Methods of cleansing dyed hair

(54) Title: DYED HAIR CLEANING METHODS (30) Unionist Priority: 7/17/2007 us 11 / 778,704 (73) Owner (s): Johnson & Johnson Consumer Companies, Inc (72) Inventor (s): anthony j. cossa, josephj. librizzi,

RUSSELM. WALTERS (57) Abstract: methods for cleaning dyed hair, the present invention relates to methods for cleaning dyed hair provided comprising application to dyed hair of a composition comprising anionic surfactant and a hydrophobically modified polymer capable of binding surfactant to the same.

ΡΙ0802407-3

Descriptive Report of the Invention Patent for DYED HAIR CLEANING METHODS.

Field of the Invention

The present invention relates to methods for cleaning dyed hair. More specifically, the invention relates to methods of cleaning dyed hair with improved color retention using a cleaner comprising an anionic surfactant and a hydrophobically modified polymer.

Description of the Related Art

Applicants recognized that the color in dyed hair tends to fade will be due, in part, to factors such as UV exposure and washing of dyed hair. In particular, a significant amount of hair dye loss is associated with rinsing hair dyed in water only, the surfactants present in typical shampoos tend to cause significant additional color loss during cleaning. Applicants subsequently recognized that hair dyes are often made up of multiple hair coloring agents, and each specific coloring agent tends to have a different loss rate. Therefore, in addition to fading, the color or tone of dyed hair tends to change due to the non-uniform loss of specific coloring agents.

A variety of attempts that take into account the need to maintain color / dye in hair include protecting the hair from UV damage by adding UV filters to shampoo, applying dye to new hair daily from a shampoo or from a conditioner to replenish lost hair dye, application of additional materials (conditioners) on the top of the hair to reduce loss of hair dye during rinsing, and reducing the aggressiveness of the cleaning surfactant by reducing the amount of surfactant and / or using a smoothing surfactant. However, such methods tend to be disadvantageous for numerous reasons including lack of effectiveness in preventing loss of hair coloring agents, inconsistency in maintaining color or tone, and resulting in compositions that tend to be aesthetically disadvantaged, for example, compositions with low foaming and / or poor rheological characteristics.

Correspondingly, applicants have identified a need for methods of cleaning hair with improved color and / or aesthetics retention.

Summary of the Invention

The present invention provides methods for cleaning dyed hair that overcome the disadvantages of the prior art. According to one aspect, the present invention provides methods for cleaning dyed hair comprising applying to dyed hair a composition comprising anionic surfactant and a hydrophobically modified polymer capable of binding surfactant thereto.

Brief Description of Drawings

Figure 1 is a graphical representation of the idealized tensiometry data associated with the addition of anionic surfactant to two solutions.

Figure 2 is a graphical representation of the relative delta C values ​​measured for a certain composition of the claimed invention and comparative compositions.

Figure 3 is a graphical representation of the relative delta E values ​​measured for a certain composition of the claimed invention and comparative compositions.

Figure 4 is a graphical representation of the tensiometry data associated with a composition of the present invention.

Description of Preferred Embodiments

As used herein, the term dyed hair refers to mammalian hair to which a dye or other coloring agent has been applied to change the color of the hair. As will be recognized by those skilled in the art, any of a variety of dyes and / or coloring agents are suitable for use in hair coloring, including but not limited to natural dyes, including but not limited to natural dyes , including indigo, pau-campeche, henna (Lawsonia alba), nutshell extract, chamomile (Matricaria chamiomila), and similaress, semi-permanent dyes including HC Yellow 2, HC Yellow 5, HC Red 3, HC

Blue 2, Scattered Violet 1, Scattered Blue 3, HC Orange 1, HC Red 1, Scattered Black 9, and similaress, temporary dyes including FD&C Blue 1, FD&C Red 4, FD&C Yellow 6, EXT D&C Violet 2, and similaress, dyes of direct action including nitrophenylenediamines, nitroaminophenols, an5 traquinones, azo dyes and Cl Yellow acid 1, Cl Yellow acid 3, C.í. Orange acid 7, Cl Orange acid, 87, Cl Red acid 33, Cl Acid violet 43, Cl Violet acid 73, Cl Blue acid 9, Cl Blue acid 168, Cl Green acid 25, Cl Brown acid 19, Cl brown acid 45, Cl black acid 107, Cl Yellow Basic 57, Cl Red Basic 76, Cl Blue Basic 99,

Basic Brown Cl 16, Basic Brown Cl 17, Sunset Yellow, Ponceau Red, Cl Solvent Brown 44, and the like, and any of such dyes / agents and the like, or combinations of two or more of the same, can be applied to hair to get dyed hair.

