The material used to produce the hidden/occult particle may be characterized as a water dispersible material. Suitable carrier materials include natural sodium bentonite clays.

Commercially available examples of suitable clay carriers include Montmorillonite (powdered bentonite clay, <NUM> mesh, sodium saturated, Cat. No. <NUM>-<NUM>) available through VWR, Quest Bentonite powders available through AMCOL/MTI, and SPV Bentonite available through AMCOL/MTI.

Bentonites are clays that are comprised primarily of, and whose properties are typically dictated by a smectite clay mineral (e.g. montmorillonite, hectorite, nontronite, etc.). Smectites are generally comprised of stacks of negatively charged layers (wherein each layer is comprised of two tetrahedral sheets attached to one octahedral sheet; the tetrahedra formed by silicon and oxygen atoms and the octahedra formed by aluminum and oxygen atoms together with hydroxyl radicals) balanced and/or compensated by alkaline earth metal cations (e.g. Ca<NUM>+ and/or Mg<NUM>+) and/or alkali metal cations (e.g. Na+ and/or K+). The relative amounts of the two types (alkaline earth metal and alkali metal) of cations typically determine the swelling characteristic of the clay material when placed in water. Bentonites, in which the alkaline earth metal cation Ca<NUM>+ is predominant (or is in a relative majority), are called calcium bentonites; whereas, bentonites in which the alkali metal cation Na+ is predominant (or is in a relative majority) are called sodium bentonites.

The term "natural," as used herein with respect to clay material, refers to the presence of the mineral in deposits found in the earth (formed for example via modification of volcanic ash deposits in marine basins by geological processes). Accordingly, a natural deposit of bentonite containing primarily (or a relative majority of) Na+ cations is referred to as "natural sodium bentonite;" whereas, a natural deposit of a bentonite predominantly containing (or containing a relative majority of) Ca<NUM>+ cations is referred to as "natural calcium bentonite.

Synthetic analogues of Na and Ca bentonite may also be synthesized (by using hydrothermal techniques, for example). "Synthetic sodium bentonite" may also refer to bentonite obtained by treatment of calcium bentonite with, but not limited to, sodium carbonate or sodium oxalate (to remove the calcium ion and substitute it with a sodium ion). This treatment can be varied to impart different levels of ion-exchange or Na+ for Ca<NUM>+ substitution. Herein, these materials are referred to as "partially activated" and "fully activated" grades of clay material, respectively (with "fully" referring to maximum exchange of Ca<NUM>+ for Na+).

One of the reasons for converting calcium bentonite into synthetic sodium bentonite is to impart greater swelling properties to otherwise (relatively) non-swelling calcium bentonite. There is also an aesthetic benefit associated with synthetic sodium bentonite that is lacking in natural sodium bentonite. Natural sodium bentonite (generally, irrespective of the part of the world in which the deposit is located) tends to be colored. The color can range from brown to yellow to gray. By comparison, natural calcium bentonite has a more aesthetically pleasing white color. Consequently, synthetic sodium bentonite that is obtained by treatment of this white calcium bentonite is also white. As a result, natural calcium bentonite and synthetic sodium bentonite find more widespread use in the detergent industry, as compared to natural sodium bentonite. On account of their whiter appearance, calcium or synthetic sodium bentonite would impact/reduce the perceived whiteness of uncolored laundry detergent powder to a lesser extent than natural sodium bentonite.

Applicants' previous studies (see <CIT>) have shown considerable differences in the propensity of certain coloring agents to stain textile substrates depending on the type of bentonite clay (in the form of a colored clay speckle or colored clay powder) to which the coloring agents have been applied (natural sodium vs. natural calcium bentonite; natural sodium bentonite vs. synthetic sodium bentonite; partially vs. fully activated synthetic sodium bentonite). It has been discovered that, at equal color loading, natural sodium bentonite display considerably lower propensity for staining than calcium bentonite. It has also been discovered that, at equal color loading, synthetic sodium bentonite exhibits lesser staining risk than calcium bentonite. However, at equal color loading, even fully activated synthetic sodium bentonite shows greater staining than natural sodium bentonite. The same observations were made independent of whether the color was applied to a bentonite speckle or a bentonite powder.

Applicants' current studies have shown that occult particles can be produced using natural sodium bentonites. These studies indicate that occult particles could also be produced from a carrier material that is a blend of natural sodium bentonite with a whiter bentonite (such as calcium bentonite or synthetic sodium bentonite or mixtures thereof), thereby resulting in an occult particle that does not reduce the overall lightness of the white detergent to which it is added (in comparison with an occult particle with made from <NUM>% natural Na-bentonite).

It may be preferable that the carrier material exhibits a particular range of particle size, as determined, for example, by sieving techniques according to ASTM D1921 - <NUM> ("Standard Test Method For Particle Size (Sieve Analysis) of Plastic Materials"). Alternative methods known to those skilled in the art may also be utilized for determining particle size. For example, other sieving techniques may be used or electronic laboratory equipment known for determining particle size may alternatively be employed. For the carrier materials of the present invention, it may be preferable that the carrier materials comprise a majority of particles below <NUM> in size, or more preferably below <NUM> in size.

Thus, in one aspect, the occult particles of the present invention are made of or produced from a powder carrier material that is less than <NUM> in size. Referring to the process for making the occult particle, consider a highly simplified scenario. Any additives or mixtures described in this report (e.g. coloring agent + solvent or coloring agent + solvent + diluent), when mixed with the carrier material will cause agglomeration, resulting in a carrier-coloring agent composite that has a size distribution that is different from the original carrier material if the mixing process is sufficiently mild and energy input low such that no simultaneous size reduction through grinding takes place.

The resulting carrier-coloring agent composite can be separated into various size fractions and the coloring agent loading on each fraction can be determined. As Experiments <NUM>-<NUM> will show, the distribution of the coloring agent on the various size fractions is dependent on the nature of the coloring agent, the amount and nature of the solvent and/or diluent, the dilution of the coloring agent prior to addition to the carrier material, and/or the order of addition of the coloring agent and diluent to the carrier material. Carrier-coloring agent composites that have lower amounts of coloring agent on their less than <NUM> size fractions are visually less colored.

Carrier-coloring agent composites prepared using Samples 4F and 5E, for example, look uncolored because ><NUM>% of the coloring agent is contained in the greater than <NUM>µmsize fraction which comprise <<NUM>% of the total weight of the carrier-coloring agent composite or, to be more precise, ><NUM>% of the coloring agent is contained in the greater than <NUM>µmsize fraction which comprises ~<NUM>-<NUM>% of the total carrier-coloring agent composite. The greater than <NUM>µmsize fractions can be re-ground and added back into the mixture to achieve a final size distribution optimized for producing occult particles with reasonable bleed resistance. It is understood that the re-grinding will alter the amounts of coloring agent present in the various size fractions.

The description and examples above are not to be considered limiting. The description of the process, for example, is highly simplified so as provide clear representation of a key mechanism by which occult particles may be produced. One can easily imagine a slightly more complicated process wherein agglomeration and size reduction (grinding/milling) occur simultaneously or even more intricate or complicated processes which no doubt occur during full-scale production. The exact size fraction or fractions that may be chosen for grinding, milling or regrinding may be different. As best understood, the basic concepts illustrated by the simplified description provided above and subsequent elaboration in the rest of this application are applicable and remain important to successful production of occult particles regardless of the complexity of the production process.

The coloring agent of the present invention is a polymeric colorant. The term "polymeric colorant" generally refers to a colorant having at least one chromophore portion attached to at least one oligomeric or polymeric chain, wherein the chain has at least three repeating units. The oligomeric or polymeric constituent can be bound to the chromophore via any suitable means, such as a covalent bond, an ionic bond, or suitable electrostatic interaction. Generally, the polymeric colorant may be characterized by having an absorbance in the range of <NUM>-<NUM>, as measured by UV-vis spectroscopy.

As a function of its manufacturing process, the polymeric colorant has a molecular weight that is typically represented as a molecular weight distribution. Accordingly, the molecular weight of the polymeric colorant is generally reported as an average molecular weight, as determined by its molecular weight distribution.

The chromophore group of the colorant may vary widely, and may include compounds characterized in the art as dyestuffs or as pigments. The actual group used will depend to a large extent upon, for instance, the desired color and colorfastness characteristics. The chromophore group may be attached to at least one polyalkyleneoxy-substituent through a suitable linking moiety of e.g. nitrogen, oxygen, or sulfur.

In one aspect, the chromophore group may be a neutral or an uncharged molecule. In a further aspect, the chromophore group may be nonionic, anionic, or cationic. The coloring agent may contain a chromophore that has both positive and negative charges. Further, the coloring agent may contain a chromophore that is zwitterionic or amphoteric.

