CN116963708A - Container containing shampoo composition with aesthetic design formed by air bubbles - Google Patents

Abstract

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

Description

Container containing a shampoo composition having an aesthetic design formed by bubbles

Technical Field

The present invention relates to a container containing a shampoo composition having an aesthetic design, in particular, a shampoo composition having an aesthetic design formed by gas bubbles suspended in a liquid shampoo composition.

Background Art

Some consumers desire a shampoo composition that effectively cleanses the hair while also providing an eye-catching appearance so that the product stands out on a store shelf, on a web page/app, or even in a user's shower, which can make it fun to use.

Today, shampoos provide effective cleaning but are often dull from an aesthetic point of view. One way to create a shampoo with an eye-catching appearance is to add stable suspended air bubbles.

However, it may be difficult to maintain stable suspended bubbles in a shampoo composition throughout the shelf life of the composition, which may include shipping, handling and storage at home, storage facilities and/or store shelves, and repeated distribution. Bubbles are particularly sensitive to temperature and pressure changes, which may cause them to dissolve, appear or grow. It may be particularly difficult to balance the rheological properties and chemical properties of a shampoo composition to contain stable bubbles suspended therein. These problems become more complex when the bubbles form a pattern, because even slight disruptions (including bubble migration, decomposition or coalescence) may be noticed by consumers, and the product will appear mediocre rather than having an eye-catching appearance that reflects interest and quality.

Therefore, there is a need for stable shampoo compositions that deliver excellent cleansing and stable suspended bubbles that form an attractive aesthetic design.

Summary of the invention

A container configured to hold a multi-phase shampoo composition, the multi-phase shampoo composition comprising: (a) a first cleansing phase comprising: (i) a detersive surfactant; (ii) a structurant; (b) a second cleansing phase comprising: (i) a detersive surfactant; (ii) a structurant; (iii) visually discernible stable gas bubbles suspended therein; (c) optionally, a benefit phase comprising a gel network comprising: (i) a fatty alcohol; (ii) a second surfactant selected from anionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof.

A container configured to hold a liquid shampoo composition comprising: (a) a detersive surfactant; (b) a structurant; (c) visually discernible stable gas bubbles suspended therein;

The cleansing phase has a yield stress of about 0.01 Pa to about 20 Pa at a shear rate of ^10-2 s ^-1 to ^10-4 s ^-1 , a viscosity of about 1.0 Pa.s to about 15 Pa.s at 2 s ^-1 , and a viscosity of about 0.1 Pa.s to about 4 Pa.s at 100 s ^-1 .

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims which particularly point out and distinctly claim the inventive subject matter, it is believed the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings, wherein:

FIG1 is a photograph of a bottle with a pump containing a liquid shampoo composition having an aesthetic design formed by suspended bubbles;

2 is a photograph of a bottle with a pump containing a liquid shampoo composition having an aesthetic design formed by suspended air bubbles and a suspended gel network conditioning agent.

DETAILED DESCRIPTION

Some consumers desire a shampoo composition that effectively cleans the hair while also providing an eye-catching appearance that makes the product stand out on store shelves, web pages/apps, and even in the user's shower, which can make it fun to use. Figures 1 and 2 are photographs of shampoo compositions with an aesthetic design formed by suspended bubbles suspended throughout. Figure 1 shows a bottle with a pump containing a liquid shampoo composition having a first cleansing phase 1 substantially free of visible bubbles and a second cleansing phase 2 with suspended bubbles forming an aesthetic design. Figure 2 shows a bottle with a pump containing a liquid shampoo composition having a first cleansing phase 1' substantially free of visible bubbles, a second cleansing phase 2' with suspended bubbles forming an aesthetic design, and a third suspended phase 3' containing a gel network suspended in the liquid composition. The gel network can provide a conditioning effect for the shampoo product. In Figures 1 and 2, the phases are stable, discrete, and packaged in a manner that is in physical contact with each other. In other examples, the first cleansing phase may contain suspended bubbles, and the second cleansing phase may be substantially free of bubbles. In yet another example, the shampoo composition can be a single cleansing phase and have stable gas bubbles suspended across at least a portion of the shampoo composition.

The first cleaning phase and/or the second cleaning phase can contain a surfactant system, an aqueous carrier and a structurant, and the surfactant system can include one or more detersive surfactants. In some examples, the first cleaning phase and/or the second cleaning phase can be visible and transparent, and its light transmittance is greater than 60%, alternatively greater than 80%, as measured by the light transmittance method described below. In other examples, the cleaning phase can present turbidity, turbidity or even opaque. The first cleaning phase and/or the second cleaning phase can be colored, colorless or a combination thereof.

The first cleaning phase and/or the second cleaning phase can have a visually discernible stable bubble suspended therein, which is formed by the entrained gas (which is presented as a bubble) in the liquid phase.Gas can be any suitable gas, including air and/or helium.In some examples, helium can be a preferred gas, because it can form a more stable bubble.Other gases with lower solubility in shampoo can be used to replace or assist air and/or helium to improve bubble stability.If at a distance of about 1 foot (0.30m) under the illumination of an incandescent bulb illumination at least equal to standard 100 watts, a human observer can identify one or more suspended bubbles with the naked eye (not including standard corrective lenses suitable for correcting myopia, hyperopia or astigmatism, or other corrective vision), then the bubble is visually discernible.

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

The size of the bubbles can be substantially uniform. While not wishing to be bound by theory, it is suspected that if the size of the bubbles is substantially uniform, it can mitigate migration between bubbles, limit bubble growth and/or disruption of additional phases. In some examples, the size of the stably suspended bubbles varies by no more than 25%, alternatively no more than 20%, alternatively no more than 15%, and alternatively no more than 10%.

In the shampoo composition, the bubbles may be separated by at least 0.25 cm, alternatively at least 0.5 cm, alternatively 1 cm, and alternatively 2 cm, and the shampoo composition may be stable over the shelf life of the product. Bubble stability may be increased by the spacing of the bubbles. Larger spacing may improve bubble stability because it increases the time it takes for gas to move between bubbles.

The shampoo composition may contain visible suspended bubbles having a gas volume of about 0.001 mL to about 5 mL. The shampoo composition and/or phase may have visible suspended bubbles having a gas volume of about 0.01 mL to about 3 mL, alternatively about 0.1 mL to about 0.5 mL. The shampoo composition may be 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, and alternatively about 300 mL to about 500 mL.

In some examples, the first phase and the second phase can have substantially the same chemical composition, and the first phase or the second phase can contain suspended, visually discernible, stable bubbles, and the other phase is substantially free of visually discernible bubbles. In other examples, the first phase and the second phase can have substantially different chemical compositions, and either or both phases contain suspended, visually discernible, stable bubbles. In the case where both phases contain suspended, visually discernible, stable bubbles, the average bubble size can be approximately the same, or one phase can have bubbles that are substantially larger than the other phase. In some examples, the bubble density across the phases can be substantially the same, and in other examples, the bubble density across the phases can vary.

Optionally, the shampoo composition may also include a benefit phase, which may be opaque or translucent and may be suspended throughout the shampoo composition or one or more portions of the shampoo composition. The benefit phase may help the shampoo show more conditioning without sacrificing clarity of the cleansing phase, while also providing a shampoo composition that shows a different and exciting appearance. The benefit phase may contain a gel network, which refers to a lamellar or vesicular solid crystalline phase that may include at least one fatty alcohol, at least one surfactant, and water and/or other suitable solvents.

The benefit phase and/or cleansing phase in which visually discernible stable bubbles are suspended can be uniform, non-uniform, or a combination thereof. The benefit phase and/or cleansing phase in which visually discernible stable bubbles are suspended can be any suitable shape to form an aesthetic design, including regular and/or irregular patterns, including swirls as shown in Figures 1 and 2. The shape can form an aesthetic design similar to the following non-limiting examples: bubbles, stripes, cross-hatching, zigzags, flowers, petals, herringbone, marbled, straight lines, broken stripes, checkered, spotted, veined, clustered, jumbled, spotted, bands, spirals, swirls, arrays, mottled, wavy, spirals, twists, bends, stripes, lace, basket weave, sinusoidal (including but not limited to wavy), random shapes, and combinations thereof.

The benefit phase may contain additional ingredients, including ingredients that may make the cleansing phase cloudy or opaque, such as conditioning ingredients (e.g., cationic deposition polymers, silicones having an average particle size greater than 30 nm, cross-linked silicone elastomers), anti-dandruff actives (e.g., zinc pyrithione), aesthetic ingredients (e.g., mica), and combinations thereof. Additional ingredients may be carefully selected (e.g., ingredients may not have excessively high salt concentrations) because they may disrupt the gel network, causing the gel network structure to collapse, forcing the solvent to escape, which may disrupt the aesthetic pattern and render the shampoo composition less effective.

In some examples, the shampoo benefit phase can be suspended in the cleansing phase with visually discernible stable suspended bubbles.

The appropriate rheological properties (which may include viscosity, yield stress and/or shear stress) of the shampoo composition, the cleansing phase and/or the optional benefit phase can be balanced so that the product is acceptable to consumers while maintaining visually discernible suspended stable bubbles and/or a suspended discrete stable phase. If the yield stress is not high enough to support the density difference between air and liquid, the suspended bubbles can rise to the surface. Without being bound by theory, it is believed that sufficient yield stress and/or viscosity can also slow down the diffusion/Oswalt ripening of the suspended bubbles. However, if the yield stress is too high, the composition may be too thick to be accepted by consumers. According to Herschel-Bulkley, the cleansing phase can have a yield stress of about 0.01 Pa to about 20 Pa, alternatively about 0.01 Pa to about 10 Pa, alternatively about 0.01 Pa to about 5 Pa at a shear rate of 10 ^-2 s ^-1 to 10 ^-4 s ^-1 . Yield stress was measured at 26.7°C by flow scanning at a shear rate of 100 s ^-1 to 1.0e-4 s ^-1 using a Discovery Hybrid Rheometer (DHR-3) available from TA Instruments. In order to apply the Hershel-Bulkley model, the model was fitted in logarithmic space using TA software at a shear rate of 10 ^-2 s ^-1 to 10 ^-4 s ^-1 . The geometry used to measure the yield stress and viscosity of the clean phase was a 60 mm 2° aluminum cone (with a Peltier steel plate). The geometry should be run at the gap specified by the manufacturer for the geometry. It is recommended to trim the sample during the initial adjustment step in step 1 to ensure data integrity and reproducibility. When the instrument + geometry is out of calibration, the geometry is torque mapped before running the yield stress or shear stress method. The Trios software version used to generate the rheological data for this article is TRIOS 5.1.1.

The cleansing phase and/or benefit phase may have a viscosity of from about 0.01 Pa.s to about 15 Pa.s at 2 s ^-1 . The cleansing phase may have a viscosity of from about 0.1 Pa.s to about 4 Pa.s, alternatively from about 0.1 Pa.s to about 2 Pa.s, alternatively from about 0.1 Pa.s to about 1 Pa.s at 100 s ^-1 .

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

When dispensed at 10% to 55% by volume, the shampoo composition can 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, and alternatively less than 1600 gf. The average final rinse friction can be determined using the Hair Wet Feel Friction Measurement described herein.

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 design suspended in the product from the outside of the bottle. Alternatively, the bottle can be opaque and can optionally have one or more transparent or opaque windows through which the consumer can see the suspended design. The shampoo composition can be dispensed from the bottle by squeezing. Alternatively, the shampoo composition can be dispensed with a pump, which may be preferred in some examples because the pump can reduce the disruption of the benefit phase throughout the use of the bottle.