Applicants have unexpectedly found that cleaning compositions comprising anionic surfactant and hydrophobically modified polymers capable of bonding surfactant to them can be used to clean dyed hair with significant improved color retention. For example, applicants have measured the color change and fading of dyed hair associated with the use of compositions of the present invention when compared to comparable compositions as later described in the Examples. Applicants have unexpectedly found that the present compositions tend to change the color of dyed hair significantly less than comparable compositions. In addition, on visual examination data, the present methods result in hair that appears to be half-faded as much as hair washed with comparable compositions. Applicants have further discovered that in certain embodiments, the methods of the present invention exhibit cleaning with relatively high foam / foaming stability properties, and / or other characteristics.

Although applicants do not wish to be bound by or for any particular theory of operation, polymeric materials suitable for use in the present methods are believed to act to reduce color removal from dyed hair associated with hair care compositions.

I ί

<personal data, at least in part, by surfactant binding (free surfactant molecules (unbound) and / or, especially, free surfactant micelles (unbound) to them to reduce the aggressiveness of the surfactant formulation in removal of color from the hair. By bonding surfactants and / or surfactant micelles to them, polymeric materials reduce the concentration of unbound surfactant micelles in a composition and allow a higher concentration of surfactant to be added to the composition before the free micelles are formed and / or before a particular level of aggression is reached. This desirable change in surfactant concentration is further illustrated in Figure 1.

Figure 1 is a graph 10 showing the idealized surface tension data curves associated with the addition of anionic surfactant to two compositions, a composition comprising a hydrophobically modified material of the present invention and a comparable composition free of hydrophobically modified material. Curve 11 shows the change in surface tension, measured via conventional tensiometry techniques (examples of which are described here below), a composition free of hydrophobically modified material as increasing levels of anionic surfactant are added to it. Curve 15 shows the change in surface tension of a composition comprising hydrophobically modified material as increasing levels of anionic surfactant are added to it. In curve 11, once the surfactant is added to the solution, the surfactant tends to populate the air / liquid interface, thereby reducing the surface tension of the solution, until essentially the entire surface area is filled. After that point, hereinafter the critical micelle concentration (CMC) of surfactant, point 12, essentially the totality of surfactant added to the composition forms free micelles in the solution, a formation that does not have an appreciable effect on the surface tension of the solution but it tends to increase the irritation associated with the composition. By comparison, as shown in curve 15, once anionic surfactant is added to a solution comprising a hydrophobically modified material, the surfactant both lines up over the air / liquid interface and bonds to the hydrophobically modified material up to CMC, point 16, mudoü at a significantly higher surfactant concentration when compared to curve 11, at which point the added surfactant tends to form free micelles.

In light of the above, applicants have recognized that a measure of the effectiveness of a particular hydrophobically modified material in bonding the surfactant to it can be expressed as a Delta CMC achieved by combining the hydrophobically modified material with an anionic surfactant to form a reduced irritation composition . An

Delta CMC as used here is defined as the number obtained by: (a) determining the CMC for: (i) a particular composition of the present invention comprising anionic surfactant and hydrophobically modified material, and (ii) the comparable composition of the composition in (i ), which CMC values ​​are determined using Ten15 siomtry Test reverse Titration procedures defined in the Examples below; and (b) subtracting the CMC value obtained for the composition (ii) from the value obtained for the composition (i). In certain embodiments, it is preferred to select a hydrophobically modified material for use in the present methods so that the Delta CMC associated with the resulting reduced irritation composition is a positive value. In certain more preferred embodiments, the hydrophobically modified material is selected to achieve a reduced irritation composition having a Delta CMC of about +16 or greater, more preferably, about +80 or greater, and even more preferably of about +300 or greater.

