CN116963708A - Container containing a shampoo composition having an aesthetic design formed by bubbles - Google Patents

Abstract

A container configured to hold a liquid shampoo composition having an aesthetic design formed at least in part by visually discernible stable air 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 effects as well as additional visual interest.

Description

Container containing shampoo composition with aesthetic design formed by air 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 air bubbles suspended in a liquid shampoo composition.

Background

Some consumers desire shampoo compositions that effectively clean hair while also providing a striking appearance, making the product prominent in store shelves, web pages/applications, and even in the user's shower cubicle, which can make it interesting to use.

Shampoo today provides effective cleaning but is often not interesting from an aesthetic point of view. One way to create a shampoo with a striking appearance is to add stable suspended bubbles.

However, it may be difficult to maintain stable suspended air bubbles in the 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 dispensing. Bubbles are particularly sensitive to temperature and pressure changes, which can cause them to dissolve, appear or grow. It can be particularly difficult to balance the rheological and chemical properties of shampoo compositions to include stable bubbles suspended therein. These problems become more complex when the bubbles are patterned, as even slight damage (including bubble migration, decomposition or coalescence) can be noticed by the consumer and the product will be mediocre without a striking appearance that is interesting and of quality.

Thus, there is a need for stable shampoo compositions that deliver excellent cleansing and stable suspended air bubbles that form attractive aesthetic designs.

Disclosure of 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 structuring agent; (b) a second cleansing phase comprising: (i) a detersive surfactant; (ii) a structuring agent; (iii) A visually distinguishable stable gas bubble suspended therein; (c) Optionally, a benefit phase comprising a gel network comprising: (i) a fatty alcohol; (ii) A second surfactant selected from the group consisting of 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 structuring agent; (c) A visually distinguishable stable gas bubble suspended therein;

wherein the cleansing phase has a phase of at least 10 ^-2 s ^-1 To 10 ^-4 s ^-1 A yield stress of about 0.01Pa to about 20Pa at a shear rate of 2s ^-1 A viscosity of about 1.0Pa.s to about 15Pa.s, and at 100s ^-1 The lower is a viscosity of about 0.1pa.s to about 4 pa.s.

Drawings

While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter of the present invention, it is believed that the invention will be more readily understood from the following description taken in conjunction with the accompanying drawings, wherein:

figure 1 is a photograph of a bottle with a pump containing a liquid shampoo composition having an aesthetic design formed by suspended air bubbles;

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

Detailed Description

Some consumers desire shampoo compositions that effectively clean hair while also providing a striking appearance, making the product prominent in store shelves, web pages/applications, and even in the user's shower cubicle, which can make it interesting to use. Figures 1 and 2 are photographs of shampoo compositions having an aesthetic design formed by suspended air bubbles suspended throughout. Figure 1 shows a bottle with a pump containing a liquid shampoo composition having a first cleansing phase 1 which is substantially free of visible air bubbles and a second cleansing phase 2 which has suspended air bubbles forming an aesthetic design. Figure 2 shows a bottle with a pump containing a liquid shampoo composition having a first cleansing phase 1' with substantially no visible air bubbles, a second cleansing phase 2' with suspended air bubbles forming an aesthetic design, and a third suspended phase 3' containing a gel network suspended in the liquid composition. The gel network may provide conditioning benefits to the shampoo product. In fig. 1 and 2, the phases are stable, discrete and packaged in physical contact with each other. In other examples, the first cleaning phase may contain suspended bubbles and the second cleaning phase may be substantially free of bubbles. In yet another example, the shampoo composition may be a single cleansing phase and have stable bubbles suspended across at least a portion of the shampoo composition.

The first cleaning phase and/or the second cleaning phase may contain a surfactant system, which may comprise one or more detersive surfactants, an aqueous carrier, and a structurant. In some examples, the first cleaning phase and/or the second cleaning phase may be visibly transparent with a light transmission of greater than 60%, alternatively greater than 80%, as measured by the light transmission method described below. In other examples, the cleansing phase may appear cloudy, or even opaque. The first cleaning phase and/or the second cleaning phase may be colored, colorless, or a combination thereof.

The first cleaning phase and/or the second cleaning phase may have visually discernable stable gas bubbles suspended therein, the bubbles being formed by entrained gas (which appears as bubbles) in the liquid phase. The gas may be any suitable gas including air and/or helium. In some examples, helium may be the preferred gas because it may form more stable bubbles. Other gases having lower solubility in shampoo may be used in place of or in addition to air and/or helium to improve bubble stability. Bubbles are visually discernable if one or more of the suspended bubbles are identifiable by the human observer (excluding standard corrective lenses adapted to correct myopia, hyperopia, or astigmatism, or other corrective vision) with an illumination of an incandescent bulb at least equal to standard 100 watts at a distance of about 1 foot (0.30 m).

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

The size of the bubbles may 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 may mitigate migration between the bubbles, limit bubble growth and/or destruction of the additional phase. In some examples, the size of the stable suspension bubbles does not vary by more than 25%, alternatively not more than 20%, alternatively not more than 15%, and alternatively not more than 10%.

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

The shampoo composition may comprise visible suspended gas bubbles having a gas volume of from about 0.001mL to about 5 mL. The shampoo compositions and/or phases may have a gas volume of from about 0.01mL to about 3mL, alternatively from about 0.1mL to about 0.5mL of visible suspended gas bubbles. The shampoo composition may be in a container, such as a bottle, having a volume of from about 100mL to about 1000mL, alternatively from about 250mL to about 750mL, and alternatively from about 300mL to about 500mL.

In some examples, the first phase and the second phase may have substantially the same chemical composition, and the first phase or the second phase may contain suspended, visually discernable, stable gas bubbles, and the other phase is substantially free of visually discernable gas bubbles. In other examples, the first phase and the second phase may have substantially different chemical compositions, and either or both phases contain suspended, visually discernable, stable gas bubbles. In the case where both phases contain suspended, visually discernable, stable bubbles, the average bubble size may be about the same, or one phase may have substantially larger bubbles than the other phase. In some examples, the bubble density of the crossing phases may be substantially the same, and in other examples, the bubble density of the crossing phases may be varied.

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

The benefit phase and/or cleansing phase having the visually distinguishable stable bubbles suspended therein may be uniform, non-uniform, or a combination thereof. The benefit phase and/or cleansing phase in which it is suspended may be of any suitable shape to form an aesthetic design, including regular and/or irregular patterns, including swirls as shown in fig. 1 and 2. This shape may form an aesthetic design similar to the following non-limiting example: bubbles, bands, cross-hatching, zigzags, flowers, petals, chevrons, marbled, straight lines, broken lines, grits, speckles, veins, clusters, hybrids, speckles, bands, spirals, swirls, arrays, mottled, corrugations, spirals, twists, bends, streaks, laces, basket weaves, sinusoids (including but not limited to, loops), random shapes, and combinations thereof.

The benefit phase may contain additional ingredients, including ingredients that can make the cleansing phase cloudy or opaque, such as conditioning ingredients (e.g., cationic deposition polymers, silicones having average particle sizes greater than 30nm, crosslinked silicone elastomers), anti-dandruff actives (e.g., zinc pyrithione), aesthetic ingredients (e.g., mica), and combinations thereof. The additional ingredients may be carefully selected (e.g., the ingredients may not have too high a salt concentration) because they may disrupt the gel network, resulting in collapse of the gel network structure, forcing solvent to spill over, which may disrupt the aesthetic pattern, and render the shampoo composition less effective.

In some examples, the shampoo benefit phase may be suspended in a cleansing phase having visually discernable stable suspended bubbles.

The appropriate rheological properties (which may include viscosity, yield stress, and/or shear stress) of the shampoo composition, cleansing phase, and/or optional benefit phase may be balanced so that the product is acceptable to the consumer while maintaining visually discernable suspended stable bubbles and/or suspended discrete stable phases. 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 may also slow the diffusion of suspended bubbles/Oswalt ripening. However, if the yield stress is too high, the composition may be too thick to be acceptable to the consumer. According to Herschel-Bulkley, the cleansing phase may have a phase of at least 10 ^-2 s ^-1 To 10 ^-4 s ^-1 Is from about 0.01Pa to about 20Pa, alternatively from about 0.01Pa to about 10Pa, and alternatively from about 0.01Pa to about 5 Pa. At 100s by using Discovery Hybrid Rheometer (DHR-3) available from TA Instruments ^-1 To 1.0e-4s ^-1 Flow scans at shear rate to measure yield stress at 26.7 ℃. To apply the Hershel-Bulkley model, TA software is used at 10 ^-2 s ^-1 To 10 ^-4 s ^-1 Is fit to the model in log space at the shear rate of (2). The geometry used to measure the yield stress and viscosity of the clean phase was a 60mm 2 ° aluminum cone (with peltier plates). The geometry should run at the gap specified for the geometry by the manufacturer. It is recommended to trim the sample during the initial conditioning step in step 1 to ensure data integrity and reproducibility. When the instrument + geometry is out of calibrationWhen the yield stress or shear stress method is run, the geometry is torque mapped. The Trios software version used to generate the rheological data herein is Trios 5.1.1.

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

When present, the benefit phase may have a viscosity of at 950s ^-1 At a shear rate of about 100Pa to about 300Pa, alternatively at 950s ^-1 At a shear rate of about 130Pa to about 250Pa, and alternatively at 950s ^-1 A shear stress at a shear rate of about 160Pa to about 225 Pa. At 0.1s by using Discovery Hybrid Rheometer (DHR-3) available from TA Instruments ^-1 To an initial shear rate of 1100s ^-1 The flow ramp at the final shear rate of (c) to measure shear stress at 25 ℃. The geometry used to measure the shear stress of the beneficial phase was a 40mm 2 ° steel cone (with peltier plates).

When dispensed from 10% to 55% by volume, the shampoo composition can provide an average final rinse friction of less than 2000gf, alternatively less than 1750gf, alternatively less than 1700gf, alternatively less than 1650gf, and alternatively less than 1600 gf. Average final rinse friction can be determined using the hair wet feel friction measurements described herein.

