WO2007111899A2 - Liquid treatment composition - Google Patents

Abstract

According to the present invention there is provided a pearlescent liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having DO.99 volume particle size of less than 50 μm and is present in composition at a level of from 0.02% to 2.0% by weight of the composition, or the difference in refractive index of the medium in which the pearlescent agent is suspended and the pearlescent agent is greater than 0,02 or the composition has turbity of greater than 5 and less than 3000 NTU or the composition has a viscosity of 1-1500 cp at 2Os-1 and 210C. Furthermore liquid compositions comprising a precrystallised organic pearlescent dispersion premix are disclosed.

Description

LIQUID TREATMENT COMPOSITION

TECHNICAL FIELD

The present invention relates to the field of a liquid treatment composition, preferably aqueous composition, comprising a pearlescent agent.

BACKGROUND OF THE INVENTION

In the preparation of liquid treatment compositions, it is always an aim to improve technical capabilities thereof and aesthetics. The present invention specifically relates to the aim of improving on the traditional transparent or opaque aesthetics of liquid compositions. It is also an aim of the present invention to convey the composition's technical capabilities through the aesthetics of the composition. The present invention relates to liquid compositions comprising optical modifiers that are capable of transmitting light such that the compositions appear pearlescent.

Pearlescence can be achieved by incorporation and suspension of a pearlescent agent in the liquid composition. Pearlescent agents include inorganic natural substances, such as mica, bismuth oxychloride and titanium dioxide, and organic compounds such as fish scales, metal salts of higher fatty acids, fatty glycol esters and fatty acid alkanolamides. The pearlescent agent can be acquired as a powder, suspension of the agent in a suitable suspending agent or where the agent is a crystal, it may be produced in situ.

Pearlescent agents are particulate and tend to separate from the -suspension or liquid composition over time. One solution to this problem is simply to increase the viscosity of the composition. However liquid laundry or hard surface cleaning compositions necessarily have relatively low viscosity, especially at high shear, such that they may be poured. Typically a laundry composition has viscosity of less than 1500 centipoises at 20s^"1 and 21°C. Such products generally also have low viscosity at low shear, resulting in any particulates having a tendency to separate from the liquid composition and either float or settle upon storage. In either scenario this gives an undesired, non-uniform product appearance wherein part of the product is pearly and part of it is clear and homogeneous.

Another problem associated with the use of particulates, and especially pearlescent agents, in liquid laundry and hard surface cleaning applications is the likely deposition of the pearlescent agent on the surface being treated. On fabrics, especially dark fabrics, such deposits or residues can be visible with the naked eye. Moreover they may tend to draw the eye as, by their nature, they tend to sparkle in light. On dishware or hard surfaces, such as floors, deposits are equally as unappealing as they give the consumers the perception of the surface being dirty. With regard to dishware there is the added potentially issue that consumers may view the appearance of pearlescent agent on dishware as being a health issue.

Detergent compositions and pearlescent dispersions comprising pearlescent agent fatty acid glycol ester are disclosed in the following art; US 4,717,501 (to Kao); US 5,017,305 (to Henkel); US 6,210,659 (to Henkel); US 6,835,700 (to Cognis). Liquid detergent compositions containing pearlescent agent are disclosed in US 6,956,017 (to

Procter & Gamble). Liquid detergents for washing delicate garments containing pearlescent agent are disclosed in EP 520551 Bl (to Unilever).

In spite of the advances in the art, there remains a challenge to both stably suspend pearlescent agents in liquid laundry and hard surface cleaning treatment compositions and avoid the appearance of deposits or residues on the surface being treated.

SUMMARY OF THE INVENTION According to the present invention there is provided a liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having D0.99 volume particle size of less than 50 μm and is present in composition at a level of from 0.02% to 2.0% by weight of the composition.

According to the present invention there is also provided a pearlescent liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having D0.99 volume particle size of less than 50 μm and the difference in refractive index (ΔN) of the medium in which the pearlescent agent is suspended and the pearlescent agent is greater than 0.02.

According to the present invention there is also provided a pearlescent liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having D0.99 volume particle size of less than 50 μm and the composition has turbidity of greater than 5 and less than

3000 NTU.

According to the present invention there is also provided a pearlescent liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having D0.99 volume particle size of less than 50 μm and the composition has viscosity of from 1 to 1500 mPa*s at 20s^'1 and 20⁰C.

According to another aspect of the present invention there is provided a pearlescent liquid treatment composition suitable for laundry or hard surface cleaning comprising: (a) from about 0.5% to about 20% by weight of the composition of a precrystallised organic pearlescent dispersion premix, which comprises

(i) a pearlescent agent having the formula:

wherein Ri is linear or branched C12-C22 alkyl chain; R is linear or branched C2-C4 alkylene group;

P is selected from H, C1-C4 alkyl Or-COR₂, R₂ is C4-C22 alkyl; and n = 1-3;

(ii) a surfactant selected from the group consisting of linear or branched C12-C14 alkyl sulfate, alkyl ether sulfate, and mixtures thereof; and (iii) water and adjuncts selected from the group consisting of buffers, pH modifiers, viscosity modifiers, ionic strength modifiers, fatty alcohols, amphoteric surfactants, and mixtures thereof; (b) carrier; and (c) optionally, a laundry adjunct; wherein the detergent composition has a viscosity of from about 1 to about 1000 mPa*s at 20-' and 21°C.

DETAILED DESCRIPTION OF THE INVENTION The liquid compositions of the present invention are suitable for use as laundry or hard surface cleaning treatment compositions. By the term laundry treatment composition it is meant to include all liquid compositions used in the treatment of laundry including cleaning and softening or conditioning compositions. By the term hard surface treatment compositions it is meant to include all liquid compositions used in the treatment of hard surfaces, such as kitchen or bathroom surfaces, as well as dish and cook ware in the hand or automatic dishwashing operations.

The compositions of the present invention are liquid, but may be packaged in a container or as an encapsulated and/or unitized dose. The latter form is described in more detail below. Liquid compositions may be aqueous or non-aqueous. Where the compositions are aqueous they may comprise from 2 to 90% water, more preferably from 20% to 80% water and most preferably from 25% to 65% water. Non-aqueous compositions comprise less than 12% water, preferably less than 10%, most preferably less than 9.5% water. Compositions used in unitized dose products comprising a liquid composition enveloped within a water-soluble film are often described to be non- aqueous. Compositions according to the present invention for this use comprise from 2% to 15% water, more preferably from 2% to 10% water and most preferably from 4% to 9% water.

The compositions of the present invention preferably have viscosity from 1 to

1500 centipoises (1-1500 mPa*s), more preferably from 100 to 1000 centipoises (100- 1000 τnPa*s), and most preferably from 200 to 500 centipoises (200-500 mPa*s) at 20s^"

¹ and 21°C. Viscosity can be determined by conventional methods. Viscosity according to the present invention however is measured using an AR 550 rheometer from TA instruments using a plate steel spindle at 40 mm diameter and a gap size of

500 μm. The high shear viscosity at 20s^"! and low shear viscosity at 0.05^"1 can be obtained from a logarithmic shear rate sweep from 0.F¹ to 25^"' in 3 minutes time at 21C. The preferred rheology described therein may be achieved using internal existing structuring with detergent ingredients or by employing an external rheology modifier. More preferably laundry detergent liquid compositions have a high shear rate viscosity of from about 100 centipoise to 1500 centipoise, more preferably from 100 to 1000 cps. Unit Dose laundry detergent liquid compositions have high shear rate viscosity of from 400 to lOOOcps. Laundry softening compositions have high shear rate viscosity of from 10 to 1000, more preferably from 10 to 800 cps, most preferably from 10 to 500 cps. Hand dishwashing compositions have high shear rate viscosity of from 300 to 4000 cps, more preferably 300 to 1000 cps.

The composition to which the pearlescent agent is added is preferably transparent or translucent, but may be opaque. The compositions (before adding the pearlescent agent) preferably have an absolute turbidity of 5 to 3000 NTU as measured with a turbidity meter of the nephelometric type. Turbidity according to the present invention is measures using an Analyte NEPl 60 with probe NEP260 from Mc Van Instruments, Australia. In one embodiment of the present invention it has been found that even compositions with turbidity above 2800 NTU can be made pearlescent with the appropriate amount of pearlescent material. The Applicants have found however, that as turbidity of a composition is increased, light transmittance through the composition decreases. This decrease in light transmittance results in fewer of the pearlescent particles transmitting light, which further results in a decrease in pearlescent effect. The Applicants have thus found that this effect can to a certain extent be ameliorated by the addition of higher levels of pearlescent agent. However a threshold is reached at turbidity of 3000NTU after which further addition of pearlescent agent does not improve the level of pearlescent effect.

In another embodiment, the invention includes a liquid laundry detergent comprising a pearlescent agent such as coated or uncoated mica, bismuth oxychloride or the like in combination with a high level (such as from 1% to 7% by weight of the composition) of fabric care benefit agents such as substituted or unsubstituted silicones. The latter are incorporated into the composition in pre-emulsified form. Suitable silicones are available commercially from suppliers such as Dow Corning, Wacker,

Shin-Etsu, and others. Optionally such compositions can have relatively high viscosities of at least 500 to 4000 at 20 s"¹ at 21°C and 3000 to 20000 at 0.1 s"¹. at 21°C In such compositions, a suitable external structurant is trihydroxystearin at levels in the range from about 0.05% to about 1% of the composition. Any other suitable external structurant can be used, or a surfactant-structured formulation can be employed. Deposition aids such as acrylamide/MAPTAC ex Nalco are preferably employed in such formulations at levels of from about 0.1% to 0.5% by weight of the composition. The liquid of the present invention preferably has a pH of from 3 to 10, more preferably from 5 to 9, even more preferably from 6 to 9, most preferably from 7.1 to 8.5 when measured by dissolving the liquid to a level of 1% in demineralized water.

Pearlescent Agent

The pearlescent agents according to the present invention are crystalline or glassy solids, transparent or translucent compounds capable of reflecting and refracting light to produce a pearlescent effect. Typically, the pearlescent agents are crystalline particles insoluble in the composition in which they are incorporated. Preferably the pearlescent agents have the shape of thin plates or spheres. Spheres, according to the present invention, are to be interpreted as generally spherical. Particle size is measured across the largest diameter of the sphere. Plate-like particles are such that two dimensions of the particle (length and width) are at least 5 times the third dimension (depth or thickness). Other crystal shapes like cubes or needles or other crystal shapes do not display pearlescent effect. Many pearlescent agents like mica are natural minerals having monoclinic crystals. Shape appears to affect the stability of the agents. The spherical, even more preferably, the plate-like agents being the most successfully stabilised.

Pearlescent agents are known in the literature, but generally for use in shampoo, conditioner or personal cleansing applications. They are described as materials which impart, to a composition, the appearance of mother of pearl. The mechanism of pearlescence is described by R. L. Crombie in International Journal of Cosmetic Science VoI 19, page 205-214. Without wishing to be bound by theory, it is believed that pearlescence is produced by specular reflection of light as shown in the figure below.

Light reflected from pearl platelets or spheres as they lie essentially parallel to each other at different levels in the composition creates a sense of depth and luster. Some light is reflected off the pearlescent agent, and the remainder will pass through the agent. Light passing through the pearlescent agent, may pass directly through or be refracted. Reflected, refracted light produces a different colour, brightness and luster.

The Applicants have found that in the context of both suspension and reduction in the existence of visible residues, the pearlescent agents have D0.99 (sometimes referred to as D99) volume particle size of less than 50 μm. More preferably the pearlescent agents have D0.99 of less than 40 μm, most preferably less than 30 μm. Most preferably the particles have volume particle size greater than Iμm. Most preferably the pearlescent agents have particle size distribution of from 0.1 μm to 50 μm, more preferably from 0.5 μm to 25 μm and most preferably from 1 μm to 20 μm. The D0.99 is a measure of particle size relating to particle size distribution and meaning in this instance that 99% of the particles have volume particle size of less than 50 μm. Volume particle size and particle size distribution are measured using the Hydro 2000G equipment available from Malvern Instruments Ltd. Particle size has a role in stabilization of the agents. The smaller the particle size and distribution, the more easily they are suspended. However as you decrease the particle size of the pearlescent agent, so you decrease the efficacy of the agent.

Without wishing to be bound by theory, the Applicant believes that the transmission of light at the interface of the pearlescent agent and the liquid medium in which it is suspended, is governed by the physical laws governed by the Fresnel equations. The proportion of light that will be reflected by the pearlescent agent increases as the difference in refractive index between the pearlescent agent and the liquid medium increases. The rest of the light will be refracted by virtue of the conservation of energy, and transmitted through the liquid medium until it meets another pearlescent agent surface. That being established, it is believed that the difference in refractive index must be sufficiently high so that sufficient light is reflected in proportion to the amount of light that is refracted in order for the composition containing the pearlescent agents to impart visual pearlescence.

