Container containing shampoo composition having an aesthetic design formed by foam

Abstract

A container configured to hold a liquid shampoo composition having an aesthetic design formed at least in part by a visually discernible and stable foam suspended therein. The shampoo composition can have a cleansing phase containing one or more detersive surfactants. In addition to the cleansing phase, the composition can have additional cleansing and / or benefit phases that can provide conditioning as well as additional visual interest.

Description

[Technical Field]

[0001] The present invention relates to a container containing a shampoo composition having an aesthetic design, particularly a container containing a shampoo composition having an aesthetic design formed by a foam suspended in the liquid shampoo composition. [Background technology]

[0002] Some consumers desire a shampoo composition that effectively cleanses hair while also providing a distinctive appearance that can make the product stand out on store shelves, web pages / apps, and even in the user's shower, making it enjoyable to use.

[0003] Today, shampoos provide effective cleansing but tend to be aesthetically boring. One way to create a shampoo with a distinctive appearance is to add stable floating foam.

[0004] However, it can be difficult to maintain stable floating foam in a shampoo composition throughout the shelf life of the composition, which may include transportation, handling, and storage at home, storage facility, and / or store shelf, as well as repeated dispensing.Foam is particularly sensitive to changes in temperature and pressure, which can cause it to dissolve, appear, or grow.It can be particularly difficult to balance the rheology and chemical properties of a shampoo composition to contain stable floating foam therein.These problems are exacerbated when the foam forms a pattern, because even slight disruptions, including foam migration, destruction, or coalescence, can be noticed by consumers, making the product appear ordinary instead of having a distinctive appearance that indicates enjoyment and quality. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, there is a need for a stable shampoo composition that provides excellent cleansing and a stable floating foam that forms an eye-catching aesthetic design. [Means for solving the problem]

[0006] 1. A container configured to hold a multi-phase shampoo composition, the multi-phase shampoo composition comprising: (a) a first cleansing phase comprising (i) a cleansing surfactant, and (ii) a structuring agent; (b) a second cleansing phase comprising (i) a cleansing surfactant, (ii) a structuring agent, and (iii) a visually discernible, stable foam suspended therein; and (c) optionally a benefit phase comprising a gel network comprising (i) a fatty alcohol, and (ii) a secondary surfactant selected from the group consisting of anionic, amphoteric, zwitterionic, and mixtures thereof.

[0007] 1. A container configured to hold a liquid shampoo composition, the liquid shampoo composition comprising: (a) a detersive surfactant; (b) a structuring agent; and (c) a visually discernible, stable foam suspended therein, the cleansing phase having a viscosity of 10 −2 to 10 −4 s -1 Yield stress of about 0.01 to about 20 Pa at a shear rate of 2 s -1 Viscosity of about 1.0 to about 15 Pa.s at 100 s -1 a viscosity of about 0.1 to about 4 Pa.s at 250°C. [Brief explanation of the drawings]

[0008] While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the invention, it is believed the present invention can be more readily understood from the following description taken in conjunction with the accompanying drawings. [Figure 1] 1 is a photograph of a bottle with a pump containing a liquid shampoo composition having an aesthetic design formed by floating bubbles. [Figure 2]1 is a photograph of a bottle with a pump containing a liquid shampoo composition having an aesthetic design formed by floating foam and a floating gel network conditioner. DETAILED DESCRIPTION OF THE INVENTION

[0009] Some consumers desire shampoo compositions that effectively cleanse hair while also providing a distinctive appearance that can make the product stand out on store shelves, on web pages / apps, and even in the user's shower, making it enjoyable to use. Figures 1 and 2 are photographs of shampoo compositions with an aesthetic design formed by floating bubbles suspended throughout. Figure 1 shows a bottle with a pump containing a liquid shampoo composition having a first cleansing phase 1 that is substantially free of visible bubbles and a second cleansing phase 2 that has floating bubbles that form the aesthetic design. Figure 2 shows a bottle with a pump containing a liquid shampoo composition having a first cleansing phase 1' that is substantially free of visible bubbles, a second cleansing phase 2' that has floating bubbles that form the aesthetic design, and a third floating phase 3' that contains a gel network suspended in the liquid composition. The gel network can provide conditioning benefits to the shampoo product. In Figures 1 and 2, the phases are stable, separate, and packaged in physical contact with each other. In another example, the first cleansing phase may contain a floating foam and the second cleansing phase may be substantially free of foam. In yet another example, the shampoo composition may be a single cleansing phase and have a stable foam suspended throughout at least a portion of the shampoo composition.

[0010] The first and / or second cleansing phases may contain a surfactant system that may include one or more detersive surfactants, an aqueous carrier, and a structuring agent. In some examples, the first and / or second cleansing phases may be visually transparent, with a light transmittance of greater than 60% or greater than 80% as measured by the light transmittance method described below. In other examples, the cleansing phases may appear cloudy, hazy, or even opaque. The first and / or second cleansing phases may be colored, colorless, or a combination thereof.

[0011] The first and / or second cleansing phase may have a visually identifiable and stable foam suspended therein, the foam being formed by a gas trapped in the liquid phase that appears as a foam. The gas may be any suitable gas, including air and / or helium. In some instances, helium may be a preferred gas because it can form more stable foam. To improve foam stability, other gases with lower solubility in shampoo may be used instead of or in addition to air and / or helium. A foam is visually identifiable if a human observer can recognize one or more floating bubbles with the naked eye (excluding standard corrective lenses adapted to correct myopia, hyperopia, or astigmatism, or other corrective vision) at a distance of approximately 1 foot (0.30 m) under illumination at least equivalent to the illuminance of a standard 100-watt incandescent white light bulb.

[0012] The bubbles may have an average diameter of at least 0.25 mm, alternatively at least about 0.1 mm, alternatively at least about 0.5 mm, alternatively at least about 1 mm. The bubbles may have an average diameter of from about 0.1 mm to about 10 mm, alternatively from about 0.5 mm to about 8 mm, alternatively from about 1 mm to about 5 mm, alternatively from about 1.5 mm to about 3 mm.

[0013] The bubbles may be of substantially uniform size. Without being bound by theory, it is speculated that substantially uniform bubble size can reduce inter-bubble migration and limit bubble growth and / or additional phase collapse. In some examples, the size of stable floating bubbles varies by no more than 25%, alternatively no more than 20%, alternatively no more than 15%, alternatively no more than 10%.

[0014] For a shampoo composition to be stable over the shelf life of the product, the bubbles may be at least 0.25 cm apart, alternatively at least 0.5 cm, alternatively 1 cm, alternatively 2 cm. Separating the bubbles can increase foam stability. Greater separation can improve foam stability by increasing the time it takes for gas to transfer between bubbles.

[0015] The shampoo composition may contain a visible gas volume of floating foam of about 0.001 mL to about 5 mL. The shampoo composition and / or phase may have a visible gas volume of floating foam of about 0.01 mL to about 3 mL, alternatively about 0.1 mL to about 0.5 mL. The shampoo composition may be present in a container, such as a bottle, having a volume of about 100 mL to about 1000 mL, alternatively about 250 mL to about 750 mL, alternatively about 300 mL to about 500 mL.

[0016] In some examples, the first and second phases may have substantially the same chemical composition, and either the first or second phase may contain floating, visually discernible, stable bubbles, while the other phase is substantially free of visually discernible bubbles. In other examples, the first and second phases may have substantially different chemical compositions, and either one or both phases contain floating, visually discernible, stable bubbles. When both phases contain floating, visually discernible, stable bubbles, the average bubble size may be approximately the same, or one phase may have substantially larger bubbles than the other phase. In some examples, the bubble density may be substantially the same throughout the phases, while in other examples, the bubble density may vary throughout the phases.

[0017] Optionally, the shampoo composition may further contain a benefit phase, which may be opaque or translucent and may be suspended throughout the shampoo composition or throughout one or more portions of the shampoo composition. The benefit phase can help the shampoo appear more conditioning-enhancing without sacrificing the clarity of the cleansing phase, while also providing a different, more stimulating-looking shampoo composition. The benefit phase may contain a gel network, which refers to a lamellar and / or vesicular solid crystalline phase that may contain at least one fatty alcohol, at least one surfactant, and water and / or other suitable solvents.

[0018] The benefit phase and / or cleansing phase in which the visually discernible, stable foam is suspended can be uniform, non-uniform, or a combination thereof. The benefit phase and / or cleansing phase in which the visually discernible foam is suspended can be any suitable shape to form aesthetic designs including regular and / or irregular patterns, including swirls, as shown in Figures 1 and 2. Shapes can form aesthetic designs resembling the following non-limiting examples: bubbles, stripes, crosshatching, zigzags, floral, petal, herringbone, marble, straight lines, interrupted stripes, checkered, mottled, streaks, clusters, speckles, spots, ribbons, spirals, swirls, arrays, variegated, wavy, spiral, twist, curved, stripes, lace, basketweave, serpentine, random, and combinations thereof.

[0019] The benefit phase may contain additional ingredients, including ingredients that can cloud or opacify the cleansing phase, such as conditioning ingredients (e.g., cationic deposition polymers, silicones having an average particle size greater than 30 nm, crosslinked silicone elastomers), anti-dandruff actives (e.g., zinc pyrithione), aesthetic ingredients (e.g., mica), and combinations thereof. The additional ingredients may be carefully selected (e.g., the salt concentration of the ingredients cannot be too high) as they may cloud the gel network, causing the gel network structure to collapse, pushing out solvents, destroying the aesthetic pattern, and making the shampoo composition appear less effective.

[0020] In some instances, the benefit phase of the shampoo may be suspended in the cleansing phase with a visually discernible, stable floating foam.

[0021] Appropriate rheology, which may include viscosity, yield stress, and / or shear stress, of the shampoo composition, cleansing phase, and / or optional benefit phase can be balanced to ensure that the product is acceptable to the consumer while maintaining a visually discernible floating, stable foam and / or a floating, separate, stable phase. If the yield stress is not high enough to support the density difference between air and liquid, floating foam may rise to the surface. Without being bound by theory, it is believed that sufficient yield stress and / or viscosity can also retard the spreading / Oswald ripening of floating foam. However, if the yield stress is too high, the composition may be too thick and unacceptable to the consumer. The cleansing phase has a yield stress (shear rate 10) of about 0.01 to about 20 Pa, alternatively about 0.01 to about 10 Pa, alternatively about 0.01 to about 5 Pa. -2 ~10 -4 s -1 The yield stress can be measured at shear rates of 100 to 1.0e-4 s using a Discovery Hybrid Rheometer (DHR-3) available from TA Instruments. -1The temperature is measured at 26.7°C by a flow sweep at 100°C. To apply the Hershel-Bulkley model, -2 ~10 -4 s -1 Use TA software to fit a model in logarithmic space at shear rates of 100 s. The geometry used to measure the yield stress and viscosity of the cleansing phase is a 60 mm 2° aluminum cone (with a Peltier steel plate). The geometry should be run at the gap specified by the manufacturer for that geometry. To ensure data integrity and reproducibility, it is recommended to trim the sample during the initial conditioning step in Step 1. If the instrument geometry is out of calibration, torque map the geometry before running the yield stress or shear stress method. The version of Trios software used to generate the rheological data herein is TRIOS 5.1.1.

[0022] The cleansing and / or benefit phases are -1 The cleansing phase may have a viscosity of about 0.01 to about 15 Pa.s at 100 s. -1 The viscosity may be from about 0.1 to about 4 Pa·s, alternatively from about 0.1 to about 2 Pa·s, or alternatively from about 0.1 to about 1 Pa·s.

[0023] If present, the beneficial phase is -1 Shear rate of about 100 Pa to about 300 Pa, or 950 s -1 At a shear rate of about 130 Pa to about 250 Pa, or 950 s -1The shear stress may be from about 160 Pa to about 225 Pa at a shear rate of 0.1 s. The shear stress is measured at 25°C using a flow ramp with an initial shear rate of 0.1 s to a final shear rate of 1100 s using a Discovery Hybrid Rheometer (DHR-3) available from TA Instruments. The geometry used to measure the shear stress of the beneficial phase is a 40 mm 2° steel cone with a Peltier steel plate.

[0024] The shampoo composition, when dispensed at 10% to 55% by volume, may provide an average final rinse friction of less than 2000 gf, alternatively less than 1750 gf, alternatively less than 1700 gf, alternatively less than 1650 gf, alternatively less than 1600 gf. Average final rinse friction may be determined using the Hair Wet Feel Friction Measurement Method described herein.

[0025] The shampoo composition can be sold, stored, and dispensed from a bottle. The bottle can be transparent or translucent so that the user can see the floating design in the product from the outside of the bottle. Alternatively, the bottle can be opaque and optionally have one or more transparent or opaque windows through which the consumer can see the floating design. The shampoo composition can be dispensed from the bottle by squeezing. Alternatively, the shampoo composition can be dispensed using a pump, which may be preferred in some cases because the pump can reduce the breakdown of the benefit phase throughout the use of the bottle.

[0026] The shampoo composition can be in a bottle that is substantially free of headspace and / or visually recognizable air bubbles other than the floating bubbles intentionally placed in the cleansing phase to help maintain the design before use.It has been found that air bubbles, especially large and unstable air bubbles and headspace, can destroy the floating aesthetic design during transportation and handling.Headspace can also be eliminated by overfilling the bottle or by using an insert that can have a snap fit with the neck of the bottle to consume headspace volume, and an example of an insert is described in U.S. Patent Application No. 17 / 174,427, which is incorporated herein by reference.

[0027] However, it can be difficult to eliminate all air inadvertently trapped in a shampoo product. After filling, a shampoo product may typically contain approximately 4% air trapped in tiny bubbles that are not visually discernible. When a shampoo is packaged in a typical bottle or pump, over time, these unstable bubbles will coalesce due to Laplace pressure and become larger bubbles. These larger bottles will eventually reach a headspace if the stress of the liquid beauty care product is not high enough to support the density difference between air and liquid. Thus, even if a liquid beauty care product is packaged in a bottle without visible bubbles, a headspace may form within 24 to 48 hours. Increasing the yield stress of a liquid beauty care product can prevent bubbles from migrating from small bubbles to larger bubbles and into the headspace, but products with high yield stress may be less acceptable to consumers due to their poor spreadability and difficulty in dispensing.

[0028] It has been found that if the headspace is eliminated (e.g., by either overfilling and / or using an insert), the overcap can be screwed or snapped onto the neck of the bottle, creating a slight overpressure that stops trapped air bubbles from migrating without compromising the yield stress of the shampoo composition. When the user is ready to dispense the shampoo composition, the user can remove the overcap and pour the shampoo product into their hand, remove the overcap and insert a pump, or in some cases, the overcap can have a pierceable membrane and the user can punch the membrane with the pump dip tube.