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

In addition to suspended bubbles intentionally placed into the cleansing phase, the shampoo composition may be in a bottle that is substantially free of headspace and/or visually discernable bubbles to help maintain the design prior to use. It has been found that bubbles, particularly unstable large bubbles, and headspace can disrupt the suspension aesthetic design during shipping and handling. The headspace may be eliminated by overfilling the bottle or using an insert that may snap fit with the neck of the bottle to consume the headspace volume, examples of which are described in U.S. patent application No. 17/174,427, which is hereby incorporated by reference.

However, it may be difficult to eliminate all air that is inadvertently trapped in the shampoo product. After filling, the shampoo product may typically have about 4% air trapped in the visually indistinguishable microscopic bubbles. When the shampoo is packaged in a typical bottle or pump, these unstable bubbles combine into larger bubbles over time due to the laplace pressure. If the stress of the liquid cosmetic care product is not high enough to support the density differential between air and liquid, these larger bubbles will eventually rise to the headspace. Thus, even if the liquid cosmetic care product is packaged in a bottle without any visible bubbles, a headspace can be formed within 24 hours to 48 hours. Increasing the yield stress of a liquid cosmetic product may prevent bubbles from migrating from small bubbles to larger bubbles and to the headspace, however, products with high yield stress may have less acceptance by 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 cause a slight overpressure, which prevents the entrapped air bubbles from migrating without compromising the yield stress of the shampoo composition. When the user is ready to dispense the shampoo composition, they may remove the cap and pour the shampoo product into the hand, remove the cap and insert the pump, or in some cases the cap may have a pierceable membrane and the user may pierce the membrane with the pump's dip tube.

In some examples, instead of eliminating the headspace, there may be a slight overpressure in the bottle. While not wanting 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 10Pa to about 10,000Pa, alternatively from about 10Pa to about 7500Pa, alternatively from about 15Pa to about 5000Pa, alternatively from about 15Pa to about 1000Pa, alternatively from about 20Pa to about 500Pa, alternatively from about 30Pa to about 250Pa, alternatively from about 40Pa to about 200Pa, alternatively from about 50Pa to about 150Pa, alternatively from about 75Pa to about 125Pa, and alternatively less than or equal to 100Pa.

In some examples, the air bubbles remain substantially unchanged in suspension, size, and density 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 increase in the range of minutes to hours after the product is opened.

It has been found that the aesthetic design of packaged shampoo products can be followed6A shipment test (6-Amazon. Com-Over shipping, month 4 of 2018, using ASTM setup for all tests) sequence numbers 1-5 remain substantially intact. As used herein, substantially intact may refer to a human observer being unable to visually discern one or more large areas in which the suspension design is disturbed with the naked eye (excluding standard corrective lenses adapted to correct myopia, hyperopia, or astigmatism, or other corrective vision) at a distance of 1 foot (0.30 m) under illumination at least equal to the standard 100 watt incandescent bulb illumination. In some examples, pattern disruption may be assessed by taking a cross-section of the liquid cosmetic product and determining how much percentage of the cross-section is disrupted. Less than 10% of the cross-sectional area may be disturbed, or less than 7%, or less than 5%, or less than 3%, or less than 1%.

Definition of the definition

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

As used herein, the articles "a" and "an" when used in the claims should be understood to mean one or more of the substance that is claimed or described.

As used herein, "comprising" means that other steps and other ingredients that do not affect the end result may 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 and any compounds that may result from their combination.

As used herein, unless otherwise indicated, "molecular weight" or "m.wt." refers to weight average molecular weight. Molecular weight is measured using industry standard methods, gel permeation chromatography ("GPC"). The molecular weight has units of grams/mole.

As used herein, "shampoo compositions" include 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 phases and/or benefit phases appear as discrete phases that do not migrate to a human observer 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 standard 100 watt incandescent bulb illumination at about 1 foot (0.30 m) apart. The term "stable" with respect to bubbles/entrained gas means that the bubbles are discrete and visually discernable and in 6A does not migrate or coalesce during the following serial numbers 1-5 of the shipping test as determined by a human observer with the naked eye (excluding standard corrective lenses adapted to correct myopia, hyperopia, or astigmatism, or other corrective vision) under illumination at least equal to the standard 100 watt incandescent bulb illumination at about 1 foot (0.30 m) apart.

As used herein, "substantially free" means about 0 wt% to about 3 wt%, alternatively about 0 wt% to about 2 wt%, alternatively about 0 wt% to about 1 wt%, alternatively about 0 wt% to about 0.5 wt%, alternatively about 0 wt% to about 0.25 wt%, alternatively about 0 wt% to about 0.1 wt%, alternatively about 0 wt% to about 0.05 wt%, alternatively about 0 wt% to about 0.01 wt%, alternatively about 0 wt% to about 0.001 wt%, and/or alternatively free of the ingredient. As used herein, "free" means 0 wt%.

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

All percentages, parts and ratios are based on 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 byproducts that may be included in commercially available materials.

Unless otherwise indicated, all component or composition levels are in terms of the active portion of the component or composition and do not include impurities, such as residual solvents or byproducts, that may be present in commercially available sources of such components or compositions.

It is to be understood that each maximum numerical limit set forth throughout this specification includes each lower numerical limit as if such lower numerical limit were explicitly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

Cleansing phase

The multi-phase shampoo composition may comprise one or more cleansing phases. The cleansing phase may be an aqueous phase. The cleansing phase may have a light transmission (%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 transmission method described below. The cleansing phase may have a light transmission 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 transmission method described below.

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

In other examples, the cleansing phase may comprise small particle siloxanes (i.e., siloxanes having an average particle size of less than or equal to 30 nm), select cationic deposition polymers, perfumes, and/or dyes.

Detersive surfactants

The cleansing phase may contain one or more detersive surfactants. As can be appreciated, detersive surfactants provide cleaning benefits to soiled items such as hair, skin and hair follicles by facilitating the removal of oil and other soils. Surfactants generally facilitate such cleaning because the amphiphilic nature of the surfactant allows the surfactant to break up oil and other soils and form micelles around the oil and other soils, which can then be rinsed away, thereby removing the oil or soils from the soiled article. Suitable surfactants for use in shampoo compositions may include anionic moieties to allow coacervate formation with the cationic polymer. Suitable detersive surfactants may be compatible with the cleaning phase and other ingredients in the adjacent benefit phase. The detersive surfactant 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 properties. The cleansing phase may contain a surfactant system at a concentration in the range of from about 1% to about 50%, alternatively from about 3% to about 45%, alternatively from about 5% to about 40%, alternatively from about 7% to about 35%, alternatively from about 8% to about 30%, alternatively from about 8% to about 25%, alternatively from about 10% to about 20%, alternatively from about 11% to about 24%, and alternatively from about 12% to about 23%, by weight of the cleansing phase. The preferred pH range of the cleaning 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 at a concentration ranging from about 1% to 50%, alternatively from about 3% to about 40%, alternatively from about 5% to about 30%, alternatively from about 6% to about 25%, alternatively from about 8% to about 25%, by weight of the cleansing phase. The anionic surfactant may be the primary surfactant.

The shampoo composition comprises one or more detersive surfactants in the cleansing phase. Detersive surfactant components are included in the shampoo compositions to provide cleaning performance. The detersive surfactant may be selected from the group consisting of: an anionic detersive surfactant, a zwitterionic detersive surfactant, an amphoteric detersive surfactant, a cationic detersive surfactant, or a combination thereof. In some examples, the detersive surfactant may be selected from the group consisting of: an anionic detersive surfactant, a zwitterionic detersive surfactant, an amphoteric detersive surfactant, 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, where n=1 ("SLE 1S"). SLE1S is capable of achieving more effective lathering and cleansing, especially in shampoo compositions comprising high levels of conditioning actives, when compared to higher mole number ethoxylated equivalents.

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 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 25%, and alternatively from about 10% to about 17% by weight of the composition.

Additional anionic surfactants suitable for use herein include those having the formula ROSO ₃ M and RO (C) ₂ H ₄ O) _x SO ₃ Alkyl and alkyl ether sulfates of 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 having two anionic surfactant anions. 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 may be derived from a fat such as coconut oil, palm kernel oil or tallow, or may be synthetic.

Other suitable anionic surfactants include the general formula [ R ] ¹ -SO ₃ M]Water-soluble salts of organic sulfonic acids of (a). R is 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 salts of divalent magnesium ions with two anionic surfactant anions. These materials pass through SO ₂ And O ₂ With normal paraffins of suitable chain length (C) ₁₄ -C ₁₇ ) Is prepared and commercially sold as sodium alkanesulfonate.

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 monoglyceride sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, 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 tridecyl polyoxyethylene ether sulfate, sodium tridecyl sulfate, sodium methyl lauroyl taurate, sodium methyl cocoyl taurate, sodium lauroyl isethionate, sodium cocoyl isethionate, sodium lauroyl sulfosuccinate, sodium lauryl sulfosuccinate, sodium dodecyl benzene sulfonate, and mixtures thereof.

The shampoo composition may also comprise 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 compositions are described in McCutcheon, emulsifiers and Detergents, journal of 1989, m.c. publishing co. Publication, and 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: isethionates, sarcosinates, sulfonates, sulfosuccinates, sulfoacetates, acyl glycinates, acyl alanates, acyl glutamates, lactates, alkenyl lactates, glucose carboxylates, amphoacetates, taurates, phosphates, and mixtures thereof. In this case, alkyl is defined as a saturated or unsaturated, straight 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, straight or branched alkyl chain having from 7 to 17 carbon atoms, alternatively having from 9 to 13 carbon atoms.

Suitable isethionate surfactants may include the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Suitable fatty acids for isethionate surfactants may be derived from coconut oil or palm kernel oil including amides of methyl taurines. Non-limiting examples of isethionates may be selected from: sodium lauroyl methyl isethionate, sodium cocoyl isethionate, ammonium cocoyl isethionate, sodium hydrogenated cocoyl methyl isethionate, sodium lauroyl isethionate, sodium cocoyl methyl isethionate, sodium myristoyl isethionate, sodium oleoyl isethionate, sodium oleyl methyl isethionate, sodium palmitoyl isethionate, sodium stearyl methyl isethionate, and mixtures thereof.