Liquid compositions containing less water and more organic solvents will typically have a refractive index that is higher in comparison to more aqueous compositions. The Applicants have therefore found that in such compositions having a high refractive index, pearlescent agents with an insufficiently high refractive index do not impart sufficient visual pearlescence even when introduced at high level in the composition (typically more than 3%). It is therefore preferable to use a pearlescent pigment with a high refractive index in order to keep the level of pigment at a reasonably low level in the formulation. Hence the pearlescent agent is preferably chosen such that it has a refractive index of more than 1.41, more preferably more than 1.8, even more preferably more than 2.0. Preferably the difference in refractive index between the pearlescent agent and the composition or medium, to which pearlescent agent is then added, is at least 0.02. Preferably the difference in refractive index between the pearlescent agent and the composition is at least 0.2, more preferably at least 0.6. The Applicants have found that the higher the refractive index of the agent the more effective is the agent in producing pearlescent effect. This effect however is also dependent on the difference in refractive index of the agent and of the composition. The greater the difference the greater is the perception of the effect. The liquid compositions of the present invention preferably comprise from

0.01% to 2.0% by weight of the composition of a 100% active pearlescent agent. More preferably the liquid composition comprises from 0.01 % to 0.5%, more preferably from 0.01% 0.35%, even more preferably from 0.01% to 0.2% by weight of the composition of the 100% active pearlescent agents. The Applicants have found that in spite of the above mentioned particle size and level in composition, it is possible to deliver good, and consumer preferred, pearlescence to the liquid composition. The pearlescent agents may be organic or inorganic.

Organic Pearlescent Agents:

Suitable pearlescent agents include monoester and/or diester of alkylene glycols having the formula:

wherein Ri is linear or branched C12-C22 alkyl group;

R is linear or branched C2-C4 alkylene group;

P is selected from H, C1-C4 alkyl or -COR₂, R₂ is C4-C22 alkyl, preferably C12-C22 alkyl; and n = l-3.

In one embodiment of the present invention, the long chain fatty ester has the general structure described above, wherein Ri is linear or branched C16-C22 alkyl group, R is - CH₂-CH₂-, and P is selected from H, Or-COR₂, wherein R₂ is C4-C22 alkyl, preferably C12-C22 alkyl. Typical examples are monoesters and/or diesters of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol or tetraethylene glycol with fatty acids containing from about 6 to about 22, preferably from about 12 to about 18 carbon atoms, such as caproic acid, caprylic acid, 2-ethyhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid, erucic acid, and mixtures thereof.

In one embodiment, ethylene glycol monostearate (EGMS) and/or ethylene glycol distearate (EGDS) and/or polyethylene glycol monostearate (PGMS) and/or polyethyleneglycol distearate (PGDS) are the pearlescent agents used in the composition. There are several commercial sources fro these materials. For Example, PEG6000MS® is available from Stepan, Empilan EGDS/A® is available from Albright & Wilson.

In another embodiment, the pearlescent agent comprises a mixture of ethylene glycol diester/ethylene glycol monoester having the weight ratio of about 1 :2 to about 2:1. In another embodiment, the pearlescent agent comprising a mixture of EGDS/EGMS having the weight ratio of bout 60:40 to about 50:50 is found to be particularly stable in water suspension.

Co-Crystallizing Agents: Optionally, co-crystallizing agents are used to enhance the crystallization of the organic pearlescent agents such that pearlescent particles are produced in the resulting product. Suitable co-crystallizing agents include but are not limited to fatty acids and/or fatty alcohols having a linear or branched, optionally hydroxyl substituted, alkyl group containing from about 12 to about 22, preferably from about 16 to about 22, and more preferably from about 18 to 20 carbon atoms, such as palmitic acid, linoleic acid, stearic acid, oleic acid, ricinoleic acid, behenyl acid, cetearyl alcohol, hydroxystearyl alcohol, behenyl alcohol, linolyl alcohol, linolenyl alcohol, and mixtures thereof.

When the co-crystallizing agents are selected to have a higher melting point than the organic pearlescent agents, it is found that in a molten mixture of these co- crystallizing agents and the above organic pearlescent agents, the co-crystallizing agents typically solidify first to form evenly distributed particulates, which serve as nuclei for the subsequent crystallization of the pearlescent agents. With a proper selection of the ratio between the organic pearlescent agent and the co-crystallizing agent, the resulting crystals sizes can be controlled to enhance the pearlescent appearance of the resulting product. It is found that if too much co-crystallizing agent is used, the resulting product exhibits less of the attractive pearlescent appearance and more of an opaque appearance. In one embodiment where the co-crystallizing agent is present, the composition comprises 1-5 wt% C12-C20 fatty acid, C12-C20 fatty alcohol, or mixtures thereof.

In another embodiment, the weight ratio between the organic pearlescent agent and the co-crystallizing agent ranges from about 3:1 to about 10:1, or from about 5:1 to about 20:1.

One of the widely employed methods to produce organic pearlescent agent containing compositions is a method using organic pearlescent materials that are solid at room temperature. These materials are heated to above their melting points and added to the preparation of composition; upon cooling, a pearlescent luster appears in the resulting composition. This method however can have disadvantages as the entire production batch must be heated to a temperature corresponding to the melting temperature of the pearlescent material, and uniform pearlescence in the product is achieved only by making a homogeneous molten mixture and applying well controlled cooling and stirring conditions.

An alternative, and preferred method of incorporating organic pearlescent agents into a composition is to use a pre-crystallized organic pearlescent dispersion. This method is known to those skilled in the art as "cold pearl". In this alternative method, the long chain fatty esters are melted, combined with a carrier mixture and recrystallized to an optimum particle size in a carrier. The carrier mixture typically comprises surfactant, preferably from 2-50% surfactant, and the balance of water and optional adjuncts. Pearlescent crystals of a defined size are obtainable by the proper choices of surfactant carrier mixture, mixing and cooling conditions. The process of making cold pearls are described on US patents US4,620,976, US4,654,163 (both assigned to Hoechest) and WO2004/028676 (assigned to Huntsman International). A number of cold pearls are commercially available. These include trade names such as Stepan, Pearl-2 and Stepan Pearl 4 (produced by Stepan Company Northfield, IL)₅ Mackpearl 202, Mackpearl 15-DS, Mackpearl DR- 104, Mackpearl DR- 106 (all produced by Mclntyre Group, Chicago, IL), Euperlan PK900 Benz-W and Euperlan PK 3000 AM (produced by Cognis Corp).

A typical embodiment of the invention incorporating an organic pearlescent agent is a composition comprising from 0.1% to 5% by weight of composition of the organic pearlescent agent, from 0.5% to 10% by weight of the composition of a dispersing surfactant, and optionally, an effective amount of a co-crystallizing agent in a solvent system comprising water and optionally one or more organic solvents, in addition, from 5% to 40% by weight of the composition, of a detersive surfactant, and at least 0.01%, preferably at least 1% by weight of the composition, of one or more laundry adjunct materials such as perfume, fabric softener, enzyme, bleach, bleach activator, coupling agent, or combinations thereof.

The "effective amount" of co-crystallizing agent is the amount sufficient to produce the desired crystal size and size distribution of the pearlescent agents, under a given set processing parameters. In some embodiments, the amount of co-crystallizing agent ranges from 5 to 30 parts, per 100 weight parts organic pearlescent agent. Suitable dispersing surfactants for cold pearls include alkyl sulfates, alkyl ether sulfates, and mixtures thereof, wherein the alkyl group is linear or branched C12-C14 alkyls. Typical examples include but are not limited to sodium lauryl sulfate and ammonium lauryl sulfate. In one embodiment of the present invention, the composition comprises 20-

65wt% water; 5-25 wt% sodium alkyl sulfate alkyl sulfate or alkyl ether sulfate dispersing surfactant; and 0.5-15 wt% ethylene glycol monostearate and ethylene glycol distearate in the weight ratio of 1 :2 to 2:1.

In another embodiment of the present invention, the composition comprises 20- 65 wt% water; 5-30 wt% sodium alkyl sulfate or alkyl ether sulfate dispersing surfactant; 5-30 wt% long chain fatty ester and 1-5 wt% C12-C22 fatty alcohol or fatty acid, wherein the weight ratio of long chain fatty ester to fatty alcohol and/or fatty acid ranges from about 5:1 to about 20:1, or from about 3:1 to about 10:1.

In another embodiment of the invention, the composition comprises at least about 0.01%, preferably from about 0.01% to about 5% by weight of the composition of the pearlescent agents, an effective amount of the co-crystallizing agent and one or more of the following: a detersive surfactant; a fixing agent for anionic dyes; a solvent system comprising water and an organic solvent. This composition can further include other laundry and fabric care adjuncts.

Production Process for incorporating organic pearlescent agents:

The cold pearl is produced by heating the a carrier comprised of 2-50% surfactant, balance water and other adjuncts to a temperature above the melting point of the organic pearlescent agent and co-crystallizing agent, typically from about 60-90⁰C, preferably about 75-80⁰C. The organic pearlescent agent and the co-crystallizing agent are added to the mixture and mixed for about 10 minutes to about 3 hours. Optionally, the temperature is then raised to about 80-90°C. A high shear mill device may be used to produce the desired dispersion droplet size of the pearlescent agent.

The mixture is cooled down at a cooling rate of about 0.5-5°C/min. Alternatively, cooling is carried out in a two-step process, which comprises an instantaneous cooling step by passing the mixture through a single pass heat exchanger and a slow cooling step wherein the mixture is cooled at a rate of about 0.5-5°C/min. Crystallization of the pearlescent agent such as a long chain fatty ester starts when the temperature reaches about 50⁰C; the crystallization is evidenced by a substantial increase in the viscosity of the mixture. The mixture is cooled down to about 30⁰C and the stirring is stopped. The resulting cold pearl precrystallised organic pearlescent dispersion can subsequently be incorporated into the liquid composition with stirring and without any externally applied heat. The resulting product has an attractive pearlescent appearance and is stable for months under typical storage conditions. In other words, the resulting product maintains its pearlescent appearance and the cold pearl does not exhibit separation or stratification from the composition matrix for months.

Inorganic Pearlescent Agents:

Inorganic pearlescent agents include those selected from the group consisting of mica, metal oxide coated mica, silica coated mica, bismuth oxychloride coated mica, bismuth oxychloride, myristyl myristate, glass, metal oxide coated glass, guanine, glitter

(polyester or metallic) and mixtures thereof.

Suitable micas includes muscovite or potassium aluminum hydroxide fluoride.

The platelets of mica are preferably coated with a thin layer of metal oxide. Preferred metal oxides are selected from the group consisting of rutile, titanium dioxide, ferric oxide, tin oxide, alumina and mixtures thereof. The crystalline pearlescent layer is formed by calcining mica coated with a metal oxide at about 732°C. The heat creates an inert pigment that is insoluble in resins, has a stable color, and withstands the thermal stress of subsequent processing

Color in these pearlescent agents develops through interference between light rays reflecting at specular angles from the top and bottom surfaces of the metal-oxide layer. The agents lose color intensity as viewing angle shifts to non-specular angles and gives it the pearlscent appearance.

More preferably inorganic pearlescent agents are selected from the group consisting of mica and bismuth oxychloride and mixtures thereof. Most preferably inorganic pearlescent agents are mica. Commercially available suitable inorganic pearlescent agents are available from Merck under the tradenames Iriodin, Biron,

Xirona, Timiron Colorona , Dichrona, Candurin and Ronastar. Other commercially available inorganic pearlescent agent are available from BASF (Engelhard, Mearl) under tradenames Biju, Bi-Lite, Chroma-Lite, Pearl-Glo, Mearlite and Eckart under the tradenames Prestige Soft Silver and Prestige Silk Silver Star.

Organic pearlescent agent such as ethylene glycol mono stearate and ethylene glycol distearate provide pearlescence, but only when the composition is in motion.

Hence only when the composition is poured will the composition exhibit pearlescence.

Inorganic pearlescent materials are preferred as the provide both dynamic and static pearlescence. By dynamic pearlescence it is meant that the composition exhibits a pearlescent effect when the composition is in motion. By static pearlescence it is meant that the composition exhibits pearlescence when the composition is static.

Inorganic pearlescent agents are available as a powder, or as a slurry of the powder in an appropriate suspending agent. Suitable suspending agents include ethylhexyl hydroxystearate, hydrogenated castor oil. The powder or slurry of the powder can be added to the composition without the need for any additional process steps.

Optional Composition Ingredients

The liquid compositions of the present invention may comprise other ingredients selected from the list of optional ingredients set out below. Unless specified herein below, an "effective amount" of a particular laundry adjunct is preferably from 0.01%, more preferably from 0.1%, even more preferably from 1 % to 20%, more preferably to 15%, even more preferably to 10%, still even more preferably to 7%, most preferably to 5% by weight of the detergent compositions.