Examples of chromophore groups include nitroso, nitro, azo (including monoazo, diazo, bis-azo, disazo, trisazo, tetrakisazo, polyazo, formazan, azomethine and metal complexes thereof), stilbene, bis-stilbene, biphenyl, oligophenethylene, fluorene, coumarin, napthalamide, diarylmethane, triarylmethane, xanthene acridine, quinoline, methine (including polymethine), thiazole, indamine, indophenol, azine, thiazine, oxazine, aminoketone, hydroxyketone, anthraquinone (including anthrapyrazolines, anthrone, anthrapyridone, anthrapyrimidine, flavanthrone, pyranthrone, benzanthrone, perylene, perinone, naphthalimide and other structures formally related to anthraquinone), indigoid (including thioindigoid), phthalocyanine chromophore groups, and mixtures thereof.

Examples of suitable polymeric chains are polyalkyleneoxy chains. The term "polyalkyleneoxy," as used herein, generally refers to molecular structures containing the following repeating units: -CH<NUM>CH<NUM>O-, CH<NUM>CH<NUM>CH<NUM>O-, -CH<NUM>CH<NUM>CH<NUM>CH<NUM>O-, -CH<NUM>CH(CH<NUM>)O-, -CH<NUM>CH(CH<NUM>CH<NUM>)O- CH<NUM>CH<NUM>CH(CH<NUM>)O-, CH<NUM>CH(O-)(CH<NUM>O-), and any combinations thereof.

Typical of such groups which may be attached to the chromophore group are the polymeric epoxides, such as the polyalkylene oxides and copolymers thereof. Typical polyalkylene oxides and copolymers of same which may be employed to provide the colorants include those made from alkylene oxide monomers containing from two to twenty carbon atoms, or more preferably, from two to six carbon atoms. Examples include: polyethylene oxides; polypropylene oxides; polybutylene oxides; oxetanes; tetrahydrafurans; copolymers of polyethylene oxides, polypropylene oxides and polybutylene oxides; and other copolymers including block copolymers, in which a majority of the polymeric substituent is polyethylene oxide, polypropylene oxide and/or polybutylene oxide. Further, such polyalkyleneoxy group may have an average molecular weight in the range of <NUM>-<NUM>,<NUM>, preferably <NUM>-<NUM>.

It is to be understood that because the colorants may or may not be chemically bound to the carrier material, the precise chemical identity of the end group on the polyalkyleneoxy group may not be critical insofar as the proper functioning of the colorant is concerned in the composition. With this consideration in mind, certain most preferred colorants will be defined wherein certain end groups will be identified. Such recitation of end groups is not to be construed as limiting the invention in its broader embodiments in any way. According to such a most preferred embodiment the colorants may be characterized as follows:.

R{A[(alkyleneoxy constituent)nR<NUM>]m}x.

wherein R is an organic chromophore group, A is a linking moiety in said organic chromophore group selected from the group consisting of N, O, SO<NUM> or CO<NUM>, the alkylene moiety of the alkyleneoxy constituent contains <NUM>-<NUM> carbon atoms, n is an integer of <NUM>-<NUM>, m is <NUM> when A is O, SO<NUM>, CO<NUM> and <NUM> or <NUM> when A is N, x is an integer of <NUM>-<NUM>, and the product of n times x times m (n. x) is <NUM> -<NUM>, and R<NUM> is a member selected from
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and sulfonates and sulfates of each of the members of said group, wherein R<NUM> is H, C≤<NUM>-alkyl or carboxy-terminated C≤<NUM>-alkyl, j and k are OH, OM or OR<NUM> wherein M is a cation moiety of an alkali metal, an alkaline earth metal, transition metal, e.g., nickel, etc. or ammonium, and R<NUM> is C≤<NUM>-alkyl.

Examples of the oligomeric constituent include oligomeric constituents selected from (i) oligomers comprising at least three monomers, or repeating units, selected from C<NUM>-<NUM>-alkyleneoxy, glycidol, and glycidyl, (ii) aromatic or aliphatic oligomeric esters conforming to structure (I)
<CHM>
and (iii) combinations of (i) and (ii). In structure (I), R<NUM> and R<NUM> are independently selected from H and C<NUM>-<NUM>-alkyl, f is an integer of <NUM>-<NUM>, and g is any positive integer or fraction of <NUM>-<NUM>. As will be understood by those of ordinary skill in the art, suitable values for g include both integers and fractions because the length of the oligomeric constituent on the individual polymeric colorant molecules may vary. Thus, the value for g represents an average length of the ester chain for a given sample or collection of polymeric colorant molecules. In certain embodiments, the polymeric colorant can comprise one or more oligomeric constituents consisting of three or more ethylene oxide monomer groups.

Exemplary polymeric colorants include Liquitint® polymeric colorants, Cleartint® polymeric liquid concentrate colorants, Reactint® polymeric colorants, and Palmer® polymeric colorants, all of which are available from Milliken Chemical, a division of Milliken & Company of Spartanburg, SC. Liquitint® polymeric colorants are characterized in that they are water soluble, non-staining, colorants. They are widely used in laundry detergents, fabric softeners, and other consumer and industrial cleaning products. Liquitint® polymeric colorants are generally bright liquid colorants which, depending on the specific colorant, exhibit varying degrees of solubility in water. These colorants may also be characterized as being generally compatible with other chemicals present in their end-use formulations and are typically easy to handle. Liquitint® polymeric colorants may be used to provide color in both aqueous and solid systems. The unique polymeric nature of Liquitint® polymeric colorants provides reduced staining to e.g. skin, textiles, hard surfaces, and equipment.

Cleartint® polymeric liquid concentrate colorants are specially designed liquid colorants often used for coloring clarified polypropylene articles. These colorants may be incorporated into polypropylene resins easily without detrimentally affecting the clarity of the article to provide transparent, clear and brightly colored polypropylene articles. Cleartint® liquid concentrate polymeric colorants are oligomeric coloring materials which combine the exceptional aesthetics of dyes with the migration resistance of pigments. These colorants may be used as light tints to mask residual haze, or they may be used for deep, rich shades that are not possible with pigment colorants. Cleartint® liquid concentrate polymeric colorants allow clarified polypropylene to rival the beauty of higher cost plastic materials. The technical and physical property benefits of clarified polypropylene may be exploited without sacrificing product aesthetics.

Reactint® polymeric colorants are liquid polymeric colorants useful for coloring polyurethane and other thermoset resins. These colorants are reactive polymeric colorants that consist of chromophores which are chemically bound to polyols. This arrangement allows the polymeric colorant to react into the polyurethane polymer matrix. Unlike pigment pastes, which are dispersions of solid particles in a liquid, Reactint® polymeric colorants are <NUM>% homogeneous liquids that are soluble in polyol and will not settle over time. Because of this pure liquid and easy to disperse nature, it is possible to blend Reactint® colorants in-line and on-the-fly, while producing polyurethane foams and resins.

Palmer® polymer colorants are liquid colorants specially developed for use in washable applications, such as in markers, paints and other art products. They contain no heavy metals, are non-toxic, and have excellent non-staining properties on skin, fabric and other surfaces. Palmer® polymeric colorants have very good compatibility with aqueous ink formulations and provide bright colors.

There are several elements that need to be controlled in order to successfully produce the occult particles of the present invention. Aspects of the "cut color" made by combining "pure color," with a "solvent/solvent system" for example, can significantly impact successful production of occult particles. Applicants have made two unexpected and non-obvious observations in this regard:.

Consider the following illustrative/non-limiting example: a <NUM>% pure color (having a color value or CV of <NUM>) loading of a coloring agent on bentonite powder can be achieved in one of two ways:.

Both Method <NUM> and <NUM> result in bentonite powder with the same number of pure color molecules per unit weight of carrier material. However, Method <NUM> will produce a carrier-coloring agent composite that is visually less colored than the carrier-coloring agent composite of Method <NUM>.

A suitable solvent or solvent system dissolves enough pure color to produce a solution or "cut color" having at least <NUM> wt% of pure color and includes mixtures of solvents. Examples of suitable solvents include diols (such as ethylene glycol, propylene glycol, and dipropylene glycol), triols, ethers, esters (such as propylene carbonate), polyethers (such as polyethylene glycol, e.g. PEG <NUM>; and polypropylene glycol), polyols (such as monomeric, polymeric polyols, polyether polyols, and polyester polyols), glycol ethers (such as dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, and dipropylene glycol dimethyl ether), cyclic ureas (such as <NUM>,<NUM>-dimethyl-<NUM>-imidazolidinone, and <NUM>,<NUM>-dimethyl-<NUM>,<NUM>,<NUM>,<NUM>-tetrahydro-<NUM> (<NUM>)-pyrimidinone), lactams (such as N-methyl-<NUM>-pyrrolidone and other dipolar non-hydrogen bond donors), fatty acids (such as oleic acid and the like), polyesters, polycarbonates, polyaspartics, amides, hydrocarbons, water, aqueous solutions, halogenated solvents, triglycerides (such as vegetable oil) and amines (with the exception of tertiary aromatic amines) and mixtures thereof.