Non-limiting examples of sarcosinates may be selected from: sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, TEA-cocoyl sarcosinate, ammonium lauroyl sarcosinate, disodium dimer diiodolauroyl sarcosinate, disodium 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 laureth sulfosuccinate, tetrasodium N- (1, 2-dicarboxyethyl) -N-octadecyl sulfosuccinate, dipentyl ester of sodium sulfosuccinate, dihexyl ester of sodium sulfosuccinate, dioctyl ester of sodium sulfosuccinate, and combinations thereof.

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

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

Non-limiting examples of the acyl alanine salt may include sodium cocoyl alanine, sodium lauroyl alanine, sodium N-lauroyl-1-alanine, and combinations thereof.

Non-limiting examples of acyl glutamate may be selected from the group consisting of 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, sodium cocoyl glutamate sodium cocoyl sodium cocoyl sodium dipotassium cocoyl glutamate, dipotassium lauroyl glutamate, dipotassium cocoyl glutamate, potassium cocoyl glutamate hydrolysate, dipotassium cocoyl glutamate hydrolysate, sodium caprylate, disodium caprylate, potassium caprylate, dipotassium caprylate, sodium undecylenoyl glutamate, disodium undecylenoyl glutamate potassium undecylenoyl glutamate, dipotassium undecylenoyl glutamate, disodium hydrogenated tallow acyl 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 oleoyl glutamate, sodium hydrogenated tallow acyl glutamate, sodium olive oleoyl glutamate, disodium olive oleoyl glutamate, sodium palmitoyl glutamate, disodium palmitoyl glutamate, TEA-cocoyl glutamate, TEA-hydrogenated tallow acyl glutamate, TEA-lauroyl glutamate, and mixtures thereof.

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

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

Non-limiting examples of the alkenyl lactate may include sodium lauroyl alkenyl lactate, sodium cocoyl alkenyl lactate, and combinations thereof.

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

Non-limiting examples of alkyl amphoacetates can include sodium cocoyl amphoacetate, sodium lauroyl amphoacetate, and combinations thereof.

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

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

Amphoteric surfactants suitable for use in the present invention include, but are not limited to, derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, 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 guidelines in U.S.2658072, N-higher alkyl aspartic acids such as those prepared according to the guidelines in U.S.2438091 and products described in U.S.2528378, and mixtures thereof. The amphoteric surfactant may be selected from the betaine family such as lauroyl amphoacetate.

Zwitterionic surfactants suitable for use herein include, but are not limited to, derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds,wherein the aliphatic groups may be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Other zwitterionic surfactants suitable for use herein include betaines, including higher alkyl betaines such as coco dimethyl carboxymethyl betaine, coco amidopropyl betaine, coco betaine, lauramidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl di- (2-hydroxyethyl) carboxymethyl betaine, stearyl di- (2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl di- (2-hydroxypropyl) alpha-carboxyethyl betaine, and mixtures thereof. The sulfobetaines may include coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl di- (2-hydroxyethyl) sulfopropyl betaine, and mixtures thereof. Other suitable amphoteric surfactants include amidobetaines and amidosulfobetaines, where RCONH (CH ₂ ) ₃ A group wherein R is C ₁₁ -C ₁₇ An alkyl group attached to the nitrogen atom of betaine.

Nonionic cosurfactants suitable for use in the composition to increase the volume or texture of the foam include water-soluble materials such as lauryl dimethyl amine oxide, coco amidopropyl amine oxide, lauramidopropyl amine oxide, and the like, or alkyl polyethoxylates such as lauryl polyoxyethylene ether-4 to lauryl polyoxyethylene ether-7, and water-insoluble components such as coco monoethanolamide, coco diethanolamide, lauroyl monoethanolamide, alkanoyl isopropanolamides, and fatty alcohols such as cetyl alcohol and oleyl alcohol, and 2-hydroxyalkyl methyl ether, and the like.

Materials also suitable for use as cosurfactants herein include 1, 2-alkyl epoxides, 1, 2-alkanediols, branched or straight chain alkyl glyceryl ethers (such as those disclosed in EP 1696023A 1), 1, 2-alkyl cyclic carbonates and 1, 2-alkanesThe cyclic sulfites, especially those in which the alkyl group contains from 6 to 14 carbon atoms in a straight or branched configuration. Other examples include those derived from C ₁₀ Or C ₁₂ Alkyl ether alcohols in which an alpha olefin is reacted with ethylene glycol (e.g., hydroxyethyl-2-decyl ether, hydroxyethyl-2-dodecyl ether) can be prepared, for example, according to U.S.5,741,948, U.S.5,994,595, U.S.6,346,509, and U.S.6,417,408.

Other nonionic surfactants may be selected from the group consisting of glucamides, alkyl polyglucosides, sucrose cocoates, sucrose laurates, alkanolamides, ethoxylated alcohols, and mixtures thereof. The nonionic surfactant is selected from: glycerol monostearate, isostearyl polyoxyethylene ether-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glycerol laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, and mixtures thereof.

The cosurfactant may be selected from coco monoethanolamide, cocoamidopropyl betaine, lauramidopropyl betaine, coco betaine, lauryl amine oxide, sodium lauryl amphoacetate; alkyl glyceryl ethers, alkyl diglycidyl 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 from 6 to 14 carbon atoms in a linear or branched configuration; 1, 2-alkanediol (wherein the total carbon number is from 6 to 14 linear or branched carbon atoms), methyl-2-hydroxydecyl ether, hydroxyethyl-2-dodecyl ether, hydroxyethyl-2-decyl ether, and mixtures thereof.

The cationic surfactant may be derived from amines that are protonated at the pH of the formulation, such as dihydroxyethyl laurylamine, lauryl dimethylamine, lauroyl dimethylamido propylamine, cocoamido propylamine, and the like. Cationic surfactants may also be derived from aliphatic quaternary ammonium salts such as lauryl trimethyl ammonium chloride and lauramidopropyl trimethyl ammonium chloride.

Alkyl amphoacetates are suitable surfactants for use in the compositions herein for improved product mildness and foam. The most commonly used alkyl amphoacetates are lauroyl amphoacetate and cocoyl amphoacetate. Alkyl amphoacetates can be composed of monoacetate and diacetate. In some types of alkyl amphoacetates, the diacetate is an impurity or an unintended reaction product. However, when present in an amount exceeding 15% of the alkylamphoacetate, the presence of diacetate can result in a variety of undesirable composition characteristics.

Suitable nonionic surfactants for use herein are those selected from the group consisting of: glucamide, alkyl polyglucoside, sucrose cocoate, sucrose laurate, alkanolamide, ethoxylated alcohols, and mixtures thereof. In one embodiment, the nonionic surfactant is selected from the group consisting of: glycerol monostearate, isostearyl polyoxyethylene ether-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glycerol laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, and mixtures thereof.

The composition, if present, may comprise a rheology modifier, wherein the rheology modifier comprises a rheology modifier of cellulose, a crosslinked acrylate, a crosslinked maleic anhydride copolymerized methyl vinyl ether, a hydrophobically modified associative polymer, or a mixture thereof.

If used, the electrolyte itself may be added to the composition or it may be formed in situ via a counter ion contained in one of the raw materials. The electrolyte may comprise anions including phosphates, chlorides, sulphates or citrates, and cations including sodium, ammonium, potassium, magnesium or mixtures thereof. The electrolyte may be sodium chloride, ammonium chloride, sodium sulfate or ammonium sulfate. The electrolyte may be added to the composition in an amount of about 0.1 wt% to about 15 wt%, alternatively about 1 wt% to about 6 wt%, and alternatively about 3 wt% to about 6 wt%, by weight of the composition.

Structuring agent

The cleansing phase may comprise a structurant (e.g., crosslinked polyacrylate,Aqua SF-1 polymer, obtainable from +.>Obtained), which can provide high, low shear viscosity and yield stress to maintain stable discrete product phases in the shampoo composition over time, including shipping, handling, distribution, and storage at a store, warehouse, or consumer home shelf. The cleansing phase may comprise a structuring agent at a concentration effective to suspend the benefit phase in the cleansing phase and/or effective to alter the viscosity of the composition. Such concentrations may 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 cleaning phase. However, it is understood that certain glyceride crystals may be used as suitable structuring or suspending agents.

Suitable structurants may include anionic polymers and nonionic polymers. Useful herein are vinyl polymers such as crosslinked acrylic polymers under CTFA name carbomers; cellulose derivatives and modified cellulose polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethyl cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, acacia gum, tragacanth gum, galactan, carob bean gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (Cydonia oblonga Mill)), starch (rice, corn, potato, wheat), seaweed gum (algal extract); microbial polymers such as dextran, succinoglucan, pullulan; starch-based polymers such as carboxymethyl starch, methyl hydroxypropyl starch; alginic acid-based polymers such as sodium alginate, propylene glycol alginate; acrylate polymers such as sodium polyacrylate, ethyl polyacrylate, polyacrylamide, polyethylenimine; and inorganic water-soluble materials such as bentonite, magnesium aluminum silicate, laponite, hectorite, and anhydrous silicic acid.

Other suitable structuring agents may include crystalline structuring agents, which may be classified as acyl derivatives, long chain amine oxides, and mixtures thereof. Examples of such structuring agents are described in U.S. Pat. No. 4,741,855, incorporated herein by reference. Suitable structurants include ethylene glycol esters of fatty acids having from 16 to 22 carbon atoms. The structuring agent may be ethylene glycol stearate (mono-and distearate), but is especially distearate comprising less than about 7% of mono-stearate. 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 stearoyl monoethanolamide, stearoyl diethanolamide, stearoyl monoisopropanolamide, and stearoyl monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., octadecyl stearate, cetyl palmitate, etc.); long chain esters of long chain alkanolamides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate); and glycerides as described previously. 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 structuring agents.

Other long chain acyl derivatives suitable for use as structuring agents include N, N-dihydrocarbylaminobenzoic acid and water soluble salts thereof (e.g., na, K), especially N, N-di (hydrogenated) C in this class ₁₆ 、C ₁₈ And tallow amidobenzoic acids, which are commercially available from Stepan Company (Northfield, ill., USA).