As used herein, the term hydrophobically modified polymer generally refers to any polymer having one or more hydrophobic moieties attached to or incorporated therein. Such polymers can be formed, for example, by polymerizing one or more hydrophobic monomers and, optionally, one or more co-monomers, to form a polymer having hydrophobic moieties incorporated therein, and / or also by reacting polymer materials with compounds comprising hydrophobic moieties for attaching such compounds to polymers. Certain hydrophobically modified polymers and methods of producing such polymers are described in US patent no. 6,433,061, issued by Marchant and others and incorporated herein by reference.

Examples of hydrophobically modified polymers capable of binding a surfactant to it and suitable for use in the present methods include hydrophobically modified acrylic polymers, as well as hydrophobically modified cellulosics, hydrophobically modified starches, combinations of two or more of the same, and the like.

Hydrophobically modified acrylic polymers suitable for use in the present invention can be in the form of random, block, star, graft, and similar copolymers. In certain embodiments, hydrophobically modified acrylic polymers are cross-linked, anionic acrylic copolymers. Such copolymers can be synthesized from at least one acidic monomer and at least one hydrophobic ethylenically unsaturated monomer. Examples of suitable acid monomers include those ethylenically unsaturated acid monomers that can be neutralized by a base. Examples of suitable hydrophobic ethylenically unsaturated monomers include those that contain a hydrophobic chain having a carbon chain length of at least 3 carbon atoms.

In another embodiment, the hydrophobically modified cross-linked, anionic acrylic copolymer includes those compositions derived from at least one unsaturated carboxylic acid monomer; at least one hydrophobic monomer; a hydrophobic chain transfer agent comprising alkyl mercaptans, thioesters, compounds containing amino acid-mercaptan or peptide fragments, or combinations thereof; a cross-linking agent; and, optionally, a spherical stabilizer; wherein the amount of said unsaturated carboxylic acid monomer is from about 60% to about 98% by weight based on the total weight of said unsaturated monomers and said hydrophobic monomer, as indicated in US patent no. 6,433,061, which is incorporated by reference here. In a preferred embodiment, the polymer is an acrylate copolymer that is commercially available from Noveon, Inc. under the trademark, Carbopol Aqua SF-1. In another preferred embodiment, the hydrophobically modified acrylic polymer is an associative macromer having a main chain derived from methacrylate and ethylacrylate, and a hydrophobic portion derived from itaconate monomers, which polymer can be produced via emulsion polymerization. Another preferred polymer comprises an alternating octadecene / methacrylate copolymer, having a molecular weight of from about 20,000 to about 25,000, available from Chevron Phillips Chemical as PA-18, as well as derivatives of such a polymer including hydrolyzed and starched derivatives, and similaress.

Any of a variety of cellulosic or hydrophobically modified starches are suitable for use in the present invention. Examples of suitable hydrophobically modified cellulosics include hydrophobically modified hydroxyethyl cellulose (commercially available, for example, from Hercules Inc. (Wilmington, DE) as Natrosol Plus), and si15 milaress. Examples of suitable hydrophobically modified starches include hydrophobically modified hydroxypropyl starch phosphate (commercially available, for example, from National Starch (Bridgewater, NJ) as Structure XL), and the like. Examples of other suitable polymers include hydrophobically modified polysaccharides, including those derived from cellulose, starch, inulin, guar, xanthan, carrageenan, chitosan, pectin, xizophilane, and the like. Any of such polysaccharides can be nonionic hydrophilic, nonionic hydrophobic, cationic, zwitterionic or polymeric.

Any of a variety of phobically modified hydro25 inulin polysaccharides are suitable for use here. Certain preferred hydrophobically modified polysaccharides include those described in general by the formulas:

<img file="BRPI0802407A2_D0001.tif" />

where m is about 15-10,000, more preferably about 15-1,000, more preferably about 10-300; n is about 5-10,000, more preferably about 15-1,000, more preferably about 10-300; and af about 6-30, more preferably about 8-24, and most preferably about