Surfactants or Detersive Surfactants

The compositions of the present invention may comprise from about 1% to 80% by weight of a surfactant. Preferably such compositions comprise from about 5% to 50% by weight of surfactant. Surfactants of the present invention may be used in 2 ways. Firstly they may be used as a dispersing agent for the cold pearl organic or inorganic pearlescent agents as described above. Secondly they may be used as detersive surfactants for soil suspension purposes. Detersive surfactants utilized can be of the anionic, nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types. More preferably surfactants are selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof. Preferably the compositions are substantially free of betaine surfactants. Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. Anionic and nonionic surfactants are preferred.

Useful anionic surfactants can themselves be of several different types. For example, water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.

Additional non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cs-Cjg carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 1 1 to 13, abbreviated as C ₁₁ -C ₁₃ LAS .

Preferred nonionic surfactants are those of the formula R'(OC₂H₄)_nOH, wherein R¹ is a Cio-C 16 alkyl group or a Cs-C 12 alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of Ci₂-C]₅ alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C₁₂-C₁3 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.

Fabric Care Benefit Agents

According to a preferred embodiment of the compositions herein there is comprised a fabric care benefit agent. As used herein, "fabric care benefit agent" refers to any material that can provide fabric care benefits such as fabric softening, color protection, pill/fuzz reduction, anti-abrasion, anti-wrinkle, and the like to garments and fabrics, particularly on cotton and cotton-rich garments and fabrics, when an adequate amount of the material is present on the garment/fabric. Non-limiting examples of fabric care benefit agents include cationic surfactants, silicones, polyolefin waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids and mixtures thereof. Fabric care benefit agents when present in the composition, are suitably at levels of up to about 30% by weight of the composition, _more typically from about 1% to about 20%, preferably from about 2% to about 10% in certain embodiments. For the purposes of the present invention, silicone derivatives are any silicone materials which can deliver fabric care benefits and can be incorporated into a liquid treatment composition as an emulsion, latex, dispersion, suspension and the like. In laundry products these are most commonly incorporated with suitable surfactants. Any neat silicones that can be directly emulsified or dispersed into laundry products are also covered in the present invention since laundry products typically contain a number of different surfactants that can behave like emulsifϊers, dispersing agents, suspension agents, etc. thereby aiding in the emulsification, dispersion, and/or suspension of the water insoluble silicone derivative. By depositing on the fabrics, these silicone derivatives can provide one or more fabric care benefit to the fabric including anti- wrinkle, color protection, pill/fuzz reduction, anti-abrasion, fabric softening and the like. Examples of silicones useful in this invention are described in "Silicones- Fields of Application and Technology Trends" by Yoshiaki Ono, Shin-Etsu Silicones Ltd, Japan and by M.D. Berthiaume in Principles of Polymer Science and Technology in Cosmetics and Personal Care (1999).

Suitable silicones include silicone fluids such as poly(di)alkyl siloxanes, especially polydimethyl siloxanes and cyclic silicones. Poly(di)alkylsiloxanes may be branched, partially crosslinked or linear and with the following structure:

Where each Rj is independently selected from H, linear, branched and cyclic alkyl and groups having 1-20 carbon atoms, linear, branched and cyclic alkenyl groups having 2- 20 carbon atoms, alkylaryl and arylalkenyl groups with 7-20 carbon atoms, alkoxy groups having 1-20 carbon atoms, hydroxy and combinations thereof, w is selected from

3-10 and k from 2-10,000.

The polydimethylsiloxane derivatives of the present invention include, but are not limited to organofunctional silicones. One embodiment of functional silicone are the ABn type silicones disclosed in

US 6,903,061B2, US 6,833,344 and WO-02/018528. Commercially available examples of these silicones are Waro and Silsoft 843, both sold by GE Silicones, Wilton, CT.

Another embodiment of functionalized silicones is the group of silicones with general formula

R R R R

R" Si— fO— Si-}— fO Si-4-O— Si R"

R X R R - ^Q (I) wherein:

(a) each R" is independently selected from R and — X — Q; wherein: (i) R is a group selected from: a Ci-Cs alkyl or aryl group, hydrogen, a C₁-C3 alkoxy or combinations thereof; (b) X is a linking group selected from: an alkylene group — (CH2)_P— ; or -CH₂-CH(OH)-CH₂-; wherein: (i) p is from 2 to 6,

(c) Q is -(O — CHR₂ — CH₂) _q— Z; wherein q is on average from about 2 to about 20; and further wherein: (i) R2 is a group selected from: H; a Ci-C₃ alkyl; and

(ii) Z is a group selected from: - OR₃; - OC(O)R₃; - CO- R₄ - COOH; -SO₃; -

wherein:

R₃ is a group selected from: H; Ci-C₂S alkyl or substituted alkyl; C6-C₂6 aryl or substituted aryl; C₇-C₂6 alkylaryl or substituted alkylaryl; in some embodiments, R₃ is a group selected from: H; methyl; ethyl propyl; or benzyl groups; R₄ is a group selected from: — CH₂-; or -CH2CH₂-;

R₅ is a group independently selected from: H, Ci-C₃ alkyl; -(CH₂) _P-NH₂; and -X(-O-CHR₂-CH₂)_q-Z;

(d) k is on average from about 1 to about 25,000, or from about 3 to about 12,000; and

(e) m is on average from about 4 to about 50,000, or from about 10 to about 20,000. Examples of fimctionalized silicones included in the present invention are silicone polyethers, alkyl silicones, phenyl silicones, aminosillicones, silicone resins, silicone mercaptans, cationic silicones and the like.

Functionalized silicones or copolymers with one or more different types of functional groups such as amino, alkoxy, alkyl, phenyl, polyether, acrylate, silicon hydride, mercaptoproyl, carboxylic acid, quaternized nitrogen. Non-limiting examples of commercially available silicone include SM2125, Silwet 7622, commercially available from GE Silicones, and DC8822 and PP-5495, and DC-5562, all of which are commercially available from Dow Corning. Other examples include KF-888, KF-889, both of which are available from Shin Etsu Silicones, Akron, OH; Ultrasil® SW-12, Ultrasil® DW-18, Ultrasil® DW-AV, Ultrasil® Q-Plus, Ultrasil® Ca-I, Ultrasil® CA- 2, Ultrasil® SA-I and Ultrasil® PE-100 all available from Noveon Inc., Cleveland, OH. Additional non-limiting examples include Pecosil® CA-20, Pecosil® SM-40, Pecosil® PAN-150 available from Phoenix Chemical Inc., of Somerville.

In terms of silicone emulsions, the particle size can be in the range from about 1 nm to 100 microns and preferably from about 10 nm to about 10 microns including mϊcroemulsions (<150 nm), standard emulsions (about 200 nm to about 500 nm) and macroemulsions (about 1 micron to about 20 microns).

The oily sugar derivatives suitable for use in the present invention are taught in WO 98/16538. In context of the present invention, the initials CPE or RSE stand for a cyclic polyol derivatives or a reduced saccharide derivative respectively which result from 35% to 100% of the hydroxyl group of the cyclic polyol or reduced saccharide being esterifϊed and/or etherifϊed and in which at least two or more ester or ether groups are independently attached to a C8 to C22 alkyl or alkenyl chain. Typically CPE's and RSE's have 3 or more ester or ether groups or mixtures thereof. It is preferred if two or more ester or ether groups of the CPE and RSE are independently attached to a C8 to C22 alkyl or alkenyl chain. The C8 to C22 alkyl or alkenyl chain may be linear or branched. In- one embodiment 40 to 100% of the hydroxyl groups are esterified or etherified. In another embodiment, 50% to 100% of the hydroxyl groups are esterified or etherified.

In the context of the present invention, the term cyclic polyol encompasses all forms of saccharides. Especially preferred are the CPEs and RSEs from monosaccharides and disaccharides. Examples of monosaccharides include xylose, arabinose, galactose, fructose, and glucose. Example of reduced saccharide is sorbitan. Examples of disaccharides are sucrose, lactose, maltose and cellobiose. Sucrose is especially preferred.

It is preferred if the CPEs or RSEs have 4 or more ester or ether groups. If the cyclic CPE is a disaccharide, it is preferred that disaccharide has three or more ester or ether groups. Particularly preferred are sucrose esters with 4 or more ester groups. These are commercially available under the trade name Olean from Procter and Gamble Company, Cincinnati OH. If cyclic polyol is a reducing sugar, it is advantageous if the ring of the CPE has one ether group, preferably at Cl position. The remaining hydroxyl groups are esterified with alkyl groups.

All dispersible polyolefins that provide fabric care benefits can be used as the water insoluble fabric care benefit agents according to the present invention. The polyolefins can be in the form of waxes, emulsions, dispersions or suspensions. Non- limiting examples are discussed below. Preferably, the polyolefϊn is a polyethylene, polypropylene, or a mixture thereof. The polyolefϊn may be at least partially modified to contain various functional groups, such as carboxyl, alkylamide, sulfonic acid or amide groups. More preferably, the polyolefin employed in the present invention is at least partially carboxyl modified or, in other words, oxidized. In particular, oxidized or carboxyl modified polyethylene is preferred in the compositions of the present invention.

For ease of formulation, the dispersible polyolefin is preferably introduced as a suspension or an emulsion of polyolefin dispersed by use of an emulsifying agent. The polyolefin suspension or emulsion preferably comprises from about 1% to about 60%, more preferably from about 10% to about 55%, and most preferably from about 20 to about 50% by weight of polyolefin. The polyolefin preferably has a wax dropping point

(see ASTM D3954- 94, volume 15.04 — "Standard Test Method for Dropping Point of Waxes", the method incorporated herein by reference) from about 20 to 17O⁰C and more preferably from about 50 to 140⁰C. Suitable polyethylene waxes are available commercially from suppliers including but not limited to Honeywell (A-C polyethylene), Clariant (Velustrol emulsion), and BASF (LUWAX).

When an emulsion is employed, the emulsifier may be any suitable emulsification agent including anionic, cationic, or nonionic surfactants, or mixtures thereof. Almost any suitable surfactant may be employed as the emulsifier of the present invention. The dispersible polyolefin is dispersed by use of an emulsifier or suspending agent in a ratio 1:100 to about 1 :2. Preferably, the ratio ranges from about 1 :50 to 1 :5. Polymer latex is typically made by an emulsion polymerization process which includes one or more monomers, one or more emulsifiers, an initiator, and other components familiar to those of ordinary skill in the art. All polymer latexes that provide fabric care benefits can be used as water insoluble fabric care benefit agents of the present invention. Non-limiting examples of suitable polymer latexes include those disclosed in WO 02/018451 published in the name of Rhodia Chimie. Additional non- limiting examples include the monomers used in producing polymer latexes such as:

1) 100% or pure butylacrylate

2) Butylacrylate and butadiene mixtures with at least 20% (weight monomer ratio) of butylacrylate

3) Butylacrylate and less than 20% (weight monomer ratio) of other monomers excl uding butad iene

4) Alkylacrylate with an alkyl carbon chain at or greater than C6

5) Alkylacrylate with an alkyl carbon chain at or greater than C6 and less than 50% (weight monomer ratio) of other monomers

6) A third monomer (less than 20% weight monomer ratio) added into monomer systems from 1) to 5).

Polymer latexes that are suitable fabric care benefit agents in the present invention include those having a glass transition temperature of from about -12O⁰C to about 120⁰C and preferably from about -80⁰C to about 6O⁰C. Suitable emulsifϊers include anionic, cationic, nonionic and amphoteric surfactants. Suitable initiators include all initiators that are suitable for emulsion polymerization of polymer latexes. The particle size of the polymer latexes can be from about 1 nm to about 10 μm and is preferably from about 10 nm to about 1 μm.

Cationic surfactants are another class of care actives useful in this invention. Examples of cationic surfactants having the formula

have been disclosed in US2005/0164905, wherein Ri and R₂ are individually selected from the group consisting of Ci — C₄ alkyl, Ci -C₄ hydroxy alkyl, benzyl, and -(C_nHa_nO)_xH where x has a value from 2 to

5; and n has a value of 1-4; X is an anion;

R-3 and R₄ are each a Cg -C₂₂ alkyl or (2) R3 is a Cg -C₂₂ alkyl and R4 is selected from the group consisting of Cj -C₁0 alkyl, Ci -Cio hydroxy alkyl, benzyl, --(C_nHj_nO)_xH where x has a value from 2 to 5; and n has a value of 1-4.

Another preferred fabric care benefit agent is a fatty acid. When deposited on fabrics, fatty acids or soaps thereof , will provide fabric care (softness, shape retention) to laundry fabrics. Useful fatty acids (or soaps = alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of fatty acids) are the higher fatty acids containing from about 8 to about 24 carbon atoms, more preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Fatty acids can be from natural or synthetic origin, both saturated and unsaturated with linear or branched chains.