It is understood that the final choice of CV for the cut color will be a function of a variety of factors such as long term stability of cut color, ease of handling (e.g. viscosity) and other requirements.

The addition of at least one diluent to the cut color prior to application onto the carrier material can significantly aid the production of occult particles.

Thus, in one aspect, a <NUM>% pure color (having a color value or CV of <NUM>) loading of a coloring agent on bentonite powder can be achieved in one of two ways:.

If the same processing steps are followed for Methods <NUM> and <NUM>, then a relative parameter that quantifies the effectiveness of diluents at facilitating production of occult particles can be formulated as "R. " R = (wt% total coloring agent in ><NUM> fractions for Method <NUM>) / (wt% total coloring agent in ><NUM> fractions for Method <NUM>). Note <NUM>: this parameter is valid only if the same "cut color" with the same CV is used to produce the carrier-coloring agent composites in methods <NUM> and <NUM>. Note <NUM>: the "cut color" is not constrained to have CV = <NUM>. The definition of R holds for any CV of the "cut color" so long as Note <NUM> is satisfied.

In this regard, Applicants have observed the following:
Suitable diluents are molecules of mixtures of molecules for which R > <NUM> when mixed with cut color in a <NUM>:<NUM> ratio and are selected from glycerol, propylene carbonate, ethylene glycol, and mixtures thereof.

The coloring agent plus solvent plus diluent mixture may additionally contain one or more of the following: inorganic or organic salts, surfactants, hydrotopes, rheology modifiers, surface tension modifiers, wetting agents, film formers and plasticizers. For example, adding potassium chloride to water can alter the distribution of coloring agent on the various size fractions of the carrier-coloring agent composite. Also, salts can induce aggregation of dyes, and influence solution phase behavior of polymeric colorants. Emulsifying agents may also be included as an optional additive.

Inclusion of film formers can inhibit bleeding. The bleed inhibitory performance of film formers may be enhanced or improved by the inclusion of suitable plasticizers. Cases may arise where the diluent and/or solvent itself may function as a plasticizer for the film former. A non-limiting example would be the use of PEG <NUM> as a solvent, water a diluent and polyvinyl alcohol as film former, wherein the polyvinyl alcohol is present in a dissolved state in the diluent.

Non-limiting examples of film formers include vinyl alcohol homopolymers (such as polyvinyl alcohol) and copolymers (such as vinyl amine/vinyl alcohol copolymers, and vinyl pyrrolidone/vinyl alcohol copolymers), vinyl acetate homopolymers (such as polyvinyl acetate) and copolymers (such as vinyl acetate/crotonic acid copolymers, and vinyl acetate/vinyl laurate copolymers), vinyl pyrrolidone homopolymers (such as polyvinyl pyrrolidone) and copolymers (such as vinyl pyrrolidone/vinyl acetate copolymers, vinyl pyrrolidone/styrene copolymers, vinyl pyrrolidone/n-vinyl caprolactam copolymers), nitrocellulose, cellulose ethers (such as carboxymethyl cellulose, methyl cellulose, hydroxyethylcellulose, hydroxylpropyl cellulose, ethylcellulose, ethyl hydroxyethylcellulose, methyl hydroxyethyl cellulose, and hydroxyalkyl methylcellulose), cellulose esters (such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate phthalate), sulfopolyesters (such as Eastman AQ polymers), proteins (such as gelatin, whey protein, collagen and the like), polysaccharides (such as starch, modified starches, maltodextrin, chitosan, and chitosan salts), poly(meth)acrylates, copolymers of methacrylate esters ammoniated, copolymers of ethyl acrylate and methyl methacrylate, poly (methyl methacrylate), acrylics (such as styrene acrylics, e.g. Joncryl resins from BASF), ethylene vinyl acetate copolymers, ethylene vinyl acetate copolymers and mixtures thereof. It is understood that polyvinyl alcohol homopolymers are water soluble resins manufactured by polymerizing vinyl acetate and hydrolyzing the resultant polymer to produce the alcohol. It is also understood that polyvinyl alcohols with different molecular weights and % hydrolysis are available. "X% hydrolysis" means x mole% vinyl alcohol and <NUM>-x mole % vinyl acetate.

Non-limiting examples of plasticizers include polyethylene glycols, polyalkylene glycol, polypropylene glycol, sorbitol, sorbitol acetate, glycerol, glycerol ester, dibutyl sebacate, diethyl phthalate, dioctyl adipate, triethyl citrate, acetyl triethyl citrate, tributyl citrate, tributyl acetyl citrate, monostearylcitrate, soy lecithin, dipropylene glycol dibenzoate, diethylene glycol dibenzoate, dibutyl phthalate, benzyl butyl phthalate, ethylene carbonate, triacetin, ethylene glycols and derivatives, propylene glycols and derivatives, polyhydric alcohols, lactone modified polyvinyl alcohol, polyols, triethanolamine, diethylene glycol, dipropylene glycol, succinate polyesters, polyesters of polyethylene glycol and adipic or succinic acid, starch, polyvinyl alcohol, epoxidized soybean oil, sunflower oil, triethyl citrate, water, oleic acid, citric acid, propylene carbonate, stearic acid, sucrose, vegetable oils, mineral oils, phosphates, fatty acid esters, castor oil, mannitol, and mixtures thereof.

A hydrotope is a molecule that increases the solubility in water of some molecule that is insufficiently water-soluble. Non-limiting examples of hydrotopes include salts of xylene sulfonic acid, toluene sulfonic acid and cumene sulfonic acid.

Additional optional additives that may be included in the occult particles include perfumes, pigments, enzymes, bleach activators, bleaches, bleach catalysts, bleach stabilizers, foam regulators (foam boosters and antifoam agents), fluorescent whitening agents, soil repellents, corrosion inhibitors, soil antiredeposition agents, soil release agents, dye transfer inhibitors, builders, complexing agents, ion exchangers, buffering agents, and mixtures thereof. Bleed inhibitors such as film forming polymers or polymeric coatings may also be included. These additives may be included as one or more additional components comprising the occult particle, in addition to the coloring agent and the clay carrier.

As has been previously described, several elements need to be controlled in order to successfully produce occult particles including choice of solvent system and choice of diluent.

The general process steps for making the occult particle of the present invention include the following:.

Additives such as salts, surfactants, hydrotopes, rheology modifiers, surface tension modifiers, wetting agents, film formers and plasticizers may be included (as part of the solvent, diluent or both) or may be added in steps (a) and (b). Additional steps such as application of a barrier coating onto the occult particles may also be included. The temperature at which the various steps are carried out may be controlled so as to deliver or keep components in desired states of matter or to drive off solvents or control moisture levels or water content.

It is understood that Step (b) may also be useful in imparting greater bleed resistance to the occult particles (For details see Experiment <NUM>). It is also understood that the term "carrier material-cut color composite" or "carrier material-coloring agent composite," and similar, refers to the substance that results from step (d) as well.

The general methods for preparing the occult particle described herein may not be construed as limiting the scope of the present invention. There may exist additional methods, by way of alternative processing methods, to combine the carrier material and coloring agent to produce an occult particle that is indiscernible in a non-colored detergent composition, as well as other desired features, as the occult particles produced by the general methods described herein and by their equivalent methods as known to those skilled in the art.

The occult particles described in the present specification may be incorporated into a laundry care composition including but not limited to laundry detergents, laundry aids, and fabric care compositions. Such compositions comprise one or more of the occult particles and a laundry care ingredient.

The laundry care compositions including laundry detergents may be in solid or liquid form, including a gel form. The laundry care compositions including laundry detergents may also be in a unit dose pouch. The solid form of the laundry care compositions include, for example, compositions comprised of granules, powder, or flakes. For instance, the occult particles of the present invention may be added to powdered laundry detergent compositions.

The occult particles may be present in a laundry detergent composition in an amount of <NUM>-<NUM> wt%, <NUM>-<NUM> wt%, and even <NUM>-<NUM> wt% of the composition.

The laundry detergent composition typically comprises a surfactant in an amount sufficient to provide desired cleaning properties. In one embodiment, the laundry detergent composition comprises, by weight, <NUM>-<NUM>%, more specifically <NUM>-<NUM>%, and even more specifically <NUM>-<NUM>% of the surfactant. The surfactant may comprise anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.

Laundry aids include, for example, those as described in "<NPL>.

Fabric care compositions are typically added in the rinse cycle, which is after the detergent solution has been used and replaced with the rinsing solution in typical laundering processes. The fabric care compositions disclosed herein may be comprise a rinse added fabric softening active and one or more occult particles as disclosed in the present specification. The fabric care composition may comprise, based on total fabric care composition weight, <NUM>-<NUM>%, or <NUM>-<NUM>% fabric softening active. The occult particles may be present in the fabric care composition in an amount of <NUM> ppb to <NUM> ppm, or <NUM>-<NUM> ppm.