The shampoo composition can be in a bottle that is substantially free of headspace and/or visually discernible bubbles, other than the suspended bubbles intentionally placed in the cleansing phase, to help maintain the design prior to use. It has been found that bubbles, especially unstable large bubbles, and headspace can destroy the suspended aesthetic design during shipping and handling. Headspace can be eliminated by overfilling the bottle or using an insert that can snap fit with the neck of the bottle to consume the volume of the headspace, examples of which are described in U.S. Patent Application No. 17/174,427, which is hereby incorporated by reference herein.

However, it may be difficult to eliminate all the air that is inadvertently trapped in a shampoo product. After filling, a shampoo product may typically have about 4% air, which is trapped in tiny bubbles that are not visually discernible. When shampoo is packaged in a typical bottle or pump, these unstable bubbles combine into larger bubbles over time due to Laplace pressure. If the stress of the liquid beauty care product is not high enough to support the density difference between the air and the liquid, these larger bubbles will eventually rise to the head space. Therefore, even if the liquid beauty care product is packaged in a bottle without any visible bubbles, the head space can form within 24 to 48 hours. Increasing the yield stress of the liquid beauty product can prevent bubbles from migrating from small bubbles to larger bubbles and migrating to the head space, however, products with high yield stress may have lower acceptance for consumers due to lower spreadability and difficulty in dispensing.

It has been found that when the headspace is eliminated (e.g., by overfilling and/or using an insert), the cap can be screwed or snapped onto the neck of the bottle to induce a slight overpressure, which prevents trapped air bubbles from migrating without compromising the yield stress of the shampoo composition. When the user is ready to dispense the shampoo composition, they can remove the cap and pour the shampoo product into their hands, remove the cap and insert the pump, or in some cases, the cap can have a pierceable membrane, and the user can pierce the membrane with the pump's dip tube.

In some examples, instead of eliminating the headspace, a slight overpressure may exist in the bottle. While not wishing to be bound by theory, if the pressure in the headspace is higher than the Laplace pressure of the bubbles in the bottle, air migration between the bubbles and the headspace may be significantly reduced. The overpressure in 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, and alternatively less than or equal to 100 Pa.

In some examples, the bubble suspension, size, and density remain substantially constant after the user opens the bottle. In other examples, particularly when there is a slight overpressure on the headspace, the size and/or number of bubbles may grow within a range of minutes to hours after the product is opened.

It was found that the aesthetic design of packaged shampoo products can follow 6A Shipping Test (6-Amazon.com-Over Boxing, April 2018, using ASTM settings for all tests) serial numbers 1-5 and remain substantially intact. As used herein, substantially intact can mean that a human observer cannot visually discern one or more large areas in which the suspended design is disturbed with the naked eye (excluding standard corrective lenses suitable for correcting myopia, hyperopia or astigmatism, or other corrective vision) under illumination at least equal to the illumination of a standard 100-watt incandescent light bulb when standing 1 foot (0.30m) away. In some examples, pattern disruption can be assessed by taking a cross-section of the liquid beauty product and determining what percentage of the cross-section is disrupted. Less than 10% of the cross-sectional area can be disrupted, or less than 7%, or less than 5%, or less than 3%, or less than 1%.

definition

As used herein, the term "fluid" includes liquids and gels.

As used herein, articles including "a" and "an" when used in a claim should be understood to mean one or more of what is claimed or described.

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

As used herein, "mixture" is intended to include a simple combination of substances as well as any compounds that may result from their combination.

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

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

As used herein, the term "stable" with respect to phases means that one or more cleansing and/or benefit phases appear as discrete phases that do not migrate to a human observer with the unaided eye (not including standard corrective lenses suitable for correcting myopia, hyperopia, or astigmatism, or other vision correction) at a distance of about 1 foot (0.30 m) under illumination at least equal to that of a standard 100-watt incandescent light bulb. The term "stable" with respect to bubbles/entrained gas means that the bubbles are discrete and visually discernible and that There was no migration or agglomeration during the 6A Shipping Test of the following Serial Numbers 1-5 as determined by a human observer with the unaided eye (not including standard corrective lenses suitable for correcting myopia, hyperopia or astigmatism, or other vision correction) at a distance of approximately 1 foot (0.30 m) under illumination at least equal to the illuminance of a standard 100 watt incandescent light bulb.

As used herein, "substantially free" means from about 0% to about 3% by weight, 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 free of the ingredient. As used herein, "free" means 0% by weight.

As used herein, the terms "including," "comprising," and "containing" are intended to be non-limiting, and are understood to mean "having," "having," and "including," respectively.

All percentages, parts and ratios are based upon the total weight of the compositions 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.

Unless otherwise indicated, all component or composition levels are in terms of the active portion of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such component or composition.

It should be understood that each maximum numerical limit given throughout this specification includes each lower numerical limit, as if such lower numerical limits were expressly written herein. Each minimum numerical limit given throughout this specification will include each higher numerical limit, as if such higher numerical limits were expressly written herein. Each numerical range given throughout this specification will include each narrower numerical range falling within such wider numerical range, as if such narrower numerical ranges were all expressly written herein.

Cleaning phase

The multiphase 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%, and 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%, and alternatively about 90% to about 95%, as measured by the light transmittance method described below.

In some examples, the cleansing phase can be substantially free or free of ingredients that can cause the phase to be cloudy, turbid, or opaque, including silicone or other particles having an average particle size greater than 30 nm, dispersed gel network phases, liquid crystal forming synthetic polymers, and/or cationic surfactants.

In other examples, the cleansing phase may comprise small particle silicone (ie, silicone having an average particle size less than or equal to 30 nm), select cationic deposition polymers, fragrance, and/or dye.

Detergent surfactant

The cleaning phase may contain one or more detersive surfactants. As can be appreciated, detersive surfactants provide cleaning benefits to soiled articles such as hair, skin and hair follicles by promoting the removal of oil and other dirt. Surfactants generally promote such cleaning because the amphiphilic nature of the surfactant allows the surfactant to break up oil and other dirt and form micelles around the oil and other dirt, which can then be rinsed away, thereby removing the oil or dirt from the soiled articles. Suitable surfactants for shampoo compositions may include anionic moieties to allow formation of coacervates with cationic polymers. Suitable detersive surfactants may be compatible with other ingredients in the cleaning phase and adjacent beneficial phases. Detergent surfactants may be selected from anionic surfactants, amphoteric surfactants, nonionic surfactants and mixtures thereof.

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

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

The shampoo composition includes one or more detersive surfactants in the cleaning phase. The detersive surfactant component is included in the shampoo composition to provide cleaning performance. The detersive surfactant can be selected from the group consisting of anionic detersive surfactants, zwitterionic detersive surfactants, amphoteric detersive surfactants, cationic detersive surfactants, or a combination thereof. In some examples, the detersive surfactant can be selected from the group consisting of anionic detersive surfactants, zwitterionic detersive surfactants, amphoteric detersive surfactants, or a combination thereof. Such surfactants should be physically and chemically compatible with the components described herein, or should not otherwise unduly impair product stability, aesthetics, or performance. Especially suitable herein is sodium laureth-n-sulfate, wherein n=1 ("SLE1S"). When compared with higher molar ethoxylated equivalents, SLE1S can achieve more effective foaming and cleaning, especially in shampoo compositions containing high levels of conditioning actives.

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 in the composition should be sufficient to provide the desired cleaning and foaming properties, and generally ranges from about 5% to about 30%, alternatively from about 8% to about 30%, alternatively from about 8% to about 25%, and alternatively from about 10% to about 17%, by weight of the composition.

Additional anionic surfactants suitable for use herein include alkyl sulfates and alkyl ether sulfates having the formula ROSO ₃ M and RO(C ₂ H ₄ O) _x SO ₃ M, wherein R is an alkyl or alkenyl group having from about 8 to about 18 carbon atoms, x is from 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium and triethanolamine cations, or a salt of a divalent magnesium ion with two anionic surfactant anions. The alkyl ether sulfates can be made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. The alcohol can be derived from a fat, such as coconut oil, palm oil, palm kernel oil or tallow, or can be synthetic.

Other suitable anionic surfactants include water-soluble salts of organic sulfonic acids of the general formula [R ¹ -SO ₃ M]. R ¹ is a straight chain aliphatic hydrocarbon group having 13 to 17 carbon atoms, alternatively 13 to 15 carbon atoms. M is a water-soluble cation, such as ammonium, sodium, potassium and triethanolamine cations or a salt of a divalent magnesium ion with two anionic surfactant anions. These materials are prepared by the reaction of SO ₂ and O ₂ with normal alkanes (C ₁₄ -C ₁₇ ) of suitable chain lengths and are sold commercially as sodium alkane sulfonates.

Examples of suitable additional anionic surfactants include, but are not limited to, 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, sodium lauric acid monoglyceride sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laureth sulfate, and lauryl sarcosine. Sodium, Sodium Lauroyl Sarcosinate, Lauryl Sarcosine, Cocoyl Sarcosine, 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 Trideceth Sulfate, Sodium Methyl Lauroyl Taurate, Sodium Methyl Cocoyl Taurate, Sodium Lauroyl Isethionate, Sodium Cocoyl Isethionate, Sodium Laureth Sulfosuccinate, Sodium Lauryl Sulfosuccinate, Sodium Tridecylbenzene Sulfonate, Sodium Dodecylbenzene Sulfonate, and mixtures thereof.

The shampoo composition may also contain additional surfactants for use in combination with the anionic detersive surfactant component described herein. Suitable additional surfactants include cationic and nonionic surfactants.

Non-limiting examples of other anionic, zwitterionic, amphoteric, cationic, nonionic or optional additional surfactants suitable for use in the composition are described in McCutcheon, Emulsifiers and Detergents, 1989, published by M.C. Publishing Co., and in U.S. Pat. Nos. 3,929,678; 2,658,072; 2,438,091; and 2,528,378.

The shampoo compositions described herein may be substantially free of sulfate-based surfactants.

The one or more additional anionic surfactants may be selected from the group consisting of isethionates, sarcosinates, sulfonates, sulfosuccinates, sulfoacetates, acylglycinates, acylalanates, acylglumates, lactates, alkenyl lactylates, glucose carboxylates, amphoacetates, taurates, phosphates, and mixtures thereof. In this case, 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. In this case, acyl is defined as having the formula R-C(O)-, wherein R is a saturated or unsaturated, linear or branched alkyl chain having 7 to 17 carbon atoms, alternatively 9 to 13 carbon atoms.

Suitable isethionate surfactants may include the reaction product of fatty acids esterified with isethionate and neutralized with sodium hydroxide. Suitable fatty acids for isethionate surfactants may be derived from coconut oil or palm kernel oil including the amides of methyl taurine. Non-limiting examples of isethionates may be selected from: 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 kernelyl isethionate, sodium stearyl methyl isethionate, and mixtures thereof.

Non-limiting examples of sarcosinates can 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 dilauroyl glutamate/lauroyl sarcosinate, lauroamphodiacetate disodium lauroyl sarcosinate, lauroyl isopropyl 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.

Non-limiting examples of sulfosuccinate surfactants can include disodium N-octadecyl sulfosuccinate, disodium lauryl sulfosuccinate, diammonium lauryl sulfosuccinate, sodium lauryl sulfosuccinate, disodium lauryl polyoxyethylene ether 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.

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

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

Non-limiting examples of acyl alaninates can include sodium cocoyl alaninate, sodium lauroyl alaninate, sodium N-lauroyl-1-alaninate, and combinations thereof.

