RU2744989C2 - Compositions for personal hygiene containing complexing polyelectrolytes - Google Patents

Abstract

FIELD: personal hygiene.

SUBSTANCE: invention relates to personal hygiene. The composition for personal hygiene comprises a cation polyelectrolyte in a quantity of 0.6 wt.% in a cosmetically acceptable aquatic medium, at least one surfactant in the amount of 3-15 wt.%; and 0.03-0.72 wt.% of anion polyelectrolyte, wherein the mass ratio of the above-mentioned anion polyelectrolyte to the above-mentioned cation polyelectrolyte is 0.05-1.2, wherein said composition exhibits a change in viscosity below the minimum threshold of significant change (Δη_min) and exhibits the absence of a measurable yield limit or an increase in the yield limit in relation to the essentially identical composition, which does not contain the above-mentioned anion polyelectrolyte with a mass ratio of anion polyelectrolyte to cation polyelectrolyte 0.05-1.2.

EFFECT: invention enables increasing deposition efficiency.

11 cl, 11 tbl, 11 ex

Description

This application claims the benefit of US Provisional Application No. 62/352713, filed June 21, 2016, the entire contents of which are incorporated herein by reference for any purpose.

FIELD OF INVENTION

The present invention relates to compositions for personal care containing useful ingredients - complexing polyelectrolytes.

BACKGROUND OF THE INVENTION

Keratinous surfaces (eg, skin and hair) are typically cleaned of dust, dirt and excess sebum using surfactant formulations. However, the cleansing process has the disadvantages that necessary / beneficial components are removed from the keratin surfaces during cleansing. This can lead to unpleasant sensations, for example, hair can become dull, matted and "unruly", as well as lose softness and shine; and / or there may be a feeling of dryness, tightness and / or itching of the scalp or other areas, and in some cases, the skin may be red. In addition, it is desirable to provide the benefits of cleansing compositions after foaming and removing dust, dirt and excess sebum. Various approaches have been developed to mitigate the shortcomings of the cleansing process and increase the added benefit after foaming and cleansing. For example, cleansing compositions may contain (in addition to surfactants) oils such as silicone oils, vegetable oils and mineral oils, for example, to provide a soft feel and increased moisture to the cleaned surfaces. Also very often, cationic components (in most cases, cationic polymers) are included in cleansing compositions to provide improved sensory properties of the cleaned surfaces, for example, softness, or improved functional properties, for example, ease of combing of hair and anti-static benefits. These types of additives in cleansing compositions are commonly referred to as conditioning agents. Cleansing compositions may also contain additional beneficial agents such as zinc pyrithione, salicylic acid, or hyaluronic acid. In order for these conditioning agents and beneficial agents to perform their function, they must be deposited on surfaces (eg, skin and hair) during the cleansing process.

A common problem encountered with cleaning compositions is the effectiveness of the deposition of conditioning agents and beneficial agents onto cleaned surfaces. As a rule, only a part of the agents is deposited, and the rest are washed out / washed off. It is characteristic that keratin surfaces have a certain anionic surface charge; therefore, a certain degree of adhesion of cationic components to keratinous surfaces can be observed through electrostatic interaction. Thus, cationic components, in particular cationic polymers, are used as conditioning agents in cleaning compositions. In a process commonly referred to as "coacervation" or "complexation" or "dilution precipitation", cationic polymers can improve the deposition efficiency of conditioning agents such as softeners, oils, other beneficial agents, and the cationic polymers themselves. In this process, during application of the cleaning composition, ie, upon dilution, the cationic polymer forms insoluble complexes with the anionic surfactant. These insoluble complexes or coacervates can increase the precipitation efficiency of cationic polymers as well as water-insoluble components such as oils.

The concept of combining an anionic surfactant and a cationic polymer is used today in many cleaning compositions. The formation of coacervates depends on many criteria such as molecular weight, charge density, pH and temperature. Coacervate systems and the effect of these parameters have been studied previously and are described, for example, in J. Caelles, et al., Cosmetics & Toiletries , Vol. 106 , April 1991, pp 49-54, CJ van Oss, J. Dispersion Science and Technology , Vol. 9 (5.6) , 1988-89, pp 561-573, DJ Burgess, J. of Colloid and Interface Science , Vol. 140 , No. 1, November 1990, pp 227-238, S. Zhou et al., Langmuir , 20 , 2004, 8482-8489 and C. Lepilleur et al., J. Cosmet. Sci. , 62 , March / April 2011, 161-177. Therefore, approaches for improving deposition from cleaning compositions include optimizing the cationic polymer as well as the surfactant system. Optimization of a cationic polymer involves changing the cationic charge density, molecular weight, backbone chemistry, and cationic functional group chemistry. The surfactant system in the cleansing composition is usually adjusted for the particular cationic polymer used to improve the effectiveness, compatibility and stability of the composition (or vice versa). Several examples of such approaches are described in US Patent Application No. 2003/0108507 and the references cited therein.

However, this reference also describes a deposition efficiency of only 2-3% (200-300 ppm /% active agent concentration in the formulation) of small dispersed actives (i.e., beneficial agent materials insoluble in the cleaning composition and existing in the form of particles or droplets suspended in the cleaning composition) having a size less than or equal to 2 microns. Deposition efficiencies of only 2-3% indicate the overall need to improve deposition efficiencies from cleaning agent formulations. In addition, the use of the complexation of anionic surfactants and a cationic polymer results in deposition on the keratin surface of certain amounts of anionic surfactant present in the coacervate. This surfactant deposition is undesirable because anionic surfactants remaining on the skin can exhibit a high irritant potential and anionic surfactants can denature the keratin components of the skin and hair, resulting in undesirable morphological changes in these substrates.

In addition, compositions that use the complexation of an anionic surfactant and a cationic polymer generally do not provide any improvement / facilitation of the deposition of water-soluble benefit agents, since such benefit agents are not effectively trapped in polymer-surfactant coacervates upon dilution. and thus they do not precipitate.

Another approach to increasing the deposition efficiency of some beneficial agents described in the prior art is to impart cationic charges to beneficial agents such as softeners, humectants and waxes. Cationic charges can facilitate the adhesion of beneficial agents to surfaces with anionic surface charges such as hair and skin. However, this approach requires chemical modification of the beneficial agent using additional cationic functional groups or encapsulating the beneficial agent using cationic materials, both options may or may not be feasible.

The prior art teaches that the presence of an anionic polymer in compositions with a cationic polymer and an anionic surfactant does not result in any improvement in deposition efficiency. For example, anionic rheology modifying polymers such as carbomer and acrylate copolymer have a detrimental effect on the deposition efficiency, as described, for example, in WO 2014/137859 A1. In particular, this reference states that the presence of typical polymers that affect rheology, such as anionic acrylic copolymers (eg, carbopols), does not improve the deposition efficiency of silicone oils. In addition, they even significantly reduce the deposition efficiency of silicone oils when the silicone oils have a smaller particle size (for example, the average oil droplet size is less than 5 microns). This reference further states that "silicone deposition is inversely proportional to the amount of acrylic stabilizer thickener present." The reference describes the use of a nonionic amphiphilic rheology modifying polymer to stabilize the composition "without affecting the deposition of the silicone material" and says nothing about how to improve the deposition efficiency.

Thus, despite the various approaches used in the prior art to improve conditioning and deposition efficiency from cleaning compositions, the disadvantages of the prior art still persist, such as low deposition efficiency, potential irritation due to surfactant deposition, limited compatibility with anionic polymers and the lack of facilitation of precipitation of water-soluble components other than surfactants. Thus, there remains a need to provide improved cleaning compositions with optimal performance and improved deposition efficiency.

SUMMARY OF THE INVENTION

The present invention provides compositions containing, in a cosmetically acceptable aqueous medium: a) a cationic polyelectrolyte, b) at least one surfactant; and c) from about 0.01 weight percent to about 1.2 weight percent anionic polyelectrolyte. The weight ratio of anionic polyelectrolyte to cationic polyelectrolyte is from about 0.05 to about 1.2. The compositions of the present invention exhibit a change in viscosity below the minimum threshold of significant change (Δη _min ) and exhibit no measurable yield stress or an increase in yield strength compared to a substantially identical composition that does not contain from about 0.01 weight percent to about 1.2 weight percent. percent anionic polyelectrolyte at a weight ratio of anionic polyelectrolyte to cationic polyelectrolyte from about 0.05 to about 1.2.

DETAILED DESCRIPTION OF THE INVENTION

The cleaning compositions of the present invention comprise combinations of cationic and anionic polyelectrolytes. The amount of anionic polyelectrolyte is chosen so that, when diluted, it is sufficient to quantitatively increase the yield of the dry sludge mass and maintain an effective cleaning performance without undesirable effects that alter the rheological properties of the composition. If the weight ratio of the anionic polyelectrolyte to the cationic polyelectrolyte is from about 0.05 to about 1.2, the anionic polyelectrolytes do not increase the dry weight yield.

A particular combination of anionic polyelectrolyte (s) and cationic polyelectrolyte (s) in the surfactant system described herein is referred to as a "polyelectrolyte conditioning system". In the context of this document, the expression "polyelectrolyte conditioning system" means a combination of anionic polyelectrolyte (s) and cationic polyelectrolyte (s), in which anionic and cationic polyelectrolyte (s) ) are present in a weight ratio of anionic polyelectrolyte to cationic polyelectrolyte from about 0.05 to about 1.2, and the concentration of anionic polyelectrolyte, based on the total weight of the cleaning composition, is from about 0.01 to about 1.2 wt%.

Compositions of the present invention containing such a polyelectrolyte conditioning system exhibit improved deposition efficiency of conditioning agents and benefit agents compared to similar compositions not including such a polyelectrolyte conditioning system, and also provide additional benefits such as improved skin feel after application or reduced deposition of surface -active substance. Preferred weight ratios of anionic to cationic polyelectrolytes include from about 0.05 to about 1.2, or from about 0.1 to about 1.2, or from about 0.1 to about 1. Having an anionic polyelectrolyte within a certain range increases the yield. dry weight on dilution, measured as described below, by 10% or more compared to a substantially identical composition that does not contain as much anionic polyelectrolyte. More preferably, the yield of the dry sludge mass upon dilution is increased by 20% or more, or even more preferably by 40% or more.

As noted above, the weight ratio of anionic polyelectrolyte to cationic polyelectrolyte is critical. Typically, at ratios from about 0.05 to about 1.2, the compositions exhibit increased dry weight yield after dilution. Depending on the type of polyelectrolytes, the system of surfactants and other parameters of the composition, for example, salt concentration, the optimal mass ratio of anionic and cationic polyelectrolytes to achieve the maximum yield of the mass of dry sludge can vary within this range. An increase in the yield of dry sludge mass after dilution of the cleaning composition is indicative of an improved deposition efficiency of conditioning agents and beneficial agents. In addition, an increase in the dry weight yield is an indication that the anionic polyelectrolyte is part of the coacervates formed after dilution and thus also precipitates. However, the inclusion in the composition of too much anionic polyelectrolyte in comparison with the cationic polyelectrolyte, i.e., an increase in the ratio of the mass of the anionic polyelectrolyte to the mass of the cationic polyelectrolyte by more than about 1.2 times, will not lead to an improvement and even worsen the characteristics as compared with the composition without anionic polyelectrolyte.

Where appropriate, chemicals are listed according to INCI (International Nomenclature for Cosmetic Ingredients) names. For more information, including suppliers and trade names can be found in the relevant monograph of the handbook INCI International Cosmetic Ingredient Dictionary and Handbook, 15 ^th Edition, published by the Council on means for personal hygiene (PCPC), Washington, DC, USA, which is also is available on the Internet at the PCPC Information Database at http://online.personalcarecouncil.org/jsp/Home.jsp.

All percentages cited herein are wt% unless otherwise indicated. The percentages and weights of the components such as polyelectrolyte, surfactant, salt, polymers, acids, etc., listed in this description, represent the percentages and weights of the active substance of the component, excluding, for example, added solvents to the composition, such as water in aqueous sodium chloride solution.

In the context of this document, the expression "substantially identical composition" means a composition that is substantially similar to the compositions of the present invention, except for the relative amounts of anionic polyelectrolyte and cationic polyelectrolyte.

In the context of this document, the term "% mass." means mass percentage, ie. % w / w; for example, 5 g of sodium chloride in 95 g of water represents 5% of the mass. active substance sodium chloride in aqueous solution.

Anionic polyelectrolyte

An anionic polyelectrolyte is a polymer carrying many anionic charges, i.e. a polyelectrolyte that contains monomers or repeating units carrying anionic functional groups. Acceptable functional groups carrying anionic charge can be, without limitation: CO ₂ ^- , SO ₃ ^- , SO ₄ ^- , PO ₃ ^{2 -} and PO ₄ ^{2 -} . The compositions of the present invention contain from about 0.01% of the mass. up to about 1.2% of the mass. anionic polyelectrolyte.

