CA2746854C - Highly viscous detergent emulsion - Google Patents

Abstract

A liquid cleaner concentrate composition comprises a phase stable thickend emulsion comprising a continuous aqueous phase, an effective soil removing amount including 15 to 50 wt% of a source of alkalinity and 2 to 30 wt% of a non ionic surfactant; an effective water conditioning or sequestering amount including 0.1 to 10 wt% of a water conditioning or sequestering agent, an effective soil removing and emulsion stabilizing amount comprising 0 to 10 wt% of an a lky I polyglucoside surfactant, an effective thickening amount of polycarboxylic acid comprising 1 to 25 wt%, an effective thickening amount of fatty acid comprising 0.25 to 5 wt%, wherein the dispersed phase comprises a portion of the nonionic surfactant and the thickened emulsion concentrate exibits a shear thinning permitting dispensing during manufacture and use and the viscosity comprises greater than 100,000 cP at 20°C using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second.

Description

HIGHLY VISCOUS DETERGENT EMULSION
Field Of The Invention The invention relates to a high viscosity, phase stable alkaline cleaning concentrate or composition characterized by a reduced water concentration (a high concentration of active materials such as alkalinity and surfactants) and to methods of their use and preparation. In industrial or institutional applications, the materials are phase stable, have very high viscosity yet remain dispensable from automatic or programmable dispensers to a use locus where they are easily mixed with water in a use locus to form an aqueous cleaner. The thickened emulsions are easily made and are effective in soil removal in laundry, ware washing, clean-in-place and dairy applications. The compositions provide improved or enhanced soil removal properties because of high alkaline and surfactant contact.
Back2round Of The Invention Cleaning compositions have been formulated in solid block, particulate and liquid form. Solid forms provide high concentrations of actives, but must be dissolved in water to form a cleaning liquid. Substantial attention in recent years has been directed to liquid detergent concentrates and in particular, liquid detergents in emulsion form. Such detergent concentrates typically are not as highly active as solids and are often greater than 50% water. Detergent emulsion concentrates have been employed as all-purpose cleaners, warewashing detergents and in formulations for cleaning hard surfaces by diluting the concentrate with water.
The typical emulsion liquid is less than 60% actives, less than 10%
surfactant less than 30-40% alkalinity. Many of the prior art emulsions are not sufficiently phase stable meaning that they do not remain globally homogenous for storage and use in a variety of applications, have reduced actives concentration (comprise greater than 50% water) or display reduced properties compared to other useful forms of detergent or are difficult to manufacture, dispense or store.
Many prior art emulsions contain relatively low caustic content and relatively low sequestrant and surfactant contents.

Substantial attention has been directed to concentrate materials having substantially increased active content that can be manufactured as stable liquids. A
need has existed to push the active concentrate of detergent components in the emulsion to 60 to 65% in order to provide the efficacy and performance of solids.
These liquids must have a stable viscosity and a handleable viscosity such that the liquid can be reliably dispensed from a source of the material to a use locus such as a laundry machine. We have found that, if the materials of the prior art are simply increased in concentration without the introduction of new technology, the resulting materials do not form simple solutions, do not form phase stable emulsions.
While the prior art discloses a variety of liquid emulsion detergent compositions that can be used in a variety of forms, the prior art does not provide a highly alkaline, highly viscous, stable composition with a high active cleaning composition that is easy to manufacture, has acceptable cleaning properties in laundry, warewashing and other uses, and is dispensable due to its shear thinning characteristics in specialized detergent dispensers and are compatible with typical industrial or institutional cleaning equipment. We have filled a substantial need in improving composition stability with desirable cleaning properties by improving formulations and methods of manufacture. A substantially improved thickened emulsion detergent composition, methods of its use and methods of preparation have been discovered and are disclosed below Summary Of The Invention We have found an improved highly viscous, highly alkaline detergent composition having high actives content. The composition comprises a thickening system compatible with the high alkaline formula resulting in a high viscosity composition that exhibits shear thinning. The composition of the invention is particularly novel in that its rheology is unique. The composition may be defined as a solid when no shear is applied but once shear is applied, the composition begins to flow. The composition comprises a source of alkalinity, nonionic surfactant(s), a water conditioning or sequestering agent, an optional alkyl polyglucoside surfactant, and a thickening system comprising a fatty acid and a polycarboxylic acid. The resulting stable compositions are characterized by a low water content, high actives

2 concentration (greater than 60 wt % based on the concentrate composition), high alkalinity, and a viscosity greater than about 250,000 centipoise at 20 C
using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second. This improved detergent can be used for a variety of applications but preferably is used in laundry applications. We have achieved cleaner formulations that comprise greater than 30 wt % of the combined alkaline source and the surfactant load.
In laundry applications, soiled articles are contacted with an aqueous liquid cleaning liquor comprising a major proportion of water and about 0.5 to 3.0 ppm of the emulsion detergent. The clothes are contacted with the washing liquor at an elevated temperature of from about 25 C to about 80 C for a period of time to remove soil. The soil and used liquor are then rinsed from the clothing in a rinse cycle. The improved detergents of the invention are made by a process that comprises the steps of combining the nonionic surfactant or surfactant blend with anionic surfactants, chelating components, and various other textile detergent components. To this blend, the sources of alkalinity are added followed by the polyacrylic acid. Using standard mix tanks, all the components are briefly mixed until the product is homogenous, at which point it is filled and allowed to attain its end viscosity as described above. In applications other than laundry, slight adjustments can be made to the formulation such as selecting a suitable surfactant system, to make it suitable for warewashing, or hard surface cleaning.
For the purpose of this patent application, the term "thickened emulsion"
connotes a substance that behaves as a solid until a sufficiently large load or stress is applied, at which point it flows like a fluid. Rheologically, a thickened emulsion is a viscoplastic material that behaves as a rigid body at low stresses but flows as a viscous fluid at high stress. Thickened emulsions of the invention comprise two immiscible liquids. For purposes of the invention, the continuous phase is comprised substantially of caustic salts and other dissolved components in an aqueous medium. However, since no additional water is added to compositions of the invention, thickened emulsions of the invention result in a composition having a substantially low aqueous phase or low water content. For the purposes of this