Non-limiting examples of acyl glutamates can be selected from sodium cocoyl glutamate, disodium cocoyl glutamate, ammonium cocoyl glutamate, diammonium cocoyl glutamate, sodium lauroyl glutamate, disodium lauroyl glutamate, sodium cocoyl hydrolyzed wheat protein glutamate, disodium cocoyl hydrolyzed wheat protein glutamate, potassium cocoyl glutamate, dipotassium cocoyl glutamate, potassium lauroyl glutamate, dipotassium lauroyl glutamate, potassium cocoyl hydrolyzed wheat protein glutamate, dipotassium cocoyl hydrolyzed wheat protein glutamate, sodium capryloyl glutamate, disodium capryloyl glutamate, potassium capryloyl glutamate, dipotassium capryloyl glutamate, sodium undecylenyl glutamate, disodium undecylenyl glutamate, potassium undecylenyl glutamate, Dipotassium undecylenyl glutamate, disodium hydrogenated tallow glutamate, sodium stearoyl glutamate, disodium stearoyl glutamate, potassium stearoyl glutamate, dipotassium stearoyl glutamate, sodium myristoyl glutamate, disodium myristoyl glutamate, potassium myristoyl glutamate, dipotassium myristoyl glutamate, sodium cocoyl/hydrogenated tallow glutamate, sodium cocoyl/palmitoyl/sunflower oleyl glutamate, sodium hydrogenated tallow glutamate, sodium oliveoyl glutamate, disodium oliveoyl glutamate, sodium palmitoleoyl glutamate, disodium palmitoleoyl glutamate, TEA-cocoyl glutamate, TEA-hydrogenated tallow glutamate, TEA-lauroyl glutamate, and mixtures thereof.

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

Non-limiting examples of lactate salts may include sodium lactate.

Non-limiting examples of alkenyl lactylates can include sodium lauroyl lactylate, sodium cocoyl lactylate, and combinations thereof.

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

Non-limiting examples of alkyl amphoacetates can include sodium cocoamphoacetate, sodium lauroamphoacetate, and combinations thereof.

Non-limiting examples of acyl taurates can include sodium methyl cocoyl taurate, sodium methyl lauroyl taurate, sodium methyl oleoyl taurate, and combinations thereof.

The cleansing phase may contain one or more amphoteric and/or zwitterionic and/or nonionic co-surfactants in a concentration range of about 0.25% to about 50%, alternatively about 0.5% to about 30%, alternatively about 0.75% to about 15%, alternatively about 1% to about 13%, and alternatively about 2% to about 10%, by weight of the cleansing phase. Co-surfactants can be used to generate foam faster, facilitate easier rinsing, and/or reduce irritation to keratinous tissue. Co-surfactants also help produce foam with a more desirable texture, volume, and/or other properties.

Amphoteric surfactants suitable for use in the present invention include, but are not limited to, derivatives of aliphatic secondary and tertiary amines, wherein the aliphatic group may be straight or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, and one aliphatic substituent contains an anionic water-solubilizing group, such as a carboxyl, sulfonate, sulfate, phosphate, or phosphonate. Examples include sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate, sodium lauryl sarcosinate, N-alkyl taurates such as those prepared by the reaction of dodecylamine with sodium isethionate according to the guidance in U.S. 2658072, N-higher alkyl aspartic acid such as those prepared according to the guidance in U.S. 2438091 and the product described in U.S. 2528378, and mixtures thereof. Amphoteric surfactants may be selected from the betaine family, such as lauroylamphoacetate.

Suitable zwitterionic surfactants for use herein include, but are not limited to, derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic radical may be straight or branched chain and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one of the aliphatic substituents contains an anionic group such as carboxyl, sulfonate, sulfate, phosphate or phosphonate. Other zwitterionic surfactants suitable for use herein include betaines, including higher alkyl betaines such as cocodimethyl carboxymethyl betaine, cocamidopropyl betaine, cocobetaine, lauramidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl α-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl di-(2-hydroxyethyl) carboxymethyl betaine, stearyl di-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl γ-carboxypropyl betaine, lauryl di-(2-hydroxypropyl) α-carboxyethyl betaine, and mixtures thereof. Sultaines may include cocodimethyl sulphopropyl betaine, stearyl dimethyl sulphopropyl betaine, lauryl dimethyl sulphoethyl betaine, lauryl di-(2-hydroxyethyl) sulphopropyl betaine, and mixtures thereof. Other suitable amphoteric surfactants include amidobetaines and amidosulfobetaines, in which a RCONH(CH ₂ ) ₃ group, wherein R is a C ₁₁ -C ₁₇ alkyl group, is attached to the nitrogen atom of the betaine.

Nonionic auxiliary surfactants suitable for use in the composition to increase foam volume or texture include water-soluble materials such as lauryl dimethylamine oxide, cocodimethylamine oxide, cocamidopropylamine oxide, lauramidopropylamine oxide, etc., or alkyl polyethoxylates such as laureth-4 to laureth-7, and water-insoluble components such as cocoyl monoethanolamide, cocoyl diethanolamide, lauroyl monoethanolamide, alkanoyl isopropanolamide, and fatty alcohols such as cetyl alcohol and oleyl alcohol, as well as 2-hydroxyalkyl methyl ethers and the like.

Also suitable for use as auxiliary surfactants herein include 1,2-alkyl epoxides, 1,2-alkanediols, branched or linear alkyl glyceryl ethers (e.g., those disclosed in EP 1696023A1), 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 alkyl ether alcohols derived from the reaction of _C10 or _C12 alpha olefins with ethylene glycol (e.g., hydroxyethyl-2-decyl ether, hydroxyethyl-2-dodecyl ether), such as those prepared according to US5,741,948, US5,994,595, US6,346,509 and US6,417,408.

Other nonionic surfactants can be selected from glucose amide, alkyl polyglucosides, sucrose cocoate, sucrose laurate, alkanolamide, ethoxylated alcohols and mixtures thereof. Nonionic surfactants are selected from: monohydroxystearate glyceryl, isostearyl polyoxyethylene ether-2, tridecyl polyoxyethylene ether-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, monosorbitan stearate, lauric acid glyceryl, lauryl polyoxyethylene ether-2, cocamide monoethanolamine, lauramide monoethanolamine, and mixtures thereof.

The auxiliary surfactant can be selected from cocoyl monoethanolamide, cocamidopropyl betaine, lauroyl betaine, cocoyl betaine, lauryl betaine, lauryl amine oxide, sodium lauroamphoacetate; alkyl glyceryl ethers, alkyl diglyceryl 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 straight chain or branched configuration; 1,2-alkanediols (wherein the total carbon content is 6 to 14 straight chain or branched carbon atoms), methyl-2-hydroxydecyl ether, hydroxyethyl-2-dodecyl ether, hydroxyethyl-2-decyl ether, and mixtures thereof.

Cationic surfactants can be derived from amines that are protonated at the pH of the formulation, such as dihydroxyethyl laurylamine, lauryl dimethylamine, lauroyl dimethylamidopropylamine, cocoamidopropylamine, etc. Cationic surfactants can also be derived from aliphatic quaternary ammonium salts, such as lauryl trimethyl ammonium chloride and lauroamidopropyl trimethyl ammonium chloride.

Alkyl amphoacetates are suitable surfactants for use in the compositions herein for improved product mildness and lather. The most commonly used alkyl amphoacetates are lauroamphoacetate and cocoamphoacetate. Alkyl amphoacetates can consist of monoacetates and diacetates. In some types of alkyl amphoacetates, diacetates are impurities or unintended reaction products. However, when present in amounts exceeding 15% of the alkyl amphoacetate, the presence of diacetates can result in a variety of objectionable composition properties.

Suitable nonionic surfactants for use herein are those selected from the following: 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.

If present, the composition may comprise a rheology modifier, wherein the rheology modifier comprises a cellulosic rheology modifier, a cross-linked acrylate, a cross-linked maleic anhydride co-methyl vinyl ether, a hydrophobically modified associative polymer, or a mixture thereof.

If used, the electrolyte itself can be added to the composition or it can be formed in situ via a counterion contained in one of the raw materials. The electrolyte can include anions, including phosphates, chlorides, sulfates, or citrates, and cations, including sodium, ammonium, potassium, magnesium, or mixtures thereof. The electrolyte can be sodium chloride, ammonium chloride, sodium sulfate, or ammonium sulfate. The electrolyte can 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, and alternatively about 3% to about 6% by weight, based on the weight of the composition.

Structuring agent

The cleansing phase may contain a structurant (e.g., cross-linked polyacrylates, Aqua SF-1 polymer, available from The structurant can provide a high, low shear viscosity and yield stress to maintain a stable discrete product phase in the shampoo composition over time, including shipping, handling, distribution, and storage at a store, warehouse, or consumer's home shelf. The cleansing phase can include a structurant at a concentration effective to suspend the benefit phase in the cleansing phase and/or to effectively change 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%, and alternatively from about 1.5% to about 5.0%, by weight of the cleansing phase. However, it will be appreciated that certain glyceride crystals can be used as suitable structurants or suspending agents.

Suitable structurants may include anionic polymers and nonionic polymers. Useful herein are vinyl polymers such as cross-linked 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, polyvinyl pyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth gum, galactan, carob bean gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (Cydonia oblonga Mill), starch (rice, corn, potato, wheat), alginate (algae extract); microbial polymers such as dextran, succinoglucan, pullulan; 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, synthetic hectorite, hectorite and anhydrous silicic acid.

Other suitable structurants may include crystalline structurants, which may be classified as acyl derivatives, long chain amine oxides, and mixtures thereof. Examples of such structurants are described in U.S. Patent No. 4,741,855, which is incorporated herein by reference. Suitable structurants include ethylene glycol esters of fatty acids having 16 to 22 carbon atoms. The structurant may be stearic acid ethylene glycol esters (monostearates and distearates), but especially distearates containing less than about 7% of monostearate. Other suitable structurants include alkanolamides of fatty acids having from about 16 to about 22 carbon atoms, alternatively from about 16 to about 18 carbon atoms, suitable examples of which include stearyl monoethanolamide, stearyl diethanolamide, stearyl monoisopropanolamide, and stearyl 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 glycerides as described above. Long-chain acyl derivatives, ethylene glycol esters of long-chain carboxylic acids, long-chain amine oxides, and alkanolamides of long-chain carboxylic acids can also be used as structurants.

Other long chain acyl derivatives suitable for use as structurants include N,N-dialkylamidobenzoic acids and their water soluble salts (e.g., Na, K), especially N,N-di(hydrogenated) _C16 , _C18 and tallowamidobenzoic acids, which are commercially available from Stepan Company (Northfield, Ill., USA).

Examples of suitable long chain amine oxides for use as structurants include alkyl dimethyl amine oxides, such as stearyl dimethyl amine oxide.

Other suitable structurants include primary amines having a fatty alkyl moiety containing at least about 16 carbon atoms (examples of which include palmitylamine or octadecylamine) and secondary amines having two fatty alkyl moieties each containing at least about 12 carbon atoms (examples of which include dipalmitoylamine or di(hydrogenated tallow)amine). Other suitable structurants include di(hydrogenated tallow)phthalic acid amide and crosslinked maleic anhydride-methyl vinyl ether copolymers.