While not essential for the purposes of the present invention, the non-limiting list of laundry care ingredients illustrated hereinafter are suitable for use in the laundry care compositions and may be desirably incorporated in certain aspects of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with e.g. perfumes, colorants, or dyes. It is understood that such ingredients are in addition to the components that were previously listed for any particular aspect. The total amount of such adjuncts may range, once the amount of dye is taken into consideration <NUM>-<NUM> wt% of the laundry care composition.

The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Examples of suitable laundry care ingredients include fabric softening actives, polymers, for example cationic polymers, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in <CIT>, <CIT>and <CIT>.

As stated, the laundry care ingredients are not essential to Applicants' laundry care compositions. Thus, certain embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/antiredeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below:
Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C<NUM>-<NUM>-alkyl benzene sulfonic acids, preferably C<NUM>-<NUM>-alkyl benzene sulfonic acids. Preferably the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described for example in <CIT> and <CIT>. Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is <NUM>-<NUM>. Sodium C<NUM>-<NUM>, e.g., C<NUM>, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'--O--(C<NUM>H<NUM>O)n--SO<NUM>M wherein R' is C<NUM>-<NUM>-alkyl, n is <NUM>-<NUM>, and M is a salt-forming cation. In a specific embodiment, R' is C<NUM>-<NUM>-alkyl, n is <NUM>-<NUM>, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is C<NUM>-<NUM>, n is <NUM>-<NUM> and M is sodium.

The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=<NUM>. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present. Specific examples of non-alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C<NUM>-<NUM>-fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: ROSO<NUM>-M+ wherein R is typically linear C<NUM>-<NUM>-hydrocarbyl, which may be straight chain or branched chain, and M is a water-solubilizing cation. In specific embodiments, R is C<NUM>-<NUM>-alkyl, and M is alkali metal, more specifically R is C<NUM>-<NUM>- and M is sodium.

Specific, non-limiting examples of anionic surfactants useful herein include: a) C<NUM>-<NUM>-alkyl benzene sulfonates (LAS); b) C<NUM>-C<NUM> primary, branched-chain and random alkyl sulfates (AS); c) C<NUM>-<NUM>- secondary (<NUM>,<NUM>) alkyl sulfates; d) C<NUM>-<NUM>-alkyl alkoxy sulfates (AExS) wherein preferably x is <NUM>-<NUM>; e) C<NUM>-<NUM>-alkyl alkoxy carboxylates preferably comprising <NUM>-<NUM> ethoxy units; f) mid-chain branched alkyl sulfates as discussed in <CIT> and <CIT>; g) mid-chain branched alkyl alkoxy sulfates as discussed in <CIT> and <CIT>; h) modified alkylbenzene sulfonate (MLAS) as discussed in <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>; i) methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.

Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials of the formula: R<NUM>(CmH<NUM>O)nOH wherein R<NUM> is C<NUM>-<NUM>-alkyl, m is <NUM>-<NUM>, and n is <NUM>-<NUM>. Preferably R<NUM> is primary or secondary C<NUM>-<NUM>-alkyl, more preferably C<NUM>-<NUM>-alkyl. In one embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials that contain <NUM>-<NUM>,, more preferably <NUM>-<NUM> or even <NUM>-<NUM> ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) of <NUM>-<NUM>, more preferably <NUM>-<NUM>, most preferably <NUM>-<NUM>. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the trade names Neodol and Dobanol by the Shell Chemical Company.

Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are materials which are often referred to in the art as "semi-polar" nonionics. Amine oxides have the formula: R(EO)x(PO)y(BO)zN(O)(CH<NUM>R')<NUM>. In this formula, R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain <NUM>-<NUM>, preferably <NUM>-<NUM> carbon atoms, and is more preferably primary C<NUM>-<NUM>-alkyl. R' is a short-chain moiety, preferably selected from hydrogen, methyl and --CH<NUM>OH. When x+y+z is different from <NUM>, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C<NUM>-<NUM> - alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C<NUM>-<NUM>-alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C<NUM>-<NUM>-alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C<NUM>-<NUM>-alcohol and C<NUM>-<NUM>-alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; d) mid-chain branched C<NUM>-<NUM>-alcohols, BA, as discussed in <CIT>; e) mid-chain branched C<NUM>-<NUM>-alkyl alkoxylates, BAEx, wherein x if <NUM>-<NUM>, as discussed in <CIT>, <CIT> and <CIT>; f) Alkylpolysaccharides as discussed in <CIT>; specifically alkylpolyglycosides as discussed in <CIT> and <CIT>; g) Polyhydroxy fatty acid amides as discussed in U<CIT>, <CIT>, <CIT>, <CIT>, and <CIT>; and h) ether capped poly(oxyalkylated) alcohol surfactants as discussed in <CIT> and <CIT>.

In the laundry detergent compositions herein, the detersive surfactant component may comprise combinations of anionic and nonionic surfactant materials. When this is the case, the weight ratio of anionic to nonionic will typically be (<NUM>:<NUM>)-(<NUM>:<NUM>), more typically (<NUM>:<NUM>)-(<NUM>:<NUM>). In general compositions with increasing weight ratios favoring nonionic surfactants may lead to increased deposition of the inventive occult particles in a wash. Such factors must always be carefully weighed over against any risk elements that may also increase in these formulations. The ordinarily-skilled artisan is well aware of such factors and formulates accordingly.

Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to <NUM> carbon atoms. Additional examples include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed inUS <NUM>,<NUM>,<NUM>; b) dimethyl hydroxyethyl quaternary ammonium as discussed inUS <NUM>,<NUM>,<NUM>; c) polyamine cationic surfactants as discussed in <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>; d) cationic ester surfactants as discussed in <CIT>, <CIT>, <CIT> and <CIT>; and e) amino surfactants as discussed in<CIT> and <CIT>, specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See <CIT>at column <NUM>, line <NUM> through column <NUM>, line <NUM>, for examples of zwitterionic surfactants; betaine, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, C<NUM>-<NUM>- (preferably C<NUM>-<NUM>-) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-<NUM>-propane sulfonate where the alkyl group can be C<NUM>-<NUM>-, preferably C<NUM>-<NUM>-.

Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents comprises at least <NUM>, typically <NUM>-<NUM> carbon atoms, and at least one comprises an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See <CIT> at column <NUM>, lines <NUM>-<NUM>, for examples of ampholytic surfactants.

As noted, the compositions may be in the form of e.g. a solid, either in tablet or particulate form, including particles or flakes, or in the form of a liquid. The liquid detergent compositions comprise an aqueous, non-surface active liquid carrier. Generally, the amount of the aqueous, non-surface active liquid carrier employed in the compositions herein will be effective to solubilize, suspend or disperse the composition components. For example, the compositions may comprise, by weight, <NUM>-<NUM>%, more specifically <NUM>-<NUM>%, and even more specifically <NUM>-<NUM>% of the aqueous, non-surface active liquid carrier.

The most cost effective type of aqueous, non-surface active liquid carrier is, of course, water itself. Accordingly, the aqueous, non-surface active liquid carrier component will generally be mostly, if not completely, comprised of water. While other types of water-miscible liquids, such alkanols, diols, other polyols, ethers, and amines, have been conventionally been added to liquid detergent compositions as co-solvents or stabilizers, for purposes of the present invention, the utilization of such water-miscible liquids should be minimized to hold down composition cost. Accordingly, the aqueous liquid carrier component of the liquid detergent products herein will generally comprise water present in concentrations of <NUM>-<NUM>%, more preferably <NUM>-<NUM>%, by weight of the composition.

Detergent compositions may also contain bleaching agents. Suitable bleaching agents include, for example, hydrogen peroxide sources, such as those described in detail in the herein incorporated <NPL> "Bleaching Agents (Survey). " These hydrogen peroxide sources include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms of these compounds.

The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Also useful are sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.

A suitable percarbonate bleach comprises dry particles having an average particle size of <NUM>-<NUM>,<NUM>, not more than <NUM> wt% of said particles being smaller than <NUM> and not more than <NUM> wt% of said particles being larger than <NUM>,<NUM>. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Compositions of the present invention may also comprise as the bleaching agent a chlorine-type bleaching material. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less preferred for compositions which comprise enzymes.

Preferred activators are selected from tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), <NUM>-nitrobenzoylcaprolactam, <NUM>-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C<NUM>-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C<NUM>-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of <NUM>-<NUM> are those selected having an OBS or VL leaving group. Examples of preferred hydrophobic bleach activators include nonanoyloxybenzenesulphonate (NOBS); <NUM>-[N-(nonanoyl) amino hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS), an example of which is described inUS <NUM>,<NUM>,<NUM>; dodecanoyloxybenzenesulphonate (LOBS or C<NUM>-OBS); <NUM>-undecenoyloxybenzenesulfonate (UDOBS or C<NUM>-OBS with unsaturation in the <NUM> position); and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; and <CIT>, and copending Patent Application Serial No. <CIT>.