The anionic polyelectrolyte has a charge density of about 0.1 milliequivalents per gram (meq / g) or more, more preferably from about 0.1 to 10 meq / g, even more preferably from about 0.5 to 5 meq / g, and even more preferably from about 0.5 to 4 meq / g, and its weight average molecular weight (Mw) is about 10,000 g / mol or more, more preferably from about 50,000 g / mol or more. For uncrosslinked anionic polyelectrolytes, the molecular weight is from about 50,000 to 3,000,000 g / mol or more, preferably from about 50,000 g / mol to 1,000,000 g / mol. Crosslinked polyelectrolytes are usually defined by their primary particle size rather than molecular weight. The preferred primary particle sizes of the crosslinked anionic polyelectrolytes are about 0.01 micrometer (μm) or more, more preferably about 0.1 μm or more and 1000 μm or less, more preferably about 100 μm or less. Examples of anionic polyelectrolytes are crosslinked, for example, acrylates copolymer type Carbopol ^® Aqua SF-1, a primary particle size of about 0.2 microns and polyacrylate superabsorbent polymer particles of about 25-500 microns.

Acceptable anionic polyelectrolytes include, but are not limited to: 1) polyelectrolytes derived from ethylenically unsaturated monomers containing anionic or anionically ionizable monomers, 2) anionic and anionic ionizable polysaccharides and polysaccharide derivatives, and 3) other anionic polyelectrolytes such as anionic / anionic polypeptides / proteins, anionic / anionically ionizable hybrid (co) polymers containing natural polymer chains (eg polysaccharide or protein chains), as well as synthetic polymer chains (eg polyethylene glycol or acrylate (co) polymer).

Non-limiting examples of such polyelectrolytes are described in the relevant monograph of the handbook INCI International Cosmetic Ingredient Dictionary and Handbook, 15 ^th Edition, published by the Council on means for personal hygiene (PCPC), Washington, DC, USA.

Polyelectrolytes derived from ethylenically unsaturated monomers containing anionic / anionic ionizable monomers include, but are not limited to: (a) linear uncrosslinked (co) polymers, including uncrosslinked alkaline emulsion swellable (ASE) polymers, (b) crosslinked (co) polymers, including crosslinked ASE polymers (xASE), and (c) hydrophobically modified derivatives of the (co) polymers described in points (a) and (b), including uncrosslinked and crosslinked hydrophobically modified polymers, swellable under alkaline emulsion conditions (HASE and xHASE ).

Examples of anionic / anionically ionizable ethylenically unsaturated monomers include acrylic acid, methacrylic acid, vinylsulfonic acid, vinylsulfuric acid, vinylphosphonic acid, vinylphosphoric acid, vinylboronic acid, citraconic acid, maleic acid, fumacrylatel acid methacryloxyethylsulfonic acid and 2-acrylamidomethylpropane sulfonic acid (AMPSA), 2-methyl-2-propenoic acid, ethyl 2-phosphate ester (HEMA-phosphate), methacryloyloxy PPG-7 phosphate, beta-carboxyethyl acrylate-3-acrylamido acid (AMBA) and mixtures thereof.

In the context of this document, the term "(co) polymer" includes polyelectrolytes made from substantially one type of monomer (homopolymer) as well as polyelectrolytes made from more than one type of monomer (copolymer).

Anionic polyelectrolytes prepared from the ethylenically unsaturated monomers of the invention can be synthesized using free radical polymerization techniques known in the art. In another aspect, bulk polymerization, solution polymerization, precipitation polymerization, or emulsion polymerization can be used to synthesize the anionic polyelectrolytes of the invention made from ethylenically unsaturated monomers.

In the context of this document, the term "linear uncrosslinked (co) polymer" according to the invention refers to an anionic polyelectrolyte derived from ethylenically unsaturated monomers containing one or more anionic / anionically ionizable ethylenically unsaturated monomers and optionally one or more nonionic or amphoteric ethylenically unsaturated monomers. Examples of nonionic or amphoteric ethylenically unsaturated monomers include, but are not limited to, ethyl (meth) acrylate, butyl (meth) acrylate, vinyl formate, vinyl acetate, 1-methyl vinyl acetate, vinyl propionate, vinyl butyrate, (meth) acrylamide, dimethyl acrylamide, sulfobetaine propane acrylates, for example, sulfobetaine-acrylate their mixtures. Examples of anionic linear non-crosslinked (co) polymers include, without limitation, homopolymers of poly (meth) acrylic acid or copolymers of acrylamide and (meth) acrylic acid. In the context of this document, the term "(meth) acrylic" acid includes the corresponding methyl derivatives of acrylic acid, and the term "(meth) acrylate" includes the corresponding methyl derivatives of alkyl acrylate and salt forms of acrylic acid. For example, the term “(meth) acrylic acid” refers to acrylic acid and / or methacrylic acid, the term “(meth) acrylate” refers to an alkyl acrylate and / or alkyl methacrylate, and the term “sodium (meth) acrylate” refers to sodium acrylate and / or sodium methacrylate. The linear uncrosslinked (co) polymer is not hydrophobically modified.

In the context of this document, the term "crosslinked (co) polymer" according to the invention refers to a crosslinked anionic polyelectrolyte derived from ethylenically unsaturated monomers. In particular, it is a crosslinked linear non-crosslinked (co) polymer derivative as described above. Crosslinking can be achieved by various methods known to those skilled in the art, for example copolymerization with multifunctional ethylenically unsaturated monomers or post-polymerization reactions are used to induce crosslinking. Examples include, without limitation, carbomers and crosslinked acrylate polymers. Examples of carbomers are Carbopol® 934, 940, 980, Ultrez 10, Ultrez 30, ETD2050, 2984 from Lubrizol, Inc. or Ashland® 940, 941, 980, 981 from Ashland, Inc. An example of a crosslinked polymer of acrylates is crosslinked polymer-4 acrylates (Carbopol® Aqua SF-2 from Lubrizol, Inc.). Other examples include superabsorbent polymers, i.e., crosslinked sodium polyacrylate particles.

In the context of this document, the term "hydrophobically modified (co) polymers" refers to a linear uncrosslinked and crosslinked (co) polymer containing hydrophobic monomers. In particular, the term “hydrophobically modified” means that the polyelectrolyte contains some monomer (s) containing a hydrophobic side group (hydrophobic monomer, also called associative monomer). Typically, the amount of monomer (s) containing (s) hydrophobic side group is from about 0.1% of the mass. up to about 20% of the mass., more typically from about 0.5% of the mass. up to about 10% of the mass., and even more typically from about 1% of the mass. up to about 5% of the mass. They may optionally contain a crosslinking agent and / or may optionally be a crosslinked (co) polymer. Examples are acrylate / C10-30 alkyl acrylate crosslinked polymers (Carbopol® ETD2020, Ultrez 20 from Lubrizol, Inc.) and acrylate / vinyl isodecanoate crosslinked polymer (Stabylen 30 from 3V Sigma, Inc.).

In the context of this document, the term "hydrophobically unmodified" means that the polyelectrolyte has no or only minor amounts of monomers containing a hydrophobic side group (hydrophobic monomer, also called associative monomer). Typically, the amount of monomer (s) containing (s) hydrophobic side group is about 1% of the mass. or less, more typically about 0.5% of the mass. or less, and even more typically about 0.1% of the mass. or less. Exceptions are monomers / crosslinking agent molecules, which may have side chains with more than 4 carbon atoms, but are not considered a hydrophobic monomer (and their level of use in the polyelectrolyte is usually low, i.e. less than 1 wt%).

As used herein, the term "alkaline swellable emulsion polymer" or "ASE polymer" refers to a polyelectrolyte derived from ethylenically unsaturated monomers, such as an acrylate or vinyl (co) polymer, and wherein the polymer contains anionically ionizable monomers such as become ionized and swell and / or dissolve in aqueous solutions upon addition of a base (alkali). The ASE polymer may optionally contain a crosslinking agent and / or optionally may be a crosslinked polymer (xASE). In one embodiment, the ASE or xASE polymer is an acrylate (co) polymer composed of one or more (meth) acrylic acid monomers and / or one of their alkyl ethers (including methyl, ethyl, propyl, butyl ether) and hydroxyalkyl ethers (including hydroxyethyl ether, hydroxybutyl ether); and alkoxyalkyl ethers (including methoxyethyl ether, ethoxyethyl ether). "Simple" alkyl ether refers to an alkyl group having from 1 to 4 carbon atoms. The amount of simple alkyl ether (meth) acrylate monomer in the polymer is in the range of 0-80 wt%, 10-70 wt%, 20-70 wt%, 30-70 wt%, 30-60 wt%. Specific examples of the alkyl ether (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) ) acrylate, ethoxyethyl (meth) acrylate. Examples of ASE polymers are acrylate copolymer (e.g. Carbopol® Aqua SF-1 from Lubrizol, Inc. or Eliclear ™ 4U from Seppic, Inc.) or potassium acrylate copolymer (EX-968 and EX-1112 from Lubrizol, Inc. ).

In the context of this document, the term "hydrophobically modified polymer, swellable under alkaline emulsion conditions" or "HASE polymer", including "xHASE polymer", refers respectively to ASE polymers and xASE polymers containing hydrophobic monomers (see the definition of "hydrophobically modified" above) ... An example of a HASE polymer is polyacrylate-33 (Rheomer ™ 33 from Solvay, Inc.) and an example of xHASE is a cross-linked polymer of acrylates / steareth-20-methacrylate (Aculyn ™ 88 from Dow, Inc.).

Hydrophobic monomers (also called "associative" monomers) used in hydrophobically modified polyelectrolytes are described, for example, in US Pat. No. 5,292,843, US Pat. No. 6,897,253, US Pat. No. 7,288,616, US Pat. No. 3,035,004, and US Patent Publication No. 2006/0270563. the contents of each of which are hereby incorporated by reference in their entirety.

In the context of this document, the term "uncrosslinked" refers to a (co) polymer that is substantially free of covalent bonds between polymer chains.

In the context of this document, the term "crosslinked" refers to a (co) polymer with some amount of covalent bonds between the polymer chains. Such bonds are formed by the addition of certain amounts of crosslinking monomers to the (co) polymer during polymerization. Examples of crosslinking agents are allyl ethers of pentaerythritol, allyl ethers of sucrose, or allyl ethers of propylene, or trimethylolpropane triacrylate, ethylene glycol dimethacrylate. Additional crosslinking agents are described in US Pat. No. 9,187,590 B2, the contents of which are incorporated herein by reference.

Anionic polyelectrolyte derived from ethylenically unsaturated monomers may also contain other monomers. For example, vinyl esters such as vinyl acetate, vinyl propionate; N-vinyl amides such as: N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl formamide, and N-vinyl acetamide; and vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and hydroxybutyl vinyl ether; and ethylenically unsaturated aryl compounds such as styrene, acetoxyethyl (meth) acrylate; and (meth) acrylamides such as: (meth) acrylamide, dimethylacrylamide, N-methylol (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide; and ethylenically unsaturated alkyl esters of dicarboxylic acid monomers such as butyl methyl maleate.

Anionic and anionically modified polysaccharides and polysaccharide derivatives include, without limitation:

a. naturally occurring anionic polysaccharides: alginates (alginic acid), pectin, carrageenan, xanthan, hyaluronic acid, chondroitin sulfate, gum arabic, karaya gum, gum tragacanth, arabinoxylans, heparan sulfate, and

b. anionically modified polysaccharides include: starches, gums, celluloses such as carboxymethyl starch, starch phosphate, hydroxypropyl starch phosphate, starch sulfate, starch 2-hydroxypropyl citrate, carboxymethyl guar, carboxymethyl hydroxymethyl cellulose derivatives, others Aqualon ™ Sodium CMC from Ashland, Inc. or Walocel ™ CRT from Dow, Inc., polyanionic cellulose, cellulose sulfate, cellulose phosphate and carboxyethyl cellulose, and other polysaccharides such as, for example, dextran and dextrin, for example, dextran / dextrin sulfate.

Other anionic polyelectrolytes include anionic / anionic ionizable proteins, anionic polypeptides such as polyglutamic acid, polyaspartic acid, and other anionic copolymers such as polynucleic acids.

Cationic polyelectrolyte

A cationic polyelectrolyte is a polymer that carries many cationic charges, i.e., a polyelectrolyte contains repeating units that carry cationic functional groups. Cationic polyelectrolytes suitable for use in the compositions of the present invention contain cationic nitrogen-containing functional groups such as quaternary ammonium functional groups or cationic protonated amino groups. Cationic protonated amines can be primary, secondary or tertiary amines (preferably secondary or tertiary), depending on the particular species and the selected pH of the composition. Any anionic counterions can be used in combination with cationic polyelectrolytes as long as the polyelectrolytes remain water-soluble in the composition or in the coacervate phase of the composition, and as long as the counterions are physically and chemically compatible with the main components of the composition or do not adversely affect characteristics, stability or aesthetic appearance of the product. Non-limiting examples of such counterions include halides (eg, chloride, fluoride, bromide, iodide), sulfate, methyl sulfate and ethyl sulfate, citrate, acetate, and lactate.