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

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

Other suitable structuring agents include crystallizable glycerides. For example, suitable glycerides are hydrogenated castor oil, such as trihydroxystearin or dihydroxystearin. Examples of additional 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 will be appreciated that many additional glycerides are possible. For example, variations in the hydrogenation process and natural variations in castor oil may enable the production of additional suitable glycerides from castor oil.

Viscosity modifier

Viscosity modifiers may optionally be used to alter the rheological properties 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; acrylic ester/stearyl polyoxyethylene ether-20 methacrylate copolymer, commercially available from Rohm and Hass under the trade name ACRYSOL 22; nonoxyhydroxyethyl cellulose, commercially available from Amerchol under the trade designation AMERCELL POLYMER HM-1500; methylcellulose under the trade name BENECEL, hydroxyethyl cellulose under the trade name NATROSOL, hydroxypropyl cellulose under the trade name KLUCEL, cetyl hydroxyethyl cellulose under the trade name POLYSURF 67, all supplied by Hercules; ethylene oxide and/or propylene oxide based polymers, commercially available under the names CARBOWAX PEG, POLYOX WASR and UCON FLUIDS, all of which are supplied by 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.

Benefit phase

The optional benefit phase may comprise a gel network, which may contain one or more fatty alcohols. Gel networks can provide conditioning benefits. As used herein, the term "gel network" refers to a layered or porous solid crystalline phase comprising at least one fatty alcohol, at least one second surfactant and/or fatty acid, as described in detail below, and water and/or other suitable solvents. The layered or porous phase comprises a bilayer consisting of alternating first layers comprising fatty alcohols and/or fatty acids and second surfactants and/or fatty acids and second layers comprising water or other suitable solvents. In another example, the gel network may comprise at least one fatty acid, at least one secondary surfactant, and water and/or other suitable solvents. As used herein, the term "solid crystalline" refers to a structure of a lamellar or porous phase that forms at a temperature below the melt transition temperature of the layers in a gel network that comprises one or more fatty alcohols. Additional examples of multi-phase shampoo compositions having a suspended benefit phase are described in U.S. application Ser. No. 17/174,713, which is hereby incorporated by reference.

The multi-phase shampoo composition may comprise a benefit phase present in the following amounts by weight of the shampoo composition: 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%. 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 may be prepared as a separate pre-mix that mixes with the cleansing phase as a visually discrete phase after cooling. The preparation of the gel network component is discussed in more detail below and in the examples.

The cooled and preformed gel network component is then added to the shampoo composition's components therein, 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 such that a well-balanced lamellar dispersion ("ELD") is formed in the final shampoo composition. ELD is a dispersed lamellar or porous phase that results from the preformed gel network component being sufficiently balanced with detersive surfactant, water, and other optional components such as salts that may be present in the shampoo composition. This equilibration occurs 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. Wherein the shampoo composition forming ELD provides improved wet and dry conditioning benefits to hair.

For purposes of illustration, the term "ELD" as used herein refers to the same component of the shampoo compositions of the invention as the phrase "gel network phase".

The gel network is present in the premix and final shampoo compositions in the form of ELD and 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) can be in the range of about 10nm 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 scale size distribution of the gel network phase in the shampoo composition can be measured using a Horiba type LA 910 laser scattering particle size distribution analyzer (Horiba Instruments, inc. The scale size distribution in the shampoo compositions of the invention can be achieved by combining 1.75g of the shampoo composition with 30mL of 3% NH ₄ Cl, 20mL of 2% Na ₂ HPO ₄ · ₂ 7HOAnd 10mL of 1% lauryl polyoxyethylene ether-7 to form a mixture. The mixture is then stirred5 minutes. For the individual Horiba instrument used, a sample in the range of 1mL to 40mL was measured and then injected into the Horiba instrument, which contained 75mL of 3% NH ₄ Cl, 50mL of 2% Na ₂ HPO ₄ · ₂ 7HOAnd 25mL of 1% lauryl polyoxyethylene ether-7, until the Horiba instrument reads 88% T to 92% T required for scale size measurement. Once this value is obtained, the measurement is performed after 2 minutes of cycling through the Horiba instrument to provide a scale size measurement. Subsequent measurements were made using samples of the shampoo composition that were heated above the melting transition temperature of all fatty substances present in the shampoo composition, causing the gel network component to melt. This subsequent measurement allows for a scaled size distribution of all remaining materials in the shampoo to be made, which can then be compared to the scaled size distribution of the original sample and taken into analysis.

Fatty alcohols

The gel network component of the present invention may comprise 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, behenyl alcohol, C21 fatty alcohol (1-di-undecyl alcohol), C23 fatty alcohol (1-di-tridecyl alcohol), C24 fatty alcohol (tetracosyl alcohol, 1-di-tetradecyl alcohol), C26 fatty alcohol (1-hexacosyl alcohol), C28 fatty alcohol (1-octacosyl alcohol), C30 fatty alcohol (1-triacontanol), C20-40 alcohol (e.g., performacol 350 and 425 alcohol, available from New Phase Technologies), C30-50 alcohol (e.g., performacol 550 alcohol), C40-60 alcohol (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 comprise some amount of one or more fatty alcohols, or other aliphatic 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 melt transition temperature of at least about 25 ℃, alternatively at least about 28 ℃, alternatively at least about 31 ℃, alternatively at least about 34 ℃, and alternatively at least about 37 ℃.

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

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

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

A second surfactant

The gel network component of the present invention may also comprise a second surfactant. As used herein, "secondary surfactant" refers to one or more surfactants that are mixed with fatty alcohols and water to form the gel network of the present invention, separated as a premix from the other components of the shampoo composition. 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 may be the same or a 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 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, of a second surfactant as part of the preformed gel network phase.

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

In addition, certain secondary surfactants have hydrophobic tail groups with chain lengths of from about 16 to about 22 carbon atoms. For such secondary surfactants, the hydrophobic tail group may be an alkyl, alkenyl (containing up to 3 double bonds), alkylaromatic, or branched alkyl group. The second surfactant may be present in the gel network component in 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, foaming well. SLE1S can also provide enhanced lather and cleansing in shampoo compositions with high levels of conditioning actives.

Mixtures of more than one of the specified types of surfactants may be used as the secondary surfactant of the present invention.

Examples of gel network premixes can be found in U.S. patent 8,361,448 and U.S. publication 2017/0367955, which are hereby incorporated by reference.

Fatty acid

Non-limiting examples of suitable fatty acids that may be mixed with the fatty alcohol or the secondary surfactant to form a gel network may include unsaturated and/or branched long chains (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 may include short chain saturated fatty acids such as capric acid and caprylic acid. Without wishing 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, serves to "disrupt" the surfactant hydrophobic chain and induce the formation of lamellar phases. Examples of suitable liquid fatty acids may include oleic acid, isostearic acidLinoleic acid, linolenic acid, ricinoleic acid, elaidic acid, arachidonic acid, myristoleic acid, palmitoleic acid, and mixtures thereof. Examples of suitable ester derivatives may include propylene glycol isostearate, propylene glycol oleate, glyceryl isostearate, glyceryl oleate, polyglyceryl diisostearate, and mixtures thereof. Examples of the alcohol may include oleyl alcohol and isostearyl alcohol. Examples of the ether derivative may include isostearyl polyoxyethylene ether or oleyl polyoxyethylene ether carboxylic acid; or isostearyl polyoxyethylene ether or oleyl polyoxyethylene ether alcohol. Structuring agent may be defined as having a melting point of less than about 25 ℃.

Cationic deposition polymers

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

The shampoo composition may comprise a cationic polymer to allow coacervate formation. 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) a cationic guar polymer, (b) a cationic non-guar galactomannan polymer, (c) a cationic starch polymer, (d) a cationic copolymer of an acrylamide monomer and a cationic monomer, (e) a synthetic non-crosslinked cationic polymer that may or may not form lyotropic liquid crystals upon mixing with a detersive surfactant, (f) a cationic synthetic homopolymer, (g) a cationic cellulose polymer, and (h) combinations thereof. In certain 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 can have a cationic charge density of about 0.9meq/g or greater, about 1.2meq/g or greater, and about 1.5meq/g or greater. However, the cationic charge density may also be about 7meq/g or less, and alternatively about 5meq/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. The low molecular weight cationic polymer may have a higher translucency in the liquid carrier of the shampoo composition. The cationic polymer may be of a single type, such as the cationic guar polymer guar hydroxypropyl trimonium chloride having a weight average molecular weight of about 2,500,000g/mol or less, and the shampoo compositions may have the same or different types of additional cationic polymers.

Cationic guar polymers

The cationic polymer may be a cationic guar polymer which is a cationically substituted galactomannan (guar) gum derivative. Suitable guar for guar derivatives can be obtained in the form of naturally occurring materials from guar plant seeds. As can be appreciated, guar gum molecules are linear mannans branched at regular intervals with single galactose units on alternating mannose units. Mannose units are linked to each other via a β (1-4) glycosidic linkage. Galactose branching occurs via the alpha (1-6) linkage. Cationic derivatives of guar gum can be obtained by reaction between the hydroxyl groups of polygalactomannans and reactive quaternary ammonium compounds. The degree of substitution of the cationic groups onto the guar structure may be sufficient to provide the desired cationic charge density described above.

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

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

The shampoo composition can comprise 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.

The cationic guar polymer can be formed from a quaternary ammonium compound according to formula II:

wherein R is ³ 、R ⁴ And R is ⁵ Is a methyl or ethyl group; and R is ⁶ Is an alkylene oxide group having the general formula III:

or R is ⁶ Is a halohydrin group having the general formula IV:

wherein R is ⁷ Is C ₁ To C ₃ An 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 correspond to formula V:

wherein R is ⁸ Is guar gum; and wherein R is ⁴ 、R ⁵ 、R ⁶ And R is ⁷ As defined above; and wherein Z is halogen. Suitable cationic guar polymers may correspond to formula VI:

wherein R is ⁸ Is guar gum.