The mole ratio of peroxygen source (as AvO) to bleach activator in the present invention generally ranges from at least <NUM>:<NUM>, preferably from <NUM>:<NUM>, more preferably from <NUM>:<NUM> to <NUM>:<NUM>, preferably to <NUM>:<NUM>.

Quaternary substituted bleach activators may also be included. The present laundry compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP, preferably a quaternary substituted percarboxylic acid or a quaternary substituted peroxyimidic acid); more preferably, the former. Preferred QSBA structures are further described in <CIT>; <CIT>; <CIT>; <CIT>; and <CIT>.

Highly preferred bleach activators useful herein are amide-substituted as described in <CIT>; <CIT>; and <CIT>. Preferred examples of such bleach activators include: (<NUM>-octanamidocaproyl) oxybenzenesulfonate, (<NUM>-nonanamidocaproyl)oxybenzenesulfonate, (<NUM>-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof.

Other useful activators are disclosed in <CIT>; <CIT>; and <CIT>, and in <CIT>. These activators include benzoxazin-type activators, such as a C<NUM>H<NUM> ring to which is fused in the <NUM>,<NUM>-positions a moiety --C(O)OC(R<NUM>)=N-.

Nitriles, such as acetonitriles and/or ammonium nitriles and other quaternary nitrogen containing nitriles, are another class of activators that are useful herein. Non-limiting examples of such nitrile bleach activators are described in <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>, <CIT>, <CIT>, <CIT>; <CIT>, <CIT>, and <CIT>.

Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems having an in-use pH of <NUM>-<NUM>, preferably <NUM>-<NUM>. Typically, for example, activators with electron-withdrawing moieties are used for near-neutral or sub-neutral pH ranges. Alkalis and buffering agents can be used to secure such pH.

Acyl lactam activators, as described in <CIT>; <CIT> and <CIT> are very useful herein, especially the acyl caprolactams (see for example <CIT>) and acyl valerolactams (see <CIT>).

(b) Organic Peroxides, especially Diacyl Peroxides - These are extensively illustrated in <NPL> at pages <NUM>-<NUM> and especially at pages <NUM>-<NUM>. If a diacyl peroxide is used, it will preferably be one which exerts minimal adverse impact on fabric care, including color care.

(c) Metal-Containing Bleach Catalysts - The compositions and methods of the present invention can also optionally include metal-containing bleach catalysts, preferably manganese and cobalt-containing bleach catalysts.

One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity (such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations), an auxiliary metal cation having little or no bleach catalytic activity (such as zinc or aluminum cations), and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in <CIT>.

Manganese Metal Complexes - If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; and <CIT>. Preferred examples of these catalysts include MnIV<NUM>(u-O)<NUM>(<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane)<NUM>(PF<NUM>)<NUM>, MnIII<NUM>(u-O)<NUM>(u-OAc)<NUM>(<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane)<NUM>(ClO<NUM>)<NUM>, MnIV<NUM>(u-O)<NUM>(<NUM>,<NUM>,<NUM>-triazacyclononane)<NUM>(ClO<NUM>)<NUM>, MnIIIMnIV<NUM>(u-O)<NUM>(u-OAc)<NUM>-(<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane)<NUM>(ClO<NUM>)<NUM>, MnIV(<NUM>,<NUM>,<NUM>-trimethyl-<NUM>,<NUM>,<NUM>-triazacyclononane)- (OCH<NUM>)<NUM>(PF<NUM>), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in <CIT> and <CIT>. The use of manganese with various complex ligands to enhance bleaching is also reported in <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; and <CIT>.

Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are described, for example, in <CIT>; <CIT>; and <CIT>; and <NPL>. The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH<NUM>)<NUM>OAc] Ty, wherein "OAc" represents an acetate moiety and "Ty" is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH<NUM>)<NUM>OAc]Cl<NUM> as well as [Co(NH<NUM>)<NUM>OAc](OAc)<NUM>; [Co(NH<NUM>)<NUM>OAc](PF<NUM>)<NUM>; [Co(NH<NUM>)<NUM>OAc](SO<NUM>); [Co-(NH<NUM>)<NUM>OAc](BF<NUM>)<NUM>; and [Co(NH<NUM>)<NUM>OAc](NO<NUM>)<NUM> (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such as taught for example in <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; and <CIT>; in the Tobe article and the references cited therein; and in <CIT>; <NPL>; <NPL>; <NPL>); <NPL>); <NPL>); <NPL>); and <NPL>).

Transition Metal Complexes of Macropolycyclic Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycyclic rigid ligand. The amount used is a catalytically effective amount, suitably <NUM> ppb or more, , preferably <NUM>-<NUM> ppm (wherein "ppb" denotes parts per billion by weight and "ppm" denotes parts per million by weight).

Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are suitable for use in the invention compositions can in general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or laundry uses, and are non-limitingly illustrated by any of the following:.

As a practical matter, and not by way of limitation, the compositions and methods herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the composition comprising a lipophilic fluid and a bleach system, and will preferably provide <NUM>-<NUM> ppm, more preferably <NUM>-<NUM> ppm, and most preferably <NUM>-<NUM> ppm, of the bleach catalyst species in the composition comprising a lipophilic fluid and a bleach system.

(d) Bleach Boosting Compounds - The compositions herein may comprise one or more bleach boosting compounds. Bleach boosting compounds provide increased bleaching effectiveness in lower temperature applications. The bleach boosters act in conjunction with conventional peroxygen bleaching sources to provide increased bleaching effectiveness. This is normally accomplished through in situ formation of an active oxygen transfer agent such as a dioxirane, an oxaziridine, or an oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines and oxaziridiniums may be used.

Among suitable bleach boosting compounds for use in accordance with the present invention are cationic imines, zwitterionic imines, anionic imines and/or polyionic imines having a net charge of from about +<NUM> to about -<NUM>, and mixtures thereof. These imine bleach boosting compounds of the present invention include those of the general structure:
<CHM>
where R<NUM>-R<NUM> may be H or an optionally substituted radical selected from phenyl, aryl, heterocyclyl, alkyl and cycloalkyl.

Among preferred bleach boosting compounds are zwitterionic bleach boosters, which are described in <CIT> and <CIT>. Other bleach boosting compounds include cationic bleach boosters described in <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>; <CIT>, <CIT>, and <CIT>.

Peroxygen sources are well-known in the art and the peroxygen source employed in the present invention may comprise any of these well-known sources, including peroxygen compounds as well as compounds, which under consumer use conditions, provide an effective amount of peroxygen in situ. The peroxygen source may include a hydrogen peroxide source, the in situ formation of a peracid anion through the reaction of a hydrogen peroxide source and a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources. Of course, one of ordinary skill in the art will recognize that other sources of peroxygen may be employed without departing from the scope of the invention. The bleach boosting compounds, when present, are preferably employed in conjunction with a peroxygen source in the bleaching systems of the present invention.

(e) Preformed Peracids - Also suitable as bleaching agents are preformed peracids. The preformed peracid compound as used herein is any convenient compound which is stable and which under consumer use conditions provides an effective amount of peracid or peracid anion. The preformed peracid compound may be selected from percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Examples of these compounds are described in <CIT>.

One class of suitable organic peroxycarboxylic acids have the general formula:
<CHM>
wherein R is optionally substituted C<NUM>-<NUM>-alkylene or optionally substituted phenylene, and Y is H, halogen, alkyl, aryl, -C(O)OH or -C(O)OOH.

Organic peroxyacids suitable for use in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:
<CHM>
wherein Y can be, for example, H, CH<NUM>, CH<NUM>Cl, C(O)OH, or C(O)OOH; and n is an integer of <NUM>-<NUM>. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:
<CHM>
wherein Y can be, for example, H, alkyl, alkylhalogen, halogen, C(O)OH or C(O)OOH.

Typical monoperoxy acids useful herein include alkyl and aryl peroxyacids such as:.

Typical diperoxyacids useful herein include alkyl diperoxyacids and aryldiperoxyacids, such as:.

Such bleaching agents are disclosed in <CIT>, <CIT>; <CIT>; and <CIT>. Sources also include <NUM>-nonylamino-<NUM>-oxoperoxycaproic acid as described in <CIT>. Persulfate compounds such as for example OXONE, manufactured commercially by E. DuPont de Nemours of Wilmington, DE can also be employed as a suitable source of peroxymonosulfuric acid. PAP is disclosed in, for example, <CIT>; <CIT>; <CIT>; <CIT> and <CIT>.