3 invention, "emulsion" and "thickened emulsion" are used interchangeably.
However, it is noted that when used generally in the art the term "emulsion"
refers to compositions having substantially lower viscosities than those of the present invention.
Without being bound by theory, as previously mentioned, it is believed that thickened emulsions of the invention are comprised of two limitedly miscible liquid phases. Compositions of the invention may comprise a third solid particulate comprised substantially of the carboxymethylcellulose or optical brightener(s), if any is used, to formulate the thickened emulsions of the invention. If a third phase exists, this discrete phase is believed to include particles in the range of between about 1 micrometer up to about 100 microns; however, compositions of the invention may include substantially larger particles including above about 100 microns The insoluble or non-water soluble portion, typically a liquid nonionic surfactant, forms dispersed droplets having a particle size less than about 10, less than about 5 microns, preferably between about 0.5 and 8 microns. Phase stable connotes that under typical manufacturing, storage and use conditions, the dispersed phase does not substantially lose its finely divided form and separate from the aqueous phase to a degree that the material becomes not useful in a laundry or other cleaning purpose. Some small amount of separation can be tolerated as long as the thickened emulsion retains greater than 98% of the discontinuous phase (predominantly organic materials) in small emulsified form and provides cleaning activity.
The aqueous materials of the invention typically involve the emulsification of a relatively insoluble, typically organic phase and an aqueous phase. The organic phase can contain one or more components such as surfactants, water conditioning agents, brighteners, etc. while the aqueous phase can contain, in an aqueous medium, aqueous soluble components such as sodium hydroxide, water conditioning agents, brighteners, dyes and other components. The materials are typically made by dispersing the relatively "oily" organic insoluble phase in the aqueous phase

4

5 stabilized by an emulsion stabilizer composition with the application of shear. In this invention the emulsion stabilizer typically comprises the polycarboxylic acid in combination with a fatty acid at an amount that can promote a stable thickened emulsion. We have found that the alkylpolyglucoside (APG) surfactants may be added to enhance the stabilization of the emulsion. In another embodiment we have found that the emulsion stabilizers are polyacrylic acid in combination with an anionic surfactant that are sufficiently soluble in sodium hydroxide and promote small particle size formation in the typical organic phase used in the thickened emulsions of the invention. We have found that simple mixtures of aqueous sodium hydroxide and nonionic surfactant such as a alkyl ethoxylate without an emulsion stabilizer will rapidly separate into two separate phases. Such surfactants have low solubility in sodium hydroxide while sodium hydroxide is insoluble in this organic compound. The useful procedure for forming the dispersions of the invention involves combining fatty alcohol ethoxylate(s) with alkyl polyglucoside, carboxymethyl cellulose and tall oil. The APG can be added at this time and the contents of the vessel can be agitated strongly. Any optical brighteners are added to the described combination followed by adding aqueous caustic, typically 50 wt %
aqueous caustic to a large metal vessel containing agitation apparatus.
Monoethanolamine is added to the combination followed by polycarboxylic acid as the final ingredient.
Although the main emphasis is on laundry detergents, this emulsion concept could be applied elsewhere as well. This would include warewashing, clean in place cleaners and sanitizers, food and dairy formulations. In general, this emulsion concept could be used in any formulation where relatively insoluble nonionic surfactants are mixed with caustic solutions to form a thickened emulsion with properties balanced for the selected end use. The low foaming surfactants can comprise nonionics such as linear alcohol ethoxylates (Lutensol available from BASF located in Ludwigshafen, Germany), particularly the fatty alcohol C13-C15 ethoxylates having 2 to 10 polyethylene oxide groups. Thickeners useful in the invention include a combination of linear polycarboxylic acid such as Acusol (Rohm & Haas) and a fatty acid such as tall oil.

Brief Description of the Figures Figures 1-2 each have an x and y axis. The x axis in Fig. 1 is the shear rate, in Fig. 2 the deviation of concentration from a standard mixture. The y axis is viscosity in both cases.
Figure 1 is a plot illustrating the decreasing viscosity of a composition of the invention with increasing shear rate.
Figure 2 is a plot illustrating the effect of concentration variation of some of the ingredients on viscosity.
Detailed Discussion Of The Invention The term "surfactant" or "surface active agent" refers to an organic chemical that when added to a liquid changes the properties of that liquid at a surface.
The terms EO, PO, or EO/PO as used herein refer to ethylene oxide and propylene oxide, respectively. EO/PO refers to ethylene oxide and propylene oxide groups.
The term "substantially free" may refer to any component that the composition of the invention lacks or mostly lacks. When referring to "substantially free" it is intended that the component is not intentionally added to compositions of the invention. Use of the term "substantially free" of a component allows for trace amounts of that component to be included in compositions of the invention because they are present in another component. However, it is recognized that only trace or de minimus amounts of a component will be allowed when the composition is said to be "substantially free" of that component.
All numeric values are herein assumed to be modified by the term "about,"
whether or not explicitly indicated. The term "about" generally refers to a range of numbers that one of skill in the art would consider equivalent to the recited value (i.e., having the same function or result). In many instances, the terms "about" may include numbers that are rounded to the nearest significant figure.
Weight percent, percent by weight, % by weight, and the like are synonyms that refer to the concentration of a substance as the weight of that substance divided by the weight of the composition and multiplied by 100.

6 Unless otherwise stated, all weight percentages provided herein reflect the weight percentage of the raw material as provided from the manufacturer. The active weight percent of each component is easily determined from the provided information by use of product data sheets as provided from the manufacturer.
Traditionally, emulsions have concerned systems of two isotropic, substantially Newtonian liquids, one being dispersed in the other in the form of small droplets. The system is stabilized by absorbed amphiphiles which modify interfacial properties. However, we have found that a large number of emulsions act in more than two phases. A discussion of emulsions and emulsion stability will begin with the traditional two-phase system. An emulsion forms when two immiscible liquids, usually water and oil, for example, are agitated so that one liquid forms droplets dispersed within the other liquid. Emulsions are stabilized by a compound adsorbed at the interface. This compound is termed an "emulsifier."
These are molecules that possess both polar and nonpolar regions and which serve to bridge the gap between the two immiscible liquids. For example, in an oil-and-water emulsion, the polar portion of an emulsifier is soluble in the water phase, while the nonpolar region is soluble in the oil phase. In general, formation of an emulsion or emulsification involves breaking large droplets into smaller ones due to shear forces.
In order to discuss the stability of emulsions, it is necessary to first discuss how an emulsion fails. The initial step in emulsion failure is known as flocculation, in which individual droplets become attached to each other but are still separated by a thin film of the continuous phase. The next step is coalescence, in which the thin liquid film between the individual droplets destabilizes, allowing large droplets to form. As coalescence continues, the emulsion separates into an oil layer and an aqueous layer. In general, emulsions are stabilized by slowing the destabilization or flocculation process. This can be done either by reducing the droplet mobility, by increasing viscosity or by the insertion of an energy barrier between droplets. In the invention, the size of droplets or particles of the dispersed phase are less than 10 microns, preferably less than 5 microns in diameter.
Rheological Characteristics Compositions of the invention are particularly unique in the rheological characteristics they exhibit. The inventors have characterized their invention as a