[0029] In some instances, instead of eliminating the headspace, a slight overpressure may exist within the bottle. Without being bound by theory, if the pressure within the headspace is greater than the Laplace pressure of the bubbles within the bottle, air movement between the bubbles and the headspace can be significantly reduced. The overpressure within the headspace may be from about 10 Pa to about 10,000 Pa, alternatively from about 10 Pa to about 7500 Pa, alternatively from about 15 Pa to about 5000 Pa, alternatively from about 15 Pa to about 1000 Pa, alternatively from about 20 Pa to about 500 Pa, alternatively from about 30 Pa to about 250 Pa, alternatively from about 40 Pa to about 200 Pa, alternatively from about 50 Pa to about 150 Pa, alternatively from about 75 Pa to about 125 Pa, or alternatively 100 Pa or less.

[0030] In some instances, bubble suspension, size, and density remain substantially unchanged after the user opens the bottle. In other instances, bubbles may grow in size and / or number over a period of minutes to hours after the product is opened, especially if there is a slight overpressure in the headspace.

[0031] It has been found that the aesthetic design of a packaged shampoo product can remain substantially intact according to sequences 1-5 of the ISTA® 6A Ship Test (6-Amazon.com-Over Boxing, April 2018, using ASTM settings for all tests). As used herein, "substantially intact" means that a human observer with the unaided eye (excluding standard corrective lenses adapted to correct myopia, hyperopia, or astigmatism, or other corrective vision) cannot visually identify one or more large areas where the floating design is disrupted from a distance of approximately 1 foot (0.30 meters) under illumination at least equivalent to the illuminance of a standard 100-watt incandescent light bulb. In some examples, pattern opacification can be assessed by taking a cross-section of the liquid cosmetic product and determining what percentage of the cross-section is opacified. Less than 10%, alternatively less than 7%, alternatively less than 5%, alternatively less than 3%, or alternatively less than 1% of the area of ​​the cross-section can be opacified.

[0032] definition As used herein, the term "fluid" includes liquids and gels.

[0033] As used herein, articles such as "a" and "an," when used in a claim, are understood to mean one or more of what is claimed or described.

[0034] As used herein, "comprising" means that other steps and other ingredients that do not affect the end result can be added. This term encompasses the terms "consisting of" and "consisting essentially of."

[0035] As used herein, "mixture" is meant to include simple combinations of materials and any compounds that may result from those combinations.

[0036] As used herein, "molecular weight" or "M.Wt." refers to weight average molecular weight, unless otherwise specified. Molecular weight is measured using gel permeation chromatography ("GPC"), an industry standard method. Molecular weight has units of grams per mole.

[0037] As used herein, "shampoo composition" includes shampoo products such as shampoos, shampoo conditioners, conditioning shampoos, and other surfactant-based liquid compositions.

[0038] As used herein, the term "stable" with respect to phases means that the one or more cleansing and benefit phases appear as separate, non-migrating phases to a human observer with the unaided eye (excluding standard corrective lenses adapted to correct myopia, hyperopia, or astigmatism, or other corrective vision) at a distance of approximately 1 foot (0.30 m) under illumination at least equivalent to the illuminance of a standard 100-watt incandescent white light bulb. The term "stable" with respect to bubbles / trapped gas means that the bubbles are separate, visually distinguishable, and do not migrate or coalesce when following ISTA® 6A Ship Test Sequences 1-5, as determined by a human observer with the unaided eye (excluding standard corrective lenses adapted to correct myopia, hyperopia, or astigmatism, or other corrective vision) at a distance of approximately 1 foot (0.30 m) under illumination at least equivalent to the illuminance of a standard 100-watt incandescent white light bulb.

[0039] As used herein, "substantially free" means containing from about 0% to about 3% by weight of the ingredient, alternatively from about 0% to about 2% by weight, alternatively from about 0% to about 1% by weight, alternatively from about 0% to about 0.5% by weight, alternatively from about 0% to about 0.25% by weight, alternatively from about 0% to about 0.1% by weight, alternatively from about 0% to about 0.05% by weight, alternatively from about 0% to about 0.01% by weight, alternatively from about 0% to about 0.001% by weight, and / or alternatively no ingredient. As used herein, "free" means 0% by weight.

[0040] As used herein, the terms "include," "Includes," and "including" are meant to be open-ended and are understood to mean "comprise," "comprises," and "comprising," respectively.

[0041] All percentages, parts, and ratios are by weight of the total composition described herein unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include carriers or by-products that may be included in commercially available materials.

[0042] Unless otherwise noted, all component or composition levels refer to the active portion of that component or composition and exclude impurities, e.g., residual solvents or by-products, that may be present in commercial sources of such component or composition.

[0043] It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limit given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

[0044] Cleansing Phase The multi-phase shampoo composition may include one or more cleansing phases. The cleansing phase may be an aqueous phase. The cleansing phase may have a light transmittance (%T) of at least 75%, alternatively at least 80%, alternatively at least 85%, alternatively at least 90%, alternatively at least 93%, alternatively at least 95%, as measured by the Light Transmittance Method described below. The cleansing phase may have a light transmittance of about 60% to about 100%, alternatively about 70% to about 98%, alternatively about 80% to about 97%, alternatively about 85% to about 96%, alternatively about 90% to about 95%, as measured by the Light Transmittance Method described below.

[0045] In some examples, the cleansing phase may be substantially free or free of ingredients that can cloud, turbid, or opaque the phase, including silicone or other particles having an average particle size greater than 30 nm, dispersed gel network phases, synthetic polymers that form liquid crystals, and / or cationic surfactants.

[0046] In other examples, the cleansing phase may include small particle silicone (ie, silicone having an average particle size of 30 nm or less), a selective cationic deposition polymer, fragrance, and / or dye.

[0047] Detergent surfactants The cleansing phase may contain one or more detersive surfactants. As can be understood, detersive surfactants provide cleansing benefits to soiled objects such as hair, skin, and hair follicles by facilitating the removal of oil and other soils. Surfactants generally facilitate such cleaning due to their amphiphilic nature, which allows them to break down and form micelles around oil and other soils, which can then be rinsed away, thereby removing them from the soiled object. Suitable surfactants for shampoo compositions may include an anionic moiety that allows the formation of coacervates with cationic polymers. Suitable detersive surfactants may be compatible with other ingredients in the cleansing phase and the adjacent benefit phase. The detersive surfactant may be selected from the group consisting of anionic surfactants, amphoteric surfactants, nonionic surfactants, and mixtures thereof.

[0048] The surfactant in the present composition should be present at a concentration sufficient to provide the desired cleansing and foaming performance. The cleansing phase may contain a surfactant system at a concentration ranging from about 1% to about 50%, alternatively from about 3% to about 45%, alternatively from about 5% to about 40%, alternatively from about 7% to about 35%, alternatively from about 8% to about 30%, alternatively from about 8% to about 25%, alternatively from about 10% to about 20%, alternatively from about 11% to about 24%, alternatively from about 12% to about 23% by weight of the cleansing phase. The preferred pH range for the cleansing phase is from about 3 to about 10, alternatively from about 5 to about 8, alternatively from about 5 to about 7.

[0049] The cleansing phase may contain one or more anionic surfactants at a concentration ranging from about 1% to about 50%, alternatively from about 3% to about 40%, alternatively from about 5% to about 30%, alternatively from about 6% to about 25%, alternatively from about 8% to about 25% by weight of the cleansing phase. The anionic surfactant may be the primary surfactant.

[0050] The shampoo composition comprises one or more detersive surfactants in the cleansing phase. The detersive surfactant component is included in the shampoo composition to provide cleaning performance. The detersive surfactant may be selected from the group consisting of anionic, zwitterionic, amphoteric, cationic, or a combination thereof. In some examples, the detersive surfactant may be selected from the group consisting of anionic, zwitterionic, amphoteric, or a combination thereof. Such surfactants should be physically and chemically compatible with the ingredients described herein or should not otherwise unduly impair product stability, aesthetics, or performance. Sodium laureth-n-sulfate ("SLE1S"), where n=1, is particularly preferred herein. SLE1S allows for more efficient foaming and cleaning when compared to higher molar ethoxylate equivalents, especially in shampoo compositions containing high levels of conditioning actives.

[0051] Suitable anionic detersive surfactants include those known for use in hair care or other personal care shampoo compositions. The anionic detersive surfactant may be a combination of sodium lauryl sulfate and sodium laureth-n sulfate. The concentration of the anionic surfactant component in the composition should be sufficient to provide the desired cleaning and foaming performance, and generally ranges from about 5% to about 30%, alternatively from about 8% to about 30%, alternatively from about 8% to about 25%, alternatively from about 10% to about 17% by weight of the composition.

[0052] Additional anionic surfactants suitable for use herein include those of the formula ROSO3M and RO(C2H4O) xIncluded are alkyl and alkyl ether sulfates of the formula SO3M, where R is alkyl or alkenyl of about 8 to about 18 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium, and triethanolamine cation, or a salt of a divalent magnesium ion with two anionic surfactant anions. The alkyl ether sulfates may be made as the condensation product of ethylene oxide and a monohydric alcohol having about 8 to about 24 carbon atoms. The alcohol may be derived from fats, such as, for example, coconut oil, palm oil, palm kernel oil, or tallow, or may be synthetic.

[0053] Other suitable anionic surfactants include those having the general formula [R 1 -SO3M] is a water-soluble salt of organic sulfuric acid. 1 is a straight-chain aliphatic hydrocarbon group having 13 to 17 carbon atoms, or alternatively 13 to 15 carbon atoms. M is a water-soluble cation such as ammonium, sodium, potassium, and triethanolamine cation, or a salt of divalent magnesium ion with two anionic surfactant anions. These materials are prepared by the synthesis of SO2 and O2 with normal paraffins (C) of the appropriate chain length. 14 ~C 17 ) and is commercially available as sodium paraffin sulfonate.

[0054] Examples of additional anionic surfactants suitable for use include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauryl monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine

[0049] The surfactants and surfactants include, but are not limited to, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, monoethanolamine cocoyl sulfate, sodium trideceth sulfate, sodium tridecyl sulfate, sodium methyl lauroyl taurate, sodium methyl cocoyl taurate, sodium lauroyl isethionate, sodium cocoyl isethionate, sodium laureth sulfosuccinate, sodium lauryl sulfosuccinate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and mixtures thereof.

[0055] The shampoo composition may further comprise additional surfactants for use in combination with the anionic detersive surfactant component described herein. Suitable additional surfactants include cationic surfactants and nonionic surfactants.

[0056] Non-limiting examples of other anionic, zwitterionic, amphoteric, cationic, nonionic, or any additional surfactants suitable for use in the present compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by MC Publishing Co., and U.S. Pat. Nos. 3,929,678, 2,658,072, 2,438,091, and 2,528,378.

[0057] The shampoo compositions described herein may be substantially free of sulfate surfactants.

[0058] The one or more additional anionic surfactants may be selected from the group consisting of isethionates, sarcosinates, sulfonates, sulfosuccinates, sulfoacetates, acylglycinates, acylalaninates, acylglutamates, lactates, lactylates, glucosecarboxylates, amphoacetates, taurates, phosphate esters, and mixtures thereof, where alkyl is defined as a saturated or unsaturated, linear or branched alkyl chain having 7 to 17 carbon atoms, alternatively 9 to 13 carbon atoms, and acyl is defined as having the formula RC(O)-, where R is a saturated or unsaturated, linear or branched alkyl chain having 7 to 17 carbon atoms, alternatively 9 to 13 carbon atoms.

[0059] Suitable isethionate surfactants can include the reaction product of a fatty acid esterified with isethionic acid and neutralized with sodium hydroxide. Suitable fatty acids for isethionate surfactants can be derived from coconut oil or palm kernel oil, such as amides of methyl tauride. Non-limiting examples of isethionates can be selected from the group consisting of sodium lauroyl methyl isethionate, sodium cocoyl isethionate, ammonium cocoyl isethionate, hydrogenated sodium cocoyl methyl isethionate, sodium lauroyl isethionate, sodium cocoyl methyl isethionate, sodium myristoyl isethionate, sodium oleoyl isethionate, sodium oleyl methyl isethionate, sodium palm kernel oil isethionate, sodium stearoyl methyl isethionate, and mixtures thereof.

[0060] Non-limiting examples of sarcosinates may be selected from the group consisting of sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, TEA cocoyl sarcosinate, ammonium cocoyl sarcosinate, ammonium lauroyl sarcosinate, dimer dilinoleyl bis-lauroyl glutamate / lauroyl sarcosinate, disodium lauroamphodiacetate, lauroyl sarcosinic acid, isopropyl lauroyl sarcosinate, potassium cocoyl sarcosinate, potassium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium oleoyl sarcosinate, sodium palmitoyl sarcosinate, TEA cocoyl sarcosinate, TEA lauroyl sarcosinate, TEA oleoyl sarcosinate, TEA palm kernel sarcosinate, and combinations thereof.

[0061] Non-limiting examples of sulfosuccinate surfactants include disodium N-octadecyl sulfosuccinate, disodium lauryl sulfosuccinate, diammonium lauryl sulfosuccinate, sodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate, diamyl ester of sodium sulfosuccinate, dihexyl ester of sodium sulfosuccinate, dioctyl ester of sodium sulfosuccinate, and combinations thereof.

[0062] Non-limiting examples of sulfoacetates include sodium lauryl sulfoacetate, ammonium lauryl sulfoacetate, and combinations thereof.

[0063] Non-limiting examples of acyl glycinates include sodium cocoyl glycinate, sodium lauroyl glycinate, and combinations thereof.

[0064] Non-limiting examples of acyl alaninates include sodium cocoyl alaninate, sodium lauroyl alaninate, sodium N-dodecanoyl-1-alaninate, and combinations thereof.