(f) Photobleaches - Suitable photobleaches for use in the treating compositions of the present invention include, but are not limited to, the photobleaches described in <CIT> and <CIT>.

(g) Enzyme Bleaching - Enzymatic systems may be used as bleaching agents. The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in <CIT>.

The present invention compositions and methods may utilize alternative bleach systems such as ozone, chlorine dioxide and the like. Bleaching with ozone may be accomplished by introducing ozone-containing gas having ozone content of <NUM>-<NUM>/m<NUM> into the solution that is to contact the fabrics. The gas:liquid ratio in the solution should be maintained at (<NUM>:<NUM>)-(<NUM>:<NUM>). <CIT> describes a process for the utilization of ozone as an alternative to conventional bleach systems and is herein incorporated by reference.

The detergent compositions of the present invention may also include any number of additional optional ingredients. These include conventional laundry detergent composition components such as non-tinting dyes, detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and/or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibiting agents, opacifying agents, optical brighteners, perfumes and coloring agents. The various optional detergent composition ingredients, if present in the compositions herein, should be utilized at concentrations conventionally employed to bring about their desired contribution to the composition or the laundering operation. Frequently, the total amount of such optional detergent composition ingredients can be <NUM>-<NUM>%, more preferably <NUM>-<NUM>%, by weight of the composition.

The liquid detergent compositions are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, occult particle, and certain optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the liquid alcohol ethoxylate nonionic, the aqueous liquid carrier, and any other normally liquid optional ingredients. Such a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity of <NUM>-<NUM> cps, more preferably <NUM>-<NUM> cps. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #<NUM> spindle.

The liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition. In a preferred process for preparing such compositions, a liquid matrix is formed containing at least a major proportion, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination. For example, rapid stirring with a mechanical stirrer may usefully be employed. While shear agitation is maintained, substantially all of any anionic surfactants and the solid form ingredients can be added. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid-form materials have been added to this agitated mixture, particles of any enzyme material to be included, e.g., enzyme prills, are incorporated. As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After addition of all of the composition components, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for <NUM>-<NUM> minutes.

In an alternate embodiment for forming the liquid detergent compositions, the occult particle is first combined with one or more liquid components to form an occult particle premix, and this occult particle premix is added to a composition formulation containing a substantial portion, for example more than <NUM> wt%, more specifically, more than <NUM> wt%, and yet more specifically, more than <NUM> wt%, of the balance of components of the laundry detergent composition. For example, in the methodology described above, both the occult particle premix and the enzyme component are added at a final stage of component additions. In a further embodiment, the occult particle is encapsulated prior to addition to the detergent composition, the encapsulated occult particle is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the balance of components of the laundry detergent composition.

As noted previously, the detergent compositions may be in a solid form. Suitable solid forms include tablets and particulate forms, for example, granular particles or flakes. Various techniques for forming detergent compositions in such solid forms are well known in the art and may be used herein. In one embodiment, for example when the composition is in the form of a granular particle, the occult particle is provided in particulate form, optionally including additional but not all components of the laundry detergent composition. The occult particle is combined with one or more additional particulates containing a balance of components of the laundry detergent composition. Further, the occult particle, optionally including additional but not all components of the laundry detergent composition, may be provided in an encapsulated form, and the occult particle encapsulate is combined with particulates containing a substantial balance of components of the laundry detergent composition.

The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering of fabrics. Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form <NUM>-<NUM>,<NUM> ppm of composition in aqueous washing solution. More preferably, <NUM>,<NUM>-<NUM>,<NUM> ppm of the detergent compositions herein will be provided in aqueous washing solution.

In another specific embodiment, the occult particles of the present invention may be included in a fabric care composition. The fabric care composition may be comprised of at least one occult particle and a rinse added fabric softening composition ("RAFS;" also known as rinse added fabric conditioning compositions). Examples of typical rinse added softening compositions can be found in <CIT>. The rinse added fabric softening compositions of the present invention may comprise (a) fabric softening active and (b) a thiazolium dye. The rinse added fabric softening composition may comprise <NUM>-<NUM> wt%, more preferably <NUM>-<NUM> wt%, of the FSA. The occult particle may be present in the rinse added fabric softening composition in an amount of <NUM> ppb to <NUM> ppm, more preferably <NUM>-<NUM> ppm.

In one embodiment of the invention, the fabric softening active (hereinafter "FSA") is a quaternary ammonium compound suitable for softening fabric in a rinse step. In one embodiment, the FSA is formed from a reaction product of a fatty acid and an aminoalcohol obtaining mixtures of mono-, di-, and, in one embodiment, triester compounds. In another embodiment, the FSA comprises one or more softener quaternary ammonium compounds such, but not limited to, as a monoalkyquaternary ammonium compound, a diamido quaternary compound and a diester quaternary ammonium compound, or a combination thereof.

In one aspect of the invention, the FSA comprises a diester quaternary ammonium (hereinafter "DQA") compound composition. In certain embodiments of the present invention, the DQA compounds compositions also encompasses a description of diamido FSAs and FSAs with mixed amido and ester linkages as well as the aforementioned diester linkages, all herein referred to as DQA.

A first type of DQA ("DQA (<NUM>)") suitable as a FSA in the present CFSC includes a compound comprising the formula:.

{R<NUM>-m - N+ - [(CH<NUM>)n - Y - R<NUM>]m} X-.

wherein each R substituent is either H, a short chain C<NUM>-<NUM>-, preferably C<NUM>-<NUM>-alkyl or - hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, and hydroxyethyl, poly (C<NUM>-<NUM>alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; each m is <NUM> or <NUM>; each n is <NUM>-<NUM>, preferably <NUM>; each Y is -O-(O)C-, -C(O)-O-, -NR-C(O)-, or -C(O)-NR- and it is acceptable for each Y to be the same or different; the sum of carbons in each R<NUM>, plus one when Y is -O-(O)C- or -NR-C(O) -, is C<NUM>-<NUM>-, preferably C<NUM>-<NUM>, with R<NUM> each independently being optionally substituted hydrocarbyl; it is acceptable for R<NUM> to be unsaturated or saturated and branched or linear and preferably it is linear; and each R<NUM> preferably are the same; and X- can be any softener-compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, and nitrate, more preferably chloride or methyl sulfate. Preferred DQA compounds are typically made by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials that typically result from such reactions include N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium methylsulfate wherein the acyl group is derived from animal fats, unsaturated, and polyunsaturated, fatty acids, e.g., tallow, hardened tallow, oleic acid, and/or partially hydrogenated fatty acids, derived from vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, and palm oil.

Non-limiting examples of suitable fatty acids are listed in <CIT> at column <NUM>, lines <NUM>-<NUM>. In one embodiment, the FSA comprises other actives in addition to DQA (<NUM>) or DQA. In yet another embodiment, the FSA comprises only DQA (<NUM>) or DQA and is free or essentially free of any other quaternary ammonium compounds or other actives. In yet another embodiment, the FSA comprises the precursor amine that is used to produce the DQA.

In another aspect of the invention, the FSA comprises a compound, identified as DTTMAC comprising the formula:.

wherein each m is <NUM> or <NUM>, each R<NUM> is a C<NUM>-<NUM>, preferably C<NUM>-<NUM>, but no more than one being less than C<NUM> and then the other is at least C<NUM>, hydrocarbyl, or substituted hydrocarbyl substituent, preferably C<NUM>-<NUM>-alkyl or -alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as "alkylene"), most preferably C<NUM>-<NUM>-alkyl or -alkenyl, and branched or unbranched. In one embodiment, the Iodine Value (IV) of the FSA is from <NUM>-<NUM>; each R is H or a short chain C<NUM>-<NUM>-, preferably C<NUM>-<NUM>-alkyl or -hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, and hydroxyethyl, benzyl, or (R<NUM> O)<NUM>-<NUM>H where each R<NUM> is C<NUM>-<NUM>-alkylene; and A- is a softener compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or nitrate; more preferably chloride or methyl sulfate.

Examples of these FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts such as ditallowdimethylammonium and ditallowdimethylammonium methylsulfate. Examples of commercially available dialkylenedimethylammonium salts usable in the present invention are di-hydrogenated tallow dimethyl ammonium chloride and ditallowdimethyl ammonium chloride available from Degussa under the trade names Adogen® <NUM> and Adogen® <NUM> respectively. In one embodiment, the FSA comprises other actives in addition to DTTMAC. In yet another embodiment, the FSA comprises only compounds of the DTTMAC and is free or essentially free of any other quaternary ammonium compounds or other actives.

In one embodiment, the FSA comprises an FSA described in <CIT>, paragraphs <NUM>-<NUM>. In another embodiment, the FSA is one described in <CIT> , paragraphs <NUM>-<NUM>; or <CIT>, column <NUM>, line <NUM> et seq. detailing an "esterquat" or a quaternized fatty acid triethanolamine ester salt.