The compositions of the present invention contain from about 0.1% of the mass. up to about 1% of the mass. cationic polyelectrolyte, more preferably from about 0.1% of the mass. up to about 0.8% of the mass.

Preferred cationic polyelectrolytes used in the compositions of the present invention have cationic charge densities of at least about 0.2 meq / g, preferably at least about 0.6 meq / g, more preferably at least about , about 1.5 meq / g, but also preferably less than about 7 meq / g, more preferably less than about 5 meq / g, and even more preferably less than about 3 meq / g in the pH range intended for use with the composition. In the context of this document, the term "cationic charge density" of a polyelectrolyte refers to the ratio of the number of positive charges on the polyelectrolyte to the molecular weight of the polyelectrolyte. The weight average molecular weight (Mw) of such suitable cationic polyelectrolytes will substantially range from about 10,000 to about 5 million g / mol, preferably from about 50,000 to about 5 million g / mol, more preferably from about 100,000 to about 3 million g / mol. The cationic polyelectrolyte can be a crosslinked (co) polymer.

Non-limiting examples of such cationic polyelectrolyte are described in the relevant monograph of the handbook INCI International Cosmetic Ingredient Dictionary and Handbook, 15 ^th Edition, published by the Council on means for personal hygiene (PCPC), Washington, DC, USA, the content of which is included in the this document by reference.

Non-limiting examples of suitable cationic polyelectrolytes include copolymers of ethylenically unsaturated monomers having cationic protonated amine or quaternary ammonium functional groups with water-soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl methacrylates and dialkyl vinylpyrrolidone.

The cationic protonated amino and quaternary ammonium monomers suitable for inclusion in the cationic polyelectrolyte compositions of the present disclosure include ethylenically unsaturated compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkilaminoalkilakrilatom, monoalkilaminoalkilmetakrilatom, trialkilmetakriloksialkilammonievoy salt trialkilakriloksialkilammonievoy salt, salts of diallyl quaternary ammonium, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium and quaternized pyrrolidone, for example, alkylvinylimidazolium, alkylvinylpyridinium, alkylvinylpyrrolidone salts.

Other cationic polyelectrolytes suitable for use in the compositions include copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salts (eg, chloride salt) (INCI name: polyquaternium-16); copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (INCI name: polyquaternium-11); copolymers of vinylpyrrolidone and quaternized vinylimidazolium salts (INCI name: polyquaternium-44); copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammonium chloride (INCI name: polyquaternium-28); copolymers of methacryloyloxyethyltrimethylammonium methyl sulfate (METAMS) and acrylamide (INCI name: polyquaternium-5); cationic diallyl polymers containing quaternary ammonium, including, for example, homopolymer of dimethyldiallylammonium chloride, copolymers of acrylamide and dimethyldiallylammonium chloride (INCI name: polyquaternium-6 and polyquaternium-7, respectively); amphoteric copolymers of acrylic acid, including copolymers of acrylic acid and dimethyldiallylammonium chloride (INCI name: polyquaternium-22); polyampholytic (co) polymers such as polybetaines and polysulfobetaines, terpolymers of acrylic acid with dimethyldiallylammonium chloride and acrylamide (INCI name: polyquaternium-39) and acrylic acid terpolymers with methacrylamidopropyltrimethylammonium chloride (INCI name: polyacrylate). Preferred cationic substituted monomers are cationic substituted dialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides, and combinations thereof. A non-limiting specific example is polymethylacrylamidopropyltrimonium chloride. Also preferred are those copolymers of cationic monomer with nonionic monomers in which the charge density of the total copolymers is from about 0.6 to about 5 meq / gram.

Other cationic polyelectrolytes suitable for use in the composition include polysaccharide polymers such as cationic cellulose derivatives and cationic starch derivatives. Acceptable cationic polysaccharide polymers include those conforming to the formula:

,

,

where A represents an anhydroglucose residual group such as a starch or cellulose anhydroglucose residue; R represents an alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene group, or a combination thereof; R1, R2, and R3 independently represent an alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl group, each group containing up to about 18 carbon atoms, with the total number of carbon atoms in each cationic functional group (i.e., the total the number of carbon atoms in R1, R2 and R3) is preferably about 20 or less, more preferably about 10 or less; and X is an anionic counterion as described above. In one preferred embodiment, R is 2-hydroxypropyl and R ₁ , R ₂ and R ₃ are methyl.

Preferred cationic cellulose polymers are hydroxyethyl cellulose salts which have been reacted with trimethylammonium-substituted epoxy (INCI name: polyquaternium-10). Other suitable types of cationic cellulose include polymeric hydroxyethyl cellulose quaternary ammonium salts, which have reacted with lauryl dimethylammonium-substituted epoxy (INCI name: polyquaternium-24) and reacted with INCI-lauryl dimethylammonium and lauryl trimethylammonium-substituted epoxy I (67).

Other suitable cationic polyelectrolytes include cationic galactomannans such as cationic tara gum, cassia gum and guar gum derivatives such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series, commercially available from Solvay, Inc., and the N-Hance series, commercially available. from Ashland, Inc. Other suitable cationic polyelectrolytes include cellulose ethers containing quaternary nitrogen, some examples of which are described in US Pat. No. 3,962,418, the disclosure of which is incorporated herein by reference. Other suitable cationic polyelectrolytes include copolymers of esterified cellulose, guar and starch, some examples of which are described in US Pat. No. 3,958,581, the contents of which are incorporated herein by reference. Other suitable conditioning polymers include those described in US Pat. No. 5,876,705, the contents of which are incorporated herein by reference. As used herein, cationic polyelectrolytes are either soluble in the composition or soluble in the complex coacervate phase in the composition formed by the cationic polyelectrolyte and the anionic, amphoteric and / or zwitterionic cleansing surfactant described above.

Other suitable cationic polyelectrolytes may include proteins carrying cationic charges such as gelatin, ovalbumin, serum albumin, casein, and hydrolyzed wheat or rice or silk protein substituted with hydroxypropyltrimonium functional groups and cationic polypeptides such as poly (L-lysine) , poly (L-arginine), abaecin, propenine, or indolicidine.

Other suitable cationic polyelectrolytes include linear and branched polyethyleneimine (PEI) (co) polymers. Examples include PEI-2500, PEI-14M.

As such, it is recognized that cationic polyelectrolytes exist in the cleaning composition as a coacervate phase or form a coacervate phase upon dilution. If the cationic polyelectrolyte is not already a coacervate in the cleaning composition, it will preferably exist in complex coacervate form in the cleaning composition after dilution with water to a weight ratio of water to composition of about 20: 1, more preferably about 10: 1, even more preferably about 5: 1 , and even more preferably about 3: 1.

Surfactants

The compositions of the present invention contain from about 1% of the mass. up to about 25% of the mass. surfactant, more preferably from about 3% of the mass. up to about 25% of the mass. surfactant, more preferably from about 3% of the mass. up to about 15% of the mass., even more preferably from about 3% of the mass. up to about 12% of the mass. and even more preferably from about 4% of the mass. up to about 12% of the mass.

Suitable surfactants can be anionic, zwitterionic, nonionic and cationic surfactants, examples of which are described below.

In the context of this document, the term "anionic surfactant" refers to a surfactant molecule carrying at least a negative charge and having no positive charge other than the counterion (s) M ⁺ . Acceptable anionic surfactants include selected from the following classes of surfactants.

● Acylisethionates

,

,

where RCO = C ₈ -C ₂₀ acyl (linear or branched, saturated or unsaturated) or mixtures thereof, Rʹ = H or CH ₃ , M ⁺ = monovalent cation, for example sodium cocoylisethionate (RCO = cocoacyl, Rʹ = H, M ⁺ = Na ⁺ ) and sodium lauroylmethyl isethionate (RCO = lauroyl, Rʹ = CH ₃ , M ⁺ = Na ⁺ ).

● Alkyl sulfosuccinates

,

,

where R = C ₈ -C ₂₀ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation, for example disodium lauryl sulfosuccinate (R = lauryl, M ⁺ = Na ⁺ ).

● Esters of α-sulfo-fatty acid

,

,

where R = C ₆ -C ₁₆ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, Rʹ = C ₁ -C ₂ alkyl, and M ⁺ = monovalent cation, for example sodium methyl 2-sulfolaurate (R = C ₁₀ H ₂₁ , Rʹ = methyl, CH ₃ , and M ⁺ = Na ⁺ ).

● Salts of α-sulfo fatty acids

,

,

where R = C ₆ -C ₁₆ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, M ⁺ = monovalent cation, for example disodium 2-sulfolaurate (R = C ₁₀ H ₂₁ , M ⁺ = Na ⁺ ).

● Alkyl sulfoacetates

,

,

where R = C ₆ -C ₁₈ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, M ⁺ = monovalent cation, for example sodium lauryl sulfoacetate (R = lauryl, C ₁₂ H ₂₅ , M ⁺ = Na ⁺ ).

● Alkyl sulfates

,

,

where R = C ₈ -C ₂₀ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof. Specific examples include TEA lauryl sulfate (R = lauryl, C ₁₂ H ₂₅ , M ⁺ = ⁺ HN (CH ₂ CH ₂ OH) ₃ ), sodium lauryl sulfate (R = lauryl, C ₁₂ H ₂₅ , M ⁺ = Na ⁺ ) and sodium coco sulfate (R = cocoalkyl, M ⁺ = Na ⁺ ).

● Alkylglycerol ether sulfonates or alkoxylhydroxypropyl sulfonates

,

,

where R = C ₈ -C ₂₄ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, M ⁺ = monovalent cation, for example sodium cocoglycerol ether sulfonate (R = cocoalkyl, M ⁺ = Na ⁺ ).

● Alpha Olefin Sulfonates (AOS), derived from the sulfonation of long chain alpha olefins. Alpha-olefin sulfonates are composed of a mixture of alkenesulfonates,

,

,

where R = C ₄ -C ₁₈ alkyl or mixtures thereof, M ⁺ = monovalent cation, and hydroxyalkyl sulfonates,

,

,

where R = C ₄ -C ₁₈ alkyl or mixtures thereof, M ⁺ = monovalent cation. Examples include C12-14 sodium olefin sulfonate (R = C ₈ -C ₁₀ alkyl, M ⁺ = Na ⁺ ) and C14-16 sodium olefin sulfonate (R = C ₁₀ -C ₁₂ alkyl, M ⁺ = Na ⁺ ).

● Alkyl sulfonates or paraffin sulfonates

,

,

where R = C ₈ -C ₂₄ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, M ⁺ = monovalent cation. Examples include C13-17 alkanesulfonate (R = C ₁₃ -C ₁₇ alkyl, M ⁺ = Na ⁺ ) and C14-17 sodium alkylsexulfonate (R = C ₁₄ -C ₁₇ alkyl, M ⁺ = Na ⁺ ).

● Alkylarylsulfonates or linear alkylbenzenesulfonates

,

,

where R = C ₆ -C ₁₈ alkyl (linear, saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation. Examples include sodium deceylbenzenesulfonate (R = C ₁₀ alkyl, M ⁺ = Na ⁺ ) and ammonium dodecylbenzenesulfonate (R = C ₁₂ alkyl, M ⁺ = NH ₄ ⁺ ).

● Alkyl ether sulfates

,

,

where R = C ₈ -C ₂₄ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, n = 1-12, and M ⁺ = monovalent cation. Examples include sodium laureth sulfate (R = C ₁₂ alkyl, M ⁺ = Na ⁺ , n = 1-3), ammonium laureth sulfate (R = C ₁₂ alkyl, M ⁺ = NH ₄ ⁺ , n = 1-3) and sodium polyoxyethylene tridecyl sulfate ( R = C ₁₃ alkyl, M ⁺ = Na ⁺ , n = 1-4).

● Alkyl monoglyceride sulfates

,

,

where RCO = C ₈ -C ₂₄ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation. Examples include sodium coco monoglyceride sulfate (RCO = cocoacyl, M ⁺ = Na ⁺ ) and ammonium coco monoglyceride sulfate (RCO = cocoacyl, M ⁺ = NH ₄ ⁺ ).

● Alkyl ether carboxylate

,

,

where R = C ₈ -C ₂₄ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, n = 1-20, and M ⁺ = monovalent cation. Examples include sodium laureth 13-carboxylate (R = C ₁₂ alkyl M ⁺ = Na ⁺ , n = 13) and sodium laureth 3-carboxylate (R = C ₁₂ alkyl, M ⁺ = Na ⁺ , n = 3).

● Alkyl ether sulfosuccinates

,

,

where R = C ₈ -C ₂₀ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, n = 1-12, and M ⁺ = monovalent cation, for example disodium laureth sulfosuccinate (R = lauryl, n = 1-4, and M ⁺ = Na ⁺ ).