[0065] Non-limiting examples of acyl glutamates include sodium cocoyl glutamate, disodium cocoyl glutamate, ammonium cocoyl glutamate, diammonium cocoyl glutamate, sodium lauroyl glutamate, disodium lauroyl glutamate, cocoyl hydrolyzed wheat protein sodium glutamate, cocoyl hydrolyzed wheat protein disodium glutamate, potassium cocoyl glutamate, dipotassium cocoyl glutamate, potassium lauroyl glutamate, dipotassium lauroyl glutamate, cocoyl hydrolyzed wheat protein potassium glutamate, cocoyl hydrolyzed wheat protein dipotassium glutamate, sodium capryloyl glutamate, disodium capryloyl glutamate, potassium capryloyl glutamate, dipotassium capryloyl glutamate, sodium undecylenoyl glutamate, disodium undecylenoyl glutamate, potassium undecylenoyl glutamate, undecylenoyl glutamate, dipotassium lauroyl glutamate, hydrogenated tallow glutamate disodium, sodium stearoyl glutamate, disodium stearoyl glutamate, potassium stearoyl glutamate, dipotassium stearoyl glutamate, sodium myristoyl glutamate, disodium myristoyl glutamate, potassium myristoyl glutamate, dipotassium myristoyl glutamate, cocoyl / hydrogenated tallow glutamate, cocoyl / palmoyl / sunflower oil sodium glutamate, hydrogenated tallow oil sodium glutamate, sodium olivoyl glutamate, disodium olivoyl glutamate, sodium palmoyl glutamate, disodium palmoyl glutamate, TEA-cocoyl glutamate, hydrogenated tallow oil glutamate, TEA-lauroyl glutamate, and mixtures thereof.

[0066] Non-limiting examples of acyl glycinates include sodium cocoyl glycinate, sodium lauroyl glycinate, and combinations thereof.

[0067] A non-limiting example of a lactate can include sodium lactate.

[0068] Non-limiting examples of lactylates include sodium lauroyl lactylate, sodium cocoyl lactylate, and combinations thereof.

[0069] Non-limiting examples of glucose carboxylates include sodium lauryl glucoside carboxylate, sodium cocoyl glucoside carboxylate, and combinations thereof.

[0070] Non-limiting examples of alkylamphoacetates include sodium cocoylamphoacetate, sodium lauroylamphoacetate, and combinations thereof.

[0071] Non-limiting examples of acyltaurates include sodium methyl cocoyl taurate, sodium methyl lauroyl taurate, sodium methyl oleoyl taurate, and combinations thereof.

[0072] The cleansing phase may contain one or more amphoteric and / or zwitterionic and / or nonionic co-surfactants at concentrations ranging from about 0.25% to about 50%, alternatively from about 0.5% to about 30%, alternatively from about 0.75% to about 15%, alternatively from about 1% to about 13%, alternatively from about 2% to about 10% by weight of the cleansing phase. Co-surfactants can serve to generate lather more quickly, promote easier rinsing, and / or reduce harshness on keratinous tissue. Co-surfactants can also assist in generating lather with more desirable texture, volume, and / or other properties.

[0073] Suitable amphoteric surfactants for use herein include, but are not limited to, derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical can be straight or branched, where one of the aliphatic substituents contains about 8 to about 18 carbon atoms and one contains an anionic water-soluble group, such as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples include sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate, sodium lauryl sarcosinate, N-alkyltaurines such as those prepared by reacting dodecylamine with sodium isethionate according to the teachings of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those prepared according to the teachings of U.S. Pat. No. 2,438,091, and the products described in U.S. Pat. No. 2,528,378, as well as mixtures thereof. The amphoteric surfactant can be selected from the betaine group, such as lauroamphoacetic acid.

[0074] Zwitterionic surfactants suitable for use herein include, but are not limited to, derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, wherein the aliphatic group can be straight or branched chain, one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, and one substituent contains an anionic group, such as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Other zwitterionic surfactants suitable for use herein include betaines, including higher alkyl betaines, such as cocodimethylcarboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, laurylamidopropyl betaine, oleyl betaine, lauryldimethylcarboxymethyl betaine, lauryldimethylalphacarboxyethyl betaine, cetyldimethylcarboxymethyl betaine, laurylbis-(2-hydroxyethyl)carboxymethyl betaine, stearylbis-(2-hydroxypropyl)carboxymethyl betaine, oleyldimethylgamma-carboxypropyl betaine, laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine, and mixtures thereof. Sulfobetaines can include cocodimethylsulfopropyl betaine, stearyldimethylsulfopropyl betaine, lauryldimethylsulfoethyl betaine, laurylbis-(2-hydroxyethyl)sulfopropyl betaine, and mixtures thereof. Other suitable amphoteric surfactants include amidobetaines and amidosulfobetaines, which are represented by the RCONH(CH2)3 radical (where R is C 11 ~C 17 The alkyl group is attached to the nitrogen atom of the betaine.

[0075] Suitable nonionic co-surfactants for use in the present compositions to enhance lather volume or texture include water-soluble materials such as lauryl dimethylamine oxide, coco dimethylamine oxide, cocoamidopropylamine oxide, laurylamidopropylamine oxide, and the like, or alkyl polyethoxylates such as laureth-4 through laureth-7, and water-insoluble ingredients such as coco monoethanolamide, coco diethanolamide, lauroyl monoethanolamide, alkanoyl isopropanolamide, and fatty alcohols such as cetyl alcohol and oleyl alcohol, and 2-hydroxyalkyl methyl ethers.

[0076] Further suitable materials as co-surfactants herein include 1,2-alkyl epoxides, 1,2-alkanediols, branched or linear alkyl glyceryl ethers (such as those described in EP 1696023 A1), 1,2-alkyl cyclic carbonates, and 1,2-alkyl cyclic sulfites, especially those in which the alkyl group contains 6 to 14 carbon atoms in a linear or branched configuration. Other examples include C 10 or C 12 Included are alkyl ether alcohols derived from reacting alpha olefins with ethylene glycol (e.g., hydroxyethyl-2-decyl ether, hydroxyethyl-2-dodecyl ether), which can be made according to U.S. Pat. Nos. 5,741,948, 5,994,595, 6,346,509, and 6,417,408.

[0077] Other nonionic surfactants may be selected from the group consisting of glucose amides, alkyl polyglucosides, sucrose cocoate, sucrose lauryl sulfate, alkanolamides, ethoxylated alcohols, and mixtures thereof. Nonionic surfactants may be selected from the group consisting of glyceryl monohydroxystearate, isosteareth-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glyceryl laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, and mixtures thereof.

[0078] The co-surfactant may be selected from the group consisting of coco monoethanolamide, cocoamidopropyl betaine, laurylamidopropyl betaine, cocobetaine, lauryl betaine, lauryl amine oxide, sodium laurylamphoacetate; alkyl glyceryl ethers, alkyl-di-glyceryl ethers, 1,2-alkyl cyclic sulfites, 1,2-alkyl cyclic carbonates, 1,2-alkyl-epoxides, alkyl glycidyl ethers, and alkyl-1,3-dioxolanes (wherein the alkyl group contains 6 to 14 carbon atoms in a linear or branched chain configuration); 1,2-alkanediols having a total carbon content of 6 to 14 carbon atoms in a linear or branched chain, methyl-2-hydroxy-decyl ether, hydroxyethyl-2-dodecyl ether, hydroxyethyl-2-decyl ether, and mixtures thereof.

[0079] Cationic surfactants may be derived from amines that are protonated at the pH of the formulation, such as bis-hydroxyethyl laurylamine, lauryl dimethylamine, lauroyl dimethylamidopropylamine, cocoyl amidopropylamine, etc. Cationic surfactants may also be derived from fatty quaternary ammonium salts, such as lauryl trimethyl ammonium chloride and lauroyl amidopropyl trimethyl ammonium chloride.

[0080] Alkylamphoacetates are suitable surfactants for use in the compositions herein to improve the mildness and lather of the product.The most commonly used alkylamphoacetates are lauroamphoacetate and cocoamphoacetate.Alkylamphoacetates can be composed of monoacetate and diacetate.In some types of alkylamphoacetates, diacetate is an impurity or an unintended reaction product.However, the presence of diacetate can cause various undesirable composition characteristics when present in an amount exceeding 15% of the alkylamphoacetate.

[0081] Suitable nonionic surfactants for use herein are selected from the group consisting of glucose amides, alkyl polyglucosides, sucrose cocoate, sucrose laurate, alkanolamides, ethoxylated alcohols, and mixtures thereof. In one embodiment, the nonionic surfactant is selected from the group consisting of glyceryl monohydroxystearate, isosteareth-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glyceryl laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, and mixtures thereof.

[0082] When present, the composition may include a rheology modifier, which includes a cellulosic rheology modifier, a crosslinked acrylate, a crosslinked maleic anhydride co-methyl vinyl ether, a hydrophobically modified associative polymer, or a mixture thereof.

[0083] When used, the electrolyte may be added to the composition itself or may be formed in situ via a counterion contained in one of the raw materials. The electrolyte may include an anion including phosphate, chloride, sulfate, or citrate, and a cation including sodium, ammonium, potassium, magnesium, or a mixture thereof. The electrolyte may be sodium chloride, ammonium chloride, sodium sulfate, or ammonium sulfate. The electrolyte may be added to the composition in an amount of about 0.1% to about 15% by weight, alternatively about 1% to about 6% by weight, alternatively about 3% to about 6% by weight, based on the weight of the composition.

[0084] structuring agent The cleansing phase can include a structuring agent (e.g., a crosslinked polyacrylate, Carbopol® Aqua SF-1 polymer, available from Lubrizol®) that can provide a high, low shear viscosity and yield stress to maintain a stable, separate product phase in the shampoo composition over time, including transportation, handling, distribution, and shelf storage in stores, warehouses, or at the consumer's home. The cleansing phase can include a structuring agent at a concentration effective to suspend the benefit phase in the cleansing phase and / or adjust the viscosity of the composition. Such concentrations can range from about 0.05% to about 10%, alternatively from about 0.3% to about 5.0%, alternatively from about 1.5% to about 5.0%, by weight of the cleansing phase. However, as can be appreciated, certain glyceride ester crystals can act as suitable structuring or suspending agents.

[0085] Suitable structuring agents include anionic and nonionic polymers. Vinyl polymers, such as crosslinked acrylic acid polymers with the CTFA name Carbomer, cellulose derivatives and modified cellulose polymers, such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carragheenin, pectin, agar, quince seed (Cydonia oblonga Mill. Mill), starches (rice, corn, potato, wheat), algal colloids (algae extracts), microbiological polymers such as dextran, succinoglucan, pulleran, starch-based polymers such as carboxymethyl starch, methylhydroxypropyl starch, alginic acid-based polymers such as sodium alginate, propylene glycol alginate, acrylate polymers such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, polyethyleneimine, and inorganic water-soluble materials such as bentonite, magnesium aluminum silicate, laponite, hectonite, and silicic anhydride are useful herein.

[0086] Other suitable structuring agents include crystalline structuring agents that can be classified as acyl derivatives, long-chain amine oxides, and mixtures thereof. Examples of such structuring agents are described in U.S. Pat. No. 4,741,855, incorporated herein by reference. Suitable structuring agents include ethylene glycol esters of fatty acids having 16 to 22 carbon atoms. The structuring agent can be ethylene glycol stearates, both monostearate and distearate, but particularly distearates containing less than about 7% monostearate. Other suitable structuring agents include alkanolamides of fatty acids having about 16 to about 22 carbon atoms, or about 16 to 18 carbon atoms, suitable examples of which include stearic acid monoethanolamide, stearic acid diethanolamide, stearic acid monoisopropanolamide, and stearic acid monoethanolamide stearate. Other long-chain acyl derivatives include long-chain esters of long-chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.), long-chain esters of long-chain alkanolamides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate), and glyceryl esters of the foregoing. Long-chain acyl derivatives, ethylene glycol esters of long-chain carboxylic acids, long-chain amine oxides, and alkanolamides of long-chain carboxylic acids may also be used as structuring agents.

[0087] Other long chain acyl derivatives suitable for use as structuring agents include N,N-dihydrocarbylamidobenzoic acids and their soluble salts (e.g., Na, K), particularly N,N-di(hydrogenated) C 16 , C 18 and tallowamidobenzoic acid species, which are commercially available from Stepan Company (Northfield, Ill., USA).

[0088] Examples of long chain amine oxides suitable for use as structuring agents include alkyl dimethyl amine oxides, such as stearyl dimethyl amine oxide.

[0089] Other suitable structuring agents include primary amines having a fatty acid alkyl moiety of at least about 16 carbon atoms (examples of which include palmitamine or stearamine) and secondary amines having two fatty acid alkyl moieties, each having at least about 12 carbon atoms (examples of which include dipalmitoylamine or di(hydrogenated tallow)amine). Still other suitable structuring agents include di(hydrogenated tallow)phthalamide and crosslinked maleic anhydride-methyl vinyl ether copolymer.

[0090] Other suitable structuring agents include crystalline glyceride esters. For example, a suitable glyceride ester is hydrogenated castor oil (such as trihydroxystearin or dihydroxystearin). An example of additional crystalline glyceride esters can include substantially pure triglyceride of 12-hydroxystearic acid. 12-hydroxystearic acid is the pure form of the triglyceride of fully hydrogenated 12-hydroxy-9-cis-octadecenoic acid. As can be understood, many additional glyceride esters are possible. For example, variations in the hydrogenation process and natural variations in castor oil may allow the production of additional suitable glyceride esters from castor oil.

[0091] Viscosity modifier Optionally, viscosity modifier can be used to adjust the rheology of cleansing phase.Suitable viscosity modifier can include carbomer with trade name Carbopol934, Carbopol940, Carbopol950, Carbopol980 and Carbopol981, all available from BFGoodrich Company; acrylate / steareth-20 methacrylate copolymer with trade name ACRYSOL22, all available from Rohm and Hass; nonoxynyl hydroxyethyl cellulose with trade name AMERCELL POLYMER HM-1500, all available from Amerchol; methylcellulose with trade name BENECEL, hydroxyethyl cellulose with trade name NATROSOL, hydroxypropyl cellulose with trade name KLUCEL, cetyl hydroxyethyl cellulose with trade name POLYSURF67, all available from Amerchol; ethylene oxide and / or propylene oxide-based polymer with trade name CARBOWAX PEG, POLYOX WASR and UCON FLUIDS, all available from Amerchol. Sodium chloride can also be used as a viscosity modifier. Other suitable rheology modifiers include crosslinked acrylates, crosslinked maleic anhydride comethyl vinyl ether, hydrophobically modified associative polymers, and mixtures thereof.

[0092] beneficial phase The optional benefit phase may comprise a gel network, which may contain one or more fatty alcohols. The gel network may provide conditioning benefits. As used herein, the term "gel network" refers to a lamellar or vesicular solid crystalline phase comprising at least one fatty alcohol, as specified below, at least one secondary surfactant and / or fatty acid, as specified below, and water and / or other suitable solvents. The lamellar or vesicular phase comprises a bilayer consisting of a first layer comprising a fatty alcohol and / or fatty acid and a secondary surfactant and / or fatty acid, alternating with a second layer comprising water or other suitable solvents. In another example, the gel network may comprise at least one fatty acid, at least one secondary surfactant, and water and / or other suitable solvents. As used herein, the term "solid crystal" refers to a lamellar or vesicular phase structure formed at a temperature below the melting transition temperature of the layer in the gel network comprising one or more fatty alcohols. Additional examples of multi-phase shampoo compositions having a floating benefit phase are described in US Patent Application No. 17 / 174,713, which is incorporated herein by reference.