7 "thickened emulsion" despite the fact that compositions of the invention behave differently than any presently known emulsions. The compositions are characterized as emulsions because they are comprised of at least two immiscible phases as is commonly known in the emulsion art. However, the thickened emulsions of the invention exhibit characteristics of a solid when they are not under shear.
The thickened emulsions of the invention exhibit a viscosity of greater than 1,000,000 centipoise at zero shear. As shear increases, the rheology of the invention composition changes substantially until, when the compositions of the invention are under high shear, they exhibit properties of a liquid.
Compositions of the invention exhibit unusually high viscosity. In an embodiment thickened emulsions of the invention exhibit a viscosity of greater than 100,000 centipoise at 20 degrees centigrade when using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second. In other embodiments, thickened emulsions of the invention exhibit a viscosity of greater than 300,000, greater than 500,000, greater than 700,000, greater than 900,000, greater than 1,100,000, greater than 1,300,000, up to greater than 1.5 million centipoise at 20 degrees centigrade when measured using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second. The viscosity of the invention compositions may be engineered to suit a specific use or dispensing system. Generally, as the amount of thickening agents such as fatty acid and polycarboxylic acid are increased, the viscosity of the composition increases.
It has been discovered that fatty acids, polyacrylates positively influence the viscosity of the present invention. Compositions otherwise prepared according to the invention except they lack fatty acids are viscous fluids with viscosities of about 10 Pas when taken at 0.2s-1. Increasing the content of fatty acids from 0% to 1%
results in a continuous increase of shear viscosity up to several hundreds of Pas along with the appearance changing from a flowing liquid to a solid gel or paste.
Similar observations are made when modifying the concentration of polycarboxylic acid. As previously mentioned, without polycarboxylic acid the composition appears as a viscous liquid with shear viscosity below 10 Pas (0.2s-1). With the concentration of polycarboxylic acid between 5 and 8 weight percent, the

8 composition turns into a paste resulting in viscosities in the range of 100-1000 Pas (0.2s-1).
Alkalinity Source A source of alkalinity is needed to control the pH of the use detergent solution. The alkalinity source is selected from the group consisting of alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide or mixtures thereof;
an alkali metal silicate such as sodium metasilicate and carbonate salts may also be used. The preferred source, which is the most cost-effective, is commercially available sodium hydroxide which can be obtained in aqueous solutions in a concentration of about 50 wt-% and in a variety of solid forms in varying particle sizes. The sodium hydroxide can be employed in the invention in either liquid or solid form or a mixture of both. Other sources of alkalinity are useful but not limited to the following: alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali metal borates and alkali metal silicate. In an embodiment, between about 40 to about 80 weight percent, between about 45 to about 75 weight percent, and between about 50 to about 70 weight percent sodium hydroxide (50%

actives) is included in the composition of the invention.
Nonionic Surfactant Conventional, nonionic detersive surfactants that can be used with the invention include the alcohol ethoxylates. A combination of nonionic surfactants is preferred. These include linear and branched alcohol ethoxylates. Suitable alcohol ethoxylates include those having between about 5 and 10 EO, between about 6 and 8 EO and a linear alcohol ethoxylate having between about 1 and 6 EO, between about 2 and 5 EO. Examples of these include the fatty alcohol C13-C15 ethoxylate (7E0) commercially available as Lutensol A07 and the fatty alcohol C13-C15 ethoxylate (3E0) commercially available as Lutensol A03, both available from BASF.
Dehydol surfactants available from Cognis and Malipal surfactants available from Sasol are also useful in the present invention. Lutensol surfactants are ethoxylates of oxo-alcohols which are synthetic alcohols. Yet other examples of nonionic surfactants suitable for use in the present invention include but are not limited to

9 ethylene oxide/propylene oxide copolymers, ethylene oxide/propylene oxide/ethylene oxide copolymers, propylene oxide/ethylene oxide/propylene oxide copolymers (such as those available under the PluronicsTM mark and Pluronics R from BASF, those surfactants sold under the Plurafacs mark from BASF and those sold under the Polytergents mark also from BASF).
In an embodiment compositions of the invention include between about 5 and 35 weight percent nonionic surfactant or nonionic surfactant mixture, between about 10 and 30 weight percent, and between about 15 and 25 weight percent. In another embodiment, the composition comprises between about 2 to about 25 weight percent, between about 5 and about 20 weight percent, and between about 8 and 17 weight percent of a first nonionic surfactant; and between about 0.5 and about 15 weight percent, between about 2 and 13 weight percent, and between about 5 and 10 weight percent of a second nonionic surfactant for a total of between 2.5 and 40 weight percent non-ionic surfactant in total.
Stabilizers Alkyl Polyglucoside Surfactant We have found that the thickened emulsions of the invention are stabilized using a soap and polycarboxylic acid and alkyl polyglucosides optionally improve consistency, stability, and homogeneity of the thickened emulsions of the invention. Such surfactants have a strongly hydrophobic alkyl group with a strongly hydrophilic glycoside group that can have its hydrophilicity modified by the presence of ethylene oxide groups.
We have found these materials are effective emulsion stabilizers when the material is soluble in the aqueous phase and can promote small particle size emulsions. The alkyl polyglucoside, GlucoponTM 215 contains a hydrophobic group with an alkyl straight chain of C8 to C10.
This material has good solubility in sodium hydroxide solutions. There are other commercially available alkyl polyglucosides with different alkyl groups and DP's. The general class of alkyl polyglucosides produces low interfacial tension between mineral oil and water. Low interfacial tension is probably responsible for the success of these surfactants in stabilizing the thickened emulsion. The system that is being used is different than the typical emulsion. The oil phase is the surfactant (fatty alcohol ethoxylate) while the aqueous phase is the sodium hydroxide solution along with other materials.
Without being bound by theory, it is believed that the surfactant droplets are stabilized by the presence of a surfactant at the interface and the unusually high viscosity of the system. The surfactant (fatty alcohol ethoxylate) has essentially no solubility in the sodium hydroxide solution and the sodium hydroxide has essentially no solubility in the surfactant phase.
The alkyl polyglucosides is a surfactant useful as an emulsifier and it is known from the literature that it reduces the interfacial tension between the sodium hydroxide solution phase and surfactant phase. With this general concept it can be envisioned that other surfactants can be used and would stabilize the thickened emulsion in these systems if they reduced the interfacial tension of sodium hydroxide solution with a surfactant. In an embodiment, compositions of the invention optionally comprise between about 0.01 to about 10 weight percent alkyl polyglucoside, between about 0.5 to between about 8 weight percent, and between about 1 and about 5 weight percent (50% active).
It has been found that alkylpolyglucosides ("APGs") have a synergistic thickening, stabilizing, and homogenizing effect when used in combination with certain other thickening agents. In one embodiment APG is used in combination with a fatty acid and/or a polycarboxylic acid. In another embodiment APG is used in combination with a polyacrylate copolymer. In yet another embodiment APG is used in combination with an alcohol ethoxylate and/or an acrylic acid polymer and/or a polycarboxylic acid. Each of these thickening agents is discussed in more detail below.
Thickening agents Fatty Acid It has surprisingly been found that the combination of fatty acid with polycarboxylic acid and optionally alkylpolyglucoside in the present formulation provides a composition having a sufficiently high viscosity, improved homogeneity and stability even at the high alkalinity required. At the elevated pH and high caustic content provided in the formulation of the invention, it was found that other thickening agents widely known in the industry such as CMC, guar gums, xanthan gums, polyethylene glycol to name a few break down and are therefore ineffective at creating a high viscosity formulation. It is unusual for a composition having such a , high caustic content and alkalinity to achieve a high viscosity as exhibited by compositions of the present invention.
A fatty acid of choice in compositions of the invention comprises tall oil.
Tall oil is also referred to as liquid resin and is a resinous yellow-black oily liquid composed of a mixture of rosins, fatty acids, sterols, high-molecular alcohols, and other alkyl chain materials. The crude tall oil is distilled into tall oil rosin (having the rosin content of 10 -35%), further refinery gives to tall oil fatty acid (the rosin content of 1 -