Detersive enzymes

Suitable detersive enzymes for use herein include protease, amylase, lipase, cellulase, carbohydrase including mannanase and endoglucanase, and mixtures thereof. Enzymes can be used at their art-taught levels, for example at levels recommended by suppliers such as Novo and Genencor. Typical levels in the compositions are from about 0.0001% to about 5%. When enzymes are present, they can be used at very low levels, e.g., from about 0.001% or lower, in certain embodiments of the invention; or they can be used in heavier-duty laundry detergent formulations in accordance with the invention at higher levels, e.g., about 0.1% and higher. In accordance with a preference of some consumers for "non-biological" detergents, the present invention includes both enzyme-containing and enzyme-free embodiments.

Deposition Aid As used herein, "deposition aid" refers to any cationic polymer or combination of cationic polymers that significantly enhance the deposition of the fabric care benefit agent onto the fabric during laundering.

An effective deposition aid preferably has a strong binding capability with the water insoluble fabric care benefit agents via physical forces such as van der Waals forces or non-covalent chemical bonds such as hydrogen bonding and/or ionic bonding.

It preferably has a very strong affinity to natural textile fibers, particularly cotton fibers.

The deposition aid should be water soluble and have a flexible molecular structure so that it can cover the water insoluble fabric care benefit agent particle surface or hold several particles together. Therefore, the deposition aid is preferably not cross-linked and preferably does not have a network structure as these both tend to lack molecular flexibility.

In order to drive the fabric care benefit agent onto the fabric, the net charge of the deposition aid is preferably positive in order to overcome the repulsion between the fabric care benefit agent and the fabric since most fabrics are comprised of textile fibers that have a slightly negative charge in aqueous environments. Examples of fibers exhibiting a slightly negative charge in water include but are not limited to cotton, rayon, silk, wool, etc. Preferably, the deposition aid is a cationic or amphoteric polymer. The amphoteric polymers of the present invention will also have a net cationic charge, i.e.; the total cationic charges on these polymers will exceed the total anionic charge. The cationic charge density of the polymer ranges from about 0.05 milliequivalents/g to about 6 milliequivalents/g. The charge density is calculated by dividing the number of net charge per repeating unit by the molecular weight of the repeating unit. In one embodiment, the charge density varies from about 0.1 mϊlliequivants/g to about 3 milliequivalents/g. The positive charges could be on the backbone of the polymers or the side chains of polymers.

Nonlimiting examples of deposition enhancing agents are cationic polysaccharides, chitosan and its derivatives and cationic synthetic polymers. a. Cationic Polysaccharides: Cationic polysaccharides include but not limited to cationic cellulose derivatives, cationic guar gum derivatives, chitosan and derivatives and cationic starches. Cationic polysacchrides have a molecular weight from about 50,000 to about 2 million, preferably from about 100,000 to about 1,000,000. Most preferably, cationic cellulose have a molecular weight from about 200,000 to about 800,000 and cationic guars from about 500,000 to 1.5 million.

One group of preferred cationic polysaccharides are cationic cellulose derivatives, preferably cationic cellulose ethers. These cationic materials have repeating substituted anhydroglucose units that correspond to the general Structural Formula I as follows:

STRUCTURAL FORMULA I

Wherein R , 1₅ R τ>2 , „ R3 are each independently H₃ CH₃, Cg-₂₄ alkyl (linear or branched),

wherein n is from about 1 to about 10; Rx is H,

CH3, Cg-24 alkyl (linear or branched)

r mixtures thereof, wherein Z is a water soluble anion, preferably a chlorine ion and/or a bromine ion; R⁵ is H, CH3, CH₂CH₃, or mixtures thereof; R⁷ is CH3, CH2CH₃, a phenyl group, a C»-24 alkyl group (linear or branched), or mixture thereof; and R⁸ and R⁹ are each independently CH3, CH2CH3, phenyl, or mixtures thereof: _Z.pΛ. _H R is H, ^{v Jm} , or mixtures thereof wherein P is a repeat unit of an addition polymer

formed by radical polymerization of a catϊonic monomer such as wherein Z' is a water-soluble anion, preferably chlorine ion, bromine ion or mixtures thereof and q is from about 1 to about 10. Alkyl substitution on the anhydroglucose rings of the polymer ranges from about

0.01% to 5% per glucose unit, more preferably from about 0.05% to 2% per glucose unit, of the polymeric material.

The cationic cellulose ethers of Structural Formula I likewise include those which are commercially available and further include materials which can be prepared by conventional chemical modification of commercially available materials. Commercially available cellulose ethers of the Structural Formula I type include the JR 30M, JR 400, JR 125, LR 400 and LK 400 polymers, all of which are marketed byAmerchol Corporation , Edgewater NJ and Celquat H200 and Celquat L-200 available from National Starch and Chemical Company or Bridgewater, NJ.

Cationic starches useful in the present invention are described by D. B. Solarek in Modified Starches, Properties and Uses published by CRC Press (1986). Cationic starches are commercially available from National Starch and Chemical Company under the Trade Name Cato.

The cationic guar derivatives suitable in the present invention are

Where G is the glactaomanan backbone, R₇ is CH3, CH2CH3, a phenyl group, a Cs-₂₄ alkyl group (linear or branched), or mixture thereof; and Rs and R₉ are each independently CH3, CH₂CH₃, phenyl, or mixtures thereof, Z^" is a suitable anion. Preferred guar derivatives are guar hydroxypropyltrimethyl ammonium chloride.

Examples of cationic guar gums are Jaguar Cl 3 and Jaguar Excel available from Rhodia, Inc of Cranburry NJ. b. Synthetic Cationic Polymers Cationic polymers in general and their method of manufacture are known in the literature. For example, a detailed description of cationic polymers can be found in an article by M. Fred Hoover that was published in the Journal of Macromolecular Science-Chemistry, A4(6), pp 1327-1417, October, 1970. The entire disclosure of the Hoover article is incorporated herein by reference. Other suitable cationic polymers are those used as retention aids in the manufacture of paper. They are described in "Pulp and Paper, Chemistry and Chemical Technology Volume HI edited by James Casey (1981). The Molecular weight of these polymers is in the range of 2000-5 million.

The synthetic cationic polymers of this invention will be better understood when read in light of the Hoover article and the Casey book, the present disclosure and the Examples herein. Synthetic polymers include but are not limited to synthetic addition polymers of the general structure

wherein R¹, R², and Z are defined herein below. Preferably, the linear polymer units are formed from linearly polymerizing monomers. Linearly polymerizing monomers are defined herein as monomers which under standard polymerizing conditions result in a linear polymer chain or alternatively which linearly propagate polymerization. The linearly polymerizing monomers of the present invention have the formula: p i _R2

>=<

R^]/ Z ; however, those of skill in the art recognize that many useful linear monomer units are introduced indirectly, inter alia, vinyl amine units, vinyl alcohol units, and not by way of linearly polymerizing monomers. For example, vinyl acetate monomers once incorporated into the backbone are hydrolyzed to form vinyl alcohol units. For the purposes of the present invention, linear polymer units may be directly introduced, i.e. via linearly polymerizing units, or indirectly, i.e. via a precursor as in the case of vinyl alcohol cited herein above.

Each R¹ is independently hydrogen, Ci-C₄ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures thereof. Preferably R¹ is hydrogen, C1-C4 alkyl, phenyl, and mixtures thereof, more preferably hydrogen and methyl.

Each R² is independently hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures thereof. Preferred R² is hydrogen, C₁-C₄ alkyl, and mixtures thereof.

Each Z is independently hydrogen; hydroxyl; halogen; -(CHb)_1nR, wherein R is hydrogen, hydroxyl, halogen, nitrilo, -OR³, -O(CH₂)_nN(R³)₂, -OCCH^N⁺CR^X ^", - C(O)O(CH₂)_nN(R³)₂, -C(O)O(CH₂)nN⁺(R³)₃X ^", -OCO(CH₂)_nN(R³)₂, - OCO(CH₂)_nN⁺(R³)₃X \ -C(O)NH-(CH₂)_nN(R³)₂, -C(O)NH(CH₂)_nN⁺(R³)₃X ', - (CH₂)_nN(R³)2, ~(CH₂)_nN⁺(R³)3X ^", a non-aromatic nitrogen heterocycle comprising a quaternary ammonium ion, a non-aromatic nitrogen heterocycle comprising an N-oxide moiety, an aromatic nitrogen containing heterocyclic wherein one or more or the nitrogen atoms is quaternized; an aromatic nitrogen containing heterocycle wherein at least one nitrogen is an N-oxide; -NHCHO (formamide), or mixtures thereof; wherein each R³ is independently hydrogen, Ci-Cs alkyl, C₂-Cs hydroxyalkyl, and mixtures thereof; X is a water soluble anion; the index n is from 1 to 6; carbocyclic, heterocyclic, or mixtures thereof; -(CH₂)_mCOR' wherein R' is -OR³, -O(CH₂)_nN(R³)₂, - O(CH₂)_nlsr(R³)3X ^', -NR³(CH₂)_nN(R³)₂, -NR³(CH₂)_nN⁺(R³)₃X ^", -(CH₂)_nN(R³)₂, - (CH2)_nN⁺(R³)3X ^", or mixtures thereof, wherein R³, X, and n are the same as defined herein above. A preferred Z is -O(CH₂)_nN⁺(R³)₃X ^", wherein the index n is 2 to 4. The index m is from 0 to 6, preferably 0 to 2, more preferably 0.

Non-limiting examples of addition polymerizing monomers comprising a heterocyclic Z unit includes l-vinyl-2-pyrrolidinone, l-vinylimidazole, 2-vinyl-l,3- dioxolane, 4-vinyl-l-cyclohexenel,2-epoxide, and 2τvinylpyridine. The polymers and co-polymers of the present invention comprise Z units which have a cationic charge or which result in a unit which forms a cationic charge in situ. When the co-polymers of the present invention comprise more than one Z unit, for example, Z¹, Z²,...Zⁿ units, at least about 1% of the monomers which comprise the co- polymers will comprise a cationic unit. A non-limiting example of a Z unit which can be made to form a cationic charge in situ is the -NHCHO unit, formamide. The formulator can prepare a polymer or co-polymer comprising formamide units some of which are subsequently hydrolyzed to form vinyl amine equivalents. Cyclic Units Derived from Cyclically Polymerizing Monomers The polymers or co-polymers of the present invention can comprise one or more cyclic polymer units which are derived from cyclically polymerizing monomers. Cyclically polymerizing monomers are defined herein as monomers which under standard polymerizing conditions result in a cyclic polymer residue as well as serving to linearly propagate polymerization. Preferred cyclically polymerizing monomers of the present invention have the formula:

wherein each R⁴ is independently an olefin comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R⁴ unit; R⁵ is C1-C12 linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble anion.

Non-limiting examples of R⁴ units include allyl and alkyl substituted allyl units. Preferably the resulting cyclic residue is a six-member ring comprising a quaternary nitrogen atom.

R⁵ is preferably C1-C4 alkyl, preferably methyl. An example of a cyclically polymerizing monomer is dimethyl diallyl ammonium having the formula:

which results in a polymer or co-polymer having units with the formula:

wherein preferably the index z is from about 10 to about 50,000. And mixtures thereof

Nonlimiting examples of preferred polymers according to the present invention include copolymers comprising a) a cationic monomer selected from a group consisting N,N-diaUcylaminoalkyl methacrylate, N,N-dialkyIaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, N.N-dialkylaminoalkylmethacrylamide, their quaternized deriavtives, vinylamine and its derivatives, allylamine and its derivatives, vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium chloride. b) And a second monomer selected from a group consisting of acrylamide (AM), N,N-dialkyl acrylamide, methacrylamide, N,N-dialkylmethacrylamide, C1-C12 alkyl acrylate, Cl -C 12 hydroxyalkyl acrylate, Cl -C 12 hydroxyetheralkyl acrylate, C1-C12 alkyl methacrylate, C1-C12 hydroxyalkyl methacrylate, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl butyrate and derivatives and mixures thereof.

Preferred cationic monomers include N,N-dimethyI aminoethyl acrylate, N,N- dimethyl aminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]tri- methylammonium chloride (QDMAM), N,N-dimethylaminopropyl acrylamide (DMAPA), N,N-dimethylaminopropyl methacrylamide (DMAPMA), acrylamidopropyl trimethyl ammonium chloride, methacrylamidopropyl trimethylammonium chloride (MAPTAC), quaternized vinyl imidazole and diallyldimethylammonium chloride and derivatives thereof.