In one embodiment, the FSA is chosen from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof.

In one embodiment, the FSA may also include amide containing compound compositions. Examples of diamide comprising compounds may include but not limited to methyl-bis(tallowamidoethyl)-<NUM>-hydroxyethylammonium methyl sulfate (available from Degussa under the trade names Varisoft <NUM> and Varisoft <NUM>). An example of an amide-ester containing compound is N-[<NUM>-(stearoylamino)propyl]-N-[<NUM>-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.

Another specific embodiment of the invention provides for a rinse added fabric softening composition further comprising a cationic starch. Cationic starches are disclosed in <CIT>. In one embodiment, the rinse added fabric softening composition comprises <NUM>-<NUM>% of cationic starch by weight of the fabric softening composition. In one embodiment, the cationic starch is HCP401 from National Starch.

While not essential for the purposes of the present invention, the non-limiting list of laundry care ingredients illustrated hereinafter are suitable for use in the laundry care compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. For example, to obtain other aesthetic colors in a detergent, the present dyes may be mixed with additional dyes or colorants, such as with a blue triphenylmethane dye. It is understood that such ingredients are in addition to the components that were previously listed for any particular embodiment. The total amount of such adjuncts may be <NUM>-<NUM>%, or even <NUM>-<NUM>%, by weight of the laundry care composition.

The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Examples of suitable laundry care ingredients include polymers, for example cationic polymers, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in <CIT>, <CIT> and <CIT>.

As stated, the laundry care ingredients are not essential to Applicants' laundry care compositions. Thus, certain embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/antiredeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below:.

If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in <CIT>.

Cobalt bleach catalysts useful herein are known, and are described, for example, in <CIT> and <CIT>. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in <CIT>, and <CIT>.

Compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand - abbreviated as "MRL". As a practical matter, and not by way of limitation, the compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the benefit agent MRL species in the aqueous washing medium, and may provide <NUM>-<NUM> ppm, <NUM>-<NUM> ppm, or even <NUM>-<NUM> ppm, of the MRL in the wash liquor.

Preferred transition-metals in the instant transition-metal bleach catalyst include manganese, iron and chromium. Preferred MRL's herein are a special type of ultra-rigid ligand that is cross-bridged such as <NUM>,<NUM>-diethyl-<NUM>,<NUM>,<NUM>,<NUM>-tetraazabicyclo[<NUM>. <NUM>]hexa-decane.

Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in <CIT>, and <CIT>.

Certain of the consumer products disclosed herein can be used to clean or treat a situs inter alia a surface or fabric. Typically at least a portion of the situs is contacted with an embodiment of Applicants' consumer product, in neat form or diluted in a liquor, for example, a wash liquor and then the situs may be optionally washed and/or rinsed. In one aspect, a situs is optionally washed and/or rinsed, contacted with an aspect of the consumer product and then optionally washed and/or rinsed. For purposes of the present invention, washing includes but is not limited to, scrubbing, and mechanical agitation. The fabric may comprise most any fabric capable of being laundered or treated in normal consumer use conditions. Liquors that may comprise the disclosed compositions may have a pH of <NUM>-<NUM>. Such compositions are typically employed at concentrations of <NUM>-<NUM>,<NUM> ppm in solution. When the wash solvent is water, the water temperature typically is <NUM>-<NUM> and, when the situs comprises a fabric, the water to fabric ratio is typically f(<NUM>:<NUM>)-(<NUM>:<NUM>). Employing one or more of the aforementioned methods results in a treated situs.

The invention may be further understood by reference to the following examples which are not to be construed as limiting the scope of the present invention.

The following examples were prepared to illustrate that, at equal color loadings and particle size, occult particles prepared according to the methods of the present invention are indiscernible in a non-colored (e.g. white) detergent composition. Furthermore, the occult particles provide a desirable whitening effect to textile substrates treated therewith, yet they do not stain the treated textile substrates. Also, the occult particles of the present invention do not bleed into the surrounding granular detergent composition.

Results: Samples 1B and 1C produced much more intensely colored carrier-coloring agent composite than Samples 1A and 1D. This result supports the theory that tertiary aromatic amine solvents (An5EO and Mtol5EO) are detrimental to hiding of the coloring agent on the clay carrier. Sample 1D supports the theory that primary aromatic amine solvents are not as detrimental to hiding the coloring agent on the clay carrier (AnPEG10 is a primary aromatic amine solvent).

Results: Samples 2A, 2B, 2C and 2D produced carrier-coloring agent composites that progressively exhibited more visual coloration from A through D. The carrier-coloring agent composites prepared with Samples 2A, 2B, 2C and 2D were all lighter in color than the carrier-coloring agent composite prepared with Sample 2F. The carrier-coloring agent composite prepared with Sample 2F was in turn lighter than the one produced with Sample 2E. The carrier-coloring agent composite prepared with Sample 2E exhibited, by far, the most visual coloration. This result supports the theory that the presence of >25wt% of a tertiary aromatic amine solvent is detrimental to hiding of the coloring agent on the clay carrier.

Note <NUM>: Sample 2D contained approximately 22wt% Mtol5EO. (Represents estimated Mtol5EO % in Violet DD + Mtol5EO mixture without water).

Note <NUM>: The carrier-coloring agent composite prepared with Sample 2F represented a borderline case of a colored clay that can produce a relatively uncolored white powdered detergent (or that can successfully hide Violet DD: details in Note <NUM>). Consequently, the carrier-coloring agent composite prepared with Sample 2E (40wt% Mtol5EO) represents a failure to hide Violet DD in the white detergent. The carrier-coloring agent composites prepared with Samples 2A, 2B, 2C and 2D (containing <NUM>. 75wt%, 9wt%, 13wt% and 22wt% Mtol5EO, respectively) are representative of the occult particles of the present invention as they successfully hide the coloring agent on/within the carrier material when the occult particle is visually observed in a non-colored (i.e. white) detergent composition.

Note <NUM>: The carrier-coloring agent composite prepared with Sample 2F was next incorporated into AATCC <NUM> Standard Reference Detergent without Brightener detergent composition at <NUM>. 6wt% and mixed well. Visual assessment of this mixture against a reference of AATCC detergent only showed no obvious color perception on the detergent. The mix of the carrier-coloring agent composite prepared with Sample 2F in the detergent did make the detergent look whiter and exhibited a dE*cmc = <NUM> (The carrier-coloring agent composite prepared with Sample 2F+AATCC vs ref AATCC only).

Thus, the term "substantially indiscernible" as used herein generally refers to a detergent composition containing a carrier-coloring agent composite of the present invention and having a dE*cmc ≤ <NUM>, or even a dE*cmc ≤ <NUM>, or even a dE*cmc ≤ <NUM>, when compared to the detergent composition containing only the carrier material (no coloring agent).

It is understood that spectrophotometric (reflectance) measurements on powders or granules are subject to many sources of variability. One such source of variability is how the granules or powders pack in the measuring container or cuvette. The values quoted above are to be taken as guidelines and not strict limits. Also, the color of the detergent substrate can impact the dE*cmc limit as it pertains to what the human eye perceives as a difference.

Results: The carrier-coloring agent composite prepared with Sample 3A was noticeably lighter than the carrier-coloring agent composite prepared with Sample 3B. The carrier-coloring agent composite prepared with Sample 3B was in turn noticeably lighter than the carrier-coloring agent composite prepared with Sample 3C. Note that the final concentration of color on the clay carrier was the same in all three cases. By limiting the amount of solvent (PEG <NUM> in this specific case), the coloring agent was better hidden on/within the clay carrier.

This experiment supports the theory that the higher the concentration of pure color in the cut color (or the higher the CV), the more effective is the hiding of the occult particle in the detergent composition. It is believed the reason for this effect is that as the amount of PEG <NUM> is increased (CV is decreased), more color spreads onto the lower particle size fractions (<<NUM>) of the clay powder, consequently producing more colored powders.

Note: The distribution of color on the various size fractions of the clay is determined through sieve analysis followed by color extraction. Thus, in the carrier-coloring agent composite prepared with Sample 3A, approximately <NUM>% of Violet DD ends up on the <<NUM> clay fractions. This is compared to approximately <NUM>% for the carrier-coloring agent composite prepared with Sample 3B and about <NUM>% for the carrier-coloring agent composite prepared with Sample 3C.

Results: The carrier-coloring agent composites prepared with Samples 4C through 4F were noticeably lighter in color than the carrier-coloring agent composite prepared with Sample 4A. The carrier-coloring agent composite prepared with Sample 4A was in turn noticeably lighter in color than the carrier-coloring agent composite prepared with Sample 4B. It is believed the reason for this effect is that when used as diluents, Ethylene Glycol, Ethoquad® O12/PG, Glycerol and Propylene Glycol reduce the ability of the color to spread onto the lower particle size fractions (<<NUM>) of the clay carrier. In contrast, when PEG <NUM> is used as a diluent, colorant-containing particles that include PEG <NUM> result in more color spreading onto the lower particle size fractions (<<NUM>) of the clay carrier.