[0093] The multi-phase shampoo composition may include a benefit phase, which may be present in an amount of from about 1% to about 90%, alternatively from about 2% to about 50%, alternatively from about 5% to about 40%, alternatively from about 7% to about 30%, alternatively from about 10% to about 25%, by weight of the shampoo composition. The benefit phase may have a transmittance of less than 55%, alternatively less than 50%, alternatively less than 40%, alternatively less than 30%, alternatively less than 25%, as measured by the Light Transmission Method described below. In some examples, the benefit phase may be substantially free of structuring agents. In other examples, the benefit phase may be free of cationic surfactants and / or anionic surfactants.

[0094] The gel network described herein can be prepared as a separate premix that, after cooling, is combined with the cleansing phase as a visually separate phase. The preparation of the gel network components is discussed in more detail below as well as in the Examples.

[0095] The cooled, pre-formed gel network component is then added to the other components of the shampoo composition, including the detersive surfactant component. Without intending to be bound by theory, it is believed that incorporating the cooled, pre-formed gel network component with the detersive surfactant and other components of the shampoo composition allows for the formation of a substantially equilibrated lamellar dispersion ("ELD") in the final shampoo composition. The ELD is a dispersed lamellar or vesicular phase resulting from the pre-formed gel network component that is substantially equilibrated with the detersive surfactant, water, and other optional ingredients, such as salt, that may be present in the shampoo composition. This equilibration occurs upon incorporation of the pre-formed gel network component with the other components of the shampoo composition and is effectively completed within about 24 hours after preparation. The shampoo composition in which the ELD is formed provides improved wet / dry conditioning benefits to hair.

[0096] For clarity, as used herein, the term "ELD" refers to the same component of the shampoo compositions of the present invention as the phrase "gel network phase."

[0097] The presence of a gel network in the form of ELDs in the premix and final shampoo compositions can be confirmed by means known to those skilled in the art, such as X-ray analysis, optical microscopy, electron microscopy, and differential scanning calorimetry. A method for differential scanning calorimetry is described below. For X-ray analysis, see U.S. Published Patent Application No. 2006 / 0024256(A1).

[0098] The scale size of the gel network phase in the shampoo composition (i.e., ELD) can range from about 10 nm to about 500 nm. The scale size of the gel network phase in the shampoo composition can range from about 0.5 μm to about 10 μm. Alternatively, the scale size of the gel network phase in the shampoo composition can range from about 10 μm to about 150 μm.

[0099] The scale size distribution of the gel network phase in a shampoo composition can be measured by laser light scattering techniques using a Horiba Model LA910 Laser Scattering Particle Size Distribution Analyzer (Horiba Instruments, Inc.) (Irvine, California, USA). The scale size distribution in a shampoo composition of the present invention can be measured by combining 1.75 g of shampoo composition with 30 mL of 3% NH4Cl, 20 mL of 2% Na2HPO4·7H2O, and 10 mL of 1% Laureth-7 to form a mixture. This mixture is then stirred for 5 minutes. Depending on the particular Horiba instrument used, a sample ranging from 1 to 40 mL is taken and then injected into a Horiba instrument containing 75 mL of 3% NH4Cl, 50 mL of 2% Na2HPO4·7H2O, and 25 mL of 1% Laureth-7 until the Horiba instrument reading reaches 88-92% T, the required scale size measurement. Once this is achieved, after 2 minutes of circulation, it is measured through the Horiba instrument to provide a scale size measurement. This subsequent measurement is performed using a sample of the shampoo composition that has been heated above the melting transition temperature of all fatty materials present in the shampoo composition, such that the gel network components melt. From this subsequent measurement, a scale size distribution is taken of all of the remaining materials in the shampoo, which can then be compared to the scale size distribution of the initial sample to aid in analysis.

[0100] fatty alcohols The gel network component of the present invention can include at least one fatty alcohol. An individual fatty alcohol compound or a combination of two or more different fatty alcohol compounds may be selected.

[0101] Fatty alcohols suitable for use in the present invention can include those having from about 16 to about 70 carbon atoms, alternatively from about 16 to about 60 carbon atoms, alternatively from about 16 to about 50 carbon atoms, alternatively from about 16 to about 40 carbon atoms, or alternatively from about 16 to about 22 carbon atoms. These fatty alcohols can be straight or branched chain alcohols and can be saturated or unsaturated. Non-limiting examples of suitable fatty alcohols include stearyl alcohol, arachidyl alcohol, behenyl alcohol, C21 fatty alcohol (1-heneicosanol), C23 fatty alcohol (1-tricosanol), C24 fatty alcohol (lignoceryl alcohol, 1-tetracosanol), C26 fatty alcohol (1-hexacosanol), C28 fatty alcohol (1-octacosanol), C30 fatty alcohol (1-triacontanol), C20-40 alcohols (e.g., Performacol 350 and 425 alcohols, available from New Phase Technologies), C30-50 alcohols (e.g., Performacol 550 alcohol), C40-60 alcohols (e.g., Performacol 700 alcohol), cetyl alcohol, and mixtures thereof.

[0102] Mixtures of different fatty alcohols, including one or more fatty alcohols having from about 16 to about 70 carbon atoms, which may also contain amounts of one or more fatty alcohols having less than about 16 carbon atoms or more than about 70 carbon atoms, or other fatty amphiphiles, are considered within the scope of the present invention so long as the resulting gel network phase has a melt transition temperature of at least about 25°C, alternatively at least about 28°C, alternatively at least about 31°C, alternatively at least about 34°C, or alternatively at least about 37°C.

[0103] Such fatty alcohols suitable for use in the present invention may be of natural or plant origin, or they may be of synthetic origin.

[0104] The benefit phase, as part of the gel network phase, may comprise fatty alcohol in an amount of at least about 2.8%, alternatively from about 2.8% to about 25%, alternatively from about 4% to about 23%, alternatively from about 5% to about 20%, alternatively from about 6% to about 18%, alternatively from about 7% to about 15%, alternatively from about 8% to about 13% by weight of the benefit phase.

[0105] In embodiments of the invention, the weight ratio of fatty alcohol to secondary surfactant in the gel network component is greater than about 1:9, alternatively from about 1:5 to about 100:1, alternatively from about 1:1 to about 50:1.

[0106] Secondary Surfactants The gel network component of the present invention may also include a secondary surfactant. As used herein, "secondary surfactant" refers to one or more surfactants that are combined with a fatty alcohol and water to form the gel network of the present invention as a premix separate from the other components of the shampoo composition. The secondary surfactant is separate from and is added to the cleansing surfactant component of the cleansing phase. However, the secondary surfactant may be the same or a different type of surfactant(s) as those selected for the cleansing surfactant component described above.

[0107] The benefit phase of the present invention comprises, as part of the pre-formed gel network phase, a secondary surfactant in an amount of from about 0.01% to about 15%, alternatively from about 0.5% to about 12%, alternatively from about 0.7% to about 10%, alternatively from about 1% to about 6% by weight of the benefit phase.

[0108] Suitable secondary surfactants include anionic, zwitterionic, amphoteric, cationic and nonionic surfactants.Secondary surfactants can be selected from anionic, cationic and nonionic surfactants, and mixtures thereof.For further information on suitable secondary surfactants for use in the present invention, please refer to US Patent Application Publication No. 2006 / 0024256(A1).

[0109] Additionally, certain secondary surfactants have a hydrophobic tail group with a chain length of about 16 to about 22 carbon atoms. In such secondary surfactants, the hydrophobic tail group may be alkyl, alkenyl (containing up to three double bonds), alkylaromatic, or branched alkyl. The secondary surfactant may be present in the gel network component relative to the fatty alcohol in a weight ratio of about 1:5 to about 5:1. SLE1S may be particularly useful because it is a highly efficient surfactant with good lathering. In shampoo compositions containing high levels of conditioning actives, SLE1S can further enhance lathering and cleansing. Mixtures of two or more of the above-specified surfactants may be used as secondary surfactants in the present invention.

[0110] Examples of gel network premixes can be found in U.S. Pat. No. 8,361,448 and U.S. Patent Application Publication No. 2017 / 0367955, which are incorporated herein by reference.

[0111] fatty acid Non-limiting examples of suitable fatty acids that can be combined with either the fatty alcohol or the secondary surfactant to form a gel network include unsaturated and / or branched long chain (C8-C9) fatty acids. 24) liquid fatty acids or their ester derivatives, unsaturated and / or branched long-chain liquid alcohols or their ether derivatives, and mixtures thereof. Fatty acids may include short-chain saturated fatty acids such as capric acid and caprylic acid. Without being limited by theory, it is believed that the unsaturated portion of the fatty acid or alcohol, or the branched portion of the fatty acid or alcohol, plays a role in "perturbing" the hydrophobic chain of the surfactant and inducing the formation of a lamellar phase. Examples of suitable liquid fatty acids include oleic acid, isostearic acid, linoleic acid, linolenic acid, ricinoleic acid, elaidic acid, arachidonic acid, myristoleic acid, palmitoleic acid, and mixtures thereof. Examples of suitable ester derivatives include propylene glycol isostearate, propylene glycol oleate, glyceryl isostearate, glyceryl oleate, polyglyceryl diisostearate, and mixtures thereof. Examples of alcohols include oleyl alcohol and isostearyl alcohol. Examples of ether derivatives include isosteareth or oleth carboxylates, or isosteareth or oleth alcohols. Structuring agents may be defined as having a melting point below about 25°C.

[0112] Cationic Deposition Polymer The benefit phase and / or cleansing phase may contain a cationic deposition polymer. In some examples, the cleansing phase may be substantially free of any cationic deposition polymer or level thereof (e.g., polyquaternium-6) that may cause the composition to appear hazy or cloudy to the naked eye of a human observer. The cationic deposition polymer may be added at a level of from about 0.1% to about 15%, preferably from about 0.5% to about 8%, more preferably from about 1% to about 5% cationic deposition polymer by weight of the benefit phase, cleansing phase, or shampoo composition.

[0113] The shampoo composition can include a cationic polymer that allows for the formation of coacervates. As can be appreciated, the cationic charge of the cationic polymer can interact with the anionic charge of the surfactant to form coacervates. Suitable cationic polymers include (a) cationic guar polymers, (b) cationic non-guar galactomannan polymers, (c) cationic starch polymers, (d) cationic copolymers of acrylamide monomers and cationic monomers, (e) synthetic non-crosslinked cationic polymers that may or may not form lyotropic liquid crystals when combined with a detersive surfactant, (f) cationic synthetic homopolymers, (g) cationic cellulose polymers, and (h) combinations thereof. In certain examples, two or more cationic polymers can be included. The cationic polymer can be selected from guar hydroxypropyltrimonium chloride, polyquaternium 10, polyquaternium 6, and combinations thereof.

[0114] The cationic polymer may have a cationic charge density of about 0.9 meq / g or more, about 1.2 meq / g or more, and about 1.5 meq / g or more. However, the cationic charge density may be about 7 meq / g or less, or even 5 meq / g or less. The charge density may be measured at the pH of the shampoo composition's intended use (e.g., about pH 3 to about pH 9, or about pH 4 to about pH 8). The average molecular weight of the cationic polymer generally may be about 10,000 to about 10,000,000, about 50,000 to about 5,000,000, about 100,000 to about 3,000,000, about 300,000 to about 3,000,000, and about 100,000 to about 2,500,000. Low molecular weight cationic polymers may also be used. A lower molecular weight cationic polymer can have greater optical transparency within the liquid carrier of the shampoo composition. The cationic polymer can be of a single type, such as guar hydroxypropyltrimonium chloride, a cationic guar polymer having a weight average molecular weight of about 2,500,000 g / mol or less, and the shampoo composition can have additional cationic polymers of the same or different types.

[0115] Cationic Guar Polymer The cationic polymer may be a cationic guar polymer, which is a cationically substituted galactomannan (guar) gum derivative. Suitable guar gum for the guar gum derivative can be obtained as a naturally occurring material from the seeds of the guar plant. As can be understood, the guar molecule is a linear mannan in which single-membered galactose units branch at regular intervals on alternating mannose units. The mannose units are linked to each other by b(1-4) glycosidic bonds. The galactose branches are formed by a(1-6) bonds. The cationic derivative of guar gum can be obtained through the reaction between the hydroxyl groups of the polygalactomannan and a reactive quaternary ammonium compound. The degree of substitution of cationic groups on the guar structure can be sufficient to provide the required cationic charge density described above.

[0116] The cationic guar polymer can have a weight average molecular weight ("molecular weight") of less than about 3,000,000 g / mole and a charge density of from about 0.05 meq / g to about 2.5 meq / g. Alternatively, the cationic guar polymer can have a weight average molecular weight of less than 1,500,000 g / mole, from about 150,000 g / mole to about 1,500,000 g / mole, from about 200,000 g / mole to about 1,500,000 g / mole, from about 300,000 g / mole to about 1,500,000 g / mole, and from about 700,000,000 g / mole to about 1,500,000 g / mole. The cationic guar polymer can have a charge density of from about 0.2 meq / g to about 2.2 meq / g, from about 0.3 meq / g to about 2.0 meq / g, from about 0.4 meq / g to about 1.8 meq / g, and from about 0.5 meq / g to about 1.7 meq / g.

[0117] The cationic guar polymer can have a weight average molecular weight of less than about 1,000,000 g / mol and can have a charge density of from about 0.1 meq / g to about 2.5 meq / g. The cationic guar polymer can have a weight average molecular weight of less than 900,000 g / mol, from about 150,000 to about 800,000 g / mol, from about 200,000 g / mol to about 700,000 g / mol, from about 300,000 to about 700,000 g / mol, from about 400,000 to about 600,000 g / mol, from about 150,000 g / mol to about 800,000 g / mol, from about 200,000 g / mol to about 700,000 g / mol, from about 300,000 g / mol to about 700,000 g / mol, and from about 400,000 g / mol to about 600,000 g / mol. The cationic guar polymers have a charge density of from about 0.2 meq / g to about 2.2 meq / g, from about 0.3 meq / g to about 2.0 meq / g, from about 0.4 meq / g to about 1.8 meq / g, and from about 0.5 meq / g to about 1.5 meq / g.