10%). Tall oil fatty acid is particularly preferred in compositions of the invention due to its low cost and flowability. Unlike many other fatty acids, tall oil remains a liquid at ambient temperature making it easier to handle than other fatty acids. Tall oil is an unsaturated fatty acid containing primarily a combination of oleic and linolic acids and in lesser amounts palmitic and stearic acids among others. In embodiments of the invention tall oil fatty acid comprises from about 0.01 to about 5 weight percent, from about 0.1 to about 4 weight percent, and from about 0.2 to about 3 weight percent.
Polycarboxylic acids Polycarboxylic acids are also useful as thickening agents in compositions of the invention.
ACUS OLS 445 is a partially neutralized, liquid detergent polymer. In the presently most preferred embodiment of the invention, the polyacrylate comprises ACUSOL 445, a polyacrylic acid with a molecular weight of 4500 manufactured by Rohm and Haas, Philadelphia, Pennsylvania. Other polyacrylic acids of molecular weight 4500 (CRITERIONTm 2005) and 8000 (CRITERION 2108) can be purchased from Kemira Chemicals, Kennesaw, Georgia. It is believed that other suitable examples include SoakalanTM CP5 available from BASF, CoatexTM DE185, or IsolTM Dispersant HN44.
In embodiments of the invention polycarboxylic acid comprises from about 1 to about 30 weight percent, from about 5 to about 20 weight percent, and from about 10 to about 15 weight percent.
Alcohol Ethoxylates and Acrylic Acid Polymers Alcohol ethoxylates are also useful as thickening agents in compositions of the invention. Isotridecanol ethoxylate is a nonionic surfactant available as Lutensole TO 8 from BASF that has been found effective at providing thickening, stabilizing, and homogeneity in compositions of the invention. Alcohol ethoxylates such as isotridecanol ethoxylate have improved performance as a thickening agent when combined with either a polycarboxylic acid such as Accusol 445 discussed above, and/or an acrylic acid polymer such as Carbopol ETD 2691 available from Lubrizol Corporation. Carbopol is a lightly crosslinked polyacrylic acid polymer.
In an embodiment of the invention alcohol ethoxylates are present in an amount from about 0.5 to about 10 weight percent, from about 0.75 to about 9.5 weight percent, and from about 0.9 to about 9.0 weight percent.
Polyacrylate copolymer Polyacrylate copolymers are also useful thickening, stabilizing, and homogenizing agents when incorporated into compositions of the invention. An example of such a copolymer is Cosmedia available from Cognis. Cosmedia is an emulsifying copolymer consisting of methacrylic acid and acryclic acid ethyl and butyl ester.
In an embodiment of the invention polyacrylate copolymers are present in an amount from about 0.5 to about 10 weight percent, from about 0.75 to about 9.5 weight percent, and from about 0.9 to about 9.0 weight percent.
Water Conditioners Compositions of the invention preferably include water conditioning agents.
The thickened emulsion compositions of the invention can comprise a polyvalent metal complexing, sequestering or chelating agent that aids in metal compound soil removal and in reducing harmful effects of hardness components in service water.
Typically, a polyvalent metal cation or compound such as a calcium, a magnesium, an iron, a manganese, a molybdenum, etc. cation or compound, or mixtures thereof, can be present in service water and in complex soils. Such compounds or cations can comprise a stubborn soil or can interfere with the action of either washing compositions or rinsing compositions during a cleaning regimen. A chelating agent can effectively complex and remove such compounds or cations from soiled surfaces and can reduce or eliminate the inappropriate interaction with active ingredients including the nonionic surfactants and anionic surfactants of the invention.
Both organic and inorganic chelating agents are common and can be used. Inorganic chelating agents include such compounds as sodium tripolyphosphate and other higher linear and cyclic polyphosphates species. Organic chelating agents include both polymeric and small molecule chelating agents. Organic small molecule chelating agents are typically organocarboxylate compounds or organophosphate chelating agents. Polymeric chelating agents commonly comprise polyanionic compositions such as polyacrylic acid compounds. Small molecule organic chelating agents include sodium gluconate, sodium glucoheptonate, N-hydroxyethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), nitrilotriaacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraproprionic acid, triethylenetetraaminehexaacetic acid (TTHA), and the respective alkali metal, ammonium and substituted ammonium salts thereof, ethylenediaminetetraacetic acid tetrasodium salt (EDTA), nitrilotriacetic acid trisodium salt (NTA), ethanoldiglycine disodium salt (EDG), diethanolglycine sodium-salt (DEG), and 1,3-propylenediaminetetraacetic acid (PDTA), dicarboxymethyl glutamic acid tetrasodium salt (GLDA), methylglycine-N-N-diacetic acid trisodium salt (MGDA), and iminodisuccinate sodium salt (IDS).
All of these are known and commercially available. Small molecule organic chelating agents also include biodegradable sequestrants having combinations of chelating and hydrotroping functionalities from EDG, MGDA and GLDA-type molecules.
Preferred sequestrants include ethanoldiglycine disodium salt (EDG), dicarboxymethyl glutamic acid tetrasodium salt (GLDA), and methylglycine-N-N-diacetic acid trisodium salt (MGDA), due to their biodegradability and their ability to bind easily with hydrotropes to form ultra-compact concentrates. Yet other sequestrants that are suitable to include in compositions of the invention include anionic polyelectrolytes such as polyacrylates and acrylic acid copolymers, itaconic acid copolymers such as an acrylic/itaconic acid copolymer, maleates, sulfonates and their copolymers, alkali metal gluconates. Also suitable chelating agents are organic phosphonates such as 1-hydroxyethylidene-1,1-diphosphonic acid, amino tri(methylene phosphonic acid), hexamethylene diamine tetra(methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), and 2-phosphonobutane-1,2,4-tricarboxylic acid and other commercially available organic .. PCT/1B2008/055571 phosphonates water conditioning agents. Most conventional agents appear to work since they are compatible in either the continuous phase or the droplet phase.
In an embodiment, a chelating agent is present in the composition concentrate in an amount of between about 0.05 and about 15 weight percent, more preferably about 1 to about 10 wt%, most preferably 3 to about 8 wt%.
Dequest 2010 may be included in compositions of the invention as the sequestering or chelating agent. Dequest 2010 is 1-Hydroxyethylidene -1,1,-diphosphonic acid, acts as a sequestrant in the present invention, and is a commercially available from ClearTech Industries, Inc. located in Saskatoon, Saskatchewan, Canada. In an embodiment compositions of the invention comprise between about 0.01 to about 10 weight percent sequestrant, between about 0.5 to between about 8 weight percent, and between about 1 and about 5 weight percent (60% active).
Baypure CX100 may be included in compositions of the invention as a chelating agent. Baypure CX100 is a medium-strength complexing agent with low remobilization of heavy metals. It is effective at complexing iron, copper and calcium ions and is biodegradable. If Baypure CX100 is included in compositions of the invention it is included in amount from about 1 up to about 30 weight percent, from about 2 up to about 20 weight percent, and from about 3 up to about 10 weight percent for a 34% actives solution of Baypure .
As one skilled in the art will recognize, either one or a combination of sequestrants may be included in the invention.
Water The composition of the invention does not generally include additional water. While it is recognized that certain ingredients contain some amount of water because they are provided as a solution in water, additional water is not generally added to compositions of the invention. This is important in particular to maintain the high viscosity required of compositions of the invention. Compositions of the invention can be formulated without any additional water or can be provided with a relatively small amount of water in order to reduce the expense of transporting the composition.