8-18. Hm-inulin is a hm-polyfructose that is extracted from the roots of chicory (Cichorium intybus). Naturally occurring inulin is a polydispersed polysaccharide that consists mainly of units of beta (2-1) fructose fructose with normally, but not necessarily, a unit of glucopyranose at the reducing end. Inulin is hydrophobically modified with alkyl groups (C₄-Ci₈) that are randomly distributed in the main sugar chain in the primary as well as in the secondary hydroxyl functions. An example of a preferred inulin polymer is commercially available from Orafti as Inutec SP-1. Inutec SP-1 hm-inulin has a degree of polymerization of about 50 and a molecular weight (Mw) of about 5000 g / mol. The hydrophobic alkyl chain in the main chain is a chain length distribution with an average alkyl chain length of about Ci₂In certain preferred embodiments, the hydrophobically modified polymers selected for use in the present invention are low molecular weight polymers. As used herein, the term low molecular weight polymer refers to a polymer having an average molecular weight by weight of less than about 10,000,000 grams per mol (g / mol). Certain preferred low molecular weight polymers include polymers having an average molecular weight by weight of from about 1,500 to about

10,000,000 g / mol. Certain preferred low molecular weight polymers include polymers having an average molecular weight by weight of from about 2,500 to about 5,000,000 g / mol, more preferably from about 3,000 to about 1,000,000 g / mol, with more preferably from about 3,500 to about 500,000. In certain particularly preferred embodiments, the low molecular weight polymers include polymers having an average molecular weight by weight of from about 3,500 to about 100,000 g / mol, more preferably about 3,500 to about 60,000 g / mol, in certain embodiments preferably about 5,000 to about 60,000 g / mol, and most preferably about 15,000 to about 50,000.

Any variety of anionic surfactants can be combined with hydrophobically modified polymer material to form a composition for use in the preferred embodiments of the present methods. According to certain embodiments, suitable anionic surfactants include those selected from the following classes of surfactants: alkyl sulfates, alkyl ether sulfates, alkyl monoglyceryl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl sulfosuccinates, alkyl amidosulfosuccinates, alkyl alkyl carboxylates, starch alkyls alkyl, fatty acyl sarcosinates, fatty acyl amino acids, fatty acyl taurates, fatty alkyl sulfoacetates, alkyl phosphates, and mixtures of two or more of the same. Examples of certain preferred anionic surfactants include:

alkyl sulfates of the formula

FT-CHsOSOsX ';

alkyl ether sulfates of the formula RXOCHsCHsjvOSOsX ';

monoglyceryl alkyl ether sulfates of the formula

ROCH2 &lt;pHCH2OSO₃X '

OH monoglyceride alkyl sulfates ether of the formula

<img file="BRPI0802407A2_D0002.tif" />

R'CO2CH2 &lt;pHCH2OSO3X ';

OH alkyl monoglyceride sulfonates of the formula R'CO2CH2 ^ HCH2SO3X ';

OH alkyl sulfonates of the formula R'-SO₃X ';

alkylaryl sulfonates of the formula

R '

ONLY₃X ';

alkyl sulfosuccinates of the formula: R'O₂Ç.

CO₂X ';

<img file="BRPI0802407A2_D0003.tif" />

SO3X 'alkyl ether sulfosuccinates of the formula: R' - (OCH₂CH₂)_V-O₂Ç

<img file="BRPI0802407A2_D0004.tif" />

CO₂X ';

SO3X 'alkyl sulfosuccinates of the formula:

<img file="BRPI0802407A2_D0005.tif" />

alkyl amidosulfosuccinates of the formula

R'— C — NH — CH₂CH2 ^ -OCH₂CH2 ^ w O₂Ç

<img file="BRPI0802407A2_D0006.tif" />

CO₂X ';

SO3X 'alkyl carboxylates of the formula:

R '- (OCH₂CH2)_w-OCH2CO2X ';

alkyl amidoetercarboxylates of the formula:

R'— C — NH — CH₂CH2-6OCH2CH2- ^ vOCH₂CO₂X ';

alkyl succinates of the formula:

R '·

CO₂X ';

fatty acyl sarcosinates of the formula:

R'-C — y — CH₂CO₂X '; ch₃ fatty acyl amino acids of the formula:

ÂJl

R NH CO₂X '; fatty acyl taurates of the formula:

<img file="BRPI0802407A2_D0007.tif" />

fatty alkyl sulfoacetates of the formula:

R'0 CH2SO3X '; alkyl phosphates of the formula:

R '- (OCH₂CH₂)_w-O— P — OX ';

Oh where

R 'is an alkyl group having from about 7 to about 22, and preferably from about 7 to about 16 carbon atoms,

R'1 is an alkyl group having from about 1 to about 18, and preferably from about 8 to about 14 carbon atoms,

R'2 is a substitute for a natural or synthetic I-amino acid,

X 'is selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from about 1 to about 3 substituents, each of the substituents can be equal or different and are selected from the group consisting of 1 to 4 carbon atoms and hydroxyalkyl groups having from about 2 to about 4 carbon atoms and v is an integer from 1 to 6; w is an integer from 0 to 20;

and their mixtures.