● Dialkyl sulfosuccinates

,

,

where R = C ₆ -C ₂₀ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation, for example sodium diethylhexyl sulfosuccinate (R = 2-ethylhexyl, M ⁺ = Na ⁺ ).

● Alkylamidoalkyl sulfosuccinates

,

,

where R = C ₈ -C ₂₀ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, Rʹ = C ₂ -C ₄ alkyl (linear or branched), and M ⁺ = monovalent cation, for example disodium cocamide-MIPA-sulfosuccinate (RCO = cocoacyl, Rʹ = isopropyl, M ⁺ = Na ⁺ ).

● Alkyl sulfosuccinamates

,

,

where R = C ₈ -C ₂₀ alkyl (linear or branched, saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation, for example disodium stearyl sulfosuccinamate (R = stearyl, C ₁₈ H ₃₇ , M ⁺ = Na ⁺ ).

● Acylglutamates

,

,

where RCO = C ₆ -C ₂₀ acyl (linear or branched, saturated or unsaturated) or mixtures thereof, Rʹ = H or CH ₃ , M ⁺ = monovalent cation, for example disodium cocoylglutamate (RCO = cocoacyl, Rʹ = H, M ⁺ = Na ⁺ ) and disodium lauroylglutamate (RCO = lauroyl, Rʹ = H, M ⁺ = Na ⁺ ).

● Acylaspartates

,

,

where RCO = C ₆ -C ₂₀ acyl (linear or branched, saturated or unsaturated) or mixtures thereof, Rʹ = H or CH ₃ , M ⁺ = monovalent cation, for example N-lauroyl aspartate disodium (RCO = lauroyl, Rʹ = H, M ⁺ = Na ⁺ ).

● Acyltaurates

,

,

where RCO = C ₆ -C ₂₀ acyl (linear or branched, saturated or unsaturated) or mixtures thereof, Rʹ = H or CH ₃ , M ⁺ = monovalent cation, for example sodium methyl cocoyl taurate (RCO = cocoacyl, Rʹ = CH ₃ , M ⁺ = Na ⁺ ) and sodium cocoyl taurate (RCO = lauroyl, Rʹ = H, M ⁺ = Na ⁺ ).

● Acyllactylates

,

,

where RCO = C ₈ -C ₂₀ acyl (linear or branched, saturated or unsaturated) or mixtures thereof, M ⁺ = monovalent cation, for example sodium lauroyl lactylate (RCO = lauroyl, M ⁺ = Na ⁺ ).

● Acylglycinates and acylsarcosinates

,

,

where RCO = C ₈ -C ₂₀ acyl (linear or branched, saturated or unsaturated) or mixtures thereof, Rʹ = H (glycinate) or CH ₃ (sarcosinate), M ⁺ = monovalent cation, for example sodium cocoyl glycinate (RCO = cocoacyl, Rʹ = H, M ⁺ = Na ⁺ ), ammonium cocoyl sarcosinate (RCO = cocoacyl, Rʹ = CH ₃ , M ⁺ = NH ₄ ⁺ ) and sodium lauroyl sarcosinate (RCO = lauroyl, Rʹ = CH ₃ , M ⁺ = Na ⁺ ).

● Anionic derivatives of alkyl polyglucosides, including: sodium lauryl glucoside carboxylate, disodium cocoglucoside citrate, sodium cocoglucoside tartrate, disodium cocoglucoside sulphosuccinate; sodium cocoglucoside hydroxypropyl sulfonate, sodium decyl glucoside hydroxypropyl sulfonate, sodium lauryl glucoside hydroxypropyl sulfonate; a crosslinked polymer of hydroxypropyl sulfonate and sodium cocoglucoside, a crosslinked polymer of hydroxypropyl sulfonate and sodium decylglucoside, a crosslinked polymer of hydroxypropyl sulfonate and sodium lauryl glucoside; anionic polymeric derivatives of APG, such as those described in O'Lenick publication, US Pat. Nos. 7,507,399; 7,375,064 and 7,335,627; and combinations of two or more of them, etc.

In the context of this document, the term "sulfated anionic surfactant" refers to anionic surfactants containing an —SO ₄ ^- M ⁺ group, where M ⁺ or H ⁺ or NH ₄ ⁺ or Na ⁺ or K is absent. ⁺ , or another monovalent or multivalent anion. Examples of sulfated anionic surfactants include, without limitation, sodium lauryl sulfate and sodium laureth sulfate. In some embodiments, the compositions of the present invention are substantially free of sulfated anionic surfactant and preferably are free of sulfated anionic surfactant.

In some embodiments, the compositions of the present invention are substantially free of anionic surfactant, and preferably free of anionic surfactant.

In some embodiments, implementation of the present invention, the composition may contain a zwitterionic surfactant. Acceptable concentrations of the zwitterionic surfactant are from about 0% by weight. up to 15 wt%, preferably about 1-10 wt%, more preferably from about 2 wt%. up to 6% of the mass.

In some embodiments, the implementation of the compositions of the present invention contain one or more anionic and one or more zwitterionic surfactants. The weight ratios of anionic surfactant (s) to zwitterionic surfactant (s) in the composition can range from 1: 0 to 0: 1. Typical ranges of anionic: zwitterionic surfactant ratio are from 4: 1 up to 1: 4.

In the context of this document, the term "zwitterionic surfactant" refers to an amphiphilic molecule containing a hydrophobic group and one or more hydrophilic groups containing two functional groups with opposite formal charges or capable of carrying opposite formal charges (depending on the acid-base properties and pH of the solution). Sometimes such surfactants are also referred to as "amphoteric surfactants".

Acceptable zwitterionic surfactants include, without limitation, surfactants represented by the formulas:

и

,

and

,

where R ₁ represents a linear, branched, saturated or unsaturated hydrophobic group from C5 to C21;

R ₂ represents a linear, branched or cyclic alkyl, hydroxyalkyl or aromatic group;

R ₃ represents a linear or branched alkyl, hydroxyalkyl or aromatic group;

R ₄ represents a linear or branched alkyl, hydroxyalkyl or aromatic group;

R ₅ represents a linear or branched alkyl, hydroxyalkyl or aromatic group; and

any of R ₂ , R _4, or R ₅ can be linked to a cyclic structure; and

Y is -N (H) -, -N (R3) -, -O-, -S-; and

X is —CO2—, —SO3— or —SO4— or phosphate or phosphonate.

Examples of zwitterionic surfactants include those listed below.

Alkylamidoalkylbetaines of the formula:

,

,

where RCO = C ₆ -C ₂₄ acyl (saturated or unsaturated), or mixtures thereof, and x = 1-4. Examples include cocamidoethyl betaine (RCO = cocoacyl, x = 2), cocamidopropyl betaine (RCO = cocoacyl, x = 3), lauramidopropyl betaine (RCO = lauroyl, and x = 3), myristamidopropyl betaine (RCO = myristoyl, and x = 3), sopropyl (R = soy acyl, x = 3) and oleamidopropyl betaine (RCO = oleoyl, and x = 3).

Alkylamidoalkylhydroxysultaines of the formula:

,

,

where RCO = C ₆ -C ₂₄ acyl (saturated or unsaturated), or mixtures thereof. Examples include kokamidopropilgidroksisultain (RCO = kokoatsil, x = 3), lauramidopropilgidroksisultain (RCO = lauroyl, and x = 3), miristamidopropilgidroksisultain (RCO = myristoyl, and x = 3) and oleamidopropilgidroksisultain (RCO = oleoyl, and x = 3).

Alkylamidoalkylsultaines of the formula:

,

,

where RCO = C ₆ -C ₂₄ acyl (saturated or unsaturated), or mixtures thereof. Examples include cocamidopropyl sultaine (RCO = cocoacyl, x = 3), lauramidopropyl sultaine (RCO = lauroyl, and x = 3), myristamidopropyl sultaine (RCO = myristoyl, and x = 3), soy amidopropyl betaine (RCO = 3 acyl) and soy, x oleamidopropyl betaine (RCO = oleoyl and x = 3).

Amphoacetates of the formula:

,

,

where RCO = C ₆ -C ₂₄ acyl (saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation. Examples include sodium lauroamphoacetate (RCO = lauroyl and M ⁺ = Na ⁺ ) and sodium cocoamphoacetate (RCO = cocoacyl and M ⁺ = Na ⁺ ).

Amphodiacetates of the formula:

,

,

where RCO = C ₆ -C ₂₄ acyl (saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation. Examples include disodium lauroamphodiacetate (RCO = lauroyl and M = Na ⁺ ) and disodium cocoamphodiacetate (RCO = cocoacyl and M = Na ⁺ ).

Amphopropionates formulas:

,

,

where RCO = C ₆ -C ₂₄ acyl (saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation. Examples include sodium lauroamphopropionate (RCO = lauroyl and M ⁺ = Na ⁺ ) and sodium cocoamphopropionate (RCO = cocoacyl and M ⁺ = Na ⁺ ).

Amphodipropionates Formulas:

,

,

where RCO = C ₆ -C ₂₄ acyl (saturated or unsaturated) or mixtures thereof, and M ⁺ = monovalent cation. Examples include disodium lauroamphodipropionate (RCO = lauroyl and M ⁺ = Na ⁺ ) and disodium cocoamphodipropionate (RCO = cocoacyl and M ⁺ = Na ⁺ ).

Amphohydroxypropyl sulfonates of the formula:

,

,

where RCO = C ₆ -C ₂₄ acyl (saturated or unsaturated), or mixtures thereof, and M ⁺ is a monovalent cation, for example sodium lauroamphohydroxypropyl sulfonate (RCO = lauroyl, and M ⁺ = Na ⁺ ) and sodium cocoamphohydroxypropyl sulfonate (RCO = cocoacyl, and M ⁺ = Na ⁺ ).

Other examples include amphohydroxyalkyl phosphates and alkylamidoalkylamine oxides.

In some embodiments, implementation of the present invention, the composition may contain a nonionic surfactant. Acceptable concentrations of nonionic surfactant are from about 0% of the mass. up to about 15 wt%, usually about 1-10 wt%, more typically from about 2 wt%. up to about 6% of the mass. In the context of this document, the term "nonionic surfactant" refers to a surfactant molecule that does not have an electrostatic charge. Any of a variety of nonionic surfactants are suitable for use in the present invention. Examples of suitable nonionic surfactants include, but are not limited to, fatty alcohol or fatty acid amide ethoxylates, monoglyceride ethoxylates, sorbitan ester ethoxylates, alkyl polyglucosides, mixtures thereof, and the like. polyol esters, wherein the polyethyleneoxy derivative of the polyol ester (1) is derived from (a) a fatty acid having from about 8 to about 22, and preferably from about 10 to about 14 carbon atoms, and (b) a polyol selected from sorbitol , sorbitan, glucose, α-methylglucoside, polyglucose having an average of about 1 to about 3 glucose residues per molecule, glycerol, pentaerythritol, and mixtures thereof, (2) contains an average of about 10 to about 120, and preferably from about 20 to about 80 ethylene oxide units; and (3) has an average of about 1 to about 3 fatty acid residues per mole of polyethyleneoxy derivative of the polyol ester. Examples of such preferred polyethylene oxy derivatives of polyol esters include, but are not limited to, PEG-80 sorbitan laurate and polysorbate 20. PEG-80 sorbitan laurate is a sorbitan monoester of lauric acid ethoxylated using an average of about 80 moles of ethylene oxide. Polysorbate 20 is a laurate monoester of a mixture of sorbitol and sorbitol anhydrides condensed using about 20 moles of ethylene oxide.

Another class of suitable nonionic surfactants includes long chain alkyl glucosides or polyglucosides, which are condensation products of (a) a long chain alcohol containing from about 6 to about 22, and preferably from about 8 to about 14 carbon atoms, with (b) glucose or glucose-containing polymer ... Preferred alkyl glucosides contain from about 1 to about 6 glucose residues per alkyl glucoside molecule. The preferred glucoside is decyl glucoside, which is a condensation product of a decyl alcohol with a glucose oligomer.

Another class of acceptable nonionic surfactants is the class of polyglycerol nonionic surfactants. Examples of polyglycerol nonionic surfactants include, but are not limited to, polyglycerol esters (PGE), for example, polyglycerol-10 laurate.

In the context of this document, the term "polyglycerol non-ionic surfactant" means an amphiphilic molecule containing one or more non-ionic hydrophilic moieties consisting of a polyglycerol functional group and one or more hydrophobic functional groups. Examples of polyglycerol nonionic surfactants include, without limitation, polyglycerol esters (PGE) such as polyglycerol-10 laurate, where PG = polyglycerol functional group containing ten (10) glycerol repeating units and R = C11H23:

,

,

as well as polyglycerol-10 caprylate / caprate, polyglycerol-10 cocoate, polyglycerol-10 myristate, polyglycerol-10 palmitate, polyglycerol-10 oleate, polyglyceryl-12 laurate, etc. ethers (i.e., PGEs can be monoesters, diesters, triesters, etc.). Other polyglycerol nonionic surfactants include polyglycerol ethers such as polyglycerol-10 lauryl ether, where PG = polyglycerol functional group containing 10 glycerol repeating units and R = C12H25:

etc. Other polyglycerol nonionic surfactants include polyglycerol sorbitan fatty acid esters such as polyglycerol-20 sorbitan laurate, where PG = polyglycerol, the sum of all repeating units (RU) PG = 20, and R = C11H23 (see. Bevinakatti, et al. WO 2009016375, assigned to Croda International PLC)

.