Suitable cationic guar polymers may also include cationic guar derivatives such as guar hydroxypropyl trimethylammonium chloride. Suitable examples of guar hydroxypropyl trimethylammonium chloride can include those commercially available from SolvaySASeries, hi-Care series from Rhodia and N-Hance and AquaCat from Ashland Inc.C-500 has a charge density of 0.8meq/g and 500,000g/mol m.wt.; jaguar Optima has a cationic charge density of about 1.25meg/g and an M.Wt. of about 500,000 g/mol;C-17 has a cationic charge density of about 0.6meq/g and an M.Wt. of about 2,200,000 g/mol; / >Having a cationic charge density of about 0.8 meq/g; hi-Care 1000 has a charge density of about 0.7meq/g and an M.Wt. of about 600,000 g/mol; N-Hance 3269 and N-Hance 3270 have a charge density of about 0.7meq/g and an M.Wt. of about 425,000 g/mole; N-Hance 3196 has a charge density of about 0.8meq/g and an M.Wt. of about 1,100,000 g/mol; and AquaCat CG518 has a charge density of about 0.9meq/g and an m.wt. of about 50,000 g/mol. N-Hance BF-13 and N-Hance BF-17 are guar polymers that are free of borates (boron). N-Hance BF-13 has a charge density of about 1.1meq/g and an M.W.t of about 800,000, and N-Hance BF-17 has a charge density of about 1.7meq/g and an M.W.t of about 800,000. BF-17 has a charge density of about 1.7meq/g and an M.W.t. of about 800,000. BF-17 has a charge density of about 1.7meq/g and an M.W.t. of about 800,000. BF-17 has a charge density of about 1.7meq/g and an M.W.t. of about 800,000. BF-17 has a charge density of about 1.7meq/g and an M.W.t. of about 800,000.

Cationic non-guar galactomannan polymers

The cationic polymer may be a galactomannan polymer derivative. Suitable galactomannan polymers may have a mannose to galactose ratio of greater than 2:1 on a monomer to monomer basis and may be cationic galactomannan polymer derivatives or amphoteric galactomannan polymer derivatives having a net positive charge. As used herein, the term "cationic galactomannan" refers to a galactomannan polymer to which cationic groups are added. The term "amphoteric galactomannan" refers to a galactomannan polymer to which cationic groups and anionic groups are added such that the polymer has a net positive charge.

The galactomannan polymer may be present in the endosperm of leguminous seeds. The galactomannan polymer is composed of a combination of mannose monomers and galactose monomers. The galactomannan molecules are linear mannans branched at regular intervals with a single galactose unit over a specific mannose unit. Mannose units are linked to each other via a β (1-4) glycosidic linkage. Galactose branching occurs via the alpha (1-6) linkage. The ratio of mannose monomers to galactose monomers varies depending on the variety of plants and can be affected by the climate. The non-guar galactomannan polymer derivative may have a mannose to galactose ratio of 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 mannose to galactose ratios is well known in the art and is generally based on measurement of galactose content.

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

The non-guar galactomannan polymer derivative can have an m.wt. of about 1,000g/mol to about 10,000,000g/mol and an m.wt. of about 5,000g/mol to about 3,000,000 g/mol.

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

The galactomannan polymer derivative may be a cationic derivative of a non-guar galactomannan polymer, the cationic derivative being obtained from the reaction between the hydroxyl groups of the polygalactomannan polymer and the reactive quaternary ammonium compound. Suitable quaternary ammonium compounds for forming the cationic galactomannan polymer derivative include compounds according to formulas II through VI as defined above.

The cationic non-guar galactomannan polymer derivative formed from the reagents described above may be represented by formula VII:

wherein R is a gum. The cationic galactomannan derivative may be the gum hydroxypropyl trimethylammonium chloride, which may be more specifically represented by 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 can have a mannose to galactose ratio of greater than about 4:1, an m.wt. of about 100,000g/mol to about 500,000g/mol, an m.wt. of about 50,000g/mol to about 400,000g/mol, and a cationic charge density of about 1meq/g to about 5meq/g and about 2meq/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% of the galactomannan polymer derivative by weight of the composition.

Cationic starch polymers

Suitable cationic polymers may also be water-soluble cationic modified starch polymers. As used herein, the term "cationically modified starch" refers to a starch to which cationic groups are added before degrading the starch to have a smaller molecular weight, or to which cationic groups are added after modifying the starch to obtain the desired molecular weight. The definition of the term "cationically modified starch" also includes amphiprotic modified starches. The term "amphiphilically modified starch" refers to starch hydrolysates to which cationic 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 the cationically modified starch polymer.

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

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

The cationic modified starch polymer may have a charge density of from about 0.2meq/g to about 5meq/g, and from about 0.2meq/g to about 2 meq/g. Chemical modifications to achieve such charge densities may include adding amino and/or ammonium groups to the starch molecule. Non-limiting examples of such ammonium groups may include substituents such as hydroxypropyl trimethylammonium chloride, trimethylhydroxypropyl ammonium chloride, dimethyl stearyl hydroxypropyl ammonium chloride, and dimethyl dodecyl hydroxypropyl ammonium chloride. Additional details are described in Solarek, d.b., cationic Starches in Modified Starches: properties and Uses (Wurzburg, o.b. editions, CRC Press, inc., boca Raton, fla.1986, pages 113-125, which are incorporated herein by reference) cationic groups may be added to the starch before it is degraded to have a smaller molecular weight, or cationic groups may be added to the starch after such modification.

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. The substitution degree is expressed as moles of substituents per mole of anhydroglucose unit, on a molar average. Can enableBy proton nuclear magnetic resonance spectroscopy (known in the art) " ¹ H NMR ") method to determine the degree of substitution. Suitable for ¹ H NMR techniques include those described in "Observation on NMR Spectra of Starches in Dimethyl Sulfoxide, iodine-completing, 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 prior to chemical modification may be selected from a variety of sources such as tubers, legumes, cereals and grains. For example, the starch source may include corn starch, wheat starch, rice starch, waxy corn starch, oat starch, tapioca starch, waxy barley starch, waxy rice starch, gluten rice starch, waxy rice starch, amylopectin starch, potato starch, tapioca starch, oat starch, sago starch, sweet rice starch, or mixtures thereof. Suitable cationically modified starch polymers may be selected from the group consisting of degraded cationic corn starch, cationic tapioca, cationic potato starch, and mixtures thereof. The cationic modified starch polymer is cationic corn starch and cationic cassava.

The starch may include one or more additional modifications either before degradation to have a smaller molecular weight or after modification to have a smaller molecular weight. For example, these modifications may include crosslinking, stabilization reactions, phosphorylation, and hydrolysis. The stability reaction may include alkylation and esterification.

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

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

Cationic copolymers of acrylamide monomers and cationic monomers

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 1.0meq/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 is ⁹ Is H or C _1-4 An alkyl group; and R is ¹⁰ And R is ¹¹ 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 according to formula X:

wherein k=1, v' and v″ are each independently an integer from 1 to 6, w is zero or an integer from 1 to 10, and X ^- Is anionic.

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 may 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 ^- A structure for forming the following formula XII:

the structure of formula XII may be referred to as a tri-quaternary ammonium salt.

The acrylamide monomer may be acrylamide or methacrylamide.

The cationic copolymer may be AM, which is a copolymer of acrylamide and N- [2- [ [ [ dimethyl [3- [ (2-methyl-1-oxo-2-propenyl) amino ] propyl ] amino ] acetyl ] amino ] ethyl ] 2-hydroxy-N, N, N ', N ', N ' -pentamethyl-1, 3-propanediammonium trichloride. AM:TRIQUAT is also known as polyquaternium 76 (PQ 76). AM TRIQUAT may have a charge density of 1.6meq/g and an 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 the group consisting of: dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide; ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; trimethyl ammonium ethyl (meth) acrylate, trimethyl ammonium ethyl methyl sulfate (meth) acrylate, dimethyl benzyl ammonium ethyl chloride (meth) acrylate, 4-benzoyl benzyl dimethyl ammonium ethyl chloride, trimethyl ammonium ethyl (meth) acrylamide, trimethyl ammonium propyl (meth) acrylamide, vinyl benzyl trimethyl ammonium chloride, diallyl dimethyl ammonium chloride, and mixtures thereof.

The cationic copolymer may comprise a cationic monomer selected from the group consisting of: (meth) acryloyloxyethyl trimethyl ammonium chloride, (meth) acryloyloxyethyl trimethyl ammonium sulfate, (meth) acryloyloxyethyl benzyl dimethyl ammonium chloride, 4-benzoylbenzyl acryloyloxyethyl dimethyl ammonium chloride, (meth) acrylamidoethyl trimethyl ammonium chloride, (meth) acrylamidopropyl trimethyl ammonium chloride, vinylbenzyl trimethyl ammonium chloride, and mixtures thereof.

The cationic copolymer may be formed from: (1) Copolymers of (meth) acrylamide and (meth) acrylamide-based cationic monomers and/or hydrolytically stable cationic monomers, (2) terpolymers of (meth) acrylamide, cationic (meth) acrylate-based monomers, (meth) acrylamide-based monomers and/or hydrolytically stable cationic monomers. The cationic (meth) acrylate-based monomer may be a cationized ester of (meth) acrylic acid containing a quaternized N atom. The cationized esters of (meth) acrylic acid containing a quaternized N atom can be those having C in the alkyl and alkylene groups ₁ To C ₃ A quaternized dialkylaminoalkyl (meth) acrylate. The cationized esters of (meth) acrylic acid comprising a quaternized N atom may be selected from: ammonium salts of dimethylaminomethyl (meth) acrylate quaternized with methyl chloride, 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 comprising a quaternized N atom may be dimethylaminoethyl acrylate (ADAME-Quat) quaternized with haloalkane or with chloromethane or benzyl chloride or dimethyl sulfate. When based on (meth) acrylamide, the cationic monomer is one having C in the alkyl and alkylene groups ₁ To C ₃ Quaternized dialkylaminoalkyl (meth) acrylamides or dimethylaminopropyl acrylamides quaternized with haloalkanes or chloromethane or benzyl chloride or dimethyl sulfate.

The cationic (meth) acrylamide-based monomer may be one having C in the alkyl and alkylene groups ₁ To C ₃ Quaternized dialkylaminoalkyl (meth) acrylamides. Based on (methyl group) The cationic monomer of acrylamide may be dimethylaminopropyl acrylamide, quaternized with haloalkanes (especially methyl chloride) or benzyl chloride or dimethyl sulfate.