Other suitable structurants include crystallizable glycerides. For example, a suitable glyceride is hydrogenated castor oil, such as trihydroxystearin or dihydroxystearin. Additional examples of crystallizable glycerides may include substantially pure triglycerides of 12-hydroxystearic acid. 12-hydroxystearic acid is a triglyceride of fully hydrogenated 12-hydroxy-9-cis-octadecenoic acid in pure form. It is understood that many other glycerides are possible. For example, variations in the hydrogenation process and natural variations in castor oil may enable the production of other suitable glycerides from castor oil.

Viscosity modifier

Viscosity modifiers may optionally be used to modify the rheology of the cleansing phase. Suitable viscosity modifiers may include Carbomers available under the trade names Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980 and Carbopol 981, all available from B.F. Goodrich Company; acrylates/stearyl polyoxyethylene eth-20 methacrylate copolymers available under the trade name ACRYSOL 22, available from Rohm and Hass; nonoxy hydroxyethyl cellulose available under the trade name AMERCELL POLYMER HM-1500, available from Amerchol; methyl cellulose available under the trade name BENECEL, hydroxyethyl cellulose available under the trade name NATROSOL, hydroxypropyl cellulose available under the trade name KLUCEL, cetyl hydroxyethyl cellulose available under the trade name POLYSURF 67, all available from Hercules; ethylene oxide and/or propylene oxide based polymers available under the trade names CARBOWAX PEG, POLYOX WASR and UCON FLUIDS, all available from Amerchol. Sodium chloride may also be used as a viscosity modifier. Other suitable rheology modifiers may include crosslinked acrylates, crosslinked maleic anhydride co-methyl vinyl ether, hydrophobically modified associative polymers, and mixtures thereof.

Beneficial

The optional beneficial phase may include a gel network that 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 porous solid crystalline phase that includes at least one fatty alcohol described in detail below, at least one second surfactant and/or fatty acid described in detail below, and water and/or other suitable solvents. The lamellar or porous phase includes a bilayer that is composed of a first layer containing fatty alcohols and/or fatty acids and a second surfactant and/or fatty acid and a second layer containing water or other suitable solvents alternately. In another example, the gel network may include at least one fatty acid, at least one second surfactant, and water and/or other suitable solvents. As used herein, the term "solid crystals" refers to the structure of a lamellar or porous phase that is formed at a temperature below the melting transition temperature of the layer in the gel network, and the gel network includes one or more fatty alcohols. Additional examples of multiphase shampoo compositions with suspended beneficial phases are described in U.S. Application No. 17/174,713, which is hereby incorporated by reference.

The multi-phase shampoo composition may include a benefit phase present in an amount of about 1% to about 90%, alternatively about 2% to about 50%, alternatively about 5% to about 40%, alternatively about 7% to about 30%, alternatively about 10% to about 25%, based on the 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%, and alternatively less than 25%, as measured by the light transmittance method described below. In some examples, the benefit phase may be substantially free of structurants. In other examples, the benefit phase may be free of cationic surfactants and/or anionic surfactants.

The gel network as described herein can be prepared as a separate premix that is mixed with the cleansing phase as a visually discrete phase after cooling. The preparation of the gel network components is discussed in more detail below and in the Examples.

The cooled and preformed gel network component is then added to the components of the shampoo composition, including the detersive surfactant component. Without being bound by theory, it is believed that the cooled and preformed gel network component is mixed with the detersive surfactant and other components of the shampoo composition so that a fully balanced lamellar dispersion ("ELD") is formed in the final shampoo composition. The ELD is a dispersed lamellar or porous phase that is produced by the preformed gel network component being fully balanced with the detersive surfactant, water, and other optional components that may be present in the shampoo composition, such as salts. The equilibrium is carried out after the preformed gel network component is mixed with the other components of the shampoo composition and is effectively completed within about 24 hours after initiation. The shampoo composition in which the ELD is formed provides improved wet and dry conditioning benefits to the hair.

For purposes of this description, 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."

The gel network is present in the form of ELD in the premix and the final shampoo composition, which can be confirmed by methods known to those skilled in the art, such as X-ray analysis, optical microscopy, electron microscopy and differential scanning calorimetry. The method of differential scanning calorimetry is described below. For X-ray analysis methods, see U.S. 2006/0024256A1.

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

The distribution of the scale size of the gel network phase in the shampoo composition can be measured using a Horiba Model LA 910 Laser Scattering Particle Size Distribution Analyzer (Horiba Instruments, Inc. Irvine California, USA) using a laser scattering technique. The scale size distribution in the shampoo composition of the present invention can be measured by mixing 1.75 g of the shampoo composition with 30 mL of 3% NH ₄ Cl, 20 mL of 2% Na ₂ HPO ₄ · 7H ₂ O, and 10 mL of 1% Laureth-7 to form a mixture. The mixture is then stirred for 5 minutes. A sample ranging from 1 mL to 40 mL, appropriate for the individual Horiba instrument being used, containing 75 mL of 3% NH ₄ Cl, 50 mL of 2% Na ₂ HPO ₄ · 7H ₂ O , and 25 mL of 1% Laureth-7, is measured and then injected into the Horiba instrument until the Horiba instrument reads 88% T to 92% T required for the scale size measurement. Once this value is obtained, a measurement is made after a 2 minute cycle through the Horiba instrument to provide the scale size measurement. A subsequent measurement is made using a sample of the shampoo composition which has been heated above the melting transition temperature of all fatty materials present in the shampoo composition, causing the gel network component to melt. This subsequent measurement allows for a scale size distribution of all remaining materials in the shampoo, which can then be compared to the scale size distribution of the initial sample and included in the analysis.

Fatty alcohol

The gel network component of the present invention may include at least one fatty alcohol. A single fatty alcohol compound or a combination of two or more different fatty alcohol compounds may be selected.

Fatty alcohols suitable for use in the present invention may 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, and alternatively from about 16 to about 22 carbon atoms. These fatty alcohols may be straight or branched chain alcohols and may be saturated or unsaturated. Non-limiting examples of suitable fatty alcohols include stearyl alcohol, eicosanol, behenyl alcohol, C21 fatty alcohol (1-henicosanol), C23 fatty alcohol (1-tricosanol), C24 fatty alcohol (tetracosanol, 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.

Mixtures of different fatty alcohols comprising one or more fatty alcohols having from about 16 to about 70 carbon atoms may also contain some amounts of one or more fatty alcohols, or other fatty amphiphiles having less than about 16 carbon atoms or greater than about 70 carbon atoms, and still be considered to be within the scope of the present invention, provided that the resulting gel network phase may have a melting 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, and alternatively at least about 37°C.

Such fatty alcohols suitable for use herein may be of natural or plant origin, or they may be of synthetic origin.

The benefit phase may comprise as part of the gel network phase 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% fatty alcohol by weight of the benefit phase.

In one embodiment of the present invention, the weight ratio of fatty alcohol to second surfactant in the gel network component is greater than about 1:9, alternatively from about 1:5 to about 100:1, and alternatively from about 1:1 to about 50:1.

Second surfactant

The gel network component of the present invention may also include a second surfactant. As used herein, "second surfactant" refers to one or more surfactants that are mixed with the fatty alcohol and water to form the gel network of the present invention, separated from the other components of the shampoo composition as a premix. The second surfactant is separated from the cleaning composition and is in addition to the detersive surfactant component in the cleaning phase. However, the second surfactant can be the same or different type of surfactant, or a detersive surfactant as described above, or selected from those of the detersive surfactants described above.

The benefit phase of the present invention comprises a secondary surfactant as part of a preformed gel network phase measured at from about 0.01% to about 15%, alternatively from about 0.5% to about 12%, alternatively from about 0.7% to about 10%, and alternatively from about 1% to about 6%, by weight of the benefit phase.

Suitable second surfactants include anionic, zwitterionic, amphoteric, cationic and nonionic surfactants. The second surfactant can be selected from anionic, cationic and nonionic surfactants, and mixtures thereof. For additional discussion of the second surfactant suitable for use in the present invention, see U.S.2006/0024256 A1.

In addition, some secondary surfactants have a hydrophobic tail group with a chain length of about 16 to about 22 carbon atoms. For such secondary surfactants, the hydrophobic tail group can be an alkyl, alkenyl (containing up to 3 double bonds), alkyl aromatic, or branched alkyl. The secondary surfactant can be present in the gel network component at a weight ratio of about 1:5 to about 5:1 relative to the fatty alcohol. SLE1S can be particularly useful because SLE1S is a very efficient surfactant that foams well. In shampoo compositions with high levels of conditioning actives, SLE1S can also provide enhanced foam and cleaning effects.

Mixtures of more than one surfactant of the above specified types may be used as the second surfactant in the present invention.

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

fatty acid

Non-limiting examples of suitable fatty acids that can be mixed with fatty alcohols or second surfactants to form a gel network can include unsaturated and/or branched long-chain (C ₈ -C 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 can include short-chain saturated fatty acids, such as capric acid and caprylic acid. Not wanting to be bound 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 is used to "disrupt" the surfactant hydrophobic chain and induce the formation of a lamellar phase. Examples of suitable liquid fatty acids can 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 can include propylene glycol isostearate, propylene glycol oleate, glyceryl isostearate, glyceryl oleate, polyglyceryl diisostearate, and mixtures thereof. Examples of alcohols can include oleyl alcohol and isostearyl alcohol. Examples of ether derivatives may include isostearyl ethoxylate or oleyl ethoxylate carboxylic acid; or isostearyl ethoxylate or oleyl ethoxylate alcohol. The structuring agent may be defined as having a melting point below about 25°C.

Cationic deposition polymers

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

The shampoo composition may include a cationic polymer to allow for the formation of a coacervate. As can be appreciated, the cationic charge of the cationic polymer can interact with the anionic charge of the surfactant to form a coacervate. Suitable cationic polymers may 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 after mixing with detersive surfactants, (f) cationic synthetic homopolymers, (g) cationic cellulose polymers, and (h) combinations thereof. In some examples, more than one cationic polymer may be included. The cationic polymer may be selected from guar hydroxypropyltrimonium chloride, polyquaternium 10, polyquaternium 6, and combinations thereof.

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 also be about 7 meq/g or less, and alternatively about 5 meq/g or less. The charge density may be measured at the pH of the intended use of the shampoo composition. (e.g., at about pH 3 to about pH 9; or at about pH 4 to about pH 8). The average molecular weight of the cationic polymer may generally be between about 10,000 and 10,000,000, between about 50,000 and about 5,000,000, and between about 100,000 and about 3,000,000, and between about 300,000 and about 3,000,000, and between about 100,000 and about 2,500,000. Low molecular weight cationic polymers may be used. Low molecular weight cationic polymers can provide greater translucency in the liquid carrier of the shampoo composition. The cationic polymer can be a single type, such as a cationic guar polymer guar hydroxypropyltrimonium chloride 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.

Cationic guar gum polymer

The cationic polymer may be a cationic guar polymer, which is a galactomannan (guar) gum derivative substituted with cations. Suitable guar gum for guar gum derivatives can be obtained in the form of naturally occurring material from guar gum plant seeds. As can be appreciated, the guar gum molecule is a linear mannan branched with a single galactose unit on alternating mannose units at regular intervals. The mannose units are connected to each other via a β (1-4) glycosidic bond linker. Galactose branching occurs via an α (1-6) bond. Cationic derivatives of guar gum can be obtained by reaction between the hydroxyl groups of polygalactomannan and a reactive quaternary ammonium compound. The degree of substitution of the cationic groups onto the guar gum structure may be sufficient to provide the desired cationic charge density as described above.