...

Another class of suitable nonionic surfactants includes alkanolamides such as cocamide monoethanolamine (MEA) and cocamide diethanolamine (DEA).

In some embodiments, implementation of the present invention, the composition may further comprise an inorganic salt. Inorganic salts suitable for use in this invention include, without limitation, sodium chloride, potassium chloride, sodium bromide, potassium bromide, ammonium chloride, ammonium bromide, and other salts containing both monovalent and multivalent ions. Typically, the compositions of the present invention contain from about 0.05% of the mass. up to about 6% of the mass. inorganic salt, or from about 0.1% of the mass. up to about 4% of the mass. inorganic salt, or from about 0.1% of the mass. up to about 2% of the mass. inorganic salt, or from about 0.1% of the mass. up to about 1.5% of the mass. inorganic salt.

In some embodiments, implementation of the present invention, the composition may further comprise a cationic surfactant. Classes of cationic surfactants suitable for use in this invention include, but are not limited to, alkyl quaternary compounds (mono-, di-, or tri-), benzyl quaternary compounds, ester quaternary compounds, ethoxylated quaternary compounds, alkylamines, and mixtures thereof, the alkyl group having from about 6 carbon atoms to about 30 carbon atoms, preferably from about 8 to about 22 carbon atoms.

The composition of this invention may additionally contain any other ingredients or additives commonly used in personal care products, for example dermatological or cosmetic formulations, including active ingredients. Examples of additional ingredients or additives are surfactants, emulsifiers, viscosity adjusting agents, lubricants, chelating agents, fillers, binders, antioxidants, preservatives and preservative potency enhancers, colorants, buffering agents, pH adjusters, solvents and benefit agents. such as active ingredients, fragrances, exfoliating agents, emollients, moisturizers, humectants, pigments, opacifiers and the like, provided that they are physically and chemically compatible with the other components of the composition. The active ingredients may include, without limitation, anti-inflammatory agents, antibacterial agents, antifungal agents, antipruritic agents, moisturizing agents, herbal extracts, vitamins, and the like. They also include sunscreen actives, which may be inorganic or organic in nature.

The composition of this invention may further comprise thickeners, suspending agents and rheology modifiers that are not part of the "polyelectrolyte conditioning system". Examples include, but are not limited to: a) naturally occurring polysaccharides, including Cyamopsis tetragonoloba (guar) gum, cassia gum, microcrystalline cellulose, ethoxylated and non-ethoxylated cellulose derivatives (eg, hydroxyethyl and hydroxypropyl methylcellulose, etc.) b) synthetic polymers including acrylate polymers such as surfactant-reactive microgels (as described, for example, in U.S. Patent No. 9,096,755 B2, examples include Beheneth-25 / HEMA acrylate / methacrylate crosslinked polymer and acrylates crosslinked polymer-2 / methacrylate Beheneth-25 / HEMA) and copolymer of acrylates / aminoacrylates / C10-30 alkyl PEG-20 itaconate; c) micellar thickeners such as MIPA cocamide, lauryl lactyl lactate or sorbitan sesquicaprylate, or polyethylene glycol thickeners such as PEG-150 distearate and PEG-120 methyl glucose dioleate and trioleate, and d) other thickeners such as silicones, waxes, clays, silicas , salts, natural and synthetic esters or fatty alcohols, and e) combinations of two or more of the listed substances, etc.

Examples of preservatives and preservative potency enhancers include, but are not limited to, organic acids (e.g., benzoic acid, lactic acid, salicylic acid), benzyl alcohol, caprylyl glycol, decylene glycol, ethylhexylglycerol, gluconolactone, methylisotazolinone, and combinations of two or more of them, etc.

The composition of the present invention may include dispersed insoluble particles. The dispersed particles can be useful agents such as oil droplets, zinc pyrithione particles, mica particles, colloidal oatmeal, and ground walnut shells. In the composition of the present invention, it is preferable to include at least 0.025% of the mass. dispersed particles, more preferably at least 0.05 wt%, even more preferably at least 0.1 wt%, even more preferably at least 0.25 wt%, and even more preferably at least 0.5% of the mass. dispersed particles. In the compositions of the present invention, it is preferred to include not more than about 30% of the mass. dispersed particles, more preferably not more than about 15 wt%, and even more preferably not more than 10 wt%.

The pH of the compositions of the present invention is preferably adjusted to about 3 to about 7, more preferably from about 3 to about 6.5, more preferably from about 3 to about 6, more preferably from about 3 to about 5.5, more preferably from about 3 to about 5, and most preferably about 3 to about 4.5. The pH of the composition can be adjusted to 3, provided there is no negative impact on the stability and characteristics of the composition (eg, foaming, softness and viscosity). The pH of the composition can be adjusted to an appropriate acidity value by using any cosmetically acceptable organic or inorganic acid such as citric acid, acetic acid, glycolic acid, lactic acid, malic acid, tartaric acid, hydrochloric acid, combinations of two or more of them, etc. . P.

Examples of

The examples below are intended to illustrate the present invention and not to limit it.

The methods used in the examples are described below.

Analysis of dry sludge mass yield

Measurements of coacervate deposition in diluted cleaning compositions were carried out using the procedure described below. First, 2.5 g of the cleansing composition was added to a 20 ml glass scintillation vial containing 7.5 g of deionized (DI) water. The vial was closed and the contents were mixed on a VWR analog vortex mixer for 20 seconds. Immediately after mixing, 1 ml of the main volume of the diluted solution was pipetted into a 1.5 ml microcentrifuge tube and preweighed on a Mettler Toledo XS105 analytical balance. After measuring the weight of a centrifuge tube containing 1 ml of solution, the tube was centrifuged in a VWR Galaxy microcentrifuge at 13,000 rpm. If after centrifugation a visible pellet was observed, the supernatant was removed with a pipette, leaving only a pellet with a high polyelectrolyte content. After that, a centrifuge tube with an open lid was placed overnight in a thermostat with a temperature of 50 ° C to remove water from the sediment. Then the centrifuge tube containing only dry sediment was reweighed. Thereafter, the total weight of the diluted solution and dry sediment was calculated by subtracting the weight of the centrifuge tube from the corresponding measurements of the weight of the centrifuge tube containing 1 ml of the diluted solution and the dry sediment.

The dry sediment mass yield was calculated as the ratio of the dry sediment mass to the total mass of the cationic and anionic polyelectrolytes contained in the diluted solution added to the microcentrifuge tube. In some cases, instead of a solid / viscous sediment appearing at the bottom of the tube, a single phase was observed. These samples were noted as showing one phase on dilution / centrifugation and the dry weight yield was recorded as 0.

Viscosity studies and criteria for significant viscosity change

Determinations of the apparent viscosity of the cleaning compositions were performed on a controlled shear rheometer (AR-2000, TA Instruments Ltd., New Castle, Delaware, USA). The steady-state shear rate oscillation range was determined at 25.0 ± 0.1 ° C using a cone-plate geometry (50 mm diameter, 1 ° cone angle). Data collection and analysis was performed using Rheology Advantage v5.7.0 software (TA Instruments Ltd., New Castle, Delaware, USA). Medium shear viscosities are derived from steady-state flow measurements at a shear rate of 10 s ^-1 and are expressed in centipoise (cP). Low shear viscosities are derived from steady-state flow measurements at a shear rate of 1 s ^-1 and are expressed in centipoise (cP).

In the context of this document, the minimum threshold of significant change is defined as Δη _min = 82.65 × η ^0.396 , where η is the viscosity measured according to the protocol described above. This relationship between measurable differences in viscosity is consistent with qualitative observations, rates reported in the literature, and general predictions for exponential law relationships between physical quantities and perceived quantities (Bergmann Tiest, WM, Vision Research, 109 , 2015, 178-184, Bergmann Tiest et al., IEEE Transactions on Haptics , 6 , 2013, 24-34, Stevens, JC & Guirao, M., Science , 144 , 1964, 1157-1158). Then, in cases where the polyelectrolyte is added to the composition with a viscosity of η ₀ , the researchers determine the minimum viscosity required to state an observed / noticeable change in viscosity by the formula η _min = Δη _min + η ₀ = 82.65 × η ₀ ^0.396 + η ₀ .

Yield Strength Testing

In the context of this document, the term "yield point" indicates that the viscoelastic material / sample has a predominant solid behavior. In other words, the elastic modulus should be higher than the viscosity modulus in the low stress / stress plateau of the amplitude range. The stress at the intersection of the storage modulus Gʹ and the loss modulus Gʺ (Gʹ = Gʺ) was then taken as the yield point and expressed in pascals (Pa).

The cleaning compositions of the present invention substantially lack the yield stress associated with, or inherent in, the polyelectrolyte conditioning system. That is, the compositions do not contain anionic polyelectrolytes in the polyelectrolyte conditioning system in an amount sufficient to provide a composition with measurable yield strength or an increase in yield strength as determined by the method described herein. The measurable increase in the yield stress index is usually about 0.01 Pa or more, or even more typically about 0.05 Pa or more, or even more typically about 0.1 Pa or more.

Determination of the yield strength of the cleansing compositions was carried out on a controlled shear rheometer (AR-2000, TA Instruments Ltd., New Castle, Delaware, USA). The ranges of the vibration voltage amplitude of 0.1% -1000% were determined at 25.0 ± 0.1 ° C using the cone-plate geometry (diameter 50 mm, cone angle 1 °) at a vibration frequency of 1 rad / s. Data collection and analysis was performed using Rheology Advantage v5.7.0 software (TA Instruments Ltd., New Castle, Delaware, USA). The oscillatory stress was taken as an indicator of the yield strength, below which the accumulation modulus Gʹ exceeds the loss modulus Gʹʹ and above which Gʹʹ exceeds Gʹ. In cases where Gʹ did not exceed Gʹʹ at any oscillatory voltage higher than the sensitivity of the tool, the yield point was noted as equal to 0 Pa. Unless otherwise stated, yield strength values are given in pascals (Pa).

Polyelectrolyte Deposition Ellipsometry Test

Evaluations of the deposition efficiency of polyelectrolytes of the comparative and inventive examples during cleaning were carried out on a surface model and measurements were made using ellipsometry. First, 2.5 g of the cleansing composition was added to a 20 ml glass scintillation vial containing 7.5 g DI water heated to 40 ° C. The vial was closed and the contents were mixed on a VWR analog vortex mixer for 20 seconds. Immediately after mixing, 100 μl of the diluted solution was pipetted onto a cut chip from a 2 cm x 2 cm test grade silicon wafer (University Wafer) (pre-cleaned with deionized (DI) water and ethanol and dried), spread over the surface and left for 30 seconds. ... After tilting the silicon wafer at an angle of ~ 45 °, 5 ml of DI water was dropped onto the silicon chip at 40 ° C, rinsing the diluted cleaning solution from the surface. The chip was then gently blotted with a tissue and allowed to dry for 3-4 minutes.

The thickness of the deposit on the silicon wafer was measured on an alpha-SE spectroscopic ellipsometer (J. A. Woolam Co., Inc) at 5 different locations on each chip before and after treatment with the cleaning solution. The layer thickness was calculated by applying a standard fit to the raw ellipsometric data for a transparent film on a silicon substrate using the CompleteEASE® software package. The final average deposited layer thickness was then calculated by subtracting the average layer thickness measured before application of the diluted composition from the average layer thickness measured after application of the diluted composition.

Dimethicone precipitation test

Evaluations of the effectiveness of the deposition of silicone on the skin of the compositions having the features of the invention and comparative examples were carried out on the forearm of a human volunteer and measured using infrared spectroscopy of the impaired total internal reflection with Fourier transform (ATR-FTIR), similar to previous evaluations performed for silicone on human skin. (Klimisch, HM & G. Chandra, J. Soc. Cosmet. Chem., 37 , 1986, 73-87). ATR-FTIR measurements were performed using a REMSPEC IR TissueView ™ ATR FTIR spectrometer. The acquired spectra were determined in the "wavenumber" range from 900 cm ^-1 to 3500 cm ^-1 at intervals of 2 cm ^-1 .

The dimethicone-containing formulations of the inventive and comparative examples were prepared by including a sufficient amount of pre-emulsified dimethicone having a dimethicone droplet size of about 0.65 microns in the composition to give 5 wt%. active substance dimethicone in the finished composition. For example, 0.78 g of Xiameter MEM-1352 (64 wt% dimethicone active) was added to 9.22 g of the formulation to achieve a total content of 0.5 g of dimethicone per 10.0 g of the formulation.