The water of dilution that can be used to dilute the composition to form a use composition is preferably soft water. That is, it is preferable that water of dilution be substantially free of hardness. Water can be characterized as hard water when it includes at least 1 grain hardness.
Minor Ingredients Detergents typically contain a number of conventional, important but minor ingredients. These can include optical brighteners, soil antiredeposition agents, antifoam agents, low foaming surfactants, defoaming surfactants, pigments and dyes, which are used in these formulas. The compositions can also include chlorine and oxygen bleaches, which are not currently used in these formulas. Such materials can be formulated with the other ingredients or added during cleaning operations.
Color Stabilizing Agent Compositions of the invention optionally include a component to inhibit discoloration or browning of the formulation otherwise referred to as a color stabilizing agent. Such a color stabilizer is optional; however, due to the off-putting nature of discolored laundry detergent it is a desirable option to include. In compositions of the invention this color stabilizer is monoethanolamine. In an embodiment of the invention, a color stabilizing agent comprises from about 0.01 to about 5 weight percent, from about 0.05 to about 3 weight percent, and from about 0.10 to about 2 weight percent.
Optical Brighteners Optical brighteners may also be optionally added to compositions of the invention. Brighteners are commonly added to laundry detergents to replace whitening agents removed during washing and to make the clothes appear cleaner.
Optical brighteners are commonly dyes that absorb light in the ultraviolet and violet region (usually 340-370nm) of the electromagnetic spectrum, and re-emit light in the blue region (typically 420-470nm). These additives are often used to enhance the appearance of color of fabric, causing a perceived "whitening" effect, making materials look less yellow by increasing the overall amount of blue light reflected.

Optical brighteners may or may not be a desirable addition to compositions of the invention. Whether or not it is desirable to include optical brighteners is dependent upon the user. For instance, a side effect of optical whitening is to make the treated fabrics more visible with night vision devices than non-treated ones. For military or other applications such an effect would likely be undesirable.
Examples of class types of optical brighteners include triazine-stilbenes (di-, tetra-or hexa- sulfonated), coumarins, imidazolines, diazoles, triazoles, benzoxazolines and biphenyl-stilbenes to name a few. A single optical brightener or combinations of optical brighteners may be useful in compositions of the invention. In an embodiment of compositions of the invention optical brighteners comprise from about 0.1 to about 5 weight percent, from about 0.15 to about 3 weight percent, and from about 0.2 to about 2 weight percent. Examples of commercially available optical brighteners suitable for use in compositions of the invention include but are not limited to DMS-XTm and CBS-XTM, a distyryl biphenyl derivative, both available from Vesta- Intracon BV.
Soil Antiredeposition Agents Compositions of the invention may further include antiredeposition agents.
Antiredeposition agents may be made from complex cellulosic materials such as carboxymethylcellulose (CMC), or synthetic materials such as polyethylene glycol and polyacrylates. They aid in preventing loosened soil from redepositing onto cleaned fabrics.
Polyphosphate builders also help in reducing redeposition.
Colorants Colorants are optionally added to compositions of the invention. Colorants may be in the form of a pigment or dye and may be added to provide a certain color to the composition. Additionally, blue colorants may be added to provide a bluing that imparts a desirable blue/white color to white fabrics.
Fragrances Fragrances are optionally added to compositions of the invention.
Fragrances generally provide three functions, regardless of the scent used.
They cover the chemical odor of the detergent and the odor of soils in the washing solution and they impart a pleasant scent to fabrics, thus reinforcing the clean performance. Additionally, a fragrance may contribute to the character of the product. In an alternative embodiment, compositions of the invention may omit a fragrance in order to provide an unscented version thereby appealing to consumers who prefer low or no scent on laundry or to those whose skin is sensitive to fragrance ingredients.
The following table includes exemplary ingredients and amounts to prepare compositions of the invention:
Ingredient % by % by % by % by % by weight weight weight weight weight Sodium hydroxide 40-80 45-75 50-70 30-50 30-60 (50%) Fatty alcohol C13- 4-20 9-15 10-14 4-20 C15 Ethoxylate (7E0) Fatty alcohol C13- 7-15 6-12 4-10 C15 Ethoxylate (3E0) C10 Alcohol 0.5-10 ethoxylate Fatty alcohol 0.5-10 (C12-C14) EOPO
Isotridecanol 2-20 ethoxylate Polycarboxylic 2-25 4-20 5-15 5-15 acid (20%) Monoethanol- 0.01-5 0.05-3 0.1-2.0 amine Alkyl 0.1-7 0.5-5 1.0-3.0 0.1-5 0.1-5 Polyglucoside Polyacrylate 0.5-10 copolymer Acrylic Acid 0.01-2 Polymer Hydroxyethylidene 0.1-7 0.5-5 1.0-3.0 0.5-5 0.5-5 diphosphonic acid (60%) Iminodisuccinate, 3-15 3-15 sodium salt (34%) GLDA 0.5-10 Carboxymethyl 0.1-7 0.5-5 1.0-3.0 0.5-5 0.5-5 cellulose Distyryl Biphenyl 0.1-5 0.25-3 0.5-2.0 0.1-5 0.1-5 derivative Fatty Acid 0.1-5 0.15-3 0.25-2.0 Polycarboxylic 2-30 5-25 8-20 5-25 acid (20%) Water 10-30 0-10 Optical brightener 0-5 0-2 0-1 0-1 0-1 Defoamer 0-3 0-3 Preparing Compositions of the Invention Compositions of the invention are prepared by combining a nonionic surfactant, an alkyl polyglucoside composition, CMC and tall oil. The APG may be added at this time along with strong agitation. Any optical brighteners are added to the combination followed by addition of an aqueous base, the aqueous base comprising 50 wt. % active aqueous sodium hydroxide, to form an alkaline surfactant blend. Monoethanolamine is added to the combination followed by polycarboxylic acid as the final ingredient. The final mixture is exposed to high shear to form a stable thickened emulsion characterized by a viscosity of greater than about 250,000 centipoise at 20 degrees C using Bohlin CVO rheometer with air bearing and thermostat. Measurement is taken using two parallel plates each having 20mm diameter with a distance of 2mm between the plates. The sample is confined in the gap between the two plates at a constant temperature of 20 degrees C.
The measurement is performed in such way that the upper plate is rotating at a certain speed (shear rate) and the lower plate is fixed, thereby shearing the sample between the plates. The torque that is required to maintain a certain shear rate is measured.
The shear stress on the sample is calculated from the torque and the viscosity results as the ratio of shear stress and shear rate.
Methods of Using Compositions of the Invention The present invention also includes methods of use. Such methods include contacting soiled laundry items with a wash liquor comprising a major proportion of water and about 0.5 to 3.0 ppm of a liquid cleaner concentrate composition in the form of an aqueous emulsion having a continuous phase and a dispersed phase, the thickened emulsion having a stable viscosity and dispersed phase particle size, the composition comprising a phase stable thickened emulsion comprising a continuous phase; an effective soil removing amount comprising about 15 to about 50 wt %
of a source of alkalinity; an effective soil removing amount comprising about 10 to about wt % of a nonionic surfactant; an effective water conditioning or sequestering amount about 0.1 to about 20 wt % of a water conditioning or sequestering agent; an effective soil removing and emulsion stabilizing amount comprising up to about 25 wt % of an alkyl polyglucoside surfactant; an effective thickening amount of polycarboxylic acid comprising about 1 to 20 wt %; and an effective thickening amount of fatty acid comprising about 0.1 to 5 wt %; wherein the dispersed phase comprises at least a portion of the nonionic surfactant and the thickened emulsion concentrate has a viscosity of greater than 250,000 cps at 20 C using a Bohlin CVO
30 rheometer measured in rotating shear mode at the shear rate of 0.2 per second and exhibits shear thinning thereby permitting dispensing during manufacture and use to form a washed laundry; and rinsing the washed laundry with an aqueous rinse.