Preferred second monomersn include acrylamide, N,N-dimethyl acrylamide, C1-C4 alkyl acrylate, C1-C4 hydroxyalkylacrylate, vinyl formamide, vinyl acetate, and vinyl alcohol. Most preferred nonionic monomers are acrylamide, hydroxyethyl acrylate

(HEA), hydroxypropyl acrylate and derivative thereof, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethane sulfonic acid (AMPS) and their salts The polymer may optionally be cross-linked. Crosslinking monomers include, but are not limited to, ethylene glycoldiacrylatate, divinylbenzene, butadiene. The most preferred polymers are poly(acrylarnide-co-diallyldirnethylarnrnoniurn chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate), poly(acrylamide-co-N,N- dimethyl aminoethyl methacrylate), polyφydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate), polyφydroxpropylacrylate-co-methacrylamidopropyltrimethylammonium chloride).

In order for the deposition polymers to be formulable and stable in the composition, it is important that the monomers are incorporated in the polymer to form a copolymer, especially true when monomers have widely different reactivity ratios are used. In contrast to the commercial copolymers, the deposition polymers herein have a free monomer content less than 10%, preferably less than 5%, by weight of the monomers. Preferred synthesis conditions to produce reaction products containing the deposition polymers and low free monomer content are described below. The deposition assisting polymers can be random, blocky or grafted. They can be linear or branched. The deposition assisting polymers comprises from about 1 to about 60 mol percent, preferably from about 1 to about 40 mol percent, of the cationic monomer repeat units and from about 98 to about 40 mol percent, from about 60 to about 95 mol percent, of the nonionic monomer repeat units. The deposition assisting polymer has a charge density of about 0.1 to about 5.0 miHiequivalents/g (meq/g) of dry polymer, preferably about 0.1 to about 3 meq/g. This refers to the charge density of the polymer itself and is often different from the monomer feedstock. For example, for the copolymer of acrylamide and diallyldimethylammonium chloride with a monomer feed ratio of 70:30, the charge density of the feed monomers is about 3.05 meq/g. However, if only 50% of diallyldimethylammonium is polymerized, the polymer charge density is only about 1.6 meq/g. The polymer charge density is measured by dialyzing the polymer with a dialysisis membrane or by NMR. For polymers with amine monomers, the charge density depends on the pH of the carrier. For these polymers, charge density is measured at a pH of 7.

The weight-average molecular weight of the polymer will generally be between 10,000 and 5,000,000, preferably from 100,000 to 2,000,000 and even more preferably from 200,000 and 1,500,000, as determined by size exclusion chromatography relative to polyethyleneoxide standards with RI detection. The mobile phase used is a solution of 20% methanol in 0.4M MEA, 0.1 M NaNO₃, 3% acetic acid on a Waters Linear Ultrahdyrogel column, 2 in series. Columns and detectors are kept at 40⁰C. Flow is set to 0.5 mL/min.

Other suitable aids include polyethyleneimine and its derivatives. These are commercially available under the trade name Lupasol ex. BASF AG of Ludwigschaefen, Germany. Other suitable aids include Polyamidoamine- epichlorohydrin (PAE) Resins which are condensation products of polyalkylenepolyamine with polycarboxyic acid. The most common PAE resins are the condensation products of diethylenetriamine with adipic acid followed by a subsequent reaction with epichlorohydrin. They are available from Hercules Inc. of Wilmington DE under the trade name Kymene or from BASF A.G. under the trade name Luresin. These polymers are described in Wet Strength resins and their applications edited by L. L. Chan, TAPPI Press(1994).

Rheology Modifier

In a preferred embodiment of the present invention, the composition comprises a rheology modifier. The rheology modifier is selected from the group consisting of non- polymeric crystalline, hydroxy-functional materials, polymeric rheology modifiers which impart shear thinning characteristics to the aqueous liquid matrix of the composition. Such rheology modifiers are preferably those which impart to the aqueous liquid composition a high shear viscosity at 20 sec^"1 at 21⁰C of from 1 to 1500 cps and a viscosity at low shear (0.05 sec^"1 at 21⁰C) of greater than 5000 cps. Viscosity according to the present invention is measured _usj_{ng an AR} 550 rheometer from TA instruments using a plate steel spindle at 40 mm diameter and a gap size of 500 μm. The high shear viscosity at 20s^"1 and low shear viscosity at 0.5^"1 can be obtained from a logarithmic shear rate sweep from 0.1"¹ to 25'¹ in 3 minutes time at 21C. Crystalline, hydroxy- functional materials are rheology modifiers which form thread-like structuring systems throughout the matrix of the composition upon in situ crystallization in the matrix. Polymeric rheology modifiers are preferably selected from polyacrylates, polymeric gums, other non-gum polysaccharides, and combinations of these polymeric materials.

The overall objective in adding such a rheology modifier to the compositions herein is to arrive at liquid compositions which are suitably functional and aesthetically pleasing from the standpoint of product thickness, product pourability, product optical properties, and/or particles suspension performance. Thus the rheology modifier will generally serve to establish appropriate rheological characteristics of the liquid product and will do so without imparting any undesirable attributes to the product such as unacceptable optical properties or unwanted phase separation. Generally the rheology modifier will comprise from 0.01% to 1% by weight, preferably from 0.05% to 0.75% by weight, more preferably from 0.1% to 0.5% by weight, of the compositions herein. The rheology modifier component of the compositions herein can be characterized as an "external" or "internal" rheology modifier. Preferably the rheology modifier of the present invention is an external rheology modifier. An "external" rheology modifier, for purposes of this invention, is a material which has as its primary function that of providing rheological alteration of the liquid matrix. Generally, therefore, an external rheology modifier will not, in and of itself, provide any significant fabric cleaning or fabric care benefit or any significant ingredient solubilization benefit. An external rheology modifier is thus distinct from an "internal" rheology modifier which may also alter matrix rheology but which has been incorporated into the liquid product for some additional primary purpose. Thus, for example, a preferred internal rheology modifier would be anionic surfactants which can serve to alter rheological properties of liquid detergents, but which have been added to the product primarily to act as the cleaning ingredient.

The external rheology modifier of the compositions of the present invention is used to provide an aqueous liquid matrix for the composition which has certain rheological characteristics. The principal one of these characteristics is that the matrix must be "shear-thinning". A shear-thinning fluid is one with a viscosity which decreases as shear is applied to the fluid. Thus, at rest, i.e., during storage or shipping of the liquid detergent product, the liquid matrix of the composition should have a relatively high viscosity. When shear is applied to the composition, however, such as in the act of pouring or squeezing the composition from its container, the viscosity of the matrix should be lowered to the extent that dispensing of the fluid product is easily and readily accomplished.

The at-rest viscosity of the compositions herein will ideally be high enough to accomplish several purposes. Chief among these purposes is that the composition at rest should be sufficiently viscous to suitably suspend the pearlescent, another essential component of the invention herein. A secondary benefit of a relatively high at-rest viscosity is an aesthetic one of giving the composition the appearance of a thick, strong, effective product as opposed to a thin, weak, watery one. Finally, the requisite rheological characteristics of the liquid matrix should be provided via an external rheology modifier which does not disadvantageously detract from the visibility of the aesthetic agent suspended within the composition, i.e., by making the matrix opaque to the extent that the suspended obscured.aesthetic agent is obscured.

Materials which form shear-thinning fluids when combined with water or other aqueous liquids are generally known in the art. Such materials can be selected for use in the compositions herein provided they can be used to form an aqueous liquid matrix having the rheological characteristics set forth hereinbefore. One type of structuring agent which is especially useful in the compositions of the present invention comprises non-polymeric (except for conventional alkoxylation) , crystalline hydroxy-functional materials which can form thread-like structuring systems throughout the liquid matrix when they are crystallized within the matrix in situ. Such materials can be generally characterized as crystalline, hydroxyl-containing fatty acids, fatty esters or fatty waxes. Such materials will generally be selected from those having the following formulas:

I)

CH₂-OR¹ CH — OR^{2 1} 3

CH₂-OR³ wherein:

O R¹ is — C-R⁴

R² is R¹ or H;

R³ Js R¹ Or H;

R⁴ is independently C10-C22 alkyl or alkenyl comprising at least one hydroxyl group;

II)

O

7 ■> R -C-OM wherein:

O

R^? fa __C_R⁴

R⁴ is as defined above in i);

M is Na⁺, K⁺, Mg⁺* or Al³⁺, or H; and

III) Z-(CH(OH))a-Z'

where a is from 2 to 4, preferably 2; Z and Z' are hydrophobic groups, especially selected from Ce-C₂O alkyl or cycloalkyl, C6-C24 alkaryl or aralkyl, C6-C20 aryl or mixtures thereof. Optionally Z can contain one or more nonpolar oxygen atoms as in ethers or esters. Materials of the Formula I type are preferred. They can be more particularly defined by the following formula:

wherein:

(x + a) is from between 11 and 17; (y + b) is from between 11 and 17; and (z + c) is from between 11 and 17. Preferably, in this formula x = y = z =10 and/or a = b = c = 5.

Specific examples of preferred crystalline, hydroxyl-containϊng rheology modifiers include castor oil and its derivatives. Especially preferred are hydrogenated castor oil derivatives such as hydrogenated castor oil and hydrogenated castor wax. Commercially available, castor oil-based, crystalline, hydroxyl-containing rheology modifiers include THIXCIN® from Rheox, Inc. (now Elementis).

Alternative commercially available materials that are suitable for use as crystalline, hydroxyl-containing rheology modifiers are those of Formula III hereinbefore. An example of a rheology modifier of this type is 1 ,4-di-O-benzyl-D- Threitol in the R₅R, and S₅S forms and any mixtures, optically active or not. All of these crystalline, hydroxyl-containing rheology modifiers as hereinbefore described are believed to function by forming thread-like structuring systems when they are crystallized in situ within the aqueous liquid matrix of the compositions herein or within a pre-mix which is used to form such an aqueous liquid matrix. Such crystallization is brought about by heating an aqueous mixture of these materials to a temperature above the melting point of the rheology modifier, followed by cooling of the mixture to room temperature while maintaining the liquid under agitation. Under certain conditions, the crystalline, hydroxyl-containing rheology modifiers will, upon cooling, form the thread-like structuring system within the aqueous liquid matrix. This thread-like system can comprise a fibrous or entangled thread-like network. Non-fibrous particles in the form of "rosettas" may also be formed. The particles in this network can have an aspect ratio of from 1.5:1 to 200:1 , more preferably from 10:1 to 200:1. Such fibers and non-fibrous particles can have a minor dimension which ranges from 1 micron to 100 microns, more preferably from 5 microns to 15 microns.

These crystalline, hydroxyl-containing materials are especially preferred rheology modifiers for providing the detergent compositions herein with shear-thinning rheology. They can effectively be used for this purpose at concentrations which are low enough that the compositions are not rendered so undesirably opaque that bead visibility is restricted. These materials and the networks they form also serve to stabilize the compositions herein against liquid-liquid or solid-liquid (except, of course, for the beads and the structuring system particles) phase separation. Their use thus permits the formulator to use less of relatively expensive non-aqueous solvents or phase stabilizers which might otherwise have to be used in higher concentrations to minimize undesirable phase separation. These preferred crystalline, hydroxyl-containing rheology modifiers, and their incorporation into aqueous shear-thinning matrices, are described in greater detail in U.S. Patent No. 6,080,708 and in PCT Publication No. WO 02/40627.

Other types of rheology modifiers, besides the non-polymeric, crystalline, hydroxyl-containing rheology modifiers described hereinbefore, may be utilized in the liquid detergent compositions herein. Polymeric materials which will provide shear- thinning characteristics to the aqueous liquid matrix may also be employed. Suitable polymeric rheology modifiers include those of the polyacrylate, polysaccharide or polysaccharide derivative type. Polysaccharide derivatives typically used as rheology modifiers comprise polymeric gum materials. Such gums include pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum and guar gum. If polymeric rheology modifiers are employed herein, a preferred material of this type is gellan gum. Gellan gum is a heteropolysaccharide prepared by fermentation of Pseudomonaselodea ATCC 31461. Gellan gum is commercially marketed by CP Kelco U.S., Inc. under the KELCOGEL tradeneme. Processes for preparing gellan gum are described in U.S. Patent Nos. 4,326,052; 4,326,053; 4,377,636 and 4,385,123.

A further alternative and suitable rheology modifier is a combination of a solvent and a polycarboxylate polymer. More specifically the solvent is preferably an alkylene glycol. More preferably the solvent is dipropy glycol. Preferably the polycarboxylate polymer is a polyacrylate, polymethacrylate or mixtures thereof. The solvent is preferably present at a level of from 0.5 to 15%, preferably from 2 to 9% of the composition. The polycarboxylate polymer is preferably present at a level of from 0.1 to 10%, more preferably 2 to 5% of the composition. The solvent component preferably comprises a mixture of dipropyleneglycol and 1,2-propanediol. The ratio of dipropyleneglycol to 1,2-propanediol is preferably 3:1 to 1:3, more preferably preferably 1 :1. The polyacrylate ispreferably a copolymer of unsaturated mono- or di-carbonic acid and 1-30C alkyl ester of the (meth) acrylic acid. In an other preferred embodiment the rheology modifier is a polyacrylate of unsaturated mono- or di-carbonic acid and 1-30C alkyl ester of the (meth) acrylic acid. Such copolymers are available from Noveon Inc under the tradeπame Carbopol Aqua 30.