According to certain embodiments, the anionic surfactant of the present invention preferably comprises one or more alkyl ether sulfates, or mixtures thereof. In certain more preferred embodiments, the anionic surfactant of the present invention comprises sodium trideceth sulfate. Sodium trideceth sulfate is the sodium salt of sulfated ethoxylated tridecyl alcohol that adapts in general to the following formula, Ci3H27 (OCH₂CH2) nOSO₃Na, where n has a value between 1 and 4, and is commercially available from the Stepan Company of Northfield, Illinois under the trademark, Cedapal TD-403M. Applicants have recognized that sodium trideceth sulfate can be used with particular advantage to obtain compositions having significantly reduced irritation associated therewith according to the present invention.

Any amounts of hydrophobically modified polymer and anionic surfactants suitable to produce an improved color retention composition can be combined according to the present methods. According to certain embodiments, sufficient hydrophobically modified material is used to produce a composition comprising from more than zero to about 5.0% by weight of the hydrophobically modified material active in the composition. Preferably, sufficient hydrophobically modified material is used to produce a reduced irritation composition comprising from about 0.01 to about 4.0%, more preferably from about 0.3 to about 3.0%, even more preferably from about 0.5 to about 2.5%, and even more preferably from about 0.7 to about 2.0% of the hydrophobically modified material active in the composition. The amount of anionic surfactant used in the present invention is preferably an amount sufficient to produce a composition comprising from about 0.1 to about 30.0%, more preferably from about 1% to about 25.0% , even more preferably from about 3.0 to about 17.0% of the total active anionic surfactant in the composition.

The hydrophobically modified material and the anionic surfactant can be combined according to the present invention via any conventional methods of combining two or more fluids. For example, one or more compositions comprising, consisting essentially of, or consisting of at least one hydrophobically modified material and one or more compositions comprising, consisting essentially of, or consisting of at least one anionic surfactant can be combined by pouring, mixing, adding , drip, pipetting, pumping, and the like, one of the compositions comprising hydrophobically modified material or anionic surfactant in or with the other in any order using any conventional equipment such as a mechanically agitated propellant, shovel, and the like. According to certain embodiments, the combining step comprises combining a composition comprising anionic surfactant in or with a composition comprising hydrophobically modified material. According to certain other embodiments, the combining step comprises combining a composition comprising material hydrophobically modified in or with a composition comprising anionic surfactant.

The compositions for use in the present methods may further comprise any of a variety of other components not exclusively including one or more non-ionic, amphoteric and / or cationic surfactants, pearlescent or opacifying agents, thickening agents, secondary conditioners, humectants, agents chelation, and additives that enhance the appearance, feel and fragrance of compositions, such as colorants, fragrances, preservatives, pH-adjusting agents, and similaress.

Any 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 acid or amide ethoxylates, monoglyceride ethoxylates, alkyl polyglycoside ethoxylate sorbitan esters, mixtures thereof, and the like. Certain preferred nonionic surfactants include polyoxyethylene derivatives of polyol esters, wherein the polyoxyethylene derivative of polyol ester (1) is derived from (a) a fatty acid containing 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-methyl glycoside, polyglucose having an average of about 1 to about 3 glucose residues per molecule, glycerin , pentaerythritol and mixtures thereof, (2) contains an average of from about 10 to about 120, and preferably about 20 to about 80 oxyethylene units; and (3) has an average of about 1 to about 3 fatty acid residues per mole of polyoxyethylene derivative of polyol ester. Examples of such preferred polyoxyethylene derivatives of polyol esters include, but are not limited to, PEG-80 sorbitan laurate and Polysorbate 20. PEG-80 sorbitan monolaurate, which is an ethoxylated lauric acid sorbitan monoester with an average of about 80 moles of ethylene oxide, is commercially available from ICI Surfactants of Wilmington, Delaware under the trademark, Atlas G-4280 . Polysorbate 20, which is the laurate monoester of a mixture of sorbitol and sorbitol anhydrides condensed with about 20 moles of ethylene oxide, is commercially available from ICI Surfactants of Wilmington, Delaware under the trademark Tween 20.