EXAMPLES
Example I
Compositions were prepared according to the invention except that they lacked fatty acids. These comparative compositions were viscous fluids with viscosities of about 10 Pas when taken at 0.2s-1. Increasing the content of fatty acids from 0% to 1% resulted in a continuous increase of shear viscosity with the appearance changing from a flowing liquid to a solid gel or paste.
Compositions were prepared according to the invention except that they lacked polycarboxylic acid. Without polycarboxylic acid the composition appears as a viscous liquid with shear viscosity below 10 Pas (0.2s-1). With the concentration of polycarboxylic acid between 5 and 8 weight percent, the composition turns into a paste resulting in viscosities in the range of 100-1000 Pas (0.2s-1).
Compositions were prepared according to the following tables.

Fatty alcohol C13-15 15% 15% 15% 15% 15%
ethoxylate (7E0) Fatty alcohol C13-15 4% 4% 4% 4% 4%
ethoxylate (3E0) Alkyl Polyglycoside 2% 2% 2% 2% 2%
(50%) Carboxymethyl cellulose 2% 2% 2% 2% 2%
Tall Oil fatty acids 0% 0.4% 0.65% 0.75% 1%
Optical Brightener DMS- 0.5% 0.5% 0.5% 0.5% 0.5%
X
Distyryl Biphenyl 0.25% 0.25% 0.25% 0.25% 0.25%
Derivative Hydroxyethylidene 2% 2% 2% 2% 2%
Diphoyphonic Acid (60%) Sodium Hydroxide 61% 60.6% 60.35 60.25 60%
Solution (50%) % %
Monoethanol amine 0.25% 0.25% 0.25% 0.25% 0.25%
Polycarboxylic acid 13% 13% 13% 13% 13%
(48%) Fatty alcohol C13-15 15% 15% 15%
ethoxylate (7E0) Fatty alcohol C13-15 4% 4% 4%
ethoxylate (3E0) Alkyl Polyglycoside 2% 2% 2%
(50%) Carboxymethyl cellulose 2% 2% 2%
Tall Oil fatty acids 0.75% 0.75% 0.75%
Optical Brightener DMS- 0.5% 0.5% 0.5%
X
Distyryl Biphenyl 0.25% 0.25% 0.25%
Derivative Hydroxyethylidene 2% 2% 2%
Diphoyphonic Acid (60%) Sodium Hydroxide 73.25 69.25 59.25 Solution (50%) % % %
Monoethanol amine 0.25% 0.25% 0.25%
Polycarboxylic acid 0% 4% 14%
(48%) Viscosity was measured using a parallel plate system with each plate having 20 mm diameter with a 2 mm gap distance between the plates. Measurements were taken at 20 degrees C. Each sample was confined in the gap between the two plates and the measurement was performed in such way that the upper plate was rotating at a certain speed (shear rate) and the lower plate was fixed, thereby shearing the sample between the plates. The torque that was required to maintain a certain shear rate was measured. The shear stress on the sample is calculated from the torque and the viscosity results as the ratio of shear stress and shear rate.
Results are provided in the tables below:

Tall Oil 0 0.4 0.65 0.75 1 conc. (wt %) Viscosity 12 28 118 711 928 (0.2s"
')(Pas) Polycarboxylic 0 4 14 acid conc. (%) Viscosity (0.2s" 4 80 215 1)(Pas) The results show that with increasing tall oil concentration and increasing polyearboxylic acid concentration, the viscosity increases.
Example H
This Comparative Example demonstrates that not all thickening polymers are useful in the present invention. Compositions were prepared using Sokalan'AT

from BASF, CarbopolTMEZ3 and EZ 4 from Noveon and Acusorm 805S from Kohut &
Haas but the .resultant tnixtures were not stable and separated into two viscous liquid phases. Compositions were prepared according to the following table:
Ingredient IC 2C 3C 4C
Water 10,95% 10.95% 10.95% 10.95%
KOH, 50% 25.00% 25.00% 25.00% 25.00%
DMS-X, Stilbene Disulfonic Acid 0.30% 0.30% 0.30% 0.30%