The cationic monomer may be a hydrolytically stable cationic monomer. In addition to dialkylaminoalkyl (meth) acrylamides, the hydrolytically stable cationic monomers can be any monomers that can be considered stable by the OECD hydrolysis test. The cationic monomer may be hydrolytically stable, and the hydrolytically stable cationic monomer may be selected from: diallyl dimethyl ammonium chloride and water-soluble cationic styrene derivatives.

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

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

The cationic copolymer can have an m.wt. of about 100,000 to about 2,000,000g/mol, about 300,000 to about 1,800,000g/mol, about 500,000 to about 1,600,000g/mol, about 700,000 to about 1,400,000g/mol, and about 900,000 to about 1,200,000 g/mol.

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

Synthetic polymers

The cationic polymer may be a synthetic polymer formed from:

i) One or more cationic monomer units, and optionally

ii) one or more monomer units bearing a negative charge, and/or

iii) A nonionic monomer which is capable of reacting with the nonionic monomer,

wherein the subsequent charge of the copolymer is positive. The ratio of the three types of monomers is given as "m", "p", and "q", where "m" is the number of cationic monomers, "p" is the number of monomers bearing 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 may 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 alkylaryl oxy; .

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

wherein r1= H, C1-C4 straight or branched alkyl;

wherein s=0 or 1, n=0 or more than or equal to 1;

wherein T and r7=c1-C22 alkyl; and is also provided with

Wherein X- = halogen, hydroxide, alkanol, sulfate or alkylsulfate.

Wherein the negatively charged monomer is defined by: r2' = H, C ₁ To C ₄ Linear or branched alkyl, and R3 is:

wherein d= O, N or S;

wherein q=nh ₂ Or O;

wherein u=1 to 6;

wherein t=0 to 1; and is also provided with

Where j=an oxidizing functional group containing the following element P, S, C.

Wherein the nonionic monomer is defined by: r2 "= H, C ₁ To C ₄ Straight-chain or branched alkyl, r6=straight-chain or branched alkyl, alkylaryl, aryloxy, alkoxy, alkylaryl oxy, and β is defined as

And is also provided with

Wherein G' and G "are O, S or N-H independently of each other, and l=0 or 1.

Suitable monomers may include aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides; monomers comprising at least one secondary, tertiary or quaternary ammonium function, or a heterocyclic group containing a nitrogen atom, vinylamine or ethyleneimine; diallyl dialkyl ammonium salts; mixtures thereof, salts thereof and macromers derived therefrom.

Further examples of suitable cationic monomers may include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine, (meth) acryloyloxyethyl trimethylammonium chloride, (meth) acryloyloxyethyl trimethylammonium sulfate, (meth) acryloyloxyethyl benzyl dimethylammonium chloride, 4-benzoylbenzyl acryloyloxyethyl dimethylammonium chloride, (meth) acrylamidoethyl trimethylammonium propyl chloride, diallyldimethylammonium chloride.

Suitable cationic monomers may include those 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 optionally bearing a hydroxyl group and containing an anion (counter ion). Examples of suitable anions include halides (such as chloride, bromide), sulfate, bisulfate, alkylsulfate (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 sulfate, (meth) acryloyloxyethyl benzyl dimethyl ammonium chloride, 4-benzoylbenzyl acryloyloxyethyl dimethyl ammonium chloride, (meth) acrylamidoethyl trimethyl ammonium chloride, (meth) acrylamidopropyl trimethyl ammonium chloride, vinylbenzyl trimethyl ammonium chloride. Additional suitable cationic monomers may include (meth) acrylamidopropyl trimethylammonium chloride.

Examples of the negatively charged monomer include an α -ethylenically unsaturated monomer containing a phosphate group or a phosphonate group, an α -ethylenically unsaturated monocarboxylic acid, a monoalkyl ester of an α -ethylenically unsaturated dicarboxylic acid, a monoalkylamide of an α -ethylenically unsaturated dicarboxylic acid, an α -ethylenically unsaturated compound containing a sulfonate group, and a salt of an α -ethylenically unsaturated compound containing a sulfonate group.

Suitable monomers having a negative charge may include acrylic acid, methacrylic acid, vinylsulfonic acid, salts of vinylsulfonic acid, vinylbenzenesulfonic acid, salts of vinylbenzenesulfonic acid, alpha-acrylamidomethylpropane sulfonic acid, salts of alpha-acrylamidomethylpropane sulfonic acid, 2-sulfoethyl methacrylate, salts of 2-sulfoethyl methacrylate, acrylamido-2-methylpropane sulfonic Acid (AMPS), salts of acrylamido-2-methylpropane sulfonic acid, and Styrene Sulfonate (SS).

Examples of nonionic monomers may include vinyl acetate, amides of alpha-ethylenically unsaturated carboxylic acids, esters of alpha-ethylenically unsaturated monocarboxylic acids with hydrogenated or fluorinated alcohols, polyethylene oxide (meth) acrylates (i.e., polyethoxylated (meth) acrylic acid), monoalkyl esters of alpha-ethylenically unsaturated dicarboxylic acids, monoalkyl amides of alpha-ethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinyl amine amides, vinyl alcohols, vinyl pyrrolidinone, and vinyl aromatics.

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.

Anionic counterions associated with the synthetic cationic polymers (X ^- ) Any known counterion can be used as long as the polymer remains dissolved or dispersed in the water, in the shampoo composition, or in the coacervate phase in the shampoo composition, and as 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 counter ions may include halide (e.g., chloride, fluoride, bromide, iodide), sulfate, and methosulfate.

The cationic polymers described herein may also help repair damaged hair, particularly chemically treated hair, by providing an alternative hydrophobic F-layer. The extremely thin F-layer helps to seal moisture and prevent further damage while providing natural weatherability. Chemical treatments can damage the hair cuticle and cause its protective F-layer to delaminate. When the F-layer is peeled off, 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 look 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 fibers and protects the hair as does the natural F-layer. The hydrophobic layer may restore the hair to a substantially 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 compositions. Synthetic cationic polymers have a relatively high charge density. It should be noted that some synthetic polymers having relatively high cationic charge densities do not form lyotropic liquid crystals, mainly due to their unusual linear charge density. Such synthetic cationic polymers are described in PCT patent application WO 94/06403, the disclosure of which is incorporated by reference. The synthetic polymers described herein may be formulated in stable shampoo compositions that provide improved conditioning performance for damaged hair.

The lyotropic liquid crystalline cationic synthetic polymer has a cationic charge density of about 2meq/gm to about 7meq/gm, and/or about 3meq/gm to about 7meq/gm, and/or about 4meq/gm to about 7 meq/gm. The cationic charge density was about 6.2meq/gm. The polymer also has 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 the need to form lyotropic liquid crystals can have cationic charge densities of about 0.7meq/gm to about 7meq/gm, and/or about 0.8meq/gm to about 5meq/gm, and/or about 1.0meq/gm to about 3 meq/gm. The polymer also has an m.wt. of about 1,000 to about 5,000,000g/mol, about 10,000 to about 2,000,000g/mol, and about 100,000a to about 2,000,000 g/mol.

Cationic cellulose polymers

Suitable cationic polymers may be cellulosic polymers. Suitable cellulose polymers may include salts of hydroxyethyl cellulose reacted with trimethylammonium substituted epoxides, which salts are known in the industry (CTFA) as polyquaternium 10 and are available as Polymer LR, JR and KG Polymer series from Dwo/Amerchol corp. (Edison, n.j., USA). Other suitable types of cationic celluloses may include polymeric quaternary ammonium salts resulting from the reaction of hydroxyethyl cellulose with lauryl dimethyl ammonium-substituted epoxide, which is known in the industry (CTFA) as polyquaternary ammonium salt 24. These materials are available under the trade name Polymer LM-200 from Dow/Amerchol Corp. Other suitable types of cationic celluloses may include polymeric quaternary ammonium salts resulting from the reaction of hydroxyethyl cellulose with lauryl dimethyl ammonium-substituted epoxide and trimethyl ammonium-substituted epoxide, which are known in the industry (CTFA) as polyquaternary ammonium salts 67. These materials are available from Dow/Amerchol Corp under the trade names SoftCAT Polymer SL-5, softCAT Polymer SL-30, polymer SL-60, polymer SL-100, polymer SK-L, polymer SK-M, polymer SK-MH, and Polymer SK-H.

Additional cationic polymers are also described in CTFA Cosmetic Ingredient Dictionary, 3 rd edition, edited by Estrin, crosley and Haynes, (The Cosmetic, toolry, and Fragrance Association, inc., washington, d.c. (1982)), 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 stage of dilution. Such coacervate phases may be identified as additional emulsified phases in the composition. The use of dyes can help distinguish the coacervate phase from other insoluble phases dispersed in the composition. Additional details regarding the use of cationic polymers and coacervates are disclosed in U.S. patent No. 9,272,164, which is incorporated by reference.

Silicone

The shampoo composition may comprise a silicone conditioning agent. The silicone conditioning agent may be in the benefit phase and/or the cleansing phase. Suitable silicone conditioning agents can include volatile silicones, nonvolatile silicones, or combinations thereof. If included, the silicone conditioning agent may be included in an amount of from about 0.01% to about 10% by weight of the composition, from about 0.1% to about 8% by weight of the cleansing phase, benefit phase, or composition, from about 0.1% to about 5%, and/or from about 0.2% to about 2%. Examples of suitable silicone conditioning agents and optional suspending agents for the silicone are described in U.S. reissue patent No. 34,584, U.S. patent No. 5,104,646, and U.S. patent No. 5,106,609, each of which is incorporated herein by reference. Suitable silicone conditioning agents may have viscosities of from about 20 centistokes ("csk") to about 2,000,000csk, from about 1,000,000 csk to about 1,800,000csk, from about 50,000csk to about 1,500,000csk, and from about 100,000csk to about 1,500,000csk, as measured at 25 ℃.

The dispersed silicone conditioning agent particles can have a volume average particle size in the range of about 0.01 microns to about 50 microns. For small particles applied to 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 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 materials regarding silicones including the section on silicone fluids, silicone gums, and silicone resins, and silicone preparations, can be found in "Encyclopedia of Polymer Science and Engineering", volume 15, 2 nd edition, pages 204-308, john Wiley & Sons, inc. (1989), incorporated herein by reference.