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

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

The shampoo composition may include from about 0.01 wt % to less than about 0.7 wt %, from about 0.04 wt % to about 0.55 wt %, from about 0.08 wt % to about 0.5 wt %, from about 0.16 wt % to about 0.5 wt %, from about 0.2 wt % to about 0.5 wt %, from about 0.3 wt % to about 0.5 wt %, and from about 0.4 wt % to about 0.5 wt % of the cationic guar polymer, based on the weight of the shampoo composition.

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

wherein R ³ , R ⁴ and R ⁵ are methyl or ethyl groups; and R ⁶ is an alkylene oxide group having the general formula III:

Or ^R6 is a halohydrin group having the general formula IV:

wherein R ⁷ is a C ₁ to C ₃ alkylene group; X is chlorine or bromine, and Z is an anion such as Cl-, Br-, I- or HSO ₄ -.

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

wherein R ⁸ is guar gum; and wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above; and wherein Z is halogen. Suitable cationic guar gum polymers may conform to Formula VI:

Wherein R ⁸ is guar gum.

Suitable cationic guar polymers may also include cationic guar derivatives such as guar hydroxypropyltrimonium chloride. Suitable examples of guar hydroxypropyltrimonium chloride may include the commercially available guar polymers from Solvay SA. series, the Hi-Care series from Rhodia and the N-Hance and AquaCat from Ashland Inc. C-500 has a charge density of 0.8 meq/g and an M.Wt. of 500,000 g/mol; Jaguar Optima has a cationic charge density of about 1.25 meg/g and an M.Wt. of about 500,000 g/mol; C-17 has a cationic charge density of about 0.6 meq/g and a M.Wt. of about 2,200,000 g/mol; has a cationic charge density of about 0.8 meq/g; Hi-Care 1000 has a charge density of about 0.7 meq/g and an M.Wt. of about 600,000 g/mol; N-Hance 3269 and N-Hance 3270 have a charge density of about 0.7 meq/g, and an M.Wt. of about 425,000 g/mole; N-Hance 3196 has a charge density of about 0.8 meq/g and an M.Wt. of about 1,100,000 g/mol; and AquaCat CG518 has a charge density of about 0.9 meq/g and an M.Wt. of about 50,000 g/mol. N-Hance BF-13 and N-Hance BF-17 are guar polymers that do not contain borate (boron). N-Hance BF-13 has a charge density of about 1.1 meq/g and a MWt of about 800,000, and N-Hance BF-17 has a charge density of about 1.7 meq/g and a MWt of about 800,000. BF-17 has a charge density of about 1.7 meq/g and a MWt of about 800,000. BF-17 has a charge density of about 1.7 meq/g and a MWt of about 800,000. BF-17 has a charge density of about 1.7 meq/g and a MWt of about 800,000. BF-17 has a charge density of about 1.7 meq/g and a MWt of about 800,000. BF-17 has a charge density of about 1.7 meq/g and a MWt of about 800,000.

Cationic non-guar galactomannan polymer

The cationic polymer may be a galactomannan polymer derivative. Suitable galactomannan polymers may have a ratio of mannose to galactose 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 a cationic group has been added. The term "amphoteric galactomannan" refers to a galactomannan polymer to which a cationic group and an anionic group have been added so that the polymer has a net positive charge.

Galactomannan polymers may be present in the endosperm of leguminous seeds. Galactomannan polymers are composed of a combination of mannose monomers and galactose monomers. Galactomannan molecules are linear mannans branched with single-segment galactose units at regular intervals on specific mannose units. The mannose units are linked to each other via β (1-4) glycosidic linkages. Galactose branching occurs via α (1-6) bonds. The ratio of mannose monomers to galactose monomers varies depending on the variety of the plant and may be affected by climate. Non-guar galactomannan polymer derivatives may have a ratio of mannose to galactose greater than 2:1 on a monomer to monomer basis. Suitable ratios of mannose to galactose 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 generally based on the measurement of galactose content.

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

The non-guar galactomannan polymer derivatives may have a M.Wt. of about 1,000 g/mol to about 10,000,000 g/mol and a M.Wt. of about 5,000 g/mol to about 3,000,000 g/mol.

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

The galactomannan polymer derivative may be a cationic derivative of a non-guar galactomannan polymer obtained by reaction between the hydroxyl groups of the polygalactomannan polymer and a reactive quaternary ammonium compound. Suitable quaternary ammonium compounds for forming cationic galactomannan polymer derivatives include compounds conforming to Formula II to VI as defined above.

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

Wherein R is gum. The cationic galactomannan derivative may be gum hydroxypropyltrimethylammonium chloride, which may be more specifically represented by the general formula VIII:

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.

The cationic non-guar galactomannans may have a mannose to galactose ratio of greater than about 4:1, an M.Wt. of about 100,000 g/mol to about 500,000 g/mol, an M.Wt. 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.

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

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 are added before the starch is degraded to have a smaller molecular weight, or to which cationic groups are added after the starch is modified to obtain a desired molecular weight. The definition of the term "cationically modified starch" also includes amphoteric modified starches. The term "amphoteric modified starch" refers to a starch hydrolysate to which cationic groups and anionic groups are added.

The shampoo compositions described herein may comprise in the range of from about 0.01% to about 10%, and/or from about 0.05% to about 5%, by weight of the composition, of a cationically modified starch polymer.

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

The cationically modified starch polymer may have a molecular weight of about 850,000 g/mol to about 15,000,000 g/mol, and about 900,000 g/mol to about 5,000,000 g/mol.

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 obtain such charge density can include adding amino and/or ammonium groups to starch molecules. Non-limiting examples of such ammonium groups can include substituents, such as hydroxypropyltrimethylammonium chloride, trimethylhydroxypropylammonium chloride, dimethylstearylhydroxypropylammonium chloride and dimethyldodecylhydroxypropylammonium chloride. Additional details are described in Solarek, D.B., Cationic Starches in Modified Starches: Properties and Uses (Wurzburg, O.B., ed., CRC Press, Inc., Boca Raton, Fla. 1986, pp. 113-125, which is incorporated herein by reference. Cationic groups can be added to starch before starch is degraded to have a smaller molecular weight, or cationic groups can be added thereto after such modifications.

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 an average measure of the number of hydroxyl groups on each anhydroglucose unit derived from a substituent. Since each anhydroglucose unit has three hydroxyl groups that can be substituted, the maximum possible degree of substitution is 3. On a molar average, the degree of substitution is expressed as the number of moles of substituents per mole of anhydroglucose unit. The degree of substitution can be determined using proton nuclear magnetic resonance spectroscopy (" ¹ H NMR") methods well known in the art. ^Suitable1H NMR techniques 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.

The starch source before chemical modification can be selected from a variety of sources, such as tubers, beans, cereals and grains. For example, the starch source can include corn starch, wheat starch, rice starch, waxy corn starch, oat starch, tapioca starch, waxy barley starch, waxy rice starch, gluten rice starch, gluten rice starch, amylopectin, potato starch, tapioca starch, oat starch, sago starch, sweet rice starch or their mixture. Suitable cationically modified starch polymers can be selected from degraded cationic corn starch, cationic cassava, cationic potato starch and their mixture. Cationic modified starch polymers are cationic corn starch and cationic cassava.

Before degradation to have a smaller molecular weight or after modification to have a smaller molecular weight, the starch may include one or more additional modifications. For example, these modifications may include cross-linking, stabilization reactions, phosphorylation and hydrolysis. Stability reactions may include alkylation and esterification.

The cationic modified starch polymer may be included in the shampoo composition in the form of hydrolyzed starch (e.g. acid, enzyme or alkali degradation), oxidized starch (e.g. peroxide, peracid, hypochlorite, alkali or any other oxidizing agent), physically/mechanically degraded starch (e.g. via thermomechanical energy input to the processing equipment) or a combination thereof.

Starch is readily soluble in water and can form a substantially translucent solution in water. The clarity of the composition is measured by ultraviolet/visible ("UV/VIS") spectrophotometry, which uses a Gretag Macbeth colorimeter to measure the absorption or transmission of UV/VIS light by a sample. It has been shown that a wavelength of light of 600 nm is sufficient to characterize the clarity of a shampoo composition.

Cationic copolymer of acrylamide monomer and cationic monomer

The shampoo composition may comprise a cationic copolymer of an acrylamide monomer and a cationic monomer, wherein the copolymer has a charge density of from about 1.0 meq/g to about 3.0 meq/g. The cationic copolymer may be a synthetic cationic copolymer of an acrylamide monomer and a cationic monomer.

Suitable cationic polymers may include:

(i) an acrylamide monomer having the following formula IX:

wherein R ⁹ is H or C _1-4 alkyl; and R ¹⁰ and R ¹¹ are independently selected from H, C _1-4 alkyl, CH ₂ OCH ₃ , CH ₂ OCH ₂ CH(CH ₃ ) ₂ and phenyl, or taken together are C _3-6 cycloalkyl; and

(ii) a cationic monomer conforming to formula X:

wherein k=1, each of v, v′ and v″ is independently an integer from 1 to 6, w is zero or an integer from 1 to 10, and X ⁻ is an anion.

The cationic monomer may conform to Formula X, wherein k=1, v=3, and w=0, z=1, and X- ^{is Cl-} , to form the following structure (Formula XI):

As can be appreciated, the above structure can be referred to as a diquaternary ammonium salt.

The cationic monomer may conform to Formula X, wherein v and v″ are each 3, v′=1, w=1, y=1, and X ⁻ is Cl ⁻ , to form the following structure of Formula XII:

The structure of Formula XII can be referred to as a triquaternary ammonium salt.

The acrylamide monomer may be acrylamide or methacrylamide.

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

The cationic copolymer may comprise an acrylamide monomer and a cationic monomer, wherein the cationic monomer is selected from: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, di-tert-butylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide; ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; trimethylammonium ethyl chloride (meth)acrylate, trimethylammonium ethyl methylsulfate (meth)acrylate, dimethylbenzylammonium ethyl chloride (meth)acrylate, 4-benzoylbenzyldimethylammonium ethyl chloride acrylate, trimethylammonium chloride ethyl (meth)acrylamide, trimethylammonium chloride propyl (meth)acrylamide, vinylbenzyltrimethylammonium chloride, diallyldimethylammonium chloride, and mixtures thereof.

The cationic copolymer may comprise a cationic monomer selected from the group consisting of (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltrimethylammonium methyl sulfate, (meth)acryloyloxyethylbenzyldimethylammonium chloride, 4-benzoylbenzylacryloyloxyethyldimethylammonium chloride, (meth)acrylamidoethyltrimethylammonium chloride, (meth)acrylamidopropyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, and mixtures thereof.

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, (2) a terpolymer of (meth)acrylamide, a cationic (meth)acrylate-based monomer, a (meth)acrylamide-based monomer and/or a hydrolytically stable cationic monomer. The cationic (meth)acrylate-based monomer may be a cationized ester of (meth)acrylic acid containing a quaternized N atom. The cationized ester of (meth)acrylic acid containing a quaternized N atom may be a quaternized dialkylaminoalkyl (meth)acrylate having _C1 to _C3 in the alkyl and alkylene groups. The cationized ester of (meth)acrylic acid containing a quaternized N atom may be selected from the group consisting of: ammonium salts of dimethylaminomethyl (meth)acrylate, ammonium salts of dimethylaminoethyl (meth)acrylate, ammonium salts of dimethylaminopropyl (meth)acrylate, ammonium salts of diethylaminomethyl (meth)acrylate, ammonium salts of diethylaminoethyl (meth)acrylate, and ammonium salts of diethylaminopropyl (meth)acrylate. The cationized ester of (meth)acrylic acid containing a quaternized N atom may be dimethylaminoethyl acrylate (ADAME-Quat) quaternized with an alkyl halide or with methyl chloride or benzyl chloride or dimethyl sulfate. When based on (meth)acrylamide, the cationic monomer is a quaternized dialkylaminoalkyl (meth)acrylamide having _C1 to _C3 in the alkyl and alkylene groups or dimethylaminopropyl acrylamide quaternized with an alkyl halide or methyl chloride or benzyl chloride or dimethyl sulfate.