CBS-X, Distyryl Biphenyl Derivative 0.10% 0.10% 0.10% 0.10%
Hydroxyethylene Diphosphonic Acid (60%) 2.50% 2.50% 2.50% 2.50%
Sodium silicate (40%) 10.00% 10.00% 10.00% 10.00%
Iminodisuccinate Sodium Salt (34%) 14.75% 14.75% 14.75% 14.75%
Methyl gylcine diacetic acid, trisodium salt (40%) 7.50% 7.50% 7.50% 7.50%
Polyacrylic Acid Copolymer 7.50% 7.50% 7.50% 7.50%
Silicone Emulsion 0.20% 0.20% 0.20% 0.20%
Fatty alcohol ethoxylate blend 5.00% 5.00% 5.00% 5.00%
Alkyl benzene sulfonate 0.50% 0.50% 0.50% 0.50%
Fatty alcohol (C12-14)E0P0 9.50% 9.50% 9.50% 9.50%
Ethoxylated C10 (iso) longchain alcohol polymer 5.00% 5.00% 5.00% 5.00%
Perfume 0.20% 0.20% 0.20% 0.20%
1% 1% 1% 1%
Carbopol Carbopol Sokalan Acusol Thickener EZ3 EZ4 AT10 805S
Viscosities of each of the comparative compositions was taken as described in Comparative Example I. The results are shown in the table below:
Formulation 1C 2C 3C 4C
Viscosity 205 Pas 152 Pas 0.09 Pas 88 Pas The viscosity was measured at a shear rate of 0.1s-1. As all of these systems separate fast, the given values are only approximate.
Example III
Increasing shear was applied to a sample prepared according to the formulation of sample 6A. Figure 1 shows shear thinning of a sample 6A of the invention. As shear is increased, viscosity decreases by about five orders of magnitude. As can be seen from the graph of Figure 1, the viscosity varies over more than 5 orders of magnitude in a shear rate range between 0.01 and 500s-1.
Example IV
This Example demonstrates that both tall oil and polycarboxylic acid have positive influences upon viscosity of compositions of the invention.
Compositions were prepared according to the following table:
Ingredient % by weight Fatty alcohol C13-15 ethoxylate (7E0) 10-14%
Fatty alcohol C13-15 ethoxylate (3E0) 5-9%
Alkyl Polyglycoside (50%) 2%
Carboxymethyl cellulose 0.5-2%
Tall Oil fatty acids 0.25%4/75%
Optical Brightener DMS-X 0.5%
Distyryl Biphenyl Derivative 0.25%
Hydroxyethylidene Diphoyphonic Acid (60%) 2%
Sodium Hydroxide Solution (50%) 40-60%
Monoethanol amine 0.25%
Polycarboxylic acid (48%) 11.7-14.3%
This experiment was performed on the basis of a statistical method named DOE (Design of Experiment) ¨ Mixture Design. Some ingredients were kept at a constant concentration whereas the content of others was varied within the limits given in the above table. Evaluation of the measured viscosities with statistical methods resulted in the graph shown In Figure 2 which demonstrates the effect of the varied ingredient.s A-F on viscosity when their concentrations are increased.
The viscosity of each composition from the above table was taken according to the protocol provided in Example I. The graph of Figure 2 illustrates the results.
As can be seen, both tall oil and polycarboxylic acid (Rheosolve or Acusol) have a strong positive effect on viscosity, NaOH and Lutensol A()3 (fatty alcohol ethoxylate) have a negative effect and Lutensol A07 (fatty alcohol ethoxylate) and CMC do not largely influence the viscosity.
Example V
This Example demonstrates that the thickened emulsion of the invention performed well in cleaning a variety of stains. A composition of the invention was prepared according to the following table:
Ingredient Manufacturer % by weight ,utensol A07 BASF 15.00 Lutensol A03 BASF 4.00 Glucopon 215 UP Cognis /.00 CMC Hercules 2.00 Tall Oil Mosselman 0.50 DMS-X Ciba 1.00 CBS-X Hebei 0.25 Dequest 2010 Thermphos 2.00 Na011 (50%) BASF 60.00 Monethanolamine BASF 0.25 AccusolTm 445 Rohm & Haas 13.00 The pH of a 1% solution of the above-identified 'formulation was in the range Of 11.1 to 11.9.
Standard test stains which are commercially available from WFK
I() (Krefeld/Germany) were used for this Example. The test stains were produced in a standardized manner and were placed on test strips. These were included in a washing machine together with 6.5kg of polyester textiles. 1:.,ach procedure was repeated 4 times in 4 different washing machines, the values in the tables below are the averages of the 4 results for each procedure. The above-prepared composition was included in a dosage of 1.5g/1 along with 1m1/1 of a bleaching agent (Ozonit super available from Ecolab, Inc.) was added in each test. The washing time was 10 minutes, temperature 70 C, bath ratio 1:5; soft water was used. After finalizing the wash test, the stain removal from the test strips was measured with an optical tnethocl, the light transmission at a fixed wave length is measured with the stain before and after washing. The results are the remission values shown in the tables.
The tables below compare lab wash results of the thickened emulsion of the invention with a commercially available detergent. The top two tables show the results of wash performance with fatipigment stains, the bottom table shows enzymatic stains. The results demonstrate that the thickened emulsion of the invention pertbnyied as well or better than the commercially available detergent in most situations.
Pigment/ Pigment/ Pigment/ Pigment/ Soot/Min Soot/Min Lanolin Lanolin on Sebum on Sebum on Oil on Oil on on Cotton Polyester/ Cotton Polyester/ Cotton PES/CO
Cotton Cotton Commercially 62.2 45.7 60.4 62.6 34.3 37.3 available detergent Thickened 63.2 49.9 62.7 68 35 38.7 Emulsion Used Motor Used Motor Oil Make up on Make up on Oil on on Cotton Polyester/Cotton Cotton Polyester/Cotton Commercially 44.6 34.2 75 80.3 available detergent Thickened 44.4 34.5 753 81.9 liniuision Blood Blood Blood/Milk/ Milk Blood/Milk/ Egg Soot aged unaged Ink on cocoa Soot on on C
cotton unaged cotton Commercially 87.4 85.4 32.9 43.9 53.7 48 available detergent Thickened 87 86.1 40 52 69.3 58 Emulsion The invention has been described with reference to various specific and preferred embodiments and techniques. However, the scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.