[0118] The shampoo composition may comprise from about 0.01% to less than about 0.7%, from about 0.04% to about 0.55%, from about 0.08% to about 0.5%, from about 0.16% to about 0.5%, from about 0.2% to about 0.5%, from about 0.3% to about 0.5%, and from about 0.4% to about 0.5%, by weight of the shampoo composition, of cationic guar polymer.

[0119] Cationic guar polymers can be formed from quaternary ammonium compounds conforming to general formula II:

[0120] [ka] In the formula, R 3 , R 4 , and R 5 is a methyl group or an ethyl group, and R 6 is an epoxyalkyl group of general formula III,

[0121] [ka] Or R 6 is a halohydrin group of general formula IV,

[0122] [ka] In the formula, R 7 is a C1-C3 alkylene, X is chlorine or bromine, and Z is an anion such as Cl-, Br-, I-, or HSO4-.

[0123] Suitable cationic guar polymers may conform to the general formula V:

[0124] [ka] In the formula, R 8 is guar gum, R 4 , R 5 , R 6 , and R 7 is as defined above and Z is a halogen. Suitable cationic guar polymers can conform to formula VI:

[0125] [ka] In the formula, R 8 is guar gum.

[0126] Suitable cationic guar polymers may also include cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride. Suitable examples of guar hydroxypropyltrimonium chloride include the Jaguar series available from Solvay SA, the Hi-Care series available from Rhodia, and N-Hance and AquaCat available from Ashland Inc. Jaguar C-500 has a charge density of 0.8 meq / g and a molecular weight of 500,000 g / mol; Optima has a cationic charge density of about 1.25 meq / g and a molecular weight of about 500,000 g / mole, Jaguar® C-17 has a cationic charge density of about 0.6 meq / g and a molecular weight of about 2,200,000 g / mole, Jaguar® and a cationic charge density of about 0.8 meq / g, Hi-Care 1000 has a charge density of about 0.7 meq / g and a molecular weight of about 600,000 g / mole, N-Hance 3269 and N-Hance 3270 have a charge density of about 0.7 meq / g and a molecular weight of about 425,000 g / mole, N-Hance 3196 has a charge density of about 0.8 meq / g and a molecular weight of about 1,100,000 g / mole, and AquaCat CG518 has a charge density of about 0.9 meq / g and a molecular weight of about 50,000 g / mol. N-Hance BF-13 and N-Hance BF-17 are borate (boron)-free guar polymers. N-Hance BF-13 has a charge density of about 1.1 meq / g and a molecular weight of about 800,000, and N-Hance BF-17 has a charge density of about 1.7 meq / g and a molecular weight of about 800,000. BF-17 has a charge density of about 1.7 meq / g and a molecular weight of about 800,000. BF-17 has a charge density of about 1.7 meq / g and a molecular weight of about 800,000. BF-17 has a charge density of about 1.7 meq / g and a molecular weight of about 800,000.

[0127] Cationic Non-Guar Galactomannan Polymers The cationic polymer may be a galactomannan polymer derivative. Suitable galactomannan polymers may have a mannose to galactose ratio of greater than 2:1 on a monomer to monomer basis and may be a cationic galactomannan polymer derivative or an amphoteric galactomannan polymer derivative having a net positive charge. As used herein, the term "cationic galactomannan" refers to a galactomannan polymer to which cationic groups have been added. The term "amphoteric galactomannan" refers to a galactomannan polymer to which cationic and anionic groups have been added such that the polymer has a net positive charge.

[0128] Galactomannan polymers can be present in the endosperm of legume seeds. Galactomannan polymers are composed of a combination of mannose and galactose monomers. Galactomannan molecules are linear mannans in which single-membered galactose units branch at regular intervals on specific mannose units. The mannose units are linked to each other by β(1-4) glycosidic bonds. Galactose branches occur via α(1-6) linkages. The ratio of mannose to galactose monomers varies depending on the plant species and may also be affected by climate. Non-guar galactomannan polymer derivatives may have a mannose-to-galactose ratio greater than 2:1 on a monomer-to-monomer basis. Suitable mannose-to-galactose ratios may also be greater than 3:1 or greater than 4:1. Analysis of the mannose-to-galactose ratio is well known in the art and is typically based on measuring galactose content.

[0129] The gums used to prepare the non-guar galactomannan polymer derivatives can be obtained from naturally occurring materials such as plant seeds or beans. Examples of various non-guar galactomannan polymers include tara gum (3 parts mannose / 1 part galactose), carob or lob (4 parts mannose / 1 part galactose), and cassia gum (5 parts mannose / 1 part galactose).

[0130] The non-guar galactomannan polymer derivatives can have a molecular weight of from about 1,000 g / mol to about 10,000,000 g / mol, and from about 5,000 g / mol to about 3,000,000 g / mol.

[0131] The shampoo compositions described herein may include a galactomannan polymer derivative having a cationic charge density of about 0.5 meq / g to about 7 meq / g. The galactomannan polymer derivative may have a cationic charge density of about 1 meq / g to about 5 meq / g. The degree of substitution of cationic groups onto the galactomannan structure may be sufficient to provide the required cationic charge density.

[0132] The galactomannan polymer derivative may be a cationic derivative of a non-guar galactomannan polymer, obtained by reacting the hydroxyl groups of the polygalactomannan polymer with a reactive quaternary ammonium compound. Suitable quaternary ammonium compounds for use in forming the cationic galactomannan polymer derivative include those conforming to the general formulas II-VI defined above.

[0133] The cationic non-guar galactomannan polymer derivatives formed from the above reagents can be represented by the general formula VII:

[0134] [ka] wherein R is a gum. The cationic galactomannan derivative can be gum hydroxypropyltrimethylammonium chloride, which can be more specifically represented by general formula VIII:

[0135] [ka]

[0136] The galactomannan polymer derivative may be an amphoteric galactomannan polymer derivative having a net positive charge, which is obtained when the cationic galactomannan polymer derivative further comprises an anionic group.

[0137] The cationic non-guar galactomannans can have a mannose to galactose ratio of greater than about 4:1, a molecular weight of about 100,000 g / mol to about 500,000 g / mol, a molecular weight of about 50,000 g / mol to about 400,000 g / mol, and a cationic charge density of about 1 meq / g to about 5 meq / g, and about 2 meq / g to about 4 meq / g.

[0138] The shampoo composition may comprise at least about 0.05% of the galactomannan polymer derivative by weight of the composition.The shampoo composition may comprise from about 0.05% to about 2% of the galactomannan polymer derivative by weight of the composition.

[0139] Cationic Starch Polymer Suitable cationic polymers may also be water-soluble cationically modified starch polymers. As used herein, the term "cationically modified starch" refers to starch to which cationic groups have been added before the starch is degraded to a smaller molecular weight, or to starch to which cationic groups have been added after the starch has been modified to achieve a desired molecular weight. The definition of the term "cationically modified starch" also includes amphoterically modified starch. The term "amphoterically modified starch" refers to a starch hydrolysate to which cationic and anionic groups have been added.

[0140] The shampoo compositions described herein may comprise cationic modified starch polymers in the range of about 0.01% to about 10%, and / or about 0.05% to about 5%, by weight of the composition.

[0141] The cationically modified starch polymers disclosed herein have a percentage of bound nitrogen of from about 0.5% to about 4%.

[0142] The cationically modified starch polymers can have a molecular weight of from about 850,000 g / mol to about 15,000,000 g / mol, and from about 900,000 g / mol to about 5,000,000 g / mol.

[0143] Cationic modified starch polymers can have a charge density of about 0.2 meq / g to about 5 meq / g, and about 0.2 meq / g to about 2 meq / g. Chemical modifications to achieve such charge densities can include adding amino and / or ammonium groups to the starch molecule. Non-limiting examples of such ammonium groups include substituents such as hydroxypropyltrimonium chloride, trimethylhydroxypropylammonium chloride, dimethylstearylhydroxypropylammonium chloride, and dimethyldodecylhydroxypropylammonium chloride. Further details are provided in Solarek, DB, *Cationic Starches in Modified Starches: Properties and Uses*, Wurzburg, OB, Ed., CRC Press, Inc. (Boca Raton, Fla.), 1986, pp. 113-125, which is incorporated herein by reference. Cationic groups can be added to the starch before it is degraded to smaller molecular weights, or the cationic groups can be added after such modification.

[0144] The cationically modified starch polymer may have a degree of substitution of cationic groups of from about 0.2 to about 2.5. As used herein, the "degree of substitution" of a cationically modified starch polymer is the average number of hydroxyl groups on each anhydroglucose unit that are derivatized with a substituent. Because each anhydroglucose unit has three possible hydroxyl groups available for substitution, the maximum possible degree of substitution is 3. The degree of substitution is expressed on a molar average basis as the number of moles of substituent per mole of anhydroglucose unit. The degree of substitution can be determined by proton nuclear magnetic resonance spectroscopy ("NMR"), a method well known in the art. 1 The NMR can be determined using 1 H NMR. 1Examples of H NMR methods include those described in "Observation on NMR Spectra of Starches in Dimethyl Sulfoxide, Iodine-Complexing, and Solvating in Water-Dimethyl Sulfoxide," Qin-Ji Peng and Arthur S. Perlin, Carbohydrate Research, 160 (1987), 57-72; and "An Approach to the Structural Analysis of Oligosaccharides by NMR Spectroscopy," J. Howard Bradbury and J. Grant Collins, Carbohydrate Research, 71 (1979), 15-25.

[0145] The starch source before chemical modification can be selected from various sources, such as tubers, legumes, cereals, and grains. For example, the starch source can include corn starch, wheat starch, rice starch, waxy corn starch, oat starch, cassava starch, barley, waxy rice starch, gluten-like rice starch, sweet rice starch, amioca, potato starch, tapioca starch, oat starch, sago starch, sweet rice, or a mixture thereof. Suitable cationic modified starch polymers can be selected from degraded cationic corn starch, cationic tapioca, cationic potato starch, and a mixture thereof. Cationic modified starch polymers include cationic corn starch and cationic tapioca.

[0146] Starch may contain one or more additional modifications before or after degradation to smaller molecular weights. For example, these modifications may include cross-linking, stabilization, phosphorylation, and hydrolysis. Stabilization may include alkylation and esterification.

[0147] The cationically modified starch polymer may be included in the shampoo composition in the form of hydrolyzed starch (e.g., acid, enzymatic, or alkaline degradation), oxidized starch (e.g., peroxide, peracid, hypochlorite, alkali, or any other oxidizing agent), physically / mechanically degraded starch (e.g., by thermomechanical energy input in processing equipment), or combinations thereof.

[0148] Starch can be easily dissolved in water and can form a substantially translucent solution in water. The transmittance of the composition is measured by ultraviolet-visible ("UV / VIS") absorbance measurement. This measurement method uses a Gretag Macbeth Colorimeter Color to measure the absorbance or transmittance of UV / VIS light of a sample. A light wavelength of 600 nm has been shown to be suitable for characterizing the transparency of shampoo compositions.

[0149] Cationic copolymer of acrylamide monomer and cationic monomer The shampoo composition can include a cationic copolymer of acrylamide monomers and cationic monomers, the copolymer having a charge density of about 1.0 meq / g to about 3.0 meq / g. The cationic copolymer can be a synthetic cationic copolymer of acrylamide monomers and cationic monomers.

[0150] Suitable cationic polymers can include: (i) an acrylamide monomer of formula IX:

[0151] [ka] In the formula, R 9 is H or C 1~4 alkyl, and R 10 and R 11 are independently H, C 1~4 alkyl, CH2OCH3, CH2OCH2CH(CH3)2, and phenyl, or together selected from the group consisting of C 3~6It is cycloalkyl. (ii) Cationic monomers conforming to formula X:

[0152] [ka] In the formula, k=1, v, v′, and v″ are each independently an integer of 1 to 6, w is 0 or an integer of 1 to 10, and X - is an anion.

[0153] The cationic monomer conforms to the formula X, where k=1, v=3, w=0, z=1, and X - Cl - and can form the following structure (Formula XI):

[0154] [ka]

[0155] As can be appreciated, the above structure may also be referred to as a diquat.

[0156] The cationic monomer can conform to the formula X, where v and v″ are each 3, v′=1, w=1, y=1, and X - is Cl - forming a structure of formula XII:

[0157] [ka]

[0158] The structure of formula XII can be referred to as a triquat.

[0159] The acrylamide monomer can be either acrylamide or methacrylamide.

[0160] The cationic copolymer can be AM:TRIQUAT, which can be a copolymer of acrylamide and 1,3-propanediaminium, N-[2-[[[dimethyl[3-[(2-methyl-1-oxo-2-propenyl)amino]propyl]ammonio]acetyl]amino]ethyl]2-hydroxy-N,N,N',N',N'-pentamethyl-, trichloride. AM:TRIQUAT is also known as polyquaternium 76 (PQ76). AM:TRIQUAT can have a charge density of 1.6 meq / g and a molecular weight of 1,100,000 g / mol.

[0161] The cationic copolymer may comprise an acrylamide monomer and a cationic monomer, wherein the cationic monomer is selected from the group consisting of dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide; ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethylammonium propyl (meth)acrylamido chloride, vinylbenzyl trimethylammonium chloride, diallyldimethylammonium chloride, and mixtures thereof.

[0162] The cationic copolymer can comprise a cationic monomer selected from the group consisting of trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamide chloride, trimethylammonium propyl (meth)acrylamide chloride, vinylbenzyl trimethylammonium chloride, and mixtures thereof.

[0163] The cationic copolymer may be formed from (1) a copolymer of (meth)acrylamide and a (meth)acrylamide-based cationic monomer, and / or a hydrolytically stable cationic monomer, and (2) a terpolymer of (meth)acrylamide, a cationic (meth)acrylic acid ester-based monomer, a (meth)acrylamide-based monomer, and / or a hydrolytically stable cationic monomer. The cationic (meth)acrylic acid ester-based monomer may be a cationized ester of (meth)acrylic acid containing a quaternized nitrogen atom. The cationized ester of (meth)acrylic acid containing a quaternized nitrogen atom may be a dialkylaminoalkyl (meth)acrylate quaternized at C1 to C3 in the alkyl and alkylene groups. The cationized ester of (meth)acrylic acid containing a quaternized nitrogen atom may be selected from the group consisting of ammonium salts of dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate quaternized with methyl chloride. The cationized ester of (meth)acrylic acid containing a quaternized nitrogen atom may be dimethylaminoethyl acrylate quaternized with an alkyl halide, or with methyl chloride, benzyl chloride, or dimethyl sulfate (ADAME-Quat). When the cationic monomer is based on (meth)acrylamide, it is a dialkylaminoalkyl (meth)acrylamide quaternized at C1 to C3 in the alkyl and alkylene groups, or a dimethylaminopropyl acrylamide quaternized with an alkyl halide, or with methyl chloride, benzyl chloride, or dimethyl sulfate.