Of course, any other rheology modifiers besides the foregoing specifically described materials can be employed in the aqueous liquid detergent compositions herein, provided such other rheology modifier materials produce compositions having the selected rheological characteristics hereinbefore described. Also combinations of various rheology modifiers and rheology modifier types may be utilized, again so long as the resulting aqueous matrix of the composition possesses the hereinbefore specified pour viscosity, constant stress viscosity and viscosity ratio values.

Builder

The compositions of the present invention may optionally comprise a builder.

Suitable builders are discussed below:

Suitable polycarboxylate builders include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ^* ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid

10 detergent formulations due to their availability from renewable resources and their biodegradability. Oxydisuccinates are also especially useful in such compositions and combinations.

Also suitable in the liquid compositions of the present invention are the 3,3- dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S.

I^ Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. 0 Laurylsuccinates are the preferred builders of this group, and are described in EP-A-O 200 263, published November 5, 1986.

Specific examples of nitrogen-containing, phosphor-free aminocarboxylates include ethylene diamine disuccinic acid and salts thereof (ethylene diamine disuccinates, EDDS), ethylene diamine tetraacetic acid and salts thereof (ethylene

25 diamine tetraacetates, EDTA), and diethylene triamine penta acetic acid and salts thereof (diethylene triamine penta acetates, DTPA).

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

30 water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Bleach system

Bleach system suitable for use herein contains one or more bleaching agents.

Nonlimiting examples of suitable bleaching agents are selected from the group consisting of catalytic metal complexes, activated peroxygen sources, bleach activators, bleach boosters, photobleaches, bleaching enzymes, free radical initiators, and hyohalite bleaches.

Suitable activated peroxygen sources include, but are not limited to, preformed peracids, a hydrogen peroxide source in combination with a bleach activator, or a mixture thereof. Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Suitable sources of hydrogen peroxide include, but are not limited to, compounds selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof. Suitable types and levels of activated peroxygen sources are found in U.S. Patent Nos. 5,576,282, 6,306,812 and

6,326,348.

Perfume Perfumes are preferably incorporated into the detergent compositions of the present invention. The perfume ingredients may be premixed to form a perfume accord prior to adding to the detergent compositions of the present invention. As used herein, the term "perfume" encompasses individual perfume ingredients as well as perfume accords. More preferably the compositions of the present invention comprise perfume microcapsules. Perfume microcapsules comprise perfume raw materials encapsulated within a capsule made of materials selected from the group consisting of urea and formaldehyde, melamine and formaldehyde, phenol and formaldehyde, gelatine, polyurethane, polyamides, cellulose ethers, cellulose esters, polymethacrylate and mixtures thereof. Encapsulation techniques can be found in "Microencapsulation": methods and industrial applications edited by Benita and Simon (marcel Dekker Inc 1996). The level of perfume accord in the detergent composition is typically from about 0.0001% to about 2% or higher, e.g., to about 10%; preferably from about 0.0002% to about 0.8%, more preferably from about 0.003% to about 0.6%, most preferably from about 0.005% to about 0.5% by weight of the detergent composition. The level of perfume ingredients in the perfume accord is typically from about

0.0001% (more preferably 0.01%) to about 99%, preferably from about 0.01% to about 50%, more preferably from about 0.2% to about 30%, even more preferably from about 1% to about 20%, most preferably from about 2% to about 10% by weight of the perfume accord. Exemplary perfume ingredients and perfume accords are disclosed in U.S. Pat. 5,445,747; U.S. Pat. 5,500,138; U.S. Pat. 5,531,910; U.S. Pat. 6,491,840; and U.S. Pat. 6,903,061.

Solvent system

The solvent system in the present compositions can be a solvent system containing water alone or mixtures of organic solvents with water. Preferred organic solvents include 1 ,2-propanediol, ethanol, glycerol, dipropylene glycol, methyl propane diol and mixtures thereof. Other lower alcohols, C₁-C₄ alkanolamines such as monoethanolamine and triethanol amine, can also be used. Solvent systems can be absent, for example from anhydrous solid embodiments of the invention, but more typically are present at levels in the range of from about 0.1% to about 98%, preferably at least about 10% to about 95%, more usually from about 25% to about 75%.

Fabric substantive and Hueing Dye

Dyes are conventionally defined as being acid, basic, reactive, disperse, direct, vat, sulphur or solvent dyes, etc. For the purposes of the present invention, direct dyes, acid dyes and reactive dyes are preferred, direct dyes are most preferred. Direct dye is a group of water-soluble dye taken up directly by fibers from an aqueous solution containing an electrolyte, presumably due to selective adsorption. In the Color Index system, directive dye refers to various planar, highly conjugated molecular structures that contain one or more anionic sulfonate group. Acid dye is a group of water soluble anionic dyes that is applied from an acidic solution. Reactive dye is a group of dyes containing reactive groups capable of forming covalent linkages with certain portions of the molecules of natural or synthetic fibers. From the chemical structure point of view, suitable fabric substantive dyes useful herein may be an azo compound, stilbenes, oxazines and phthalocyanines.

Suitable fabric substantive dyes for use herein include those listed in the Color Index as Direct Violet dyes, Direct Blue dyes, Acid Violet dyes and Acid Blue dyes.

In one preferred embodiment, the fabric substantive dye is an azo direct violet 99, also known as DV99 dye having the following formula:

The hueing dye is included in the laundry detergent composition in an amount sufficient to provide a tinting effect to fabric washed in a solution containing the detergent. In one embodiment, the composition comprises, by weight, from about 0.0001% to about 0.05%, more specifically from about 0.001% to about 0.01%, of the hueing dye.

Exemplary hueing dyes include triarylmethane blue and violet basic dyes as set forth in Table 2, methine blue and violet basic dyes as set forth in Table 3, anthraquinone dyes as set forth in Table 4, anthraquinone dyes basic blue 35 and basic blue 80, azo dyes basic blue 16, basic blue 65, basic blue 66 basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48, oxazine dyes basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nile blue A and xanthene dye basic violet 10, and mixtures thereof.

Encapsulated composition

The compositions of the present invention may be encapsulated within a water soluble film. The water-soluble film may be made from polyvinyl alcohol or other suitable variations, carboxy methyl cellulose, cellulose derivatives, starch, modified starch, sugars, PEG, waxes, or combinations thereof.

In another embodiment the water-soluble may include other adjuncts such as co-polymer of vinyl alcohol and a carboxylic acid. US patent 7,022,656 B2 (Monosol) describes such film compositions and their advantages. One benefit of these copolymers is the improvement of the shelf-life of the pouched detergents thanks to the better compatibility with the detergents. Another advantage of such films is their better cold water (less than 10⁰C) solubility. Where present the level of the copolymer in the film material, is at least 60% by weight of the film. The polymer can have any weight average molecular weight, preferably from 1000 daltons to 1,000,000 daltons, more preferably from 10,000 daltons to 300,000 daltons, even more preferably from 15,000 daltons to 200,000 daltons, most preferably from 20,000 daltons to 150,000 daltons. Preferably, the co-polymer present in the film is from 60% to 98% hydrolysed, more preferably 80% to 95% hydrolysed, to improve the dissolution of the material. In a highly preferred execution, the co-polymer comprises from 0.1 mol% to 30 mol%, preferably from 1 mol% to 6 mol%, of said carboxylic acid.

The water-soluble film of the present invention may further comprise additional co-monomers. Suitable additional co-monomers include sulphonates and ethoxylates. An example of preferred sulphonic acid is 2-acrylamido-2-methyl-l- propane sulphonic acid (AMPS). A suitable water-soluble film for use in the context of the present invention is commercially available under tradename M8630™ from Mono-Sol of Indiana, US. The water-soluble film herein may also comprise ingredients other than the polymer or polymer material. For example, it may be beneficial to add plasticisers, for example glycerol, ethylene glycol, diethyleneglycol, propane diol, 2-methyl-l,3-propane diol, sorbitol and mixtures thereof, additional water, disintegrating aids, fillers, anti-foaming agents, emulsifying/dispersing agents, and/or antiblocking agents. It may be useful that the pouch or water-soluble film itself comprises a detergent additive to be delivered to the wash water, for example organic polymeric soil release agents, dispersants, dye transfer inhibitors. Optionally the surface of the film of the pouch may be dusted with fine powder to reduce the coefficient of friction. Sodium aluminosilicate, silica, talc and amylose are examples of suitable fine powders.

The encapsulated pouches of the present invention can be made using any convention known techniques. More preferably the pouches are made using horizontal form filling thermoforming techniques.

Other adjuncts

Examples of other suitable cleaning adjunct materials include, but are not limited to, alkoxylated benzoic acids or salts thereof such as trimethoxy benzoic acid or a salt thereof (TMBA); enzyme stabilizing systems; chelants including aminocarboxylates, aminophosphonates, nitrogen-free phosphonates, and phosphorous- and carboxylate-free chelants; inorganic builders including inorganic builders such as zeolites and water-soluble organic builders such as polyacrylates, acrylate / maleate copolymers and the likescavenging agents including fixing agents for anionic dyes, complexing agents for anionic surfactants, and mixtures thereof; effervescent systems comprising hydrogen peroxide and catalase; optical brighteners or fluorescers; soil release polymers; dispersants; suds suppressors; dyes; colorants; filler salts such as sodium sulfate; hydrotropes such as toiuenesulfonates, cumenesulfonates and naphthalenesulfonates; photoactivators; hydrolysable surfactants; preservatives; anti- oxidants; anti-shrinkage agents; anti-wrinkle agents; germicides; fungicides; color speckles; colored beads, spheres or extrudates; sunscreens; fluorinated compounds; clays; luminescent agents or chemiluminescent agents; anti-corrosion and/or appliance protectant agents; alkalinity sources or other pH adjusting agents; solubilizing agents; processing aids; pigments; free radical scavengers, and mixtures thereof. Suitable materials include those described in U.S. Patent Nos. 5,705,464, 5,710,1 15, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Mixtures of adjuncts - Mixtures of the above components can be made in any proportion.

Composition Preparation The compositions herein can generally be prepared by mixing the ingredients together and adding the pearlescent agent. If however a rheology modifier is used, it is preferred to first form a pre-mix within which the rheology modifier is dispersed in a portion of the water eventually used to comprise the compositions. This pre-mix is formed in such a way that it comprises a structured liquid.

To this structured pre-mix can then be added, while the pre-mix is under agitation, the surfactant(s) and essential laundry adjunct materials, along with water and whatever optional detergent composition adjuncts are to be used. Any convenient order of addition of these materials, or for that matter, simultaneous addition of these composition components, to the pre-mix can be carried out. The resulting combination of structured premix with the balance of the composition components forms the aqueous liquid matrix to which the pearlescent agent will be added. In a particularly preferred embodiment wherein a crystalline, hydroyxl-containing structurant is utilized, the following steps can be used to activate the structurant:

1) A premix is formed by combining the crystalline, hydroxy 1 -stabilizing agent, preferably in an amount of from about 0.1% to about 5% by weight of the premix, with water which comprises at least 20% by weight of the premix, and one or more of the surfactants to be used in the composition, and optionally, any salts which are to be included in the detergent composition.

2) The pre-mix formed in Step 1) is heated to above the melting point of the crystalline, hydroxyl-containing structurant.

3) The heated pre-mix formed in Step 2) is cooled, while agitating the mixture, to ambient temperature such that a thread-like structuring system is formed within this mixture.

4) The rest of the detergent composition components are separately mixed in any order along with the balance of the water, to thereby form a separate mix.

5) The structured pre-mix from Step 3 and the separate mix from Step 4 are then combined under agitation to form the structured aqueous liquid matrix into which the visibly distinct beads will be incorporated.

EXAMPLES The following nonlimiting examples are illustrative of the present invention. Percentages are by weight unless otherwise specified. Examples 1-5 illustrates the preparation of cold pearl premixes of organic pearlescent agents. Example 1

To prepare a cold pearl premix, 900 grams SLS¹ is added to a jacketed vessel with an internal diameter of 120 mm and a total capacity of approximately 1200 ml.

The vessel is equipped with dual four blade impellers at a length of 38 mm each and having a pitch of 45°. SLS is heated to 77°C at which point 100 grams glycol ester-A³

(EGDS : EGMS 75:25) is added. The pre-mix is held at 77°C for approximately 2 hours at a mixing speed of 300 RPMs. The mixture is heated to 87°C and held for 30 minutes while maintaining 300 RPM. It is then cooled at a rate of 4°C/min until the pre-mix reached 22°C while maintaining 300 RPM. Once pre-mix has reached the desired temperature, mixing is stopped.