Claims (27)

WHAT IS CLAIMED IS:

1. A liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having an aqueous phase and a dispersed phase, the composition comprising a phase stable thickened emulsion comprising:
(a) a continuous aqueous phase;
(b) an effective soil removing amount comprising about 40 to about 80 wt %
of a 50% concentration, or an equivalent amount, of a source of alkalinity;
(c) an effective soil removing amount comprising about 5 to about 35 wt % of a single nonionic surfactant or about 2.5 to about 40 wt % of a mixture of nonionic surfactants;
(d) an effective water conditioning or sequestering amount comprising about 0.1 to about 10 wt % of a water conditioning or sequestering agent;
(e) an effective thickening amount of polycarboxylic acid comprising about 5 to about 25 wt %; and (f) an effective stabilizing and thickening amount of fatty acid comprising about 0.25 to about 5 wt %;
wherein the dispersed phase comprises at least a portion of the nonionic surfactant and the emulsion concentrate exhibits a shear thinning permitting dispensing during manufacture and use and the viscosity comprises greater than 100,000 centipoise at 20° C using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second, wherein the composition exhibits a viscosity of greater than 1,000,000 centipoise at zero shear, and wherein the composition comprises greater than 60 wt% active ingredients.

2. The composition of claim 1 wherein the viscosity comprises greater than 300,000 viscosity centipoise at 20° C using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second.

3. The composition of claim 1 wherein the viscosity comprises greater than 500,000 viscosity centipoise at 20° C using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second.

4. The composition of claim 1 wherein the viscosity comprises greater than 700,000 viscosity centipoise at 20° C using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second.

5. The composition of claim 1 wherein the viscosity comprises greater than 900,000 viscosity centipoise at 20° C using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second.

6. The composition of claim 1 wherein the nonionic surfactant comprises a fatty alcohol C13-15 ethoxylate having 4 to 10 moles of ethylene oxide

7. The composition of claim 1, wherein the nonionic surfactant comprises a fatty alcohol C13-15 ethoxylate having 1 to 5 moles of ethylene oxide.

8. The composition of claim 1 wherein the water conditioning agent comprises a phosphonic acid.

9. The composition of claim 1 wherein the water conditioning agent comprises hydroxyethlidene diphosphonic acid.

10. The composition of claim 1, wherein the polycarboxylic acid is comprised of a linear polyacrylic chain.

11. The composition of claim 1, wherein the fatty acid is comprised of tall oil.

12. The composition of claim 1 further comprising optical brightener, colorant, fragrance, antifoam agent, defoaming agent, bleaching agent, antiredeposition agent, or combinations thereof.

13. The composition of claim 1 further comprising a color stabilizing amount of monoethanolamine comprising about 0.01 wt. % to about 5 wt. %.

14. The composition of claim 1 further comprising an effective sod removing and emulsion stabilizing amount comprising about 0.1 to about 10 wt % of an alkyl polyglucoside surfactant.

15. A liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having an aqueous phase and a dispersed phase, the composition comprising a phase stable thickened emulsion comprising:
(a) a continuous aqueous phase;
(b) an effective soil removing amount comprising about 40 to about 80 wt %
of a 50% concentration, or an equivalent amount, at a source of alkalinity;
(c) an effective soil removing amount comprising about 5 to about 35 wt % of a single nonionic surfactant or about 2.5 to about 40 wt % of a mixture of nonionic surfactants;
(d) an effective water conditioning or sequestering amount comprising about 0.1 to about 15 wt % of a water conditioning or sequestering agent; and (e) an effective amount of thickening agent comprising about 5.25 to about 25 wt % of a mixture of polycarboxylic acid, fatty acid, and one or more components selected from the group consisting of: polyacrylate copolymer, acrylic acid polymer, and alcohol ethoxylate;
wherein the dispersed phase comprises at least a portion of the nonionic surfactant and the emulsion concentrate exhibits a shear thinning permitting dispensing during manufacture and use and the viscosity comprises greater than 100,000 centipoise at 20° C using a Bohlin CVO rheometer measured in rotating shear mode at the shear rate of 0.2 per second, wherein the composition exhibits a viscosity of greater than 1,000,000 centipoise at zero shear, and wherein the composition comprises greater than 60 wt% active ingredients.

16. The composition of claim 15, comprising at least two nonionic surfactants.

17. The composition of claim 15, comprising about 0.5 to about 5 wt % of the water conditioning composition.

18. The composition of claim 15 further comprising an effective soil removing and emulsion stabilizing amount comprising about 0.1 to about 10 wt % of an alkyl polyglucoside surfactant.

19. The composition of claim 16, wherein the first nonionic surfactant comprises a fatty alcohol C13-C15 ethoxylate.

20. The composition of claim 16 wherein a second nonionic surfactant comprises a fatty alcohol C13-C15 ethoxylate.

21. The composition of claim 15, wherein the polycarboxylic acid is comprised of a linear polyacrylic chain.

22. The composition of claim 15, wherein the fatty acid is comprised of tall oil.

23. A method of cleaning soiled laundry items comprising.
(i) contacting soiled laundry items with a wash liquor comprising a major proportion of water and about 0.5 to about 3.0 ppm of a liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having a continuous phase and a dispersed phase, the thickened emulsion having a stable viscosity and dispersed phase particle.size, the composition comprising a phase stable thickened emulsion comprising:
(a) a continuous aqueous phase;
(b) an effective soil removing amount comprising about 40 to about 80 wt % of a 50% concentration, or an equivalent amount, of a source of alkalinity;
(c) an effective soil removing amount comprising about 5 to about 35 wt % of a single nonionic surfactant or about 2.5 to about 40 wt of a mixture of nonionic surfactants;
(d) an effective water conditioning or sequestering amount about 0.1 to about 20 wt % of a water conditioning or sequestering agent;
(e) an effective thickening amount of polycarboxylic acid comprising about 5 to about 20 wt %; and (f) an effective thickening amount of fatty acid comprising about 0.1 to about 5 wt %; wherein the dispersed phase comprises at least a portion of the nonionic surfactant and the thickened emulsion concentrate has a viscosity of greater than 250,000 centipoise at 20° C using a Bohlin CVO
rheometer measured in rotating shear mode at the shear rate of 0.2 per second and exhibits shear thinning thereby permitting dispensing during manufacture and use to form a washed laundry, wherein the composition exhibits a viscosity of greater than 1,000,000 centipoise at zero shear; and wherein the composition comprises greater than 60 wt% active ingredients; and (n) rinsing the washed laundry with an aqueous rinse.

24. The method of claim 23 wherein the temperature of the wash liquor is about 25 to about 80 degrees C.

25. The method of claim 23 wherein the wash liquor comprises about 1.0 to about 2.5 ppm of the liquid cleaner.

26. The method of claim 23 further comprising an effective soil removing and emulsion stabilizing amount comprising about 0.1 to about 5 wt % of an alkyl polyglucoside surfactant.

27. The composition of claim 1 wherein the composition comprises from 10 to 30 wt% of nonionic surfactant or nonionic surfactant mixture.