[0164] The (meth)acrylamide-based cationic monomer may be a dialkylaminoalkyl(meth)acrylamide quaternized at C1 to C3 in the alkyl and alkylene groups. The (meth)acrylamide-based cationic monomer may be a dimethylaminopropylacrylamide quaternized with an alkyl halide, particularly methyl chloride or benzyl chloride or dimethyl sulfate.

[0165] The cationic monomer may be a hydrolytically stable cationic monomer. In addition to dialkylaminoalkyl (meth)acrylamide, the hydrolytically stable cationic monomer may be any monomer that can be considered stable to the OECD hydrolysis test. The cationic monomer may be hydrolytically stable, and the hydrolytically stable cationic monomer may be selected from the group consisting of diallyldimethylammonium chloride and water-soluble cationic styrene derivatives.

[0166] The cationic copolymer can be a terpolymer of acrylamide, 2-dimethylammoniumethyl(meth)acrylate quaternized with methyl chloride (ADAME-Q), and 3-dimethylammoniumpropyl(meth)acrylamide quaternized with methyl chloride (DIMAPA-Q). The cationic copolymer can be formed from acrylamide and acrylamidopropyltrimethylammonium chloride, which has a charge density of about 1.0 meq / g to about 3.0 meq / g.

[0167] The cationic copolymer can have a charge density of from about 1.1 meq / g to about 2.5 meq / g, from about 1.1 meq / g to about 2.3 meq / g, from about 1.2 meq / g to about 2.2 meq / g, from about 1.2 meq / g to about 2.1 meq / g, from about 1.3 meq / g to about 2.0 meq / g, and from about 1.3 meq / g to about 1.9 meq / g.

[0168] The cationic copolymer can have a molecular weight of about 100,000 g / mol to about 2,000,000 g / mol, about 300,000 g / mol to about 1,800,000 g / mol, about 500,000 g / mol to about 1,600,000 g / mol, about 700,000 g / mol to about 1,400,000 g / mol, and about 900,000 g / mol to about 1,200,000 g / mol.

[0169] The cationic copolymer can be trimethylammoniopropyl methacrylamide chloride-N-acrylamide copolymer, also known as AM:MAPTAC. AM:MAPTAC can have a charge density of about 1.3 meq / g and a molecular weight of about 1,100,000 g / mol. The cationic copolymer can be AM:ATPAC. AM:ATPAC can have a charge density of about 1.8 meq / g and a molecular weight of about 1,100,000 g / mol.

[0170] synthetic polymers The cationic polymer is i) one or more cationic monomer units, and optionally, ii) one or more monomeric units that have a negative charge, and / or iii) non-ionic monomers. Here, the subsequent charge of the copolymer is positive. The ratio of these three monomers is represented by "m", "p" and "q", where "m" is the number of cationic monomers, "p" is the number of monomers with a negative charge, and "q" is the number of non-ionic monomers.

[0171] The cationic polymer can be a water-soluble or dispersible, non-crosslinked synthetic cationic polymer having the structure of Formula XIII:

[0172] [ka] wherein A may be one or more of the following cationic moieties:

[0173] [ka] wherein @ is an amide, alkylamide, ester, ether, alkyl, or alkylaryl; In the formula, Y is C1 to C22 alkyl, alkoxy, alkylidene, alkyl, or aryloxy; In the formula, Ψ is C1 to C22 alkyl, alkyloxy, alkylaryl, or alkylaryloxy; In the formula, Z is C1 to C22 alkyl, alkyloxy, aryl, or aryloxy; wherein R1 is H, C1-C4 linear or branched alkyl; wherein s is 0 or 1, and n is 0 or ≧31; In the formula, T and R7 are C1-C22 alkyl; wherein X- is a halogen, hydroxide, alkoxide, sulfate, or alkyl sulfate.

[0174] Negatively charged monomers are defined by R2' being H, C1-C4 straight or branched chain alkyl, and R3 being:

[0175] [ka] wherein D is O, N, or S; wherein Q is NH or O; In the formula, u is 1 to 6, In the formula, t is 0 to 1, where J is an oxygenated functional group containing the following elements: P, S, C.

[0176] The nonionic monomer is a monomer in which R2'' is H, C1-C4 linear or branched alkyl, R6 is linear or branched alkyl, alkylaryl, aryloxy, alkyloxy, alkylaryloxy, and b is

[0177] [ka] is defined as wherein G′ and G″ are independently O, S, or NH; and L is 0 or 1.

[0178] Suitable monomers include aminoalkyl(meth)acrylates, (meth)aminoalkyl(meth)acrylamides; monomers containing at least one secondary, tertiary, or quaternary amine functional group, or a heterocyclic group containing a nitrogen atom, vinylamine, or ethyleneimine; diallyldialkylammonium salts; mixtures thereof, salts thereof, and macromonomers derived therefrom.

[0179] Further examples of suitable cationic monomers include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine, trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethylammonium propyl (meth)acrylamido chloride, vinylbenzyltrimethylammonium chloride, and diallyldimethylammonium chloride.

[0180] Suitable cationic monomers include those of the formula -NR3 +(wherein each R may be the same or different and may be a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, or a benzyl group, optionally having a hydroxyl group, and including an anion (counter ion). Examples of suitable anions include halides such as chloride and bromide, sulfate, hydrosulfate, alkyl sulfates (e.g., containing 1 to 6 carbon atoms), phosphate, citrate, formate, and acetate.

[0181] Suitable cationic monomers also include trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamide chloride, trimethylammonium propyl (meth)acrylamide chloride, vinylbenzyl trimethylammonium chloride. A further suitable cationic monomer may include trimethylammonium propyl (meth)acrylamide chloride.

[0182] Examples of negatively charged monomers include alpha-ethylenically unsaturated monomers containing a phosphate or phosphonate group, alpha-ethylenically unsaturated monocarboxylic acids, monoalkyl esters of alpha-ethylenically unsaturated dicarboxylic acids, monoalkyl amides of alpha-ethylenically unsaturated dicarboxylic acids, alpha-ethylenically unsaturated compounds containing a sulfonic acid group, and salts of alpha-ethylenically unsaturated compounds containing a sulfonic acid group.

[0183] Suitable negatively charged monomers include acrylic acid, methacrylic acid, vinyl sulfonic acid, salts of vinyl sulfonic acid, vinylbenzene sulfonic acid, salts of vinylbenzene sulfonic acid, α-acrylamidomethylpropanesulfonic acid, salts of α-acrylamidomethylpropanesulfonic acid, 2-sulfoethyl methacrylate, salts of 2-sulfoethyl methacrylate, acrylamido-2-methylpropanesulfonic acid (AMPS), salts of acrylamido-2-methylpropanesulfonic acid, and styrene sulfonate (SS).

[0184] Examples of nonionic monomers include vinyl acetate, amides of α-ethylenically unsaturated carboxylic acids, esters of α-ethylenically unsaturated monocarboxylic acids with hydrogenated or fluorinated alcohols, polyethylene oxide (meth)acrylates (i.e., polyethoxylated (meth)acrylic acids), monoalkyl esters of α-ethylenically unsaturated dicarboxylic acids, monoalkyl amides of α-ethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinylamine amides, vinyl alcohol, vinylpyrrolidone, and vinyl aromatic compounds.

[0185] Suitable nonionic monomers may also include styrene, acrylamide, methacrylamide, acrylonitrile, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, 2-ethyl-hexyl acrylate, 2-ethyl-hexyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate.

[0186] Anionic counterions (X) bound to synthetic cationic polymers -) can be any known counterion so long as the polymer remains soluble or dispersible in water, the shampoo composition, or the coacervate phase of the shampoo composition, and the counterion is physically and chemically compatible with the essential ingredients of the shampoo composition or does not significantly impair product performance, stability, or aesthetics. Non-limiting examples of suitable counterions include halides (e.g., chlorine, fluorine, bromine, iodine), sulfate, and methyl sulfate.

[0187] The cationic polymers described herein can also help repair damaged hair, particularly chemically treated hair, by providing a substitute hydrophobic F-layer. The microscopically thin F-layer provides natural weather resistance while helping to seal in moisture and prevent further damage. Chemical treatment damages the hair cuticle, causing the protective F-layer to peel off from the hair. As the F-layer peels off, the hair becomes more hydrophilic. Application of lyotropic liquid crystals to chemically treated hair has been shown to make the hair more hydrophobic, giving it the appearance and feel of untreated hair. Without being bound by any theory, it is believed that the lyotropic liquid crystal complex forms a hydrophobic layer or film that coats and protects the hair fiber in the same way that a natural F-layer protects hair. The hydrophobic layer can restore hair to a healthier state, typically resembling untreated hair. Lyotropic liquid crystals are formed by combining the synthetic cationic polymers described herein with the aforementioned anionic cleansing surfactant components of shampoo compositions.The charge density of the synthetic cationic polymers is relatively high.It should be noted that some synthetic polymers with relatively high cationic charge density do not form lyotropic liquid crystals, mainly due to their abnormal linear charge density.Such synthetic cationic polymers are described in International Publication No. 94 / 06403, which is incorporated by reference.The synthetic polymers described herein can be formulated into stable shampoo compositions that improve conditioning performance for damaged hair.

[0188] The cationic synthetic polymer capable of forming lyotropic liquid crystals has a cationic charge density of about 2 meq / gm to about 7 meq / gm, and / or about 3 meq / gm to about 7 meq / gm, and / or about 4 meq / gm to about 7 meq / gm. The cationic charge density is about 6.2 meq / gm. The polymer also has a molecular weight of about 1,000 to about 5,000,000, and / or about 10,000 to about 2,000,000, and / or about 100,000 to about 2,000,000.

[0189] Cationic synthetic polymers that provide enhanced conditioning and deposition of benefit agents, but do not necessarily form lyotropic liquid crystals, may have a cationic charge density of from about 0.7 meq / gm to about 7 meq / gm, and / or from about 0.8 meq / gm to about 5 meq / gm, and / or from about 1.0 meq / gm to about 3 meq / gm. The polymers also have molecular weights of from about 1,000 g / mole to about 5,000,000 g / mole, from about 10,000 g / mole to about 2,000,000 g / mole, and from about 100,000 g / mole to about 2,000,000 g / mole.

[0190] Cationic Cellulose Polymer A suitable cationic polymer may be a cellulose polymer. A suitable cellulose polymer may include a salt of hydroxyethyl cellulose reacted with a trimethylammonium-substituted epoxide, known in the art (CTFA) as Polyquaternium 10, available from Dow / Amerchol Corp. (Edison, NJ, USA) as the Polymer LR, JR, and KG series polymers. Another suitable type of cationic cellulose may include a polymeric quaternary ammonium salt of hydroxyethyl cellulose reacted with a lauryldimethylammonium-substituted epoxide, known in the art (CTFA) as Polyquaternium 24. These materials are available from Dow / Amerchol Corp. under the trade name Polymer LM-200. Another suitable type of cationic cellulose may include a polymeric quaternary ammonium salt of hydroxyethyl cellulose reacted with a lauryldimethylammonium-substituted epoxide and a trimethylammonium-substituted epoxide, known in the art (CTFA) as Polyquaternium 67. These materials are available from Dow / Amerchol Corp. under the trade names SoftCAT Polymer SL-5, SoftCAT Polymer SL-30, Polymer SL-60, Polymer SL-100, Polymer SK-L, Polymer SK-M, Polymer SK-MH, and Polymer SK-H.

[0191] Additional cationic polymers are also described in the CTFA Cosmetic Ingredient Dictionary, 3rd Edition, edited by Estrin, Crosley and Haynes (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, DC (1982)), which is incorporated herein by reference.

[0192] Techniques for analyzing the formation of complex coacervates are known in the art. For example, microscopic analysis of the composition at any selected dilution level can be used to determine whether a coacervate phase has formed. Such a coacervate phase can be identified as an additional emulsified phase in the composition. The use of dyes can help distinguish the coacervate phase from other insoluble phases dispersed in the composition. Further details regarding the use of cationic polymers and coacervates are disclosed in U.S. Pat. No. 9,272,164, which is incorporated herein by reference.

[0193] silicone The shampoo composition can include a silicone conditioning agent. The silicone conditioning agent can be in the benefit phase and / or the cleansing phase. Suitable silicone conditioning agents can include volatile silicones, non-volatile silicones, or combinations thereof. When a silicone conditioning agent is included, the agent can be present in an amount of from about 0.01% to about 10% by weight of the composition, from about 0.1% to about 8%, from about 0.1% to about 5%, and / or from about 0.2% to about 2% by weight of the cleansing phase, benefit phase, or composition. Examples of suitable silicone conditioning agents, and optional suspending agents for silicones, are described in U.S. Reissue Patent No. 34,584, U.S. Patent Nos. 5,104,646, and 5,106,609, each of which is incorporated herein by reference. Suitable silicone conditioning agents may have a viscosity, measured at 25° C., of from about 20 centistokes (“csk”) to about 2,000,000 csk, from about 1,000 csk to about 1,800,000 csk, from about 50,000 csk to about 1,500,000 csk, and from about 100,000 csk to about 1,500,000 csk.

[0194] The dispersed silicone conditioning agent particles can have a volume average particle size ranging from about 0.01 μm to about 50 μm. When small particles are applied to hair, the volume average particle size can range from about 0.01 μm to about 4 μm, from about 0.01 μm to about 2 μm, or from about 0.01 μm to about 0.5 μm. When large particles are applied to hair, the volume average particle size is typically in the range of about 5 μm to about 125 μm, from about 10 μm to about 90 μm, from about 15 μm to about 70 μm, and / or from about 20 μm to about 50 μm.

[0195] Further information on silicones, including sections discussing silicone fluids, rubbers, and resins, and the manufacture of silicones, can be found in Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp 204-308, John Wiley & Sons, Inc. (1989), which is incorporated herein by reference.

[0196] Suitable silicone emulsions for use in the shampoo compositions described herein include emulsions of insoluble polysiloxanes prepared according to the instructions in U.S. Pat. No. 4,476,282 and U.S. Patent Application Publication No. 2007 / 0276087, each of which is incorporated herein by reference. Suitable insoluble polysiloxanes include polysiloxanes having a molecular weight in the range of about 50,000 to about 500,000 g / mol, such as α,ω hydroxy-terminated polysiloxanes or α,ω alkoxy-terminated polysiloxanes. The average molecular weight of the insoluble polysiloxane can be in the range of about 50,000 to about 500,000 g / mol. For example, the average molecular weight of the insoluble polysiloxane may be in the range of about 60,000 to about 400,000, about 75,000 to about 300,000, or about 100,000 to about 200,000, or the average molecular weight may be about 150,000 g / mol. The insoluble polysiloxane may have an average particle size in the range of about 30 nm to about 10 micrometers. The average particle size may be, for example, in the range of about 40 nm to about 5 micrometers, about 50 nm to about 1 micrometer, about 75 nm to about 500 nm, or about 100 nm.