The palmar surface of the subject's forearm was first washed with a cleansing composition consisting of sodium laureth sulfate (SLES, 5% w / w), cocamidopropyl betaine (CAPB, 5% w / w), NaCl and sodium benzoate, adjusted to pH 4.5, thoroughly washed and dried with a sterile tissue. Thereafter, a 5 cm × 7 cm rectangular area was marked on the palmar surface of the forearm. The ATR-FTIR spectrum was then determined in the center of the marked area. Thereafter, 100 μl of the dimethicone-containing formulation and 100 μl of DI water were applied to the marked forearm area and rubbed gently with a gloved index finger and just the index finger for 30 seconds. The composition was left on the arm for another 30 seconds, and then the forearm was placed for 10 seconds under a stream of water (flow rate 3 liters per minute) at a temperature of 37 ° C supplied from a spray valve (the center of spray was aligned with the center of the marked area), at a distance 15 centimeters (6 inches). After rinsing, the hand was shaken quickly, outside the marked area the hand was dried with a sterile tissue, and the marked area was allowed to air dry (5-10 minutes). After drying in the center of the marked area, the ATR-FTIR spectrum was determined in the range from 900 cm ^-1 to 3500 cm ^-1 .

For each obtained ATR-FTIR absorption spectrum, after subtraction of the corresponding baseline levels for the silicone (Si) peak (1240-1280 cm ^-1 ) and the amide II peak (1487-1780 cm ^-1 ), the absorbance values of the silicone peak (1240-1280 cm ^-1) ) were normalized by the total area under the peak of amide II (sum of absorbance values from 1487-1780 cm ^-1 ). Then, the absorbance values for the Si peak before washing with the silicone-containing test compound were subtracted from the absorbance values for the Si peak after washing with the silicone-containing test compound. The absorbance value for the Si peak at 1260 cm ^{-1 was} then used as an indicator of the relative deposition of dimethicone, as in previous work it was used as an indicator of the concentration of dimethicone on the skin (Klimisch, HM & G. Chandra, J. Soc. Cosmet. Chem., 37 , 1986, 73-87).

Formulation of Inventive Examples and Comparative Examples

The formulations of the Inventive Examples and Comparative Examples were prepared using different types of formulation ingredients (ie, raw materials from different suppliers). These materials are listed below, along with INCI / substance names, acronyms, trade names and suppliers.

Anionic surfactants

Sodium laureth sulfate (SLES) was obtained from the BASF company under the name Texapon ^® N70.

C ₁₄ -C ₁₆ olefin sulfonate sodium was obtained from Stepan Company under the name Bio-Terge ^® AS-40 CG K.

Polioksietilentridetsilsulfat sodium was obtained from Stepan Company under the name Cedepal ^® TD403 MFLD.

Zwitterionic / amphoteric / nonionic surfactants

Cocamidopropyl Betaine (CAPB) was obtained from Evonik Inc. under the name Tego ^® Betain F50, unless otherwise specified name Tego ^® Betain L7V from Evonik.

Coco betaine was obtained from Solvay company called Mackam ^® C35

Kokamidopropilgidroksisultain (CAPHS) was obtained from Solvay company called Mirataine ^® CBS.

PEG-80 sorbitan laurate was obtained from Croda company under the name Tween-28 ^® LQ (AP).

Cationic (Quaternary) Conditioning Polyelectrolytes

Polyquaternium-7 (PQ-7) was obtained from Lubrizol Company under the name Merquat ^® 7SPR.

Polyquaternium-10 (PQ-10) was obtained from Dow Chemical Company under the name Ucare ^® JR-400.

Guar hydroxypropyltrimonium chloride (cationic guar gum) was obtained from Solvay Inc. under the name Jaguar ^® C500.

Polyquaternium-5 (PQ-5) was obtained from Lubrizol Company under the name Merquat ^® 5.

Polyquaternium-28 (PQ-28) was obtained from Ashland company called Conditioneze ^® NT-20.

Polyquaternium-44 (PQ-44) was obtained from the BASF company under the name Luviquat ^® UltraCare AT-1.

Anionic polyelectrolytes

Potassium acrylate copolymer was obtained from Lubrizol, Inc.

Acrylate copolymer was obtained from Lubrizol Company under the name Carbopol ^® Aqua SF-1.

Polyacrylate-33 was obtained from Solvay company called Rheomer ^® 33T.

Xanthan gum was obtained from Vanderbilt Minerals Company under the name Vanzan ^® NF.

Carboxymethyl cellulose (CMC) was obtained from Ashland Company under the name Aqualon ^® CMC 7MF.

Sodium polyacrylate (crosslinked) was obtained under the name AP 80HS from Evonik Stockhausen.

Humidifiers

Glycerin was obtained from P&G Chemicals under the name Moon OU Glycerin.

Chelating agents

Disodium salt of ethylenediaminetetraacetic acid (EDTA) was obtained from the company DOW under the name Versene ^® NA.

EDTA tetrasodium salt was obtained from the company DOW under the name Versene ^® 100XL.

Organic acids / preservatives

Sodium benzoate NF, FCC was obtained from Emerald Performance Materials.

Phenonip XB was obtained from Clariant.

Quaternium-15 was obtained from DOW under the name Dowicil ^® 200.

Helpful Agents

Sodium glycolate was obtained from Acros Organics.

Pre-emulsified dimethicone was obtained entitled Xiameter ^® MEM-1352 from Dow Corning company.

Other

Hexylene glycol was obtained from Penta International Crop.

The fragrance was obtained from Firmenich under the name Luxury 475537 F.

Disodium cocoamphodiacetate was obtained from Croda company called Crodateric ^® CDA 40-LQ- (AP).

Deionized water (DI water, also called water in the examples below) was obtained from the Millipore Direct-Q ™ System with a Progard ™ 2 filter.

Unless otherwise indicated, all ingredients and products obtained are added in amounts such that the compositions result in a final weight percent of active ingredient. For example, 3.5% of the mass. active substance cocamidopropyl betaine (as indicated in table 3a) corresponds to 9% of the mass. Betaine Tego ^® F50, having an activity of 39% wt .; 3.5% w / 39% w = 9% w / w

Formulation of Inventive Examples E1-E24 and Comparative Examples C1-C24, C29-C34

Formulations for Inventive Examples E1-E24 and Comparative Examples C1-C24, C29-C34 were prepared as described below. To an appropriately sized vessel equipped with a heated top drive stirrer, add the required amounts of DI water and anionic polyelectrolyte and stir at 200-250 rpm until the mixture is homogeneous. Anionic and zwitterionic / amphoteric surfactants were then added and mixed until the solution became homogeneous. Thereafter, aqueous solutions of sodium hydroxide and / or citric acid were added to adjust the pH to the desired value of 6.4-6.6. After the pH was stabilized, a cationic polyelectrolyte was added to the mixture. In the case of cationic polyelectrolytes, which were already supplied as aqueous suspensions, the polyelectrolyte solution was slowly added dropwise directly to the mixture. For polyelectrolytes supplied in the form of dry powders, 9% of the mass was first obtained. a polyelectrolyte premix in DI water and then slowly dropwise added to the mixture. After the mixture became homogeneous, sodium chloride and sodium benzoate were added and the mixture was stirred again until uniform. Thereafter, aqueous solutions of sodium hydroxide and / or citric acid in DI water were added at room temperature to adjust the pH to the desired value (unless otherwise indicated, pH 4.4-4.6). DI water was added in sufficient amount up to 100% of the mass. and the solution was continued to stir until uniform, after which it was transferred to an appropriate storage vessel.

Example 1a

Deposition measurements of inventive formulations (E1-E3) and comparative (C1-C3) examples containing anionic polyelectrolyte and cationic polyelectrolyte in various weight ratios

The compositions of Comparative Examples C1-C3 and Inventive Examples E1-E3, listed in Table 1a, together with the dry weight yield (as measured by the dry weight yield test described herein) are formulations with identical amounts and types of surfactant (9 wt.% SLES, 2 wt.% CAPB), cationic polyelectrolyte (0.6 wt.% PQ-10), salt and preservative, but with the addition of various amounts of anionic polyelectrolyte, namely a copolymer of acrylates , a well known rheology modifier and suspending agent. As shown in Table 1a, the formulations of the inventive Examples E1-E3 showed a measurable increase in dry weight yield compared to the formulation of Comparative Example C1, which did not contain the anionic polyelectrolyte. On the other hand, the compositions of Comparative Examples C2-C3 having weight ratios of anionic polyelectrolyte to cationic polyelectrolyte greater than 1.2 (namely, 1.67 and 2.5, respectively) did not show an improvement in dry weight yield compared to Example C1.

Table 1a

% mass. active substance Material Material class C1 E1 E2 E3 C2 C3 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 0.3 0.6 one 1.5 Polyquaternium-10 Cationic polyelectrolyte 0.6 0.6 0.6 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 9 9 9 9 9 9 Cocamidopropyl
betaine Amphoteric /
zwitterionic surfactant 2 2 2 2 2 2 Sodium chloride Salt 0,4 0,4 0,4 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 0.50 1.00 1.67 2.50 Dry sludge mass yield 0 1.47 2.85 2.24 0 0

Example 1b

Deposition measurements of inventive formulations (E4-E6) and comparative (C4-C6) examples containing anionic polyelectrolyte and cationic polyelectrolyte in various weight ratios

The compositions of Comparative Examples C4-C6 and Inventive Examples E4-E6 listed in Table 1b together with the dry weight yield (as measured by the dry weight yield test described herein) are compositions containing the same components, but in different concentrations and ratios, in particular, a lower concentration of the cationic polyelectrolyte PQ-10 (0.2 wt%). As shown in Table 1b, the formulations of the inventive Examples E4-E6 showed a measurable increase in dry weight yield compared to the formulation of Comparative Example C4, which did not contain the anionic polyelectrolyte. On the other hand, the compositions of Comparative Examples C5-C6 having weight ratios of anionic polyelectrolyte to cationic polyelectrolyte greater than 1.2 (namely, 1.5 and 2.5, respectively) did not show an improvement in dry weight yield compared to Example C4.

Table 1b

% mass. active substance Material Material class C4 E4 E5 E6 C5 C6 Copolymer of acrylates Anionic polyelectrolyte 0 0.03 0.1 0.2 0.3 0.5 Polyquaternium-10 Cationic polyelectrolyte 0.2 0.2 0.2 0.2 0.2 0.2 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 3.5 3.5 3.5 Cocamidopropyl
betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.15 0.50 1.00 1.50 2.50 Dry sludge mass yield 1.86 2.43 3.34 2.19 1.57 1.18

Example 2a

Deposition Measurements of Inventive (E7) and Comparative (C7 and C8) Examples Using Synthetic Cationic Polyelectrolyte (PQ-7)

The compositions of Comparative Examples C7-C8 and Inventive Example E7 listed in Table 2a together with the dry weight yield (as measured by the dry weight yield test described herein) are compositions with identical amounts and types. surfactant (9 wt.% SLES, 2 wt.% CAPB), cationic polyelectrolyte (0.6 wt.% PQ-7), salt and preservative, but with the addition of various amounts of anionic polyelectrolyte, namely a copolymer of acrylates. These compositions differ from those shown in Table 1a only in the type of cationic polyelectrolyte used (synthetic PQ-7, not natural PQ-10 based on cellulose). As shown in Table 2a, the formulation of Inventive Example E7 shows a measurable increase in dry weight yield over the formulation of Comparative Example C7 not containing the anionic polyelectrolyte. Comparative C8 formulation having anionic polyelectrolyte to cationic polyelectrolyte weight ratios greater than 1.2 (namely 2.5) did not show a measurable increase in dry weight yield compared to Comparative C7 formulation without an anionic polyelectrolyte.

Table 2a

% mass. active substance Material Material class C7 E7 C8 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 9 9 9 Cocamidopropyl Betaine Amphoteric / Zwitterionic Surfactant 2 2 2 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0 1.08 0

Examples 3a-b

Deposition measurements of formulations with features of the invention (E8-E9) and comparative (C9-C12) examples with different concentrations, ratios and chemical characteristics of surfactants

The compositions of Comparative Examples C9-C12 and Inventive Examples E8-E9, listed in Tables 3a-3b, together with the dry weight yield (as measured by the dry weight yield test described herein) are compositions, which reproduce the concentrations of the selected cationic polyelectrolyte, anionic polyelectrolyte, salt and preservatives from Tables 1a and 2a, but use a lower total surfactant concentration (only 7 wt%) and a different weight ratio of anionic surfactant to zwitterionic surfactant active substance (1: 1 SLES: CAPB). As shown in Tables 3a and 3b, the compositions of the inventive Examples E8 and E9 having anionic to cationic polyelectrolyte weight ratios of 0.17 exhibit a measurable increase in dry weight yield over the corresponding compositions of Comparative Examples C9 and C11, respectively, not containing anionic polyelectrolyte. The compositions of Comparative Examples C10 and C12 having an anionic to cationic polyelectrolyte weight ratio of 2.5 did not show a measurable increase in dry weight yield over the corresponding compositions of Comparative Examples C9 and C11, respectively, which did not contain the anionic polyelectrolyte.