Silicone emulsions suitable for use in the shampoo compositions described herein may include insoluble silicone emulsions prepared according to the description provided in U.S. patent 4,476,282 and U.S. patent application publication 2007/0276087, each of which is incorporated herein by reference. Suitable insoluble polysiloxanes include polysiloxanes having a molecular weight in the range of about 50,000g/mol to about 500,000g/mol, such as alpha, omega-hydroxy-terminated polysiloxanes or alpha, omega-alkoxy-terminated polysiloxanes. The insoluble polysiloxane can have an average molecular weight in the range of about 50,000 to about 500,000 g/mol. For example, the insoluble polysiloxane can 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 150,000g/mol. The insoluble polysiloxane can have an average particle size in the range of about 30nm to about 10 microns. The average particle size may be in the range of, for example, about 40nm to about 5 microns, about 50nm to about 1 micron, about 75nm to about 500nm, or about 100 nm.

Other classes 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 1,000,000csk measured at 25 ℃; ii) an aminosilicone comprising at least one primary, secondary or tertiary amine; iii) A cationic silicone comprising at least one quaternary ammonium functional group; iv) a silicone gum; the silicone gums include a material having a viscosity greater than or equal to 1,000,000csk measured at 25 ℃; v) a silicone resin comprising a highly crosslinked polymeric siloxane system; vi) a high refractive index silicone having 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 can 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 a minimal or insignificant concentration of the organic solvent, except for those that are additionally incorporated into the composition as minor ingredients of other components.

Aqueous carriers useful in shampoo compositions may comprise water. In another example, the shampoo composition can comprise an aqueous solution of a lower alkyl alcohol and a polyol. The lower alkyl alcohols may include monohydric alcohols having 1 to 6 carbons, in one aspect, ethanol and isopropanol. The polyols may include propylene glycol, dipropylene glycol, hexylene glycol, glycerin, and propane diol.

Optional Components

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

Suitable optional components that may be included in the shampoo composition 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), pearlizing aids, suds boosters, biocides, pH modifiers, perfumes, preservatives, chelants, proteins, skin actives, sunscreens, uv absorbers, and vitamins. A wide variety of non-limiting materials that may be incorporated into the compositions herein are described in tenth edition of CTFA Cosmetic Ingredient Handbook (published by Cosmetic, toiletry and Fragrance Association, washington) (2004) (hereinafter "CTFA").

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

Organic conditioning material

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 silicones described above. 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 pure or pre-emulsified form. Suitable examples of organic conditioning materials may include: i) A hydrocarbon oil; ii) a polyolefin; iii) A fatty ester; 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 designation PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M, and mixtures thereof.

Emulsifying agent

A variety of anionic and nonionic emulsifiers are useful 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 derivatives thereof. By way of illustration and not limitation, examples of polymers include polyacrylates, polyethylene glycol and block copolymers, and derivatives thereof. Naturally occurring emulsifiers such as lanolin, lecithin, and lignin, and their derivatives are also non-limiting examples of useful emulsifiers.

Chelating agent

The chelants may be used in shampoo compositions comprising a benefit phase and/or a cleansing phase. Suitable chelators include those listed in volume Critical Stability Constants of A E Martell & R M Smith (Plenum Press, new York & London (1974)) and Metal Complexes in Aqueous Solution of A E Martell & R D Hancock (Plenum Press, new York & London (1996)), both of which are incorporated herein by reference. When referring to chelators, the term "salts and derivatives thereof" refers to salts and derivatives having the same functional structure (e.g., the same chemical backbone) as the chelators to which they relate, as well as having similar or better chelation characteristics. The term includes alkali metal salts, alkaline earth metal salts, ammonium salts, substituted ammonium (i.e., monoethanolamine, diethanolamine, triethanolamine) salts, esters, and mixtures thereof, particularly all sodium, potassium, or ammonium salts, of chelating agents having an acidic moiety. The term "derivative" also includes "chelating surfactant" compounds such as those exemplified in U.S. patent No. 5,284,972, as well as macromolecules comprising 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. patent No. 5,747,440. U.S. patent 5,284,972 and U.S. patent 5,747,440 are each incorporated herein by reference. Suitable chelating agents may also include histidine.

The level of EDDS chelator or histidine chelator in the shampoo composition may be low. For example, about 0.01% by weight of EDDS chelator or histidine chelator may be included. Above about 10% by weight, formulation and/or human safety issues may arise. The EDDS chelator or histidine chelator may be present in an amount of at least about 0.01 wt%, at least about 0.05 wt%, at least about 0.1 wt%, at least about 0.25 wt%, at least about 0.5 wt%, at least about 1 wt%, or at least about 2 wt% by weight of the shampoo composition.

Additional cosmetic material

The shampoo composition may further comprise one or more additional cosmetic materials. Exemplary additional cosmetic materials may include, but are not limited to, particles, colorants, perfume microcapsules, gel networks, and other insoluble skin or hair conditioning agents such as skin silicones, natural oils such as sunflower oil or castor oil. The additional cosmetic material may be selected from: particles; a colorant; a perfume microcapsule; a gel network; 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

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

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

Test method

Hair wet friction measurement (final rinse friction and initial rinse friction)

Measurements were made using 4 gram hair clusters of the general population that were 8 inches long. The water temperature was set at 100°f, the hardness was 7 grains per gallon, and the flow rate was 1.6 liters per minute. For liquid form shampoos, 0.2ml of liquid shampoo is applied uniformly over the hair clusters in a zigzag pattern to cover the entire hair length using a syringe. For shampoo in aerosol foam form, the foam shampoo is dispensed onto the weighing pan of the balance. 0.2 grams of foam shampoo was removed from the weigh pan and applied evenly to the hair switches by a spatula to cover the entire hair length. The hair switches were then foamed 1 st time for 30 seconds, rinsed with water for 30 seconds, and foamed 2 nd time for 30 seconds. The water flow rate was then reduced to 0.2 liters per minute. The hair cluster was clamped under 1800 grams force using a clamp and pulled through the entire length while the water was running at a low flow rate. The pull time was 30 seconds. Friction was measured using a friction analyzer with a 5kg load cell. The pulling was repeated a total of 21 times under flushing. A total of 21 friction values were collected. The final rinse friction is the average friction of the last 7 points and the initial rinse friction is the average friction of the first 7 points. The Δfinal to initial is calculated by subtracting the final rinse friction from the initial rinse friction.

Light transmittance

The% T may be determined using an ultraviolet/visible (UV/VI) spectrophotometer that determines the transmittance of UV/VIs light through the sample. It has been demonstrated that a wavelength of light of 600nm is sufficient to characterize the light transmission through the sample. In general, it is desirable to follow specific instructions regarding the particular spectrophotometer being used. Typically, the procedure for measuring the percent transmission starts with setting the spectrophotometer to 600 nm. Then, a calibration "blank" is run, calibrating the reading of the indication to 100% transmittance. The individual test samples were then placed in cuvettes designed to fit the particular spectrophotometer, and care was taken to ensure that there were no bubbles within the samples before the spectrophotometer measured% T with the spectrophotometer at 600 nm.

Examples

The shampoo compositions illustrated in the following examples illustrate specific embodiments of the shampoo compositions of the invention, but are not intended to be limiting thereof. It will be appreciated 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 invention. Unless otherwise indicated, all exemplary amounts are listed in weight percent and are in addition to trace materials such as diluents, preservatives, colored solutions, fictitious ingredients, botanicals, and the like. All percentages are by weight unless otherwise indicated.

Shampoo compositions exemplified in the examples below can be prepared by conventional formulation methods and mixing methods. The bubbles are introduced into the cleansing phase by aeration techniques. The gel network benefit phase was prepared as follows. The water is heated to about 74 ℃, and an aliphatic compound and a secondary surfactant (e.g., sodium laureth sulfate) are added to the water. After addition, the mixture is passed through a mill and then cooled (e.g., via a heat exchanger) to about 32 ℃. As a result of this cooling step, the fatty alcohol, the second surfactant and water form a crystalline gel network.

The multi-phase shampoo composition may be prepared by using a piston filling machine that can accommodate two or more separate product streams during filling. The separate streams may create an aesthetic design in the final shampoo composition. During filling, special care is taken to minimize entrainment of air into the clean phase during filling into the bottles or other suitable primary packages. In some examples, the bottle may be overfilled using only the cleaning phase, thereby ensuring that any remaining headspace will be displaced/purged from the bottle during pump insertion. In some cases, the bottle is capped with a pump that is carefully placed to minimize shifting of the aesthetic design during filling.

Examples a-L in tables 1 and 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, wherein n is more than or equal to 1 and less than or equal to 3

(2、)

( 3) Cationic galactomannans (having a molecular weight of-200,000; charge density=3.0 meq/g )

( 4) Cationic galactomannans (having a molecular weight of-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 KG 30M%Chemical Company) having a charge density of 1.97meq/gm and a molecular weight of 2,000,000

(9)100S

(10)DM 5500E(WACKER)

(11)Dow1872(DowCorporation)

(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, wherein n is more than or equal to 1 and less than or equal to 3

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

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

(4) Polymer KG 30M%Chemical Company), whichA charge density of 1.97meq/gm and a molecular weight of 2,000,000

(5)100S

(6)CF330m(Momentive ^TM Performance Materials)

(7)DM 5500E(WACKER)

(8)Dow1872(DowCorporation)

(9)Kathon ^TM CG

The examples in table 4 below are examples of multiphase 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: multiphase shampoo compositions

Combination of two or more kinds of materials

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

a. A first cleaning phase comprising:

i. a detersive surfactant;

a structuring agent;

b. a second cleansing phase comprising:

i. a detersive surfactant;

a structuring agent;

a visually distinguishable stable gas bubble suspended therein;

c. optionally, the benefit phase comprises a gel network comprising:

i. a fatty alcohol;

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

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

a. a first cleaning phase comprising:

i. a detersive surfactant;

a structuring agent;

a visually distinguishable stable gas bubble suspended therein;

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

i. a fatty alcohol;

a second surfactant selected from the group consisting of 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 that is suspended across at least a portion of the container;

wherein the cleansing phase and the benefit phase are stable.