Note: The distribution of color on the various size fractions of the clay is determined through sieve analysis followed by color extraction. Results are shown in Table <NUM> below.

Results: The carrier-coloring agent composites prepared with Samples 5C through 5E were noticeably lighter in coloration than the carrier-coloring agent composite prepared with Sample 5A. The carrier-coloring agent composite prepared with Sample 5A was in turn noticeably lighter in coloration than the carrier-coloring agent composite prepared with Sample 5B. It is believed that the reason for this effect is that when used as diluents, Ethoquad® O12/PG, Glycerol and DI Water reduce the ability of the color to spread onto the lower particle size fractions (<<NUM>) of the clay carrier. In contrast, when PEG <NUM> is used as a diluent, colorant-containing particles that include PEG <NUM> result in more color spreading onto the lower particle size fractions (<<NUM>) of the clay carrier.

The results from Experiments <NUM> and <NUM> support the theory that diluents for which R ><NUM> may be used to significantly reduce the appearance of color on the carrier-coloring agent composite. Specific examples of suitable diluents include water, glycerol, propylene carbonate, ethylene glycol, and the like, and mixtures thereof.

Results: The carrier-coloring agent composite prepared with Sample 6C was noticeably lighter in coloration than the carrier-coloring agent composite prepared with Sample 6D. The carrier-coloring agent composite prepared with Sample 6D was in turn lighter in coloration than the carrier-coloring agent composite prepared with Sample 6E. The carrier-coloring agent composite prepared with Sample 6A was slightly darker than the carrier-coloring agent composite prepared with Sample 6E. The carrier-coloring agent composite prepared with Sample 6B was the most intensely colored clay powder. It is believed that the mechanism of hiding the coloring agent on/within the carrier material is one in which the diluent (e.g. vegetable oil or oleic acid) suppresses the intensity of the coloring agent on/within the clay by limiting the amount of color that spreads onto the <<NUM> fractions. The reason for the discrepancy in the mineral oil sample may be due to the fact that mineral oil and Violet DD are practically immiscible with one another.

The results from Experiment <NUM> support the theory that diluents for which R ><NUM> may be used to significantly reduce the appearance of color on the carrier-coloring agent composite.

Results: The carrier-coloring agent composite prepared with Sample 7B was noticeably lighter than the carrier-coloring agent composite prepared with Sample 7A. The carrier-coloring agent composite prepared with Sample 7C was the more colored than the carrier-coloring agent composite prepared with Sample 7A. The carrier-coloring agent composite prepared with Sample 7E was noticeably lighter than the carrier-coloring agent composite prepared with Sample 7D. The carrier-coloring agent composite prepared with Sample 7F was the more colored than the carrier-coloring agent composite prepared with Sample 7D. The results of Experiment <NUM> support the theory that the presence of tertiary aromatic amine solvent (Mtol5EO in this particular example) is detrimental to successfully hiding the coloring agent on the clay carrier material.

Results: The carrier-coloring agent composite prepared with Sample 8B was noticeably lighter than the carrier-coloring agent composite prepared with Sample 8A. The carrier-coloring agent composite prepared with Sample 8D was noticeably lighter than the carrier-coloring agent composite prepared with Sample 8C. The carrier-coloring agent composite prepared with Sample 8F was noticeably lighter than the carrier-coloring agent composite prepared with Sample 8E. The carrier-coloring agent composite prepared with Sample <NUM> was noticeably lighter than the carrier-coloring agent composite prepared with Sample <NUM>. The carrier-coloring agent composite prepared with Sample 8J was noticeably lighter than the carrier-coloring agent composite prepared with Sample 8I. The results of Experiment <NUM> support the theory that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite when the coloring agents used are uncharged (nonionic or neutral molecules). The mechanism employed herein is control over the amount of coloring agent that spreads onto the carrier material (e.g. <<NUM> clay fractions).

Results: The carrier-coloring agent composite prepared with Sample 9B was noticeably lighter than the carrier-coloring agent composite prepared with Sample 9A. The carrier-coloring agent composite prepared with Sample 9D was noticeably lighter than the carrier-coloring agent composite prepared with Sample 9C. The carrier-coloring agent composite prepared with Sample 9F was noticeably lighter than the carrier-coloring agent composite prepared with Sample 9E. The carrier-coloring agent composite prepared with Sample <NUM> was noticeably lighter than the carrier-coloring agent composite prepared with Sample <NUM>. The results of Experiment <NUM> support the theory that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite using a polymeric colorant. In addition, it also demonstrates that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite when the coloring agents used are anionic. The mechanism employed herein is control over the amount of coloring agent that spreads onto the carrier material (e.g. <<NUM> clay fractions).

Results: The carrier-coloring agent composite prepared with Sample 10B was noticeably lighter than the carrier-coloring agent composite prepared with Sample 10A. The carrier-coloring agent composite prepared with Sample 10D was noticeably lighter than the carrier-coloring agent composite prepared with Sample 10C. The carrier-coloring agent composite prepared with Sample 10F was noticeably lighter than the carrier-coloring agent composite prepared with Sample 10E. The carrier-coloring agent composite prepared with Sample <NUM> was noticeably lighter than the carrier-coloring agent composite prepared with Sample <NUM>. The results of Experiment <NUM> support the theory that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite using a polymeric colorant. In addition, it also demonstrates that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite when the coloring agents used are cationic. The mechanism employed herein is control over the amount of coloring agent that spreads onto the carrier material (e.g. <<NUM> clay fractions).

Results: The carrier-coloring agent composite prepared with Sample 11B was noticeably lighter than the carrier-coloring agent composite prepared with Sample 11A. The carrier-coloring agent composite prepared with Sample 11D was noticeably lighter than the carrier-coloring agent composite prepared with Sample 11C. The carrier-coloring agent composite prepared with Sample 11F was noticeably lighter than the carrier-coloring agent composite prepared with Sample 11E. The results of Experiment <NUM> support the theory that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite using a polymeric colorant. In addition, it also demonstrates that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite when the coloring agents used are pigments. The mechanism employed herein is control over the amount of coloring agent that spreads onto the carrier material (e.g. <<NUM> clay fractions).

Results: The color was successfully hidden (occult particles were produced) on all the bentonites tested in this experiment. Experiment <NUM> shows that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite regardless of the source of natural sodium bentonite carrier material. The mechanism employed herein is control over the amount of coloring agent that spreads onto the carrier material (e.g. <<NUM> clay fractions).

Results: For all three types of bentonite used in this experiment, the Trial Samples were noticeably lighter than the Control Samples. Experiment <NUM> shows that a diluent like water, for which R><NUM>, may be used to significantly reduce the appearance of color on the carrier-coloring agent composite independent of the type of bentonite carrier (natural bentonite or synthetic bentonite, Na bentonite or Ca bentonite). The mechanism employed herein is control over the amount of coloring agent that spreads onto the carrier material (e.g. <<NUM> clay fractions).

Results: Detergent Sample A was slightly less colored than Detergent Sample B. Detergent Sample C was significantly less colored than Detergent Sample A. Detergent Sample D was less colored than Detergent Sample B. Detergent Sample C was noticeably less colored than Detergent Sample D. These results show that the presence of a film former helps mitigate potential bleed issues. The film former used in this experiment was the water soluble, film forming polymer polyvinyl alcohol. This experiment also shows that the presence of PEG <NUM> in the color premix aids in bleed suppression. PEG <NUM> is a known plasticizer for polyvinyl alcohol. Without being bound by theory we speculate that the presence of the PEG <NUM> in the color premix aids polyvinyl alcohol film formation, resulting in improved resistance to bleed.

Results: The Trial detergent sample remained uncolored while the Control detergent sample turned pink. These results show that a diluent like water, for which R><NUM>, may be used to significantly reduce the bleeding risk by limiting the amount of color that spreads onto the carrier material.

Claim 1:
An occult particle, which is a particle comprising:
a) a majority by weight of at least one natural sodium bentonite clay carrier material, and
b) at least one color premix material, wherein the color premix material is comprised of:
(i) At least one cut color, which is a composition containing a polymeric coloring agent, a solvent and < <NUM> wt.-% of a tertiary aromatic amine, and
(ii) At least one diluent selected from glycerol, propylene carbonate, ethylene glycol and mixtures thereof, and
wherein the at least one carrier material and the at least one color premix material form a carrier-color premix composite; and
the carrier-color premix composite has a dE*cmc ≤ <NUM> in a non-colored granular or powdered laundry care composition when compared to the composition containing only the carrier material with no coloring agent.