Table 3a

% mass. active substance Material Material class C9 E8 C10 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-10 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric / Zwitterionic Surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 2.7 3.11 0

Table 3b

% mass. active substance Material Material class C11 E9 C12 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances
anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0.37 1.59 0

Example 3c

Deposition measurements of formulations of the inventive (E10) and comparative (C13-C14) examples with different concentrations, ratios and chemical characteristics of surfactants

The compositions of Comparative Examples C13-C14 and Inventive Example E10, listed in Table 3c, together with the dry weight yield (as measured by the dry weight yield test described herein), are compositions in which the concentrations are reproduced selected cationic polyelectrolyte, anionic polyelectrolyte, salt and preservatives from Tables 1a and 2a, but using different chemical characteristics of anionic surfactant (C14-16 sodium olefin sulfonate instead of SLES) and amphoteric / zwitterionic surfactant (CAPHS instead of CAPB). As shown in Table 3c, the formulation of Inventive Example E10 shows a measurable increase in dry weight yield over the corresponding formulations of Comparative Examples C13 not containing the anionic polyelectrolyte. Comparative C14 formulation having an anionic to cationic polyelectrolyte weight ratio of 2.5 did not show a measurable increase in dry weight yield over the corresponding C13 formulations not containing the anionic polyelectrolyte.

Table 3c

% mass. active substance Material Material class C13 E10 C14 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 0.6 C ₁₄ -C ₁₆ sodium olefin sulfonate Anionic surfactant 9 9 9 Cocamidopropylgid-
roxisultain Amphoteric /
zwitterionic surfactant 2 2 2 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances
anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0 1.17 0

Examples 4a-4d

Composition Measurements of Inventive (E11-E14) and Comparative (C15-C22) Examples Using Various Synthetic and Natural Cationic Polyelectrolytes

The compositions of Comparative Examples C15-C22 and Inventive Examples E11-E14 listed in Tables 4a-4d together with the dry weight yield (as measured by the dry weight yield test described herein) are compositions, which reproduce the concentrations of the selected anionic polyelectrolyte, salt and preservatives from Table 3a, but use different chemical characteristics of the cationic polyelectrolyte (0.6 wt% active), namely guar hydroxypropyltrimonium chloride, PQ-5, PQ-22 and PQ-44. As shown in Tables 4a-d, the formulations of the inventive examples E11-E14 show a measurable increase in dry weight yield compared to the corresponding formulations of comparative examples C15, C17, C19 and C21, respectively, not containing the anionic polyelectrolyte. Compositions of comparative examples C16, C18, C20 and C22 having a weight ratio of anionic to cationic polyelectrolytes greater than 1.2 (namely 2.5) did not show a measurable increase in the dry weight yield compared to the corresponding compositions of comparative examples C15, C17, C19 and C21, respectively, not containing the anionic polyelectrolyte.

Table 4a

% mass. active substance Material Material class C15 E11 C16 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 1.5 Guarhydroxypropyl chloride
trimony Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 2.19 2.7 0

Table 4b

% mass. active substance Material Material class C17 E12 C18 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-5 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0 0.46 0

Table 4c

% mass. active substance Material Material class C19 E13 C20 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-28 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances
anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0 0.9 0

Table 4d

% mass. active substance Material Material class C21 E14 C22 Copolymer of acrylates Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-44 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances
anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0.99 2.33 0.7

Example 5

Deposition Measurements of Inventive Formulations (E15-E17) and Comparative Examples (C7, C11, C23, C24) Using Uncrosslinked Low Molecular Weight Anionic Polyelectrolyte

The compositions of Comparative Examples C7, C11, C23 and C24 and Inventive Examples E15-E17, listed in Table 5a, together with the dry weight yield (as measured by the dry weight yield test described herein) are formulations similar to those of Tables 2a and 3b, including PQ-7 with different ratios of SLES and CAPB; however, in this case, the compositions include an alternative anionic polyelectrolyte, namely a copolymer of potassium acrylates. Unlike the acrylate copolymer (Carbopol® AQUA SF-1), which is crosslinked, the potassium acrylate copolymer is a relatively low molecular weight uncrosslinked polyelectrolyte. As shown in Tables 5a and 5b, the formulations of the inventive Examples E15-E17 show a measurable increase in dry weight yield compared to the corresponding formulations of Comparative Examples C11 and C7 not containing the anionic polyelectrolyte. Compositions of comparative examples C23 and C24 having a mass ratio of anionic to cationic polyelectrolytes greater than 1.2 (namely 2.5) did not show a measurable increase in the dry weight yield compared to corresponding compositions of comparative examples C11 and C7, respectively, not containing anionic polyelectrolyte. ...

Table 5a

% mass. active substance Material Material class C11 E15 E16 C23 Potassium acrylate copolymer Anionic polyelectrolyte 0 0.1 0.5 1.5 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 0.83 2.50 Dry sludge mass yield 0.37 0.63 0.67 0

Table 5b

% mass. active substance Material Material class C7 E17 C24 Potassium acrylate copolymer Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 9 9 9 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 2 2 2 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0 0.21 0

Example 6

Preparation of Comparative Examples (C25-C28) Formulations and Measurement of Their Deposition

The formulations of Comparative Examples C25 and C26 shown in Table 6a were prepared to reproduce the formulations of Examples 10 and 11 from International Patent Publication WO 2005/023969. The selection of raw materials and processing formulations reproduces the materials and processing mentioned in this publication using available commercial materials. These compositions were prepared as described below.

In a beaker was added 50% of the mass. DI water. When the acrylate copolymer was included, it was added to the water with stirring. Then, PEG-80 sorbitan laurate was added to the mixture with stirring. To this mixture, the following ingredients were added separately with stirring until uniformity of each respective resulting mixture was achieved: cocamidopropyl betaine (Tego Betain L7V), sodium polyoxyethylene tridecyl sulfate, glycerin, polyquaternium-10, quaternium-15, and EDTA tetrasodium salt. The pH of each resulting solution was then adjusted to either 20% of the mass. sodium hydroxide solution, or 20% of the mass. citric acid solution to obtain a final pH level of about 6.3-6.6. Thereafter, the remainder of the water was added to the mixture.

The dry weight yield was measured according to the dry weight yield test as described herein. As shown in Table 6a, the composition of Comparative Example C26 having an anionic to cationic polyelectrolyte weight ratio of 1.86 did not show a measurable increase in dry weight yield compared to corresponding compositions of Comparative Examples C25 not containing the anionic polyelectrolyte.

Table 6a

% mass. active substance Material C25 C26 Copolymer of acrylates 0.00 0.26 Polyquaternium-10 0.14 0.14 Sodium polyoxyethylene tridecyl sulfate 6.00 6.00 Cocamidopropyl Betaine 3.40 3.40 PEG-80 sorbitan laurate 3.30 3.30 Glycerol 1.88 1.88 EDTA tetrasodium salt 0.26 0.26 Quaternium-15 0.05 0.05 Sodium hydroxide ex. qty ex. qty Lemon acid ex. qty ex. qty Water ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 1.86 Dry sludge mass yield 0 0

The formulations of Comparative Examples C27 and C28 shown in Table 6b were prepared according to examples of Examples 4 and 1 described in US Pat. No. 7,776,318, respectively. The only modification to these formulations is the elimination of glycol distearate, an opalescent agent that does not dissolve in the formulations and precipitates after dilution. Such suspended solids interfere with the dry weight yield testing described herein and are thus excluded from the following formulation to provide an easy understanding of the polyelectrolyte deposition properties of these compositions. The choice of raw materials and processing of the compositions in other respects reproduces the materials and processing mentioned in this patent using currently available commercial materials. These compositions were prepared as described below.

Water, preservatives, glycerin and hexylene glycol were added to an appropriately sized vessel equipped with a heated top drive stirrer. After heating the solution to 50 ° C, some sodium laureth sulfate was added until complete dissolution. EDTA disodium salt, polyquaternium-7 and acrylate copolymer were then added sequentially with sufficient time between each addition of additional ingredient to observe complete and even distribution. Then the pH of the solution was brought to 6.4-6.6 by adding dilute sodium hydroxide. Thereafter, flavor was added to the mixture.

Later, cocobetaine was added, followed by disodium cocoamphodiacetate. Thereafter, sodium glycolate and sodium chloride were added. Finally, the pH of the solution was adjusted by dilution with sodium hydroxide and / or citric acid to a pH of 6.4-6.6 (for examples containing Phenonip XB as a preservative) and the remainder of water was added in a sufficient amount up to 100 wt%. The solution was continued to stir until uniform and then transferred to an appropriate storage vessel.

The dry weight yield was measured according to the dry weight yield test as described herein. As shown in Table 6b, composition C28 having an anionic to cationic polyelectrolyte ratio of 2.36 did not show a measurable increase in dry weight yield compared to the corresponding compositions of Comparative Examples C27 without anionic polyelectrolyte.

Table 6b

% mass. active substance Material C27 C28 Copolymer of acrylates 0 0.26 Polyquaternium-7 0.11 0.11 Sodium laureth sulfate 9.8 9.8 Cocobetaine 1.99 1.99 Disodium cocoamphodiacetate 0.6 0.6 Glycerol one one Hexylene glycol one one Disodium EDTA 0.26 0.26 Sodium glycolate 0.12 0.12 Sodium chloride 2.16 2.16 Flavoring 0.25 0.25 Preservative (Phenonip XB) one one Sodium hydroxide ex. qty ex. qty Lemon acid ex. qty ex. qty Water ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 2.36 Dry sludge mass yield 0 0

Examples 7a-7g

Deposition Measurements of Inventive Formulations (E18-E24) and Comparative Examples (C9, C11, C29-32) Using Various Anionic Polyelectrolyte Chemical Properties

The compositions of Comparative Examples C9, C11, C29-34 and Inventive Examples E18-E24, listed in Tables 7a-7g, together with the dry weight yield (as measured by the dry weight yield test described herein), are formulations that reproduce the concentrations of the selected anionic polyelectrolyte, salt, and preservatives from Tables 3a-3b, but use different concentrations and chemistries for the anionic polyelectrolyte. As shown in Tables 7a-7g, the formulations of the inventive Examples E18-E24 show a measurable increase in dry weight yield compared to the corresponding formulations of Comparative Examples C9 and C11 not containing the anionic polyelectrolyte. Comparative examples C29-34 having an anionic to cationic polyelectrolyte weight ratio greater than 1.2 (i.e., 2.5 or 3.33) did not show a measurable increase in dry weight yield compared to the corresponding compositions of comparative examples C9 and C11, respectively. not containing anionic polyelectrolyte.

Table 7a

% mass. active substance Material Material class C9 E18 C29 Polyacrylate-33 Anionic polyelectrolyte 0 0.1 2 Polyquaternium-10 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances
anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 3.33 Dry sludge mass yield 2.7 3.3 0

Table 7b

% mass. active substance Material Material class C9 E19 C30 Carboxymethyl cellulose Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-10 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances
anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 2.7 3.32 1.11

Table 7c

% mass. active substance Material Material class C11 E20 C31 Xanthan gum Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-10 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 2.7 3.13 1.23

Table 7d

% mass. active substance Material Material class C11 E21 C32 Polyacrylate-33 Anionic polyelectrolyte 0 0.1 2 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 3.33 Dry sludge mass yield 0.37 1.65 0

Table 7e

% mass. active substance Material Material class C11 E22 C33 Carboxymethyl cellulose Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric /
zwitterionic surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0.37 0.55 0.23

Table 7f

% mass. active substance Material Material class C11 E23 C34 Xanthan gum Anionic polyelectrolyte 0 0.1 1.5 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 3.5 Cocamidopropyl Betaine Amphoteric / Zwitterionic Surfactant 3.5 3.5 3.5 Sodium chloride Salt 0,4 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 2.50 Dry sludge mass yield 0.37 0.52 0.10

Table 7g

% mass. active substance Material Material class C11 E24 Sodium polyacrylate (crosslinked) Anionic polyelectrolyte 0 0.1 Polyquaternium-7 Cationic polyelectrolyte 0.6 0.6 Sodium laureth sulfate Anionic surfactant 3.5 3.5 Cocamidopropyl Betaine Amphoteric / Zwitterionic Surfactant 3.5 3.5 Sodium chloride Salt 0,4 0,4 Sodium benzoate Preservative 0.5 0.5 Lemon acid PH regulator ex. qty ex. qty Sodium hydroxide PH regulator ex. qty ex. qty Water Carrying medium ex. quantity up to 100% of the mass. ex. quantity up to 100% of the mass. Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0.00 0.17 Dry sludge mass yield 0.37 0.56

Examples 8a-8e

Comparison of rheological properties of formulations with the features of the invention (E1-E3, E7-E9, E18-E20) and comparative (C1-C3, C7-C12, C29-31) examples

A number of the previously listed formulations of comparative and inventive examples were tested in accordance with the viscosity and yield stress tests described herein. The rheological properties of the compositions shown in Table 1a are listed in Table 8a. The amount of acrylate copolymer included in the formulations of the inventive Examples E1-E3 that exhibit increased deposition (as previously shown in Table 1a) is insufficient to increase the measured viscosity above η _min , the minimum value needed to indicate a significant / significant change in viscosity across compared to the system without anionic polyelectrolyte described herein. Likewise, the inventive compositions E1-E3 exhibit no measurable yield stress. Only comparative examples C2-C3 (which do not show increased deposition) is there a sufficient amount of acrylate copolymer (1-1.5 wt%) to cause a measurable yield stress and a significant increase in viscosity. Therefore, the use of the crosslinked copolymer of ASE acrylates in the inventive Examples E1-E3 goes beyond the intended use of the polyelectrolyte as a suspending agent, thickener or rheology modifier.