The cationic monomer based on (meth)acrylamide may be a quaternized dialkylaminoalkyl (meth)acrylamide having _C1 to _C3 in the alkyl and alkylene groups. The cationic monomer based on (meth)acrylamide may be dimethylaminopropyl acrylamide quaternized with an alkyl halide (especially methyl chloride) or benzyl chloride or dimethyl sulfate.

The cationic monomer may be a hydrolytically stable cationic monomer. In addition to dialkylaminoalkyl (meth) acrylamide, the hydrolytically stable cationic monomer may also be any monomer that is considered stable according to the OECD hydrolysis test. The cationic monomer may be hydrolytically stable, and the hydrolytically stable cationic monomer may be selected from: diallyldimethylammonium chloride and a water-soluble cationic styrene derivative.

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

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

The cationic copolymer may have an M.Wt. 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.

The cationic copolymer may be trimethylammoniumpropylmethacrylamide chloride-N-acrylamide copolymer, also referred to as AM:MAPTAC. AM:MAPTAC may have a charge density of about 1.3 meq/g and an M.Wt. of about 1,100,000 g/mol. The cationic copolymer may be AM:ATPAC. AM:ATPAC may have a charge density of about 1.8 meq/g and an M.Wt. of about 1,100,000 g/mol.

Synthetic polymers

Cationic polymers may be synthetic polymers formed from:

i) one or more cationic monomer units, and optionally

ii) one or more negatively charged monomer units, and/or

iii) nonionic monomers,

The subsequent charge of the copolymer is positive. The ratios of the three types of monomers are given as "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 nonionic monomers.

The cationic polymer may be a water-soluble or water-dispersible non-crosslinked and synthetic cationic polymer having the structure of Formula XIII:

Wherein A can be one or more of the following cationic moieties:

Wherein @ = amide, alkylamide, ester, ether, alkyl, or alkylaryl;

Wherein Y＝C1-C22 alkyl, alkoxy, alkylidene, alkyl, or aryloxy;

Wherein ψ＝C1-C22 alkyl, alkoxy, alkylaryl, or alkylaryloxy;.

Wherein Z＝C1-C22 alkyl, alkoxy, aryl, or aryloxy;

Wherein R1＝H, C1-C4 straight or branched chain alkyl;

Where s = 0 or 1, n = 0 or ≥ 1;

wherein T and R7 = C1-C22 alkyl; and

wherein X-=halogen, hydroxide, alkanolate, sulfate or alkylsulfate.

The negatively charged monomer is defined as follows: R2′=H, C ₁ to C ₄ straight or branched chain alkyl, and R3 is:

Where D＝O, N or S;

Where Q = _NH2 or O;

Where u = 1 to 6;

wherein t = 0 to 1; and

Wherein J = an oxidized functional group containing the following elements P, S, C.

The nonionic monomer is defined as follows: R2″＝H, C ₁ to C ₄ straight chain or branched alkyl, R6＝straight chain or branched alkyl, alkylaryl, aryloxy, alkoxy, alkylaryloxy, and β is defined as

and

wherein G' and G" are independently O, S or N-H, and L = 0 or 1.

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

Additional examples of suitable cationic monomers may include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, di-tert-butylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine, (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltrimethylammonium methyl sulfate, (meth)acryloyloxyethylbenzyldimethylammonium chloride, 4-benzoylbenzylacryloyloxyethyldimethylammonium chloride, (meth)acrylamidoethyltrimethylammonium chloride, (meth)acrylamidopropyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, and diallyldimethylammonium chloride.

Suitable cationic monomers may include quaternary ammonium monomers of the formula -NR ₃ ⁺ , 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, the benzyl group optionally bearing a hydroxyl group and containing an anion (counter ion). Examples of suitable anions include halides (such as chloride, bromide), sulfate, bisulfate, alkyl sulfate (e.g., containing 1 to 6 carbon atoms), phosphate, citrate, formate, and acetate.

Suitable cationic monomers may also include (meth)acryloyloxyethyl trimethyl ammonium chloride, (meth)acryloyloxyethyl trimethyl ammonium methyl sulfate, (meth)acryloyloxyethyl benzyl dimethyl ammonium chloride, 4-benzoyl benzyl acryloyloxyethyl dimethyl ammonium chloride, (meth)acrylamidoethyl trimethyl ammonium chloride, (meth)acrylamidopropyl trimethyl ammonium chloride, vinyl benzyl trimethyl ammonium chloride. Additional suitable cationic monomers may include (meth)acrylamidopropyl trimethyl ammonium chloride.

Examples of monomers having a negative charge include α-ethylenically unsaturated monomers containing a phosphate or phosphonate group, α-ethylenically unsaturated monocarboxylic acids, monoalkyl esters of α-ethylenically unsaturated dicarboxylic acids, monoalkyl amides of α-ethylenically unsaturated dicarboxylic acids, α-ethylenically unsaturated compounds containing a sulfonic acid group, and salts of α-ethylenically unsaturated compounds containing a sulfonic acid group.

Suitable monomers having a negative charge may include acrylic acid, methacrylic acid, vinyl sulfonic acid, salts of vinyl sulfonic acid, vinylbenzenesulfonic acid, salts of vinylbenzenesulfonic 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).

Examples of nonionic monomers may 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, vinyl pyrrolidone, and vinyl aromatic compounds.

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.

The anionic counterion ( ^X- ) associated with the synthetic cationic polymer can be any known counterion, so long as the polymer remains dissolved or dispersed in water, in the shampoo composition, or in a coacervate phase in the shampoo composition, and so long as the counterion is physically and chemically compatible with the essential components of the shampoo composition or does not otherwise unduly impair product performance, stability, or aesthetics. Non-limiting examples of suitable counterions can include halides (e.g., chloride, fluoride, bromide, iodide), sulfate, and methylsulfate.

The cationic polymers described herein can also help repair damaged hair, especially chemically treated hair, by providing an alternative hydrophobic F-layer. The extremely thin F-layer helps seal in moisture and prevent further damage while providing natural weather resistance. Chemical treatments damage the hair cuticle and strip its protective F-layer. As the F-layer is stripped, the hair becomes increasingly hydrophilic. It has been found that when lyotropic liquid crystals are applied to chemically treated hair, the hair becomes more hydrophobic and more natural in both appearance and feel. Without being bound by any theory, it is believed that the lyotropic liquid crystal complex forms a hydrophobic layer or film that covers the hair fiber and protects the hair, just as the natural F-layer protects the hair. The hydrophobic layer can restore the hair to a roughly original, healthier state. Lyotropic liquid crystals are formed by combining the synthetic cationic polymers described herein with the anionic detersive surfactant component of the aforementioned shampoo composition. Synthetic cationic polymers have a relatively high charge density. It should be noted that some synthetic polymers with relatively high cationic charge density do not form lyotropic liquid crystals, primarily due to their abnormal linear charge density. Such synthetic cationic polymers are described in PCT Patent Application No. WO 94/06403, which publication is incorporated by reference.The synthetic polymers described herein can be formulated into stable shampoo compositions that provide improved conditioning properties for damaged hair.

The cationic synthetic polymers that can form lyotropic liquid crystals have 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 polymers also have an M.Wt. 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.

Cationic synthetic polymers that provide enhanced conditioning and benefit agent deposition without forming 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 an M.Wt. of from about 1,000 g/mol to about 5,000,000 g/mol, from about 10,000 g/mol to about 2,000,000 g/mol, and from about 100,000 a/mol to about 2,000,000 g/mol.

Cationic cellulose polymer

Suitable cationic polymers may be cellulose polymers. Suitable cellulose polymers may include salts obtained by reacting hydroxyethyl cellulose with trimethyl ammonium substituted epoxides, which are referred to as polyquaternium 10 in the industry (CTFA) and are available from Dwo/Amerchol Corp. (Edison, N.J., USA) in its Polymer LR, JR and KG polymer series. Other suitable types of cationic cellulose may include polymeric quaternary ammonium salts obtained by reacting hydroxyethyl cellulose with lauryl dimethyl ammonium substituted epoxides, which are referred to as polyquaternium 24 in the industry (CTFA). These materials are available from Dow/Amerchol Corp. under the trade name Polymer LM-200. Other suitable types of cationic cellulose may include polymeric quaternary ammonium salts obtained by reacting hydroxyethyl cellulose with lauryl dimethyl ammonium substituted epoxides and trimethyl ammonium substituted epoxides, which are referred to as polyquaternium 67 in the industry (CTFA). These materials are available from Dow/Amerchol Corp. under the trade designations 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.

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, D.C. (1982)), which is incorporated herein by reference.

Techniques for analyzing complex coacervate formation are known in the art. For example, microscopic analysis of the composition can be used to determine whether a coacervate phase has formed at any selected dilution stage. 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. Additional details on the use of cationic polymers and coacervates are disclosed in U.S. Pat. No. 9,272,164, which is incorporated by reference.

Siloxane

Shampoo compositions may include silicone conditioning agents. Silicone conditioning agents may be in the benefit phase and/or the cleansing phase. Suitable silicone conditioning agents may include volatile silicones, non-volatile silicones, or combinations thereof. If silicone conditioning agents are included, the silicone conditioning agents may be included in an amount of about 0.01% to about 10% by weight of the composition, about 0.1% to about 8% by weight of the cleansing phase, the benefit phase, or the composition, about 0.1% to about 5%, and/or about 0.2% to about 2%. Examples of suitable silicone conditioning agents and optional suspending agents for silicones are described in U.S. Reissued Patent No. 34,584, U.S. Pat. No. 5,104,646, and U.S. Pat. No. 5,106,609, each of which is incorporated herein by reference. Suitable silicone conditioning agents can have a viscosity 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 as measured at 25°C.

The dispersed silicone conditioning agent particles may have a volume average particle size in the range of about 0.01 microns to about 50 microns. For small particles applied to the hair, the volume average particle size may be in the range of about 0.01 microns to about 4 microns, about 0.01 microns to about 2 microns, about 0.01 microns to about 0.5 microns. For larger particles applied to the hair, the volume average particle size is typically in the range of about 5 microns to about 125 microns, about 10 microns to about 90 microns, about 15 microns to about 70 microns, and/or about 20 microns to about 50 microns.

Additional material on silicones, including sections discussing silicone fluids, silicone gums and silicone resins, and the preparation of silicones, can be found in "Encyclopedia of Polymer Science and Engineering", Vol. 15, 2nd Edition, pp. 204-308, John Wiley & Sons, Inc. (1989), which is incorporated herein by reference.

Silicone emulsions suitable for use in the shampoo compositions described herein may include insoluble polysiloxane emulsions prepared according to the descriptions provided 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 g/mol to about 500,000 g/mol, such as α, ω-hydroxyl-terminated polysiloxanes or α, ω-alkoxy-terminated polysiloxanes. The insoluble polysiloxane may have an average molecular weight in the range of about 50,000 to about 500,000 g/mol. For example, the insoluble polysiloxane may have an average molecular weight in the range of about 60,000 to about 400,000, about 75,000 to about 300,000, 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 microns. The average particle size may be, for example, in the range of about 40 nm to about 5 microns, about 50 nm to about 1 micron, about 75 nm to about 500 nm, or about 100 nm.