Example 2

To prepare a cold pearl premix, 900 grams ALS² and 100 grams glycol ester-A³ (EGDS : EGMS 75:25) are mixed according to the process described in Example 1.

Example 3

To prepare a cold pearl premix, 900 grams SLS¹ and 100 grams glycol ester-A³ (EGDS : EGMS 60:40) are mixed according to a process similar to the process described in Example 1, except that the mixing speed is 200 RPM and the cooling rate is 2°C/min.

Example 4:

To prepare a cold pearl premix, 900 grams SLS¹ and 100 grams glycol ester-B⁴ are mixed according to the process described in Example 1.

Example 5

To prepare a cold pearl premix, 890 grams SLS¹ is added to a jacketed vessel with an internal diameter of 120 mm and a total capacity of approximately 1200 ml. The vessel is equipped with dual four blade impellers at a length of 38 mm each and having a pitch of 45°. SLS is heated to 77°C at which point 100 grams glycol ester-C^s

(90:10) and 1Og C 12-Cl 4 fatty acid are added. The pre-mix is held at 77°C for approximately 2 hours at a mixing speed of 250 RPMs. The pre-mix is heated to 87°C and held for 30 minutes while maintaining 250 RPM. It is then cooled at a rate of 2°C/min until the pre-mix reached 22°C while maintaining 250 RPM. Once pre-mix has reached the desired temperature, mixing is stopped 5

1 : SLS = Sodium lauryl sulfate, available from Colonial Chemical Inc. South Pittsburg, TN containing 29% active sodium lauryl sulfate.

2: ALS = Ammonium lauryl sulfate, available from The Stepan Company of 10 Northfϊeld, IL Chemical Inc. containing 30% active ammonium lauryl sulfate.

3: Glycol Ester-A a. Ethylene glycol disterarate (EGDS) available from Degussa, Hopewell VA, containing 98% ethylene glycol distearate and 2% ethylene glycol monostearate); and l^b. Ethylene glycol monostearate (EGMS), available from The Stepan Company,

Northfield, IL, containing 40% ethylene glycol distearate and 60% ethylene glycol monostearate). Components are mixed in the ratio of a : b = 60:40 so as to achieve a final ratio of

EGDS: EGMS of 75:25 for Glycol Ester - A. 0

4: Glycol Ester-B c. Ethylene glycol disterarate (EGDS)supplied by Degussa, Hopewell VA, containing 98% ethylene glycol distearate and 2% ethylene glycol monostearate).

²⁵ 5: Glycol Ester-C d. Ethylene glycol disterarate (EGDS)supplied by Degussa, Hopewell VA, containing 98% ethylene glycol distearate and 2% ethylene glycol monostearate); and e. Ethylene glycol monostearate (EGMS), supplied by The Stepan Company, Northfield, IL containing 40% ethylene glycol distearate and 60% ethylene glycol

30 monostearate). Components are mixed in a ratio of d : e = 87:13 so as to achieve a final ratio of EGDS:

EGMS of 90:10 for Glycol Ester - C.

Preparation and Observation of detergent compositions containing cold pearls

Cold pearl compositions of Examples 1-5 are mixed with liquid laundry detergents with stirring and without any externally applied heat. The resulting detergent compositions have an attractive pearlescent appearance as prepared. These detergent compositions are stored at 45⁰C for 2 weeks, after which these detergent compositions _are visually inspected for stability. If the fatty esters or the cold pearls float to the top of the detergent composition, the detergent composition is considered unstable; in contrast, stable detergent composition exhibits pearlescent luster evenly throughout.

Examples: Detergent compositions containing cold pearls

Ingredient Wt%

C12-15alkyl polyethoxylate (1.8) sulfate 18.0

Ethanol 2.5

Diethy lene glycol 1.3

Propanediol 3.5

C12-13Alkyl polyethoxylate (9) 0.4

C12-14 fatty acid 2.5

Sodium cumene sulphonate 3.0

Citric acid 2.0

Sodium hydroxide (to pH 8.0) 1.5

Protease (32g/L) 0.3

Cold Pearl (see Table 1) 2.0^#

Soil suspending polymers 1.1 adjuncts* < 10

Water to 100% * adjuncts include perfume, enzymes, fabric softeners, suds suppressor, brightener, enzyme stabilizers & other optional ingredients.

# the concentration is based on the active (EGDS+ EGMS) level in the cold pearl. Table 1

Stepan Pearl-2® and Stepan Pearl 4®, all of which are available from Stepan Company Northfield, IL; Mackpearl 202®, Mackpearl 15-DS®, Mackpearl DR- 104®, Mackpearl DR-106® , all of which are available from Mclntyre Group, Chicago, IL; TegoPearl S-33® Tego Pearl B48®, all of which are available from Goldschmidt, Hopewell VA; and Euperlan PK900 Benz-W®, which is available from Cognis Corp., Cincinnati, OH.

Examples 11 to 19 are examples of suitable concentrated liquid detergent compositions Composition according to the present invention are made by mixing all ingredients and finally adding the rheology modifier, such as hydrogenated caster oil. Adding the rheology modifier earlier in the manufacturing process would break the structure or network and result in a composition which is not structured and thus not capable of suspending particulates.

¹ Cio-Ci₈ alkyl ethoxy sulfate ² C9-C15 linear alkyl benzene sulfonate

³ C12-C13 ethoxylated (EO9) alcohol

⁴ Supplied by Akzo Chemicals, Chicago, IL

⁵ Supplied by Novozymes, NC

⁶ Supplied by Ciba Specialty Chemicals, high Point, NC ⁷ as described in US 4,597,898^s as described in US 5,565,145

⁹ available under the tradename LUTENSIT® from BASF and such as those described in WO 01/05874

10 supplied by Dow Corning Corporation, Midland, MI 11 supplied by Shin-Etsu Silicones, Akron, OH 12 supplied by Nalco Chemcials of Naperville, IL

13 supplied by Ekhard America, Louisville, KY 14 Supplied by Degussa Corporation, Hopewell, VA 15 Supplied by Rhodia Chemie, France 16 Supplied by Aldrich Chemicals, Greenbay, WI 17 Supplied by Dow Chemicals, Edgewater, NJ 18 Supplied by Shell Chemicals

Further examples of Liquid Laundry Detergents are described below. Examples 20, 21 , 23 and 24 are representative of the present invention. Examples 22, 25 and 26 are comparative. :

Filtration Test Method:

• A 1 % wash solution is made by adding the laundry detergent to a beaker (ø 120mm, H 150mm) containing IL city water (2.5mmol/L hardness) at 40⁰C during mixing on a magnetic stirrer (magnetic barrel L 60mm, ø 8mm, speed = 250 RPM). The wash solution is mixed for 20 minutes at 40⁰C at a constant speed (250 RPM).

1. Immediately after mixing, the IL wash solution is poured slowly over a circular black fabric in a Buhner funnel, that is under vacuum. The black fabric are black C70 Circles (ø 90 mm) from Emperical Manufacturing Co, Inc - Catrina R Jimmar - 7616 Reinhold Rd - Cincinnati OH 45237

2. The black fabrics are assessed for pearl pigment residues after drying.

Filtration test : success criteria

The samples from the filtration test are visually graded according to the following scale, residues are particles visible to the naked eye:

Grade 1 : No visible residues

Grade 2: Acceptable residue in stressed test < 5% of fabric surface covered in residues

Grade 3: Unacceptable residue in stressed test> 5% of fabric surface covered in residues

Grade 1& 2 are acceptable and Grade 3 is a fail and not acceptable Ex.

White base composition Ex.27 28

Flagship WB 2inl WB

Active material in Wt.%

Glycerol (min 99) 5.3 7.8

1,2-propanediol 10.0 14.6

Citric Acid 0.5 -

Monoethanolamine 10.0 7.6

Caustic soda _ 1.1

Dequest 2010 1.1 -

Potassium sulfite 0.2 0.2

Nonionic Marlipal C24EO7 20.1 18.6

HLAS 24.6 24.4

Optical brightener FWA49 0.2 -

Optical brightener FWA36 - 0.3

C 12-15 Fatty acid 16.4 19.9

Polymer Lutensit Z96 2.9 _

Polyethyleneimine ethoxylate PEI600 E20 1.1 -

MgC12 0.2 -

Enzymes ppm Ppm

Water (added) 1.6 2.2

Total water (less than) 7.4 5.6

Example 29:Use of pigments vs. EGDS

29.1 29.2 29.3 29.4 29.5 29.6 29.7

Active material in Wt.%

White base from Ex. 1 ad 100 100 100 100 100 - -

White base from Ex. 2 ad - - _ - - 100 100

Perfume 1.6 1.6 1.6 1.6 1.6 1.6 1.6

Dyes ppm ppm ppm Ppm ppm ppm ppm

Silicone softener (PDMS) - - - - - 2.15 2.15

Biron Silver CO - - - 0.1 - - -

Biron® Liquid Silver (1) - - 0.1 - -

TegoPearl NlOO - 3 _ - - - 3

TegoPearl N300 - - 3 - _ - -

Hydrogenated castor oil 0.14 0.14 0.14 0.14 0.14 0.23 0.23

Total water (less than) <10 <10 <10 <10 <10 <10 <10 Refractive index 1.4690 1.4638 Pearlescence grade (0 to 10)** 0 1 1 9 9 0 1 Pearlescence Grading Method

An expert panel of 10 judges were asked to compare the present example samples with a range of samples having a graded pearlescent effect. 0 grade pearlescence is a composition showing no visible signs of pearlescence. O grade pearlescence is that produced by example 33.1. The highest pearl effect possible, grade 10, is that produced by example 33.7. The reported grading number is the average score of the 10 panelists.

Example 30:

Use of various inorganic pigments

30.1 30.2 30.3 30.4 30.5

Active material in Wt. %

White base from Ex. 1 - - - - -

White base from Ex. 2 ad 100 100 100 100 100

Perfume 1.6 1.6 1.6 1.6 1.6

Dyes ppm ppm ppm ppm ppm

Silicone softener (PDMS) 2.15 2.15 2.15 2.15 2.15

Iriodin 1 1 1 Rutile Fine Satin 0.2 - - - -

Iriodin 119 Polar White - 0.2 -

Timiron Supersilk MP-1005 - - 0.2 - -

Timiron Super Silver - - - 0.2 -

Dichrona RY _ _ 0.2

Hydrogenated castor oil 0.23 0.23 0.23 0.23 0.23

Total water (less than) <10 <10 <10 <10 <10

D 0.99 < 50μm YES YES YES NO NO

Residues as defined by filtration method

Consumer Acceptable level of PASS PASS PASS FAIL FAIL residues

Example 31:

Impact of opacifϊer on turbidity

31.1 31.2 31.3 31.4 31.5 31.6

Active material in Wt.%

White base from Ex. 1 White base from Ex. 2 ad 100 100 100 100 100 100 Perfume 1.6 1.6 1.6 1.6 1.6 1.6

Dyes ppm ppm ppm ppm ppm ppm Silicone softener (PDMS) Opacifier Acusol Op. 301 0.1 0.2 0.3 0.4 0.5 Hydrogenated castor oil 0.23 0.23 0.23 0.23 0.23 0.23

Total water (less than) <10 <10 <10 <10 <10 <10

Turbidity (NTU) 289 750 1729 1898 2514 2701

Example 32:

Impact of turbidity on pearlescence

32.1 32.2 32.3 32.4 32.5 32.6 Active material in Wt. %

White base from Ex. 1 _ _ _ _ _ _

White base from Ex. 2 ad 100 100 100 100 100 100

Perfume 1.6 1.6 1.6 1.6 1.6 1.6

Dyes ppm ppm ppm ppm ppm ppm

Opacifier Acusol Op. 301 - 0.1 0.2 0.3 0.4 0.5

Biron® Liquid Silver (1) 0.03 0.03 0.03 0.03 0.03 0.03

Hydrogenated castor oil 0.23 0.23 0.23 0.23 0.23 0.23

Total water (less than) <10 <10 <10 <10 <10 <10

Pearlescence (grading) 7.3 6.8 4.9 2.6 2.1 1.6

Example 33:

Biron level study in clear matrix

33.1 33.2 33.3 33.4 33.5 33.6 33.7 Active material in Wt. %

White base from Ex. 2 ad 100 100 100 100 100 100 100

Perfume 1.6 1.6 1.6 1.6 1.6 1.6 1.6

Dyes ppm ppm ppm ppm ppm ppm ppm

Biron® Liquid Silver (1) - 0.02 0.05 0.1 0.15 0.2 0.25

Hydrogenated castor oil 0.23 0.23 0.23 0.23 0.23 0.23 0.23

Total water (less than) <10 <10 <10 <10 <10 <10 <10

Pearlescence (grading) 0.0 5.4 6.7 8.3 9.0 9.0 10.0

Example 34;