Table 8a

The rheological properties of a composition containing 9% of the mass. SLES, 2% of the mass. CAPB and 0.6% of the mass. PQ-10 Example Concentration of anionic polyelectrolyte (% by weight of active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) η _min (cP) C1 0 0.00 0.00 569.02 Rheological properties of compositions containing 9% of the mass. SLES, 2% of the mass. CAPB, 0.6% of the mass. PQ-10 and acrylate copolymer Example Concentration of acrylate copolymer (% by weight of active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) Viscosity at medium shear forces η (cP) E1 0.1 0.17 0.00 96.1 E2 0.3 0.50 0.00 175.1 E3 0.6 1.00 0.00 465.5 C2 one 1.67 1.97 1515 C3 1.5 2.50 8.66 4435

Likewise, the use of an acrylate copolymer has been shown not to result in measurable yield stress or significant viscosity changes in inventive examples including surfactant blends and cationic polyelectrolytes with different chemical properties, as shown in Tables 8b-8d.

Table 8b

The rheological properties of a composition containing 9% of the mass. SLES, 2% of the mass. CAPB and 0.6% of the mass. PQ-7 Example Concentration of anionic polyelectrolyte (% wt. Active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) η _min (cP) C7 0 0.00 0.00 286.68 Rheological properties of compositions containing 9% SLES, 2% CAPB, 0.6% PQ-7 and acrylate copolymer Example Concentration of acrylate copolymer (% by weight of active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) Viscosity at medium shear forces η (cP) E7 0.1 0.17 0.00 24.06 C8 1.5 2.50 7.05 3426

Table 8c

The rheological properties of a composition containing 3.5% of the mass. SLES, 3.5% of the mass. CAPB and 0.6% of the mass. PQ-10 Example Concentration of anionic polyelectrolyte (% wt. Active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) η _min (cP) C11 0 0.00 0.00 3126 Rheological properties of compositions containing 9% of the mass. SLES, 2% of the mass. CAPB, 0.6% of the mass. PQ-10 and acrylate copolymer Example Concentration of acrylate copolymer (% by weight of active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) Viscosity at medium shear forces η (cP) E9 0.1 0.17 0.00 1626 C12 1.5 2.50 8.65 4963

Table 8d

The rheological properties of a composition containing 3.5% of the mass. SLES, 3.5% of the mass. CAPB and 0.6% of the mass. PQ-7 Example Concentration of anionic polyelectrolyte (% wt. Active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) η _min (cP) C9 0 0.00 0.00 1406 Rheological properties of compositions containing 3.5% of the mass. SLES, 3.5% of the mass. CAPB, 0.6% of the mass. PQ-7 and acrylate copolymer Example Concentration of acrylate copolymer (% by weight of active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) Viscosity at medium shear forces η (cP) E8 0.1 0.17 0.00 1347 C10 1.5 2.50 12.52 4435

The rheological properties of the compositions of the inventive examples E18 and E19, which use alternative anionic rheology modifying polyelectrolytes (namely carboxymethylcellulose, polyacrylate-33 and xanthan gum), are shown in Table 8e. Again, the use of these anionic polyelectrolytes at the low concentrations required to increase polyelectrolyte deposition does not impart yield stress or significant viscosity changes. Therefore, the use of these alternative anionic rheology modifiers in the inventive examples goes beyond their intended use as suspending agents, thickening agents or viscosity modifiers.

Table 8e

The viscosity of the composition containing 3.5% of the mass. SLES, 3.5% of the mass. CAPB and 0.6% of the mass. PQ-10 Example Concentration of anionic polyelectrolyte (% wt. Active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) η _min (cP) C11 0 0.00 0.00 3782 Rheological properties of compositions containing 3.5% of the mass. SLES, 3.5% of the mass. CAPB, 0.6% of the mass. PQ-10 and acrylate copolymer Example Concentration of acrylate copolymer (% by weight of active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) Low shear viscosity η (cP) E9 0.1 0.17 0.00 2065 C12 1.5 2.50 8.66 12 520 Rheological properties of compositions containing 3.5% of the mass. SLES, 3.5% of the mass. CAPB, 0.6% of the mass. PQ-10 and carboxymethyl cellulose Example Concentration of carboxymethyl cellulose (% by weight of active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) Low shear viscosity η (cP) E19 0.1 0.17 0.00 3470 C30 1.5 2.50 0.00 20970 Rheological properties of compositions containing 3.5% of the mass. SLES, 3.5% of the mass. CAPB, 0.6% of the mass. PQ-10 and polyacrylate-33 Example Concentration of polyacrylate-33 (% by weight of active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) Low shear viscosity η (cP) E18 0.1 0.17 0.00 2553 C29 1.5 2.50 4.94 6321 Rheological properties of compositions containing 3.5% of the mass. SLES, 3.5% of the mass. CAPB, 0.6% of the mass. PQ-10 and xanthan gum Example Concentration of xanthan gum (% wt. Active substance) Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte Yield Strength (Pa) Low shear viscosity η (cP) E20 0.1 0.17 0.00 2743 C31 1.5 2.50 0.00 27190

Example 9

Comparison of in-vitro deposition of a cleaning agent polyelectrolyte film on a substrate between the formulations of the Inventive (E1) and Comparative (C1, C3) Examples

The deposition efficiency of the film / polyelectrolyte in a number of compositions of comparative and inventive examples with comparable compositions, with the exception of the concentration of anionic polyelectrolyte (C1, E1 and C3 presented in Table 1a), was evaluated in accordance with the ellipsometry based polyelectrolyte deposition test, as described in this document. The results shown in Table 9 show that inventive example E1 shows an increase of ~ 40% in deposited film thickness over comparative examples C1 and C3 (with anionic / cationic polyelectrolyte active substance weight ratios of 0 and 2.5, respectively).

Table 9

Example Concentration of PQ-10 (% by weight of active substance) Concentration of acrylate copolymer (% by weight of active substance) Mass ratio of active substances of anionic / cationic polyelectrolyte Average deposited film thickness (nm) C1 0.6 0 0 1.10 E1 0.6 0.1 0.17 1.63 C3 0.6 1.5 2.5 1.25

Example 10

Evaluation and Comparison of Skin Feel Between the Formulation of Inventive Example (E9) and Comparative Example (C11)

The skin feel after rinsing with the composition of Comparative Example C8 and the Inventive Example E6 (with comparable compositions, excluding the concentration of anionic polyelectrolyte shown in Table 3b) followed by drying was compared qualitatively in three volunteers according to a sensory evaluation test. In this skin-balancing test, participants first washed their hands and forearms using 1 ml of surfactant standard solution (5% w / w sodium laureth sulfate, 5% w / w cocamidopropyl betaine, pH 4.5, DI water) ... After thorough rinsing (tap water at 35-45 ° C for 60 s at a flow rate of ~ 3 liters per minute), 1 ml of the test composition (C8 or E6, respectively) was applied to a wet palm. Participants washed their wet hands and forearms for 30 seconds, performing circular motions of the hands on the forearms. After rinsing (35-45 ° C tap water for 30 seconds at a flow rate of 3 liters per minute), participants dried their hands and forearms with a dry paper towel and air-dried their hands and forearms completely for approximately 120 seconds. They then described a sensory sensation on the skin by running their fingers over their arms and forearms. Descriptions of the feel of dry skin after using the comparative and inventive examples are shown in table 10. It shows that the addition of 0.1% of the mass. The acrylate copolymer not only significantly increases the amount of sludge measured in the comparative dry weight yield test (as shown in Table 1a), but also changes the general consensus on the skin feel from “soft” to “powdered” after cleansing and drying. This indicates a change in the tactile properties of the deposited film.

Table 10

Example C11 Example E9 Concentration PQ-7 (wt% active substance) 0.6 0.6 Copolymer of acrylates (% by weight of active substance) 0 0.1 Mass ratio of active substances of anionic polyelectrolyte / cationic polyelectrolyte 0 0.17 Subjects' comments "Soft, smooth, not powdered" "Smooth, powdered, silky"

Example 11

Comparison of Deposition of Dimethicone from Formulation when Used on Human Skin Between Formulations of Invention (E11) and Comparative (C15) Examples

The deposition efficiency of dimethicone in a pair of compositions of the comparative and inventive examples containing 0.6% of the mass. guarhydroxypropyltrimonium chloride, with identical compositions except for the concentration of the anionic polyelectrolyte, C15 (no anionic polyelectrolyte) and E11 (0.1 wt% acrylate copolymer) (as shown in Table 4a above) were evaluated according to the dimethicone precipitation test described in this document. The intensity of the Si peak at 1260 cm ^-1 , which correlates with the concentration of dimethicone on human skin, is shown in Table 11. These data indicate a marked improvement in the deposition of dimethicone from Comparative Example C15 over inventive Example E11.

Table 11

Example Mass ratio of active substances of anionic / cationic polyelectrolyte Intensity of the Si peak at 1260 cm ^-1 (abs. Units) C15 0 55 E11 0.17 234

Claims (15)

1. Composition for personal hygiene, containing in a cosmetically acceptable aqueous medium: a) cationic polyelectrolyte in the amount of 0.6 wt.%, b) at least one surfactant in an amount of 3-15 wt%; and (c) 0.03 to 0.72 wt% anionic polyelectrolyte, moreover, the mass ratio of the specified anionic polyelectrolyte and the specified cationic polyelectrolyte is from 0.05 to 1.2, while the specified composition shows a change in viscosity below the minimum threshold of significant change (Δη _min ) and demonstrates the absence of a measurable yield stress or an increase in the yield stress index compared to a substantially identical composition that does not contain 0.03 to 0.72 weight percent of said anionic polyelectrolyte in a weight ratio of anionic polyelectrolyte to cationic polyelectrolyte of 0.05 to 1.2. 2. A composition according to claim 1, wherein the weight ratio of said anionic polyelectrolyte and said cationic polyelectrolyte is from 0.1 to 1. 3. A composition according to claim 1, comprising from 0.1 wt% to 0.72 wt% of said anionic polyelectrolyte. 4. A composition according to claim 1 comprising from 3 weight percent to 12 weight percent of said surfactant. 5. The composition according to claim 1, in which the yield of the dry sludge mass upon dilution of said composition exceeds the yield of the dry sludge mass upon dilution of a substantially identical composition that does not contain from 0.03 mass percent to 0.72 mass percent of said anionic polyelectrolyte by mass the ratio of the specified anionic polyelectrolyte and the specified cationic polyelectrolyte from 0.05 to 1. 6. A composition according to claim 1, wherein the dry sludge weight yield upon dilution of said composition is increased by 10% or more as compared to a substantially identical composition that does not contain from 0.03 to 0.72 weight percent of said anionic polyelectrolyte by weight the ratio of anionic polyelectrolyte and cationic polyelectrolyte from 0.05 to 1.2. 7. A composition according to claim 1, wherein the solids yield upon dilution of said composition is increased by 20% or more as compared to a substantially identical composition that does not contain from 0.03 weight percent to 0.72 weight percent of said anionic polyelectrolyte ... 8. A composition according to claim 1, wherein the dry sludge weight yield upon dilution of said composition is increased by 40% or more as compared to a substantially identical composition that does not contain from 0.03 weight percent to 0.72 weight percent of said anionic polyelectrolyte ... 9. The composition according to claim 1, in which said anionic polyelectrolyte is selected from the group consisting of polyelectrolytes obtained from ethylenically unsaturated monomers containing anionic and anionically ionizable monomers, anionic and anionic ionizable polysaccharides and derivatives of polysaccharides and anionic or anionic ionizable , or proteins, or hybrid (co) polymers. 10. The composition of claim 1, wherein said cationic polyelectrolyte is selected from the group consisting of polyelectrolytes derived from ethylenically unsaturated monomers containing cationic protonated amine or quaternary ammonium functional groups, cationic and cationic ionizable polysaccharides and polysaccharide derivatives and cationic or cationic ionizable polypeptides, or proteins, or hybrid (co) polymers. 11. The composition of claim 1, wherein said surfactant is selected from the group consisting of anionic, zwitterionic, nonionic and cationic surfactants.