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

Alternatively, the shampoo composition may be substantially free of silicone.

Aqueous carrier

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

The aqueous carrier may comprise water, or a miscible mixture of water and an organic solvent, and in one aspect may comprise water and minimal or insignificant concentrations of organic solvents, except for those otherwise incidentally incorporated into the composition as minor ingredients of other components.

The aqueous carrier that can be used for shampoo composition can comprise water. In another example, shampoo composition can comprise aqueous solution of lower alkyl alcohol and polyol. Lower alkyl alcohol can comprise monohydric alcohol with 1 to 6 carbons, in one aspect, ethanol and isopropanol. Polyol can comprise propylene glycol, dipropylene glycol, hexylene glycol, glycerine and propanediol.

Optional components

As can be appreciated, the shampoo compositions described herein may include a variety of optional components to adjust the properties and characteristics of the compositions. As can be appreciated, suitable optional components are well known and may generally include any components that are physically and chemically compatible with the essential components of the shampoo compositions described herein. The optional components should not otherwise unduly impair the stability, aesthetics or performance of the product. The optional components may be in the cleansing phase and/or the benefit phase. The independent concentration of the optional components may generally be in the range of about 0.001% to about 10% by weight of the shampoo composition. The optional components in the cleansing phase may also be limited to components that will not impair the clarity of the translucent shampoo composition.

Suitable optional components that can be included in the shampoo compositions may include deposition aids, conditioning agents (including hydrocarbon oils, fatty acid esters, silicones), anti-dandruff agents, viscosity modifiers, dyes, non-volatile solvents or diluents (water soluble and insoluble), pearlescent aids, foam boosters, biocides, pH adjusters, fragrances, preservatives, chelating agents, proteins, skin active agents, sunscreens, UV absorbers and vitamins. The CTFA Cosmetic Ingredient Handbook, Tenth Edition (published by the Cosmetic, Toiletry and Fragrance Association, Inc., Washington) (2004) (hereinafter referred to as "CTFA") describes a wide variety of non-limiting materials that can be added to the compositions herein.

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

Organic conditioning ingredients

The organic conditioning agents in the shampoo compositions described herein may also include at least one organic conditioning material such as an oil or wax, alone or in combination with other conditioning agents such as the above-mentioned silicones. The organic conditioning material may be in the cleansing phase and/or the benefit phase. The organic conditioning agent may be 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 a pure formulation or in a pre-emulsified form. Suitable examples of organic conditioning materials may include: 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, including those having the CTFA designations PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M, and mixtures thereof.

Emulsifier

A variety of anionic and nonionic emulsifiers can be used in shampoo compositions comprising a benefit phase and/or a cleansing phase. Anionic and nonionic emulsifiers can be monomeric or polymeric in nature. For example, examples of monomers include, but are not limited to, alkyl ethoxylates, alkyl sulfates, soaps, and fatty acid esters, and their derivatives. By way of illustration and not limitation, examples of polymers include polyacrylates, polyethylene glycols, and block copolymers, and their derivatives. Naturally occurring emulsifiers such as lanolin, lecithin, and lignin, and their derivatives, are also non-limiting examples of useful emulsifiers.

Chelating agents

Chelating agents can be used in shampoo compositions comprising a benefit phase and/or a cleansing phase. Suitable chelating agents include those listed in Critical Stability Constants Vol. 1 by A.E. Martell & R.M. Smith (Plenum Press, New York & London (1974)) and Metal Complexes in Aqueous Solutions by A.E. Martell & R.D. Hancock (Plenum Press, New York & London (1996)), both of which are incorporated herein by reference. When referring to chelating agents, the term "their salts and derivatives" refers to salts and derivatives having the same functional structure (e.g., the same chemical backbone) as the chelating agent to which they refer and having similar or better chelating properties. The term includes alkali metal salts, alkaline earth metal salts, ammonium salts, substituted ammonium (i.e., monoethanolamine, diethanolamine, triethanolammonium) salts, esters, and mixtures thereof of chelating agents having an acidic portion, especially all sodium, potassium or ammonium salts. The term "derivative" also includes "chelating surfactant" compounds, such as those exemplified in U.S. Pat. No. 5,284,972, and macromolecules containing one or more chelating groups having the same functional structure as the parent chelating agent, such as the polymer EDDS (ethylenediamine disuccinic acid) disclosed in U.S. Pat. No. 5,747,440. U.S. Pat. No. 5,284,972 and U.S. Pat. No. 5,747,440 are each incorporated herein by reference. Suitable chelating agents may also include histidine.

The content of EDDS chelator or histidine chelator in the shampoo composition can be relatively low. For example, about 0.01% by weight of EDDS chelator or histidine chelator can be included. In the case of more than about 10% by weight, formulation and/or human safety issues may arise. The content of EDDS chelator or histidine chelator can be at least about 0.01% by weight, at least about 0.05% by weight, at least about 0.1% by weight, at least about 0.25% by weight, at least about 0.5% by weight, at least about 1% by weight, or at least about 2% by weight based on the weight of the shampoo composition.

Additional cosmetic materials

The shampoo composition may also contain one or more additional cosmetic materials. Exemplary additional cosmetic materials may include, but are not limited to, particles, colorants, fragrance 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 materials may be selected from: particles; colorants; fragrance 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.

Anti-dandruff active ingredients

The shampoo composition may also include an anti-dandruff active. The anti-dandruff active may be present in the cleansing phase and/or the beneficial phase. A soluble anti-dandruff active such as piroctone olamine may be present in the cleansing phase or the beneficial phase. Insoluble anti-dandruff actives such as pyrithione (e.g., zinc pyrithione) may be present in the beneficial 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 pyrithione salts, azoles, selenium sulfide, granulated 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.

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

Test Method

Hair Wet Friction Measurement (Final Rinse Friction and Initial Rinse Friction)

4 grams of general population hair clusters with 8 inches of length are used for measurement.Water temperature is set to 100 ° F, hardness is 7 grains per gallon, and flow rate is 1.6 liters per minute.For the shampoo in liquid form, 0.2ml liquid shampoo is evenly applied to the hair cluster in a zigzag pattern to cover the whole hair length using a syringe.For the shampoo in aerosol foam form, the foam shampoo is distributed on the weighing plate of a balance.From the weighing plate, take out 0.2 grams of foam shampoo, and evenly apply to the hair cluster to cover the whole hair length by a scraper.Then make the hair cluster foam for the 1st time for 30 seconds, rinse with water for 30 seconds, and foam for the 2nd time for 30 seconds.Then the water flow rate is reduced to 0.2 liter per minute.The hair cluster is clamped under 1800 grams of force using a fixture, and is pulled through the whole length while water is running at a low flow rate.The pull time is 30 seconds.The friction analyzer with a load cell of 5kg is used to measure friction. Repeat the pull under flushing for a total of 21 times. Collect a total of 21 friction values. Final flushing friction is the average friction of the last 7 points, and initial flushing friction is the average friction of the initial 7 points. Calculate ΔFinal to Initial by subtracting the Final flushing friction from the Initial flushing friction.

Light transmittance

%T can be measured using an ultraviolet/visible (UV/VI) spectrophotometer, which determines the transmittance of UV/VIS light through a sample. A wavelength of light of 600nm has been shown to be sufficient to characterize the transmittance of light through a sample. In general, it is best to follow the specific instructions for use associated with the particular spectrophotometer used. Typically, the procedure for measuring percent transmittance begins with setting the spectrophotometer to 600nm. Then, a calibration "blank" is run to calibrate the display reading to 100% transmittance. The individual test samples are then placed in a cuvette designed to fit that particular spectrophotometer, and care is taken to ensure that there are no bubbles in the sample before the spectrophotometer measures %T with the spectrophotometer at 600nm.

Example

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 should be understood that other modifications may be made to the present invention by those skilled in the art of shampoo formulations without departing from the spirit and scope of the present invention. Unless otherwise indicated, all exemplified amounts are listed in weight percentages, and except for trace materials, such as diluents, preservatives, colored solutions, imaginary ingredients, botanicals, etc. Unless otherwise indicated, all percentages are based on weight.

The shampoo compositions illustrated in the following examples can be prepared by conventional formulation and mixing methods. Gas bubbles are 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 second surfactant (e.g., sodium laureth sulfate) are added to the water. After addition, the mixture is passed through a grinder and then cooled (e.g., via a heat exchanger) to about 32°C. As a result of this cooling step, the fatty alcohol, the second surfactant, and the water form a crystalline gel network.

Multiphase shampoo compositions can be prepared using a piston filler that can accommodate two or more separate product streams during filling. The separate streams can form an aesthetic design in the final shampoo composition. During filling, special care is taken to minimize air entrained into the cleansing phase during filling into the bottle or other suitable primary packaging. In some examples, the bottle can be overfilled with only the cleansing phase, thereby ensuring that any remaining head space will be displaced/cleared from the bottle during pump insertion. In some cases, the bottle is capped with a pump that is carefully placed to minimize displacement of the aesthetic design during filling.

Examples A-L in Table 1 and Table 2 (below) are cleansing shampoos that can be used as one or more cleansing phases in a multi-phase shampoo composition.

Table 1: Cleansing Phase Premix

Table 2: Cleansing Phase Premix

(1) Sodium lauryl polyoxyethylene ether-n sulfate, where n ≥ 1 and ≤ 3

(2)

(3) Cationic galactomannan (molecular weight = 200,000; charge density = 3.0 meq/g)

(4) Cationic galactomannan (molecular weight = 200,000; charge density = 0.7 meq/g)

(5) Excel

(6)N-Hance ^TM 3196 (Ashland ^TM )

(7)UCARE ^TM LR-30M( Chemical Company

(8) Polymer KG30M( Chemical Company) with a charge density of 1.97 meq/gm and a molecular weight of 2,000,000

(9) 100S

(10) DM 5500E (WACKER)

(11)Dow 1872(Dow Corporation)

(12) Aqua SF1( Advanced Materials

(13) Aqua SF2(Lubrizol Advanced Materials)

(14) Kathon ^TM CG

Examples 1-8 in Table 3 (below) are gel networks that can be prepared and incorporated as a benefit phase.

Table 3: Benefit Phase Premix

(1) Sodium lauryl polyoxyethylene ether-n sulfate, where n ≥ 1 and ≤ 3

(2)N-Hance ^TM BF17 (Ashland ^TM )

(3)N-Hance ^TM 3196 (Ashland ^TM )

(4) Polymer KG30M( Chemical Company) with a charge density of 1.97 meq/gm and a molecular weight of 2,000,000

(5) 100S

(6)CF330m(Momentive ^TM Performance Materials)

(7) DM 5500E (WACKER)

(8)Dow 1872(Dow Corporation)

(9) Kathon ^TM CG

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

Table 4: Multi-phase shampoo composition

combination

A. A container configured to contain a multi-phase shampoo composition, the multi-phase shampoo composition comprising:

a. A first cleaning phase, the first cleaning phase comprising:

i. Detergent surfactants;

ii. Structuring agent;

b. A second cleansing phase, the second cleansing phase comprising:

i. Detergent surfactants;

ii. Structuring agent;

iii. visually discernible stable bubbles suspended therein;

c. Optionally, a benefit phase, the benefit phase comprising a gel network, the gel network comprising:

i. fatty alcohol;

ii. a second surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof.