Biron level study in opaque matrix 34.1 34.2 34.3 34.4 34.5 Active material in Wt.%

White base from Ex. 2 ad 100 100 100 100 100

Perfume 1.6 1.6 1.6 1.6 1.6

Dyes ppm ppm ppm ppm ppm

Opacifier Acusol Op. 301 0.5 0.5 0.5 0.5 0.5

B iron® Liquid Silver (1) - 0.02 0.05 0.1 0.2

Hydrogenated castor oil 0.23 0.23 0.23 0.23 0.23

Total water (less than) <10 <10 <10 <10 <10

Pearlescence (grading) 0.0 1.0 3.3 5.5 7.2

Example 35:

Biron level study in 2inl formula with silicone emulsion

35.1 35.2 35.3 35.4 35.5 35.6 Active material in Wt.%

White base from Ex. 2 ad v 100 100 100 100 100 100

Perfume 1.6 1.6 1.6 1.6 1.6 1.6

Dyes ppm ppm ppm ppm ppm ppm

Silicone softener (PDMS) 2.15 2.15 2.15 2.15 2.15 2.15

Biron® Liquid Silver (1) - 0.02 0.05 0.1 0.2 0.3

Hydrogenated castor oil 0.23 0.23 0.23 0.23 0.23 0.23

Total water (less than) <10 <10 <10 <10 <10 <10

Pearlescence (grading) 0.2 1.8 4.7 7.2 8.3 9.7

Level study on Blron LS In different liquid Unit Dose matrices (average of expert panel grading)

3: 3* 3£

000% 0.05% 0.10% 0.15% 0.20% 025%

Blron LS [Wt.%]

Effect of Increased turbidity of matrix on pearlescence at 0.03% Blron

' AvoraB° I

0.10% 0.20% 0.30% 0.40% 0.50% 0.60% Opaclflor level

¹ Dequest® 2010: Hydroxyethylidene 1,1 diphosphonic acid Na salt (ex Solutia)

² Prestige Silk Silver Star from Eckart Pigments (Particle size range: 5-25μm, average Particle Size lOμm, D0.9929.70μm)

³ Biron Silver CO from Merck, 70% dispersion of bismuth oxychloride in castor oil

4 Adjuncts include perfume, enzymes, fabric softeners, suds suppressors, brightener, enzyme stabilizers & other optional ingredients

Claims

CLAIMSWhat is claimed is:

1. A pearlescent liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having D0.99 volume particle size of less than 50 μm and is present in composition at a level of from 0.01 to 2.0% by weight of the composition, measured as 100% active.

2. A pearlescent liquid treatment composition according to claim 1 wherein the composition has viscosity of from 1 to 1500 centipoises at 20s^"1 and 21⁰C.

3. A pearlescent liquid treatment composition according to claim 1 wherein the difference in refractive index (ΔN) of the medium in which the pearlescent agent is suspended and the pearlescent agent is greater than 0.02.

4. A pearlescent liquid treatment composition according to claim 1 wherein the composition has turbidity of greater than 5 and less than 3000 NTU.

5. A pearlescent liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having D0.99 volume particle size of less than 50 μm and the difference in refractive index (ΔN) of the medium in which the pearlescent agent is suspended and the pearlescent agent is greater than 0.02 .

6. A pearlescent liquid treatment composition according to claim 5 wherein the composition has viscosity of from 1 to 1500 centipoises at 20s^"1 and 21⁰C.

7. A pearlescent liquid treatment composition according to claim 5 wherein the composition has turbidity of greater than 5NTU and less than 3000 NTU.

8. A pearlescent liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having D0.99 volume particle size of less than 50 μm and the composition has turbidity of greater than 5 and less than 3000 NTU.

9. A pearlescent liquid treatment composition according to claim 8 wherein the composition has viscosity of from 1 to 1500 centipoises at 20s^"1 and 21⁰C.

10. A pearlescent liquid treatment composition suitable for use as a laundry or hard surface cleaning composition comprising a pearlescent agent, said pearlescent agent having D0.99 volume particle size of less than 50 μm and the composition has viscosity of from 1 to 1500 centipoises at 20s^"1 and 2 TC.

11. A pearlescent liquid treatment composition according to claim 10 wherein the composition has turbidity of greater than 5 NTU and less than 3000 NTU.

12. A pearlescent liquid treatment composition according to any preceding claim wherein the pearlescent agent is selected from the group consisting of organic or inorganic pearlescent agents.

13. A pearlescent liquid treatment composition according to any preceding claim wherein the pearlescent agent is an organic pearlescent agent selected from the group having the formula:

wherein Ri is linear or branched C12-C22 alkyl chain; R is linear or branched C2-C4 alkylene group;

P is selected from H, C1-C4 alkyl Or-COR₂, R₂ is C4-C22 alkyl; and n = l-3;

14. A pearlescent liquid treatment composition according to claims 1 to 12 wherein the pearlescent agent is an inorganic pearlescent agents selected from the group consisting of mica, metal oxide coated mica bismuth oxychloride coated mica, bismuth

•> oxychloride, glass, metal oxide coated glass and mixtures thereof.

15. A pearlescent liquid treatment composition according to claim 14 wherein the inorganic pearlescent agent is selected from mica, titanium oxide coated mica, iron oxide coated mica, bismuth oxychloride and mixtures thereof. 0

16. A pearlescent liquid treatment composition according to any preceding claim additionally comprising surfactant selected from the group consisting of anionic, nonionic, cationic, zwϊterionic, amphoteric surfactants and mixtures thereof.

17. A pearlescent liquid treatment composition according to claim 16 wherein the 5 surfactant is selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof and is substantially free of betaine surfactants.

18. A pearlescent liquid treatment composition according to either of claims 16 and 17 wherein the surfactant is a linear or branched C12-C20 alkyl sulfate, alkyl alkoxy, 0 preferably ethoxy or propoxy, sulfate or mixtures thereof.

19. A pearlescent liquid treatment composition according to any preceding claim additionally comprising a viscosity modifier selected from non-polymeric crystalline, hydroxy-functional materials, polymeric rheology modifiers which impart shear 5 thinning characteristics to the composition of high shear viscosity at 20 sec^"1 at 21⁰C of from 1 to 1500 cps and a viscosity at low shear (0.05 sec^"1 at 21⁰C) of greater than 5000 cps.

20. A pearlescent liquid composition according to claim 19 wherein the viscosity 0 modifier is selected from the group consisting polyacrylates, polymeric gums, other non-gum polysaccharides, and combinations of these polymeric materials.

21. A pearlescent liquid treatment composition according to any preceding claim additionally comprising a laundry care benefit agent selected from the group consisting of cationic surfactants, silicones, polyolefϊn waxes, latexes, oily sugar derivatives, cationic polysaccharides, polyurethanes and mixtures thereof.

22. A pearlescent liquid composition according to. any preceding claim wherein the composition is packaged in a water-soluble film.

23. A pearlescent liquid treatment composition according to any preceding claim wherein the pearlescent agent is present at a level of from 0.01 to 0.5%, more preferably from 0.01 to 0.2% by weight of the composition, measured as 100% active.

24. A pearlescent liquid treatment composition according to any preceding claim wherein the D0.99 volume particle size of the pearlescent agent is less than 40 μm, more preferably less than 30 μm.

25. A pearlescent liquid treatment composition suitable for laundry or hard surface cleaning comprising: (a) from about 0.5%' to about 20% by weight of the composition of a precrystallised organic pearlescent dispersion premix, which comprises (i) a pearlescent agent having the formula:

w erein Ri is linear or branched C12-C22 alkyl chain;

R is linear or branched C2-C4 alkylene group;

P is selected from H, C1-C4 alkyl or -COR₂, R₂ is C4-C22 alkyl; and n = 1-3;

(ii) a surfactant selected from the group consisting of linear or branched C 12-Cl 4 alkyl sulfate, alkyl ether sulfate, and mixtures thereof; (iii) water and adjuncts selected from the group consisting of buffers, pH modifiers, viscosity modifiers, ionic strength modifiers, fatty alcohols, additional surfactants, and mixtures thereof; (b) carrier; and (c) optionally, a laundry adjunct; wherein the treatment composition has a viscosity of from about 1 to about 1000 mPa*s.

26. The composition according to claim 25 wherein the pearlescent agent comprises mono- and di- fatty acid ethylene glycol ester having a weight ratio ranging from about 1:2 to about 2:1.

27. The composition according to claims 25-26 wherein the pearlescent agent has one or more C12-C22 fatty acyl moieties.

28. The composition according to claims 25-27 wherein the pearlescent agent has one or more C16-C22 fatty acyl moieties.

29. The composition according to claims 25-28 wherein the pearlescent agents are ethylene glycol mono- and di- stearates.

30. The composition according to claims 25-29 further comprising a co-crystallizing agent selected from the group consisting of

(i) fatty acid having a C16-C22 alkyl, alkenyl, alkylaryl or alkoxy moiety; (ii) fatty alcohol having a C16-C22 alkyl, alkenyl, alkylaryl or alkoxy moiety; and (iii) mixtures thereof.

31. The composition according to claims 25-30 wherein a weight ratio of the pearlescent agent to the co-crystallizing agent ranges from about 3:1 to about 10:1.

32. The composition according to claims 25-31 wherein the laundry adjunct comprises an anionic surfactant selected from the group consisting of Cπ-Cis alkyl benzene sulfonates (LAS), C10-C₂0 branched-chain and random alkyl sulfates (AS), C_JO-CI_S alkyl ethoxy sulfates (AE_xS) wherein x is from 1-30, mid-chain branched alkyl sulfates, mid- chain branched alkyl alkoxy sulfates, Cio-Qs alkyl alkoxy carboxylates comprising 1-5 ethoxy units, modified alkylbenzene sulfonate (MLAS), C1₂-C₂₀ methyl ester sulfonate (MES), CiO-Ci_S alpha-olefin sulfonate (AOS)₅ Ce-C₂O sulfosuccinates, and mixtures thereof.

33. The composition according to claims 25-32 wherein the laundry adjunct comprises a nonionic surfactant selected from the group consisting of Cc,-C]8 alkyl ethoxylates, Ce- Ci₂ alkyl phenol alkoxylates, Cn-Cis alcohol and Cβ-Cπ alkyl phenol condensates with ethylene oxide/propylene oxide block polymers, C14-C22 mid-chain branched alcohols, C₁₄-C₂₂ mid-chain branched alkyl alkoxylates, alkyl polyglycosides, polyhydroxy fatty acid amides, ether capped poly(oxyalkylated) alcohols, fatty acid (Ci₂-_Is) sorbitan esters, and mixtures thereof.

34. The composition according to claims 25-33 wherein the laundry adjunct comprises a fabric softener which is selected from quaternary ammonium compounds and mixtures thereof.

35. The composition according to claims 25-34 wherein the laundry adjunct is selected from the group consisting of: a stabilizer; a nitrogen-free nonionic surfactant; a nitrogen-containing detersive surfactant; a coupling agent; a perfume; a detersive enzyme; a bleach system; a brightener; a chelant; a solvent system; an effervescent system; and mixtures thereof.

36. A pearlescent composition according to claims 25-35 wherein the composition has viscosity of from about 1 to about 800 mPa*s.

37. The composition according to claims 25-36 wherein the pearlescent agent comprises from about 0.2% to about 20% by weight of the composition.

38. The composition according to claims 25-37wherein the surfactant comprises from about 5% to about 30% by weight of the composition.

39. The composition according to claims 25-38 wherein the co-crystallizing agent comprises from about 1% to about 5% by weight of the composition.

40. The composition according to claims 25-39 wherein the laundry adjunct materials comprise from about 0.0001 to about 20% by weight of the composition.

41. The composition according to claims 25-40 wherein the laundry adjuncts are selected from the group consisting of stabilizers, nonionic surfactants, nitrogen- containing surfactants, bleaches, enzymes, perfumes, brighteners, fabric softeners, and mixtures thereof.

42. The composition according to claims 25-41 wherein the pearlescent effect is provided by crystals of the fatty acid ethylene glycol esters and the co-crystallizing agent, the crystals being dispersed in the carrier comprising the surfactant.

43. A method for producing a pearlescent detergent composition according to any of claims 25 to 42 comprising the steps of: a) forming a pearlescent dispersion by mixing an organic pearlescent agent, a surfactant, water and optionally, a co-crystallizing agent at about 60⁰C to about 90⁰C and followed by cooling the resulting mixture to room temperature at a cooling rate of about 0.5-5°C/min; b) mixing the pearlescent dispersion from a) with one or more laundry adjuncts

44. A method for treating a substrate in need of treatment comprising contacting the substrate with a pearlescent liquid treatment composition according to any of claims 1 to 42 such that the substrate is treated.