C. The container of paragraphs a-B, wherein the first cleaning phase and/or the second cleaning 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%, by weight of the cleaning phase, of detersive surfactant.

D. The container of paragraphs a-C, wherein the first cleaning phase and/or the second cleaning phase is substantially free of sulfate-based surfactants, and wherein the detersive surfactant is selected from the group consisting of isethionates, sarcosinates, sulfonates, sulfosuccinates, sulfoacetates, acyl glycinates, acyl alaninates, acyl glutamates, lactates, alkenyl lactates, 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%, by weight of the shampoo composition, of the benefit phase.

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%, by weight of the benefit phase, of fatty alcohol.

H. The container of paragraphs a-G, wherein the fatty compound of the benefit phase is a fatty alcohol selected from the group consisting of cetyl alcohol, stearyl alcohol, and combinations thereof.

I. The container of paragraphs a-H, wherein the benefit phase comprises from about 0.01% to about 15%, preferably from about 0.5% to about 12%, more preferably from about 0.7% to about 10%, and even more preferably from about 1% to about 6%, by weight of the benefit phase, of the second surfactant.

J. The container of paragraphs a-I, wherein the second surfactant is selected from the group consisting of 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.

The container of paragraphs a-K, wherein the cleansing phase and the benefit phase further comprise an aqueous carrier.

The container of paragraphs a-L, wherein the benefit phase further comprises a material selected from the group consisting of: siloxane, particulate, mica, and combinations thereof.

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.

The container of paragraphs a-N, wherein the cationic deposition polymer has a weight average molecular weight of about 100,000g/mol to about 3,000,000g/mol, preferably 300,000g/mol to about 3,000,000 g/mol.

P. the container of paragraphs a-O, wherein the cationic polymer is selected from the group consisting of cationic guar, cationic cellulose, cationic synthetic homopolymers, cationic synthetic copolymers, cationic synthetic terpolymers, and combinations thereof.

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

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

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 discernable bubbles prior to first use.

T. the container of paragraphs a-S, wherein the first cleaning phase and/or the second cleaning phase has a transmittance of at least 70%, preferably at least 80%, and more preferably at least 90%, as determined 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 determined by the light transmittance method described herein.

V. the vessel according to paragraphs A-U, wherein the first cleansing phase and/or the second cleansing phase has a composition of at least 10 according to the Herschel-Bulkley model ^-2 l/s to 10 ^-4 A yield stress at a shear rate of l/s of about 0.01Pa to about 20Pa, preferably about 0.01Pa to about 10Pa, and more preferably about 0.01Pa to about 5 Pa.

The container of paragraphs a-V, wherein the first cleansing phase and/or the second cleansing phase and/or the benefit phase has a composition of at least 2 seconds ^-1 The lower viscosity is about 0.01pa.s to about 15 pa.s. The cleansing phase may have a cleansing phase length of 100 seconds ^-1 The viscosity is from about 0.1pa.s to about 4pa.s, alternatively from about 0.1pa.s to about 2pa.s, alternatively from about 0.1pa.s to about 1 pa.s.

X. the container of paragraphs A-W, wherein the benefit phase has a viscosity of at 950s at 25℃ ^-1 At a shear rate of about 100Pa to about 300Pa, preferably at 950s ^-1 At a shear rate of about 130Pa to about 250Pa, and more preferably at 950s ^-1 A shear stress at a shear rate of about 160Pa to about 225 Pa.

The container of paragraphs a-W, wherein the first cleansing phase and/or the second cleansing phase further comprise from about 0.05% to about 10%, preferably from about 0.3% to about 5.0%, and more preferably from about 1.5% to about 5.0%, by weight of the cleansing phase, of a structuring agent selected from the group consisting of vinyl polymers, cellulose derivatives and modified cellulose polymers, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, wintergreen seeds, starches, alginates, microbial polymers, starch-based polymers, alginic acid-based polymers, acrylate polymers, inorganic water-soluble materials, and combinations thereof.

The container of paragraphs a-Y, wherein the benefit phase is substantially free of structurants.

The container of paragraphs A-Z, wherein the viscosity of the first cleansing phase and/or the second cleansing phase is at least 2 seconds ^-1 At about 1.0Pa.s to about 15Pa.s and at 100s ^-1 And from about 0.1pa.s to about 5pa.s.

BB. the container of paragraphs A-AA, wherein the bubbles and/or the benefit phase form an aesthetic design selected from the group consisting of bubbles, strips, cross-hatching, zigzags, flowers, petals, chevrons, marbleized, straight lines, broken strips, grits, speckled, veins, aggregates, hybrids, speckles, bands, spirals, eddies, alignments, mottled, corrugations, spirals, twists, bends, streaks, laces, basket, sinusoids, and combinations thereof.

The container of paragraphs a-BB, wherein the first cleaning phase and/or the second cleaning phase has a light transmittance of greater than 60%, preferably greater than 70%, and more preferably greater than 80%, as measured by the light transmittance method described below.

DD. the container of paragraphs a-CC, wherein the first cleaning phase and/or the second cleaning 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, cellulosic fibers, sodium polyacrylate starch, and mixtures thereof.

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

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

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 30nm, cationic deposition polymers, insoluble anti-dandruff actives, and combinations thereof.

HH. the container of 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.

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 a cleansing phase.

Jj. the container of paragraphs 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 distinguishable stable bubbles suspended therein.

LL. the container of paragraphs a-KK, wherein the first cleaning phase and the second cleaning phase are chemically similar.

MM. the container of paragraphs a-LL, comprising visible suspended bubbles having a gas volume of about 0.01mL to about 3 mL.

NN. the container of paragraph a-MM, wherein the air bubbles have an average diameter of about 0.5MM to about 5MM, preferably about 1MM to about 3 MM.

OO. a method of cleansing 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 shampoo composition from the bottle;

c. applying the shampoo composition to the hair of a user;

d. rinsing said shampoo composition from said hair.

PP. the method according to paragraph OO, wherein the user's hair has a final rinse friction of less than 2000gf, preferably less than 1750gf, and more preferably less than 1700gf, as determined 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 recited. Rather, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40mm" is intended to mean "about 40mm".

Each of the documents cited herein, including any cross-referenced or related patent or patent application, and any patent application or patent for which the present application claims priority or benefit from, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to the present application, or that it is not entitled to any disclosed or claimed herein, or that it is prior art with respect to itself or any combination of one or more of these references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

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

Claims (15)

1. A shampoo product comprising:

a) A container configured to hold a multi-phase shampoo composition; and

b) A multi-phase shampoo composition contained by the container, the multi-phase shampoo composition comprising:

i) A first cleaning phase comprising:

(1) A detersive surfactant, and

(2) A structuring agent;

ii) a second cleansing phase comprising:

(1) A detersive surfactant which is present in the composition,

(2) A structurant, and

(3) A visually distinguishable stable gas bubble suspended therein; and

iii) Optionally, the benefit phase comprises a gel network comprising:

(1) Fatty alcohol, and

(2) A second surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof.

2. The shampoo product of claim 1, wherein at least one of the cleansing phases comprises from 3% to 40%, preferably from 5% to 30%, more preferably from 6% to 25%, and even more preferably from 8% to 25% by weight of the cleansing phase of a detersive surfactant.

3. The shampoo product of claim 1 or 2, 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 discernable bubbles prior to first use.

4. The shampoo product according to any preceding claim, wherein at least one of the cleansing phases has a transmittance of at least 70%, preferably at least 80%, and more preferably at least 90%, as determined by the light transmittance method.

5. The shampoo product according to any preceding claim, wherein the cleansing phase is according to the Herschel-bulk modelAt least one of the cleaning phases having a phase of at least 10 ^-2 s ^-1 To 10 ^-4 s ^-1 Is 0.01Pa to 20Pa, preferably 0.01Pa to 10Pa, and more preferably 0.01Pa to 5Pa.

6. The shampoo product of any preceding claim, wherein at least one of the first cleansing phase, the second cleansing phase, and the benefit phase has a viscosity of at least 2s ^-1 The viscosity is from 0.01Pa.s to 15 Pa.s.

7. The shampoo product of any preceding claim, wherein at least one of the cleansing phases has a cleansing phase of at least 100s ^-1 The following is a viscosity of 0.1pa.s to 4pa.s, alternatively 0.1pa.s to 2pa.s, alternatively 0.1pa.s to 1 pa.s.

8. The shampoo product according to any preceding claim, wherein at least one of the cleansing phases further comprises from 0.05% to 10%, preferably from 0.3% to 5.0%, and more preferably from 1.5% to 5.0%, by weight of the cleansing phase, of a structuring agent selected from vinyl polymers, cellulose derivatives and modified cellulose polymers, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth, galactan, carob bean gum, guar gum, karaya gum, carrageenan, pectin, agar, wintergreen seeds, starch, seaweed gum, microbial polymers, starch-based polymers, alginic acid-based polymers, acrylate polymers, inorganic water-soluble materials, and combinations thereof.

9. The shampoo product of any preceding claim, wherein the benefit phase is present and a density difference between at least one of the first cleansing phase and the second cleansing phase and the benefit phase is less than 0.30g/cm3.

10. The shampoo product of any preceding claim, wherein the benefit phase further comprises a material selected from the group consisting of: silicones having an average particle size greater than 30nm, cationic deposition polymers, insoluble anti-dandruff actives, and combinations thereof.

11. The shampoo product of any preceding claim, wherein the first cleansing phase is substantially free of discernible bubbles.

12. The shampoo product of any one of claims 1-10, wherein the first cleansing phase comprises visually discernable stable bubbles suspended therein.

13. The shampoo product of any preceding claim, wherein the shampoo composition has a visible suspended gas bubble with a gas volume of from 0.01mL to 3 mL.

14. The shampoo product according to any preceding claim, wherein the air bubbles have an average diameter of from 0.5mm to 5mm, preferably from 1mm to 3 mm.

15. A method of cleaning hair comprising:

a) The shampoo product of any preceding claim, 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 shampoo composition from the bottle;

c) Applying the shampoo composition to the hair of a user; and

d) Rinsing said shampoo composition from said hair.