B. A container configured to contain a multi-phase shampoo composition, the multi-phase shampoo composition comprising:

a. A first cleaning phase, the first cleaning phase comprising:

i. Detergent surfactants;

ii. Structuring agent;

iii. visually discernible stable bubbles suspended therein;

b. a benefit phase comprising a gel network, wherein the gel network comprises:

i. fatty alcohol;

ii. a second surfactant selected from anionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof;

wherein the cleansing phase and the benefit phase are visually discrete phases in physical contact and form an aesthetic design suspended across at least a portion of the container;

wherein the cleansing phase and the benefit phase are stable.

C. A container according to paragraphs A-B, wherein the first cleansing phase and/or the 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%, of a detersive surfactant, by weight of the cleansing phase.

D. The container of paragraphs A-C, wherein the first cleansing phase and/or the second cleansing phase is substantially free of sulfate-based surfactants, and wherein the detersive surfactant is selected from isethionates, sarcosinates, sulfonates, sulfosuccinates, sulfoacetates, acyl glycinates, acyl alaninates, acyl glutamates, lactylates, alkenyl lactylates, glucose carboxylates, amphoacetates, taurates, phosphates, 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%, of a fatty alcohol, by weight of the benefit phase.

H. The container according to 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%, of a second surfactant, by weight of the benefit phase.

J. The container of paragraphs A-I, wherein the second surfactant is selected from anionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof.

K. The container of paragraphs A-J, wherein the benefit phase further comprises a nonionic 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 silicones, particulates, mica, and combinations thereof.

N. The container of paragraphs A-M, wherein the benefit phase further comprises from about 0.075% to about 2%, and 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-N, wherein the cationic deposition polymer has a weight average molecular weight of about 100,000 g/mol to about 3,000,000 g/mol, preferably 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 gum, cationic cellulose, cationic synthetic homopolymers, cationic synthetic copolymers, cationic synthetic terpolymers, and combinations thereof.

Q. The container of paragraphs A-P, wherein the cationic deposition polymer is selected from the group consisting of cationic guar gum, cationic cellulose, cationic synthetic homopolymers, cationic synthetic copolymers, and combinations thereof.

R. The container of paragraphs A-Q, wherein the cationic polymer is selected from guar hydroxypropyltrimonium chloride, polyquaternium 10, polyquaternium 6, and combinations thereof.

S. The container of paragraphs A-R, wherein the container is a bottle, wherein at least a portion of the bottle is transparent, and wherein the bottle is substantially free of headspace and substantially free of visually discernible bubbles prior to first use.

T. The container of paragraphs A-S, wherein the first cleansing phase and/or the second cleansing phase has 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 has 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 container of paragraph AU, wherein the first cleansing phase and/or the second cleansing phase has a yield stress of about 0.01 Pa to about 20 Pa, preferably about 0.01 Pa to about 10 Pa, and more preferably about 0.01 Pa to about 5 Pa at a shear rate of ^10-2 l/s to ^10-4 l/s according to the Herschel-Bulkley model.

W. A container according to paragraph AV, wherein the first cleansing phase and/or the second cleansing phase and/or the benefit phase has a viscosity of from about 0.01 Pa.s to about 15 Pa.s at 2 s ^-1 . The cleansing phase may have a viscosity of from about 0.1 Pa.s to about 4 Pa.s, alternatively from about 0.1 Pa.s to about 2 Pa.s, alternatively from about 0.1 Pa.s to about 1 Pa.s at 100 s ^- 1.

X. The container according to paragraph AW, wherein at 25°C, the benefit phase has a shear stress of about 100 Pa to about 300 Pa at a shear rate of 950 s ^{- 1} , preferably about 130 Pa to about 250 Pa at a shear rate of 950 s ^-1 , and more preferably about 160 Pa to about 225 Pa at a shear rate of 950 s-1.

Y. The container of paragraphs A-W, wherein the first cleansing phase and/or the 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 structurant selected from the group consisting of vinyl polymers, cellulose derivatives and modified cellulose polymers, polyvinyl pyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth gum, galactans, carob bean gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch, alginate, microbial polymers, starch-based polymers, alginic acid-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 structurant.

AA. The container of paragraphs AZ, wherein the viscosity of the first cleansing phase and/or the second cleansing phase is from about 1.0 Pa.s to about 15 Pa.s at 2 s ⁻¹ and from about 0.1 Pa.s to about 5 Pa.s at 100 s ^−1.

BB. A container according to paragraphs A-AA, wherein the bubbles and/or the benefit phase form an aesthetic design selected from the group consisting of bubbles, stripes, cross-hatching, zigzags, flowers, petals, herringbone, marbled, straight lines, broken stripes, checkered, speckled, veined, clustered, jumbled, speckled, bands, spirals, swirls, arrays, mottled, wavy, helices, twists, curves, stripes, lace, basket weave, sinusoidal, and combinations thereof.

CC. The container of paragraphs A-BB, wherein the first cleansing phase and/or the second cleansing phase has a light transmittance 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 cleansing phase and/or the second cleansing phase further comprises from about 0.5 wt % to about 7 wt %, preferably from about 1.5 wt % to about 5 wt % of a rheology modifier selected from the group consisting of polyacrylates, gellan gum, cellulose fibers, sodium polyacrylate starch, and mixtures thereof.

EE. The container of paragraphs A-DD, wherein the first cleansing phase and/or the second cleansing phase further comprises a silicone conditioning agent having an average particle size less than or equal to 30 nm.

FF. The container of paragraphs A-EE, wherein the density difference between the first cleansing phase and/or the second cleansing phase and the benefit phase is less than 0.30 g/cm3.

GG. The container of paragraphs A-FF, wherein the benefit phase further comprises a material selected from the group consisting of silicones having an average particle size greater than 30 nm, cationic deposition polymers, insoluble anti-dandruff actives, and combinations thereof.

HH. A container according to paragraphs A-GG, wherein the weight ratio of the cleansing phase to the 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%, by weight of the composition, of the cleansing phase.

JJ. The container of paragraph A-II, wherein the first cleansing phase is substantially free of discernible bubbles.

KK. The container of paragraphs A-JJ, wherein the first cleansing phase comprises visually discernible stable bubbles 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 of paragraphs A-LL, comprising visible suspended bubbles having a gas volume of about 0.01 mL to about 3 mL.

NN. A container according to paragraphs A-MM, wherein the bubbles have an average diameter of about 0.5 mm to about 5 mm, preferably about 1 mm to about 3 mm.

OO. A method for cleaning and conditioning hair comprising:

a. Providing a container according to paragraphs A-NN, wherein the container comprises a bottle configured to contain the multi-phase shampoo composition and a pump configured to dispense the multi-phase composition;

b. activating the pump to dispense an amount of the shampoo composition from the bottle;

c. applying the shampoo composition to the user's hair;

d. Rinse the shampoo composition from the hair.

PP. The method of paragraph OO, wherein the user's hair has a Final Rinse Friction of less than 2000 gf, preferably less than 1750 gf, and more preferably less than 1700 gf as measured using the Hair Wet Feel Friction Measurement described herein.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values cited. Instead, unless otherwise indicated, each such dimension is intended to represent the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Unless expressly excluded or otherwise limited, each document cited herein, including any cross-referenced or related patent or patent application and any patent application or patent to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art to any of the present invention disclosed or claimed herein, or an admission that it, by itself or in combination with any one or more of the references, proposes, suggests, or discloses any such invention. In addition, to the extent that any meaning or definition of a term in this invention 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 invention shall govern.

Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the present invention. Therefore, it is intended that all such changes and modifications within the scope of the present invention be covered in the appended claims.

Claims (15)

1. A shampoo product, comprising: a) a container configured to contain a multi-phase shampoo composition; and b) A multi-phase shampoo composition contained by said container, said multi-phase shampoo composition comprising: i) a first cleaning phase, said first cleaning phase comprising: (1) detersive surfactants, and (2) Structural agent; ii) a second cleaning phase comprising: (1) Detersive surfactant, (2) Structuring agent, and (3) Visually discernible stable bubbles suspended therein; and iii) Optionally, a benefit phase comprising a gel network comprising: (1) Fatty alcohols, and (2) A second surfactant selected from anionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof. 2. Shampoo product according to claim 1, wherein at least one of the cleansing phases comprises from 3% to 40%, preferably from 5% to 30%, more preferably by weight of the cleansing phase. 6% to 25%, and even more preferably 8% to 25% detersive surfactant. 3. A shampoo product according to claim 1 or 2, wherein the container is a bottle, wherein at least a portion of the bottle is transparent, and wherein the bottle has substantially no headspace and is substantially free of headspace prior to first use. There are no visually discernible air bubbles. 4. A shampoo product according to any preceding claim, wherein at least one of the cleansing phases has a transmission of at least 70%, preferably at least 80%, and more preferably at least 90%, As determined by the light transmittance method. 5. A shampoo product according to any preceding claim, wherein at least one of the cleansing phases has a cleaning phase of between ^10-2 s ^-1 and ^10-4 s ^-1 according to the Herschel-Bulkley model. Yield stress at shear rate of 0.01 Pa to 20 Pa, preferably 0.01 Pa to 10 Pa, and more preferably 0.01 Pa to 5 Pa. 6. A shampoo product according to any preceding claim, wherein at least one of the first cleansing phase, the second cleansing phase and the benefit phase has a temperature of 0.01 Pa at 2 s ⁻¹ .s to 15Pa.s viscosity. 7. A shampoo product according to any preceding claim, wherein at least one of the cleansing phases has a range of 0.1 Pa.s to 4 Pa.s, alternatively 0.1 Pa.s at 100 s ⁻¹ . s to 2 Pa.s, alternatively 0.1 Pa.s to 1 Pa.s. 8. Shampoo product according to any preceding claim, wherein at least one of the cleansing phases further comprises 0.05% to 10%, preferably 0.3% to 5.0% by weight of the cleansing phase. %, and more preferably 1.5% to 5.0% 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, acacia gum, tragacanth gum, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch , seaweed gum, microbial polymers, starch-based polymers, alginic acid-based polymers, acrylate polymers, inorganic water-soluble materials, and combinations thereof. 9. A shampoo product according to any preceding claim, wherein the benefit phase is present and between at least one of the first and second cleansing phases and the benefit phase. The density difference is less than 0.30g/cm3. 10. A shampoo product according to any preceding claim, wherein the benefit phase further comprises a material selected from the group consisting of silicones with an average particle size greater than 30 nm, cationic deposition polymers, insoluble anti-dandruff actives , and their combinations. 11. A shampoo product according to any preceding claim, wherein the first cleansing phase is substantially free of discernible air bubbles. 12. A shampoo product according to any one of claims 1 to 10, wherein the first cleansing phase contains visually discernible stable air bubbles suspended therein. 13. A shampoo product according to any preceding claim, wherein the shampoo composition has visible suspended bubbles with a gas volume of from 0.01 mL to 3 mL. 14. A shampoo product according to any preceding claim, wherein the bubbles have an average diameter of 0.5 mm to 5 mm, preferably 1 mm to 3 mm. 15. A method of cleaning hair, comprising: a) Providing a shampoo product according to any preceding claim, wherein the container comprises a bottle configured to contain the multi-phase shampoo composition and a bottle configured to dispense the multi-phase composition Pump; b) activating the pump to dispense an amount of shampoo composition from the bottle; c) applying the shampoo composition to the user's hair; and d) Rinse the shampoo composition from the hair.