[0197] Other types of silicones suitable for use in the shampoo compositions described herein include i) silicone fluids (such as silicone oils), which are flowable materials having a viscosity of less than about 1,000,000 csk when measured at 25° C.; ii) aminosilicones, which contain at least one primary, secondary, or tertiary amine; iii) cationic silicones, which contain at least one quaternary ammonium functional group; iv) silicone gums (including materials having a viscosity of 1,000,000 csk or greater when measured at 25° C.); v) silicone resins, including highly crosslinked polymeric siloxane systems; vi) high refractive index silicones, having a refractive index of at least 1.46; and vii) mixtures thereof.

[0198] Alternatively, the shampoo composition may be substantially free of silicones.

[0199] Water-based carrier Both the cleansing phase and the benefit phase may comprise an aqueous carrier. Thus, the shampoo composition formulation may be in the form of a pourable liquid (under ambient conditions). The cleansing phase may contain aqueous carrier, which may be present from about 15% to about 95%, alternatively from about 50% to about 93%, alternatively from about 60% to about 92%, alternatively from about 70% to about 90%, alternatively from about 72% to about 88%, alternatively from about 75% to about 85%, by weight of the cleansing phase. The benefit phase may contain aqueous carrier, which may be present from about 25% to about 98%, alternatively from about 40% to about 95%, alternatively from about 50% to about 90%, alternatively from about 60% to about 85%, alternatively from about 65% to about 83%, by weight of the benefit phase.

[0200] The aqueous carrier may comprise water or a miscible mixture of water and organic solvent, and in one aspect may comprise water with minimal or no significant concentrations of organic solvent, especially when incidentally incorporated into the composition as a minor component of other components.

[0201] Aqueous carriers useful in shampoo compositions can include water. In another example, the shampoo composition can include an aqueous solution of a lower alkyl alcohol and a polyhydric alcohol. The lower alkyl alcohol can include monohydric alcohols having 1 to 6 carbon atoms, such as ethanol and isopropanol. The polyhydric alcohol can include propylene glycol, dipropylene glycol, hexylene glycol, glycerin, and propanediol.

[0202] Optional ingredients As can be appreciated, the shampoo compositions described herein can include various optional ingredients to tailor the properties and characteristics of the composition. As can be appreciated, suitable optional ingredients are well known and can generally include any ingredient that is physically and chemically compatible with the essential ingredients of the shampoo compositions described herein. Optional ingredients should not otherwise unduly impair product stability, aesthetics, or performance. Optional ingredients can be present in the cleansing phase and / or the benefit phase. Individual concentrations of optional ingredients can generally range from about 0.001% to about 10% by weight of the shampoo composition. Optional ingredients in the cleansing phase can be further limited to components that do not impair the clarity of the translucent shampoo composition.

[0203] Suitable optional ingredients that may be included in the shampoo composition include deposition aids, conditioning agents (including hydrocarbon oils, fatty acid esters, and silicones), antidandruff agents, viscosity modifiers, dyes, non-volatile solvents or diluents (water-soluble and water-insoluble), pearlescent aids, foam boosters, pediculicides, pH adjusters, fragrances, preservatives, chelating agents, proteins, skin active agents, sunscreens, UV absorbers, and vitamins. The CTFA Cosmetic Ingredient Handbook, 10th Edition (published by the Cosmetic, Toiletry, and Fragrance Association, Inc. (Washington, DC)) (2004) (hereinafter "CTFA") describes various non-limiting materials that may be added to the compositions herein.

[0204] Suitable optional ingredients that can be included in the shampoo composition can include amino acids, such as water-soluble vitamins such as vitamins B1, B2, B6, B12, C, pantothenic acid, pantothenyl ethyl ether, panthenol, biotin, and derivatives thereof, water-soluble amino acids such as asparagine, alanine, indole, glutamic acid, and salts thereof, water-insoluble vitamins such as vitamins A, D, E, and derivatives thereof, and water-insoluble amino acids such as tyrosine, tryptamine, and salts thereof.

[0205] Organic Conditioning Materials The organic conditioning agents of the shampoo compositions described herein may further comprise at least one organic conditioning material, such as an oil or wax, either alone or in combination with other conditioning agents, such as the silicones described above. The organic conditioning material may be present in the cleansing phase and / or the benefit phase. The organic conditioning agent may be present in the benefit phase and / or the cleansing phase. The organic material may be non-polymeric, oligomeric, or polymeric. The organic material may be in the form of an oil or wax and may be added to the shampoo formulation in undiluted or pre-emulsified form. Suitable examples of organic conditioning materials may include, but are not limited to, i) hydrocarbon oils, ii) polyolefins, iii) fatty esters, iv) fluorinated conditioning compounds, v) fatty alcohols, vi) alkyl glucosides and alkyl glucoside derivatives, vii) quaternary ammonium compounds, viii) polyethylene glycols and polypropylene glycols having a molecular weight of up to about 2,000,000, such as those having the CTFA designations PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M, and mixtures thereof.

[0206] emulsifier A variety of anionic and nonionic emulsifiers can be used in shampoo compositions containing a benefit phase and / or a cleansing phase. The anionic and nonionic emulsifiers can be either monomeric or polymeric in nature. Examples of monomers include, but are not limited to, alkyl ethoxylates, alkyl sulfates, soaps, and fatty acid esters, and derivatives thereof. Examples of polymers include, but are not limited to, polyacrylates, polyethylene glycols, and block copolymers, and derivatives thereof. Naturally occurring emulsifiers such as lanolin, lecithin, and lignin, and derivatives thereof, are also non-limiting examples of useful emulsifiers.

[0207] chelating agents Chelating agents can be used in shampoo compositions containing the benefit phase and / or cleansing phase. Suitable chelating agents include those described in A.E. Martell & R. M. Smith, Critical Stability Constants, Vol. 1, Plenum Press, New York & London (1974) and A.E. Martell & R. D. Hancock, Metal Complexes in Aqueous Solution, Plenum Press, New York & London (1996), both of which are incorporated herein by reference. With respect to chelating agents, the term "salts and derivatives thereof" refers to salts and derivatives that contain the same functional structure (e.g., the same chemical backbone) as the referenced chelating agent and have similar or better chelating properties. This term includes alkali metal, alkaline earth, ammonium, substituted ammonium salts (i.e., monoethanolammonium, diethanolammonium, triethanolammonium) salts, esters of chelating agents with acidic moieties, and mixtures thereof, particularly all sodium, potassium, or ammonium salts. The term "derivative" also includes larger molecules containing one or more chelating groups with the same functional structure as the parent chelator, such as "chelating surfactant" compounds such as those exemplified in U.S. Pat. No. 5,284,972, and the polymer EDDS (ethylenediaminedisuccinic acid) disclosed in U.S. Pat. No. 5,747,440. U.S. Pat. Nos. 5,284,972 and 5,747,440 are each incorporated herein by reference. Suitable chelators may further contain histidine.

[0208] The concentration of the EDDS chelating agent or histidine chelating agent in the shampoo composition can be low. For example, the EDDS chelating agent or histidine chelating agent can be present at about 0.01% by weight. Above about 10% by weight, formulation and / or human safety concerns can arise. The concentration of the EDDS chelating agent or histidine chelating agent can be at least about 0.01%, at least about 0.05%, at least about 0.1%, at least about 0.25%, at least about 0.5%, at least about 1%, or at least about 2% by weight, based on the weight of the shampoo composition.

[0209] Additional cosmetic ingredients The shampoo composition can further comprise one or more additional cosmetic ingredients.Exemplary additional cosmetic ingredients can include, but are not limited to, particles, colorants, perfume microcapsules, gel networks, and other insoluble skin or hair conditioning agents such as skin silicones, natural oils such as sunflower oil or castor oil.The additional cosmetic ingredients can be selected from the group consisting of particles, colorants; perfume microcapsules; gel networks; other insoluble skin or hair conditioning agents such as skin silicones, natural oils such as sunflower oil or castor oil; and mixtures thereof.

[0210] Anti-dandruff actives The shampoo composition may also contain an anti-dandruff active. The anti-dandruff active may be present in the cleansing phase and / or the benefit phase. Soluble anti-dandruff actives, such as piroctone olamine, may be present in the cleansing phase or the benefit phase. Insoluble anti-dandruff actives, such as pyridinethiones (e.g., zinc pyrithione), may be present in the benefit phase. In some examples, the cleansing phase may be substantially free of insoluble anti-dandruff actives. Suitable non-limiting examples of anti-dandruff actives include pyridinethione salts, azoles, selenium sulfide, particulate sulfur, keratolytic agents, and mixtures thereof. Such anti-dandruff actives should be physically and chemically compatible with the components of the composition and should not otherwise unduly impair product stability, aesthetics, or performance.

[0211] When present in the composition, the anti-dandruff active is included in an amount of from about 0.01% to about 5%, alternatively from about 0.1% to about 3%, alternatively from about 0.3% to about 2% by weight of the composition, benefit phase, or cleansing phase.

[0212] Test Method Hair Wet Feel Friction Measurement (Final Rinse Friction and Initial Rinse Friction): An 8-inch length, 4-gram hair switch of general population hair is used for the measurement. The water temperature is set at 100°F, the hardness is 7 grains per gallon, and the flow rate is 1.6 liters per minute. For shampoo in liquid form, 0.2 mL of liquid shampoo is applied evenly to the hair switch in a zigzag pattern using a syringe, covering the entire length of the hair. For shampoo in aerosol foam form, the foam shampoo is dispensed into a weighing dish on a balance. 0.2 grams of foam shampoo is taken from the weighing dish and applied evenly to the hair switch using a spatula, covering the entire length of the hair. The hair switch is then first lathered for 30 seconds, rinsed with water for 30 seconds, and lathered again for 30 seconds. The flow rate is then reduced to 0.2 liters per minute. The hair switch is clamped with an 1800 gram weight and pulled over its entire length while running water at a slow rate. The pulling time is 30 seconds. Friction is measured with a friction analyzer with a 5 kg load cell. The pull under rinse was repeated a total of 21 times. A total of 21 friction values ​​are compiled. The final rinse friction is the average friction of the last 7 points, and the initial rinse friction is the average of the initial 7 points. The final to initial delta is calculated by subtracting the final rinse friction from the initial rinse friction.

[0213] light transmittance %T can be measured using ultraviolet / visible (UV / VI) spectroscopy, which determines the transmission of UV / VIS light through a sample. A light wavelength of 600 nm has been shown to be suitable for characterizing the degree of light transmittance through a sample. It is typically best to follow the specific instructions for the particular spectrophotometer being used. Generally, the procedure for measuring percent transmittance begins by setting the spectrophotometer to 600 nm. A calibration "blank" is then run to calibrate the readout to 100 percent transmittance. A single test sample is then placed in a cuvette designed to fit the particular spectrophotometer, and care is taken to ensure there are no air bubbles in the sample before measuring %T with the spectrophotometer at 600 nm. [Example]

[0214] The shampoo compositions illustrated in the following examples illustrate specific embodiments of the shampoo compositions of the present invention, but are not intended to be limiting thereof. It will be understood that other modifications of the present invention within the skill of those skilled in the art of shampoo formulation can be made without departing from the spirit and scope of the present invention. Unless otherwise noted, all exemplified amounts are listed as weight percent and exclude minor materials such as diluents, preservatives, color solutions, image ingredients, botanicals, etc. All percentages are by weight unless otherwise specified.

[0215] The shampoo compositions shown in the following examples are prepared by conventional formulation and mixing methods. Foam is introduced into the cleansing phase by aeration techniques. The gel network benefit phase is prepared as follows: Water is heated to about 74°C, and a fatty compound and a secondary surfactant (e.g., sodium laureth sulfate) are added thereto. After incorporation, the mixture is passed through a mill and then cooled (e.g., via heat exchange) to about 32°C. As a result of this cooling process, the fatty alcohol, secondary surfactant, and water form a crystalline gel network.

[0216] Multi-phase shampoo compositions can be created by using a piston filler that can accommodate two or more individual product streams during filling. The individual streams can form an aesthetic design in the final shampoo composition. During filling, special care was taken to minimize air entrapment in the cleansing phase during filling into bottles or other suitable primary packaging. In some instances, the bottle may be overfilled using only the cleansing phase to ensure any remaining headspace is displaced / removed from the bottle during pump insertion. In some cases, the bottle was capped with a carefully positioned pump to minimize aesthetic displacement during filling.

[0217] Examples A-L in Tables 1 and 2 (below) are cleansing shampoos that can be used as one or more cleansing phases in multi-phase shampoo compositions.

[0218] [Table 1]

[0219] [Table 2] (1) Sodium laureth-n sulfate, wherein n≧1 and ≦3 (2) Octirox® (Clariant®) (3) Cationic galactomannan (molecular weight approximately 200,000; charge density = 3.0 meq / g) (4) Cationic galactomannan (molecular weight approximately 200,000; charge density = 0.7 meq / g) (5) Jaguar® Excel (Solvay®) (6) N-Hance (trademark) 3196 (Ashland (trademark)) (7) UCARE (trademark) LR-30M (Dow (registered trademark) Chemical Company) (8) Polymer KG30M (Dow® Chemical Company) having a charge density of 1.97 meq / gm and a molecular weight of 2,000,000 (9) Mirapol® 100S (Solvay®) (10) Belsil® DM 5500 E (Wacker) (11) Dow Corning® 1872 (Dow Corning® Corporation) (12) Carbopol® Aqua SF 1 (Lubrizol® Advanced Materials) (13) Carbopol® Aqua SF 2 (Lubrizol Advanced Materials) (14) Kathon (trademark) CG (DuPont (registered trademark))

[0220] Examples 1-8 in Table 3 (below) are gel networks that can be made and incorporated as benefit phases.

[0221] [Table 3] (1) Sodium laureth-n sulfate, wherein n≧1 and ≦3 (2) N-Hance (trademark) BF17 (Ashland (trademark)) (3) N-Hance (trademark) 3196 (Ashland (trademark)) (4) Polymer KG30M (Dow® Chemical Company) having a charge density of 1.97 meq / gm and a molecular weight of 2,000,000 (5) Mirapol® 100S (Solvay®) (6)CF330m(Momentive(trademark) Performance Materials) (7) Belsil® DM 5500 E (Wacker) (8) Dow Corning® 1872 (Dow Corning® Corporation) (9) Kathon (trademark) CG (DuPont (registered trademark))

[0222] The examples in Table 4 below are examples of multi-phase shampoo compositions that can be made by aerating the cleansing phases of Table 1 and Table 2, combining the cleansing phases, and optionally adding the benefit phase of Table 3.

[0223] [Table 4]

[0224] combination A. A container configured to hold a multi-phase shampoo composition, the multi-phase shampoo composition comprising: a. i. detersive surfactants, and ii. structuring agents; a first cleansing phase comprising: b. i. detersive surfactants, ii. a structuring agent, and iii. Visually identifiable stable bubbles suspended in the a second cleansing phase comprising: c. optionally, i. fatty alcohols, and ii. a secondary surfactant selected from the group consisting of anionic, amphoteric, zwitterionic, and mixtures thereof; a benefit phase comprising a gel network comprising a container comprising: B. A container configured to hold a multi-phase shampoo composition, the multi-phase shampoo composition comprising: a. i. detersive surfactants, and ii. structuring agents; iii. Visually identifiable stable bubbles suspended in the a first cleansing phase comprising: b. A beneficial phase comprising a gel network, wherein the gel network i. fatty alcohols, and ii. a secondary surfactant selected from the group consisting of anionic, amphoteric, zwitterionic, and mixtures thereof; and a beneficial phase including Including, the cleansing phase and the benefit phase are visually distinct phases in physical contact and form an aesthetic design suspended over at least a portion of the container; A container in which the cleansing phase and the benefit phase are stable. C. The container of paragraphs A-B, wherein the first and / or second cleansing phase comprises from about 3% to about 40%, preferably from about 5% to about 30%, more preferably from about 6% to about 25%, and even more preferably from about 8% to about 25% detersive surfactant by weight of the cleansing phase. D. The container of paragraphs A-C, wherein the first and / or second cleansing phase is substantially free of sulfate surfactants, and the detersive surfactant is selected from the group consisting of isethionates, sarcosinates, sulfonates, sulfosuccinates, sulfoacetates, acyl glycinates, acyl alaninates, acyl glutamates, lactates, lactylates, glucose carboxylates, amphoacetates, taurates, phosphate esters, and mixtures thereof. E. The container of paragraphs A-D, wherein the detersive surfactant comprises an anionic surfactant selected from the group consisting of sodium lauryl sulfate, sodium laureth sulfate, and combinations thereof. F. The container of paragraphs A-E, wherein the shampoo composition comprises from about 1% to about 90%, preferably from about 2% to about 50%, more preferably from about 5% to about 40%, even more preferably from about 7% to about 30%, and even more preferably from about 10% to about 25% of the benefit phase, by weight of the shampoo composition. G. The container of paragraphs A-F, wherein the benefit phase comprises from about 2.8% to about 25%, preferably from about 4% to about 23%, more preferably from about 5% to about 20%, and even more preferably from about 6% to about 18% fatty alcohol by weight of the benefit phase. H. The container of paragraphs A-G, wherein the fatty compound of the benefit phase is a fatty alcohol selected from the group consisting of cetyl alcohol, stearyl alcohol, and combinations thereof. I. The container of paragraphs A-H, wherein the benefit phase comprises from about 0.01% to about 15%, preferably from about 0.5% to about 12%, more preferably from about 0.7% to about 10%, and even more preferably from about 1% to about 6% secondary surfactant, by weight of the benefit phase. J. The container of paragraphs AI, wherein the secondary surfactant is selected from the group consisting of anionic, amphoteric, zwitterionic, and combinations thereof. K. The container of paragraphs AJ, wherein the benefit phase further comprises a non-ionic surfactant. L. The container of paragraphs A-K, wherein the cleansing phase and the benefit phase further comprise an aqueous carrier. M. The container of paragraphs A-L, wherein the benefit phase further comprises a material selected from the group consisting of silicone, particulates, mica, and combinations thereof. N. The container of paragraphs AM, wherein the benefit phase further comprises from about 0.075% to about 2%, preferably from about 0.1% to about 1.0%, by weight of the benefit phase, of a cationic deposition polymer. O. The container of paragraphs A through N, wherein the cationic deposition polymer has a weight average molecular weight of from about 100,000 g / mol to about 3,000,000 g / mol, preferably from 300,000 g / mol to about 3,000,000 g / mol. P. The container of paragraphs A-O, wherein the cationic polymer is selected from the group consisting of cationic guar, cationic cellulose, cationic synthetic homopolymer, cationic synthetic copolymer, cationic synthetic terpolymer, and combinations thereof. Q. The container of paragraphs A-P, wherein the cationic deposition polymer is selected from the group consisting of cationic guar, cationic cellulose, cationic synthetic homopolymer, cationic synthetic copolymer, and combinations thereof. R. The container of paragraphs A-Q, wherein the cationic polymer is selected from the group consisting of guar hydroxypropyltrimonium chloride, polyquaternium 10, polyquaternium 6, and combinations thereof. S. The container of paragraphs A-R, wherein the container is a bottle, at least a portion of the bottle is transparent, and the bottle is substantially free of headspace and substantially free of visually discernible air bubbles prior to first use. T. The container of paragraphs A-S, wherein the first and / or second cleansing phase comprises a transmittance of at least 70%, preferably at least 80%, and more preferably at least 90%, as measured by the Light Transmittance Method described herein. U. The container of paragraphs A-T, wherein the benefit phase comprises a transmittance of less than 50%, preferably less than 40%, and most preferably less than 30%, as measured by the light transmittance method described herein. V. The first and / or second cleansing phase is / are subjected to a shear rate of 10 -2 ~10 -4The vessel of paragraphs A-U, comprising a yield stress of from about 0.01 to about 20 Pa, preferably from about 0.01 to about 10 Pa, and more preferably from about 0.01 to about 5 Pa according to the Herschel-Bulkley model at 1 / s. W. The first and / or second cleansing and / or benefit phases are -1 The container of paragraphs A-V, wherein the cleansing phase comprises a viscosity of about 0.01 to about 15 Pa.s at 100 s. -1 The viscosity may be from about 0.1 to about 4 Pa·s, alternatively from about 0.1 to about 2 Pa·s, or alternatively from about 0.1 to about 1 Pa·s. X. Beneficial phase: 25°C, 950s -1 at a shear rate of about 100 Pa to about 300 Pa, preferably 950 s -1 At a shear rate of about 130 Pa to about 250 Pa, more preferably 950 s -1 The vessel of paragraphs A-W, comprising a shear stress of about 160 Pa to about 225 Pa at a shear rate of Y. The container of paragraphs A-W, wherein the first and / or second cleansing phase further comprises from about 0.05% to about 10%, preferably from about 0.3% to about 5.0%, and more preferably from about 1.5% to about 5.0%, by weight of the cleansing phase, of a structuring agent selected from the group consisting of vinyl polymers, cellulose derivatives and modified cellulose polymers, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch, algae colloids, microbiological polymers, starch-based polymers, alginate-based polymers, acrylate polymers, inorganic water-soluble materials, and combinations thereof. Z. The container of paragraphs A-Y, wherein the benefit phase is substantially free of structuring agents. AA. The viscosity of the first and / or second cleansing phase is 2s -1 It is about 1.0 to about 15 Pa.s at 100 s -1 The container of paragraphs A-Z, wherein the viscosity is about 0.1 to about 5 Pa.s. BB. The container of paragraphs A-AA, wherein the foam and / or benefit phase form an aesthetic design selected from the group consisting of bubbles, stripes, crosshatching, zigzags, floral patterns, petals, herringbone, marbled patterns, straight lines, interrupted stripes, checkered patterns, mottled patterns, streaks, cluster patterns, speckled patterns, dotted patterns, ribbons, helical patterns, swirl patterns, array patterns, veined patterns, wavy patterns, spiral patterns, twist patterns, curved patterns, stripes, lace patterns, basketweave patterns, sine wave patterns, and combinations thereof. CC. The container of paragraphs A-BB, wherein the first and / or second cleansing phase comprises a light transmittance of greater than 60%, preferably greater than 70%, and more preferably greater than 80%, as measured by the Light Transmittance Method described below. DD. The container of paragraphs A-CC, wherein the first and / or second cleansing phase further comprises from about 0.5% to about 7%, preferably from about 1.5% to about 5%, by weight of a rheology modifier selected from the group consisting of polyacrylate, gellan gum, cellulose fiber, sodium starch polyacrylate, and mixtures thereof. EE. The container of paragraphs A-DD, wherein the first and / or second cleansing phase further comprises a silicone conditioning agent comprising an average particle size of 30 nm or less. FF. The density difference between the first and / or second cleansing phase and the benefit phase is 0.30 g / cm 3 The container of paragraphs A-EE, wherein the container is less than GG. The container of paragraphs A-FF, wherein the benefit phase further comprises a material selected from the group consisting of a silicone comprising an average particle size greater than 30 nm, a cationic deposition polymer, an insoluble anti-dandruff active, and combinations thereof. HH. The container of paragraphs A-GG, wherein the weight ratio of cleansing phase to benefit phase is from about 3:1 to about 97:3, preferably from about 4:1 to about 20:1, more preferably from about 4:1 to about 10:1, and even more preferably from about 4:1 to about 9:1. II. The container of paragraphs A-HH, wherein the multi-phase shampoo composition comprises from about 5% to about 95%, preferably from about 10% to about 90%, and more preferably from about 20% to about 80% of a cleansing phase, by weight of the composition. JJ. The container of paragraphs A-II, wherein the first cleansing phase is substantially free of discernible foam. KK. The container of paragraphs A-JJ, wherein the first cleansing phase comprises a visually discernible, stable foam suspended therein. LL. The container of paragraphs A-KK, wherein the first cleansing phase and the second cleansing phase are chemically similar. MM. The container described in paragraphs A-LL, containing a visible floating bubble of gas volume between about 0.01 mL and about 3 mL. NN. The container of paragraphs A-MM, wherein the bubbles comprise an average diameter of from about 0.5 mm to about 5 mm, preferably from about 1 mm to about 3 mm. OO. A method for cleansing and conditioning hair, comprising: a. providing a container according to paragraphs A-NN, the container comprising a bottle configured to hold a multi-phase shampoo composition and a pump configured to dispense the multi-phase composition; b. actuating a pump to dispense a quantity of shampoo composition from the bottle; c. applying the shampoo composition to the user's hair; d. rinsing the shampoo composition from the hair; A method comprising: PP. The method of paragraph OO, wherein the user's hair comprises a final rinse friction of less than 2000 gf, preferably less than 1750 gf, and more preferably less than 1700 gf, as determined using the Hair Wet Feel Friction Measurement described herein.

[0225] Dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

[0226] All documents cited herein, including any cross-referenced or related patents or patent applications, and any patent applications or patents to which this application claims priority or benefit, are incorporated herein by reference in their entirety, unless expressly stated to the contrary. The citation of any document shall not be deemed to be prior art to any invention disclosed or claimed herein, or to teach, suggest, or disclose any such invention, either alone or in combination with any other reference(s). Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

[0227] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. a) a container configured to hold a multi-phase shampoo composition; b) a multi-phase shampoo composition held by said container; and 1. A shampoo product comprising: i) (1) a detersive surfactant, and (2) Structuring Agent a first cleansing phase comprising: ii) (1) a detersive surfactant, (2) a structuring agent, and (3) Visually identifiable, stable bubbles suspended in the water a second cleansing phase comprising: iii) (1) a fatty alcohol, and (2) a secondary surfactant selected from the group consisting of anionic, amphoteric, zwitterionic, and mixtures thereof; a benefit phase comprising a gel network comprising Including, the container is a bottle, at least a portion of the bottle is transparent, the shampoo product does not contain headspace before first use, and the multi-phase shampoo composition does not contain visually discernible air bubbles other than floating bubbles in the second cleansing phase; the structuring agent is selected from the group consisting of vinyl polymers, cellulose derivatives and modified cellulose polymers, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch, algal colloids, microbiological polymers, starch-based polymers, alginate-based polymers, acrylate polymers, inorganic water-soluble materials, and combinations thereof; Shampoo products.

2. 10. The shampoo product of claim 1, wherein at least one of the cleansing phases comprises from 3% to 40% detersive surfactant, by weight of the cleansing phase.

3. 3. A shampoo product according to claim 1 or 2, wherein at least one of the cleansing phases comprises at least 70% transmittance as determined by light transmittance method.

4. At least one of the cleansing phases is subjected to a shear rate of 10 -2 ~10 -4 s -1 4. A shampoo product according to any one of claims 1 to 3, comprising a yield stress of 0.01 to 20 Pa according to the Herschel-Bulkley model in

5. At least one of the first cleansing phase, the second cleansing phase, and the benefit phase is -1 5. A shampoo product according to any one of claims 1 to 4, having a viscosity of from 0.01 to 15 Pa.s at 100°C.

6. At least one of the cleansing phases is -1 6. A shampoo product according to any one of claims 1 to 5, having a viscosity of from 0.1 to 4 Pa.s at 100°C.

7. A shampoo product according to any preceding claim, wherein at least one of the cleansing phases comprises from 0.05% to 10% structuring agent by weight of the cleansing phase.

8. wherein the benefit phase is present and the density difference between at least one of the first and second cleansing phases and the benefit phase is 0.30 g / cm 3 The shampoo product according to any one of claims 1 to 7, wherein the amount of the shampoo is less than 100%.

9. 9. The shampoo product of any one of claims 1 to 8, wherein the benefit phase further comprises a material selected from the group consisting of silicones comprising an average particle size greater than 30 nm, cationic deposition polymers, insoluble anti-dandruff actives, and combinations thereof.

10. A shampoo product according to any preceding claim, wherein the first cleansing phase does not contain any discernible foam.

11. A shampoo product according to any preceding claim, wherein the first cleansing phase comprises a visually discernible, stable foam suspended therein.

12. A shampoo product according to any preceding claim, wherein the shampoo composition has a visible floating foam with a gas volume of from 0.01 ml to 3 ml.

13. A shampoo product according to any preceding claim, wherein the bubbles have an average diameter of from 0.5mm to 5mm.

14. 1. A method of washing hair, comprising: a) providing a shampoo product according to any one of claims 1 to 13, wherein the container comprises a bottle configured to hold the multi-phase shampoo composition and a pump configured to dispense the multi-phase shampoo composition; b) actuating the pump to dispense a quantity of shampoo composition from the bottle; c) applying the shampoo composition to the user's hair; d) rinsing the shampoo composition from the hair; A method comprising:

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