Another class of suitable nonionic surfactants includes long chain alkyl glycosides or polyglycosides, which are the 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 a polymer containing glucose. Preferred alkyl glycosides comprise from about 1 to about 6 glucose residues per alkyl glycoside molecule. A preferred glycoside is decyl glycoside, which is the condensation product of decyl alcohol with a glucose polymer and is commercially available from the Henkel Corporation of Hoboken, New Jersey under the trademark, Plantaren 2000.

As used here, the term amphoteric will mean: 1) molecules that contain both acidic and basic sites such as, for example, an amino acid containing both amino (basic) and acidic functional groups (eg, carboxylic acid, acid); or 2) zwitterionic molecules that have both positive and negative charges within the same molecule. The latter charges can be either dependent on or independent of the composition's pH. Examples of zwitterionic materials include, but are not limited to, alkyl betaines and amidoalkyl betaines. Amphoteric surfactants are described here without a counter ion. Those skilled in the art will readily recognize that under the pH conditions of the compositions of the present invention, amphoteric surfactants are either electrically neutral in virtue of having a balance of positive and negative charges, or they have against ions such as against alkali, alkali metal ions earth or ammonium.

Examples of amphoteric surfactants suitable for use in the present invention include, but are not limited to, amphocarboxylates such as alkylaminoacetates (mono or di); alkyl betaines; amidoalkyl betaines; amidoalkyl sultaines; amphophosphates; phosphorylated imidazolines such as phosphobetaines and pyrophosphobetaines; carboxyalkyl alkyl polyamines; alkylimino20 dipropionates; alkylamphoglycinates (mono or di); alkylamphoproprionates (mo • no or di)); N-alkyl β-aminoproprionic acids; alkyl polyamino carboxylates;

and their mixtures.

Examples of suitable amphocarboxylate compounds include those of the formula:

A-CONH (CH₂) xN⁺R₅R₆R₇on what

A is an alkyl or alkenyl group having from about 7 to about 21, for example, from about 10 to about 16 carbon atoms;

x is an integer from about 2 to about 6;

R₅ it is hydrogen or a carboxyalkyl group containing from about 2 to about 3 carbon atoms;

Re is a hydroxyalkyl group containing from about 2 to about carbon atoms or is a group of the formula:

R₈-O- (CH₂) nCO₂· on what

R₈ is an alkylene group having from about 2 to about 3 carbon atoms and n is 1 or 2; and

R₇ it is a carboxyalkyl group containing from about 2 to about 3 carbon atoms;

Examples of suitable alkyl betaines include those compounds of the formula:

BN⁺R₉Rio (CH₂)_PC0₂· on what

B is an alkyl or alkenyl group having from about 8 to about 22, for example, from about 8 to about 16 carbon atoms;

R₉ and Rio are each independently an alkyl or hydroxyalkyl group having from about 1 to about 4 carbon atoms; ep is 1 or 2.

A preferred betaine for use in the present invention is lauryl betaine, commercially available from Albright &amp; Wilson, Ltd. of West Midlands, United Kingdom as Empigen BB / J.

Examples of suitable amidoalkyl betaines include those compounds of the formula:

D-CO-NH (CH₂)_q-N⁺Laugh _Ί Laugh₂(CH₂)_mCO₂' on what

D is an alkyl or alkenyl group having from about 7 to about 21, for example, from about 7 to about 15 carbon atoms;

Ri 1 and Ri₂ they are each independently an alkyl or hydroxyalkyl group having from about 1 to about 4 carbon atoms;

q is an integer from about 2 to about 6; in is 1 or 2.

An amidoalkyl betaine is cocamidopropyl betaine, commercially available from Goldschmidt Chemical Corporation of Hopewell, Virginia under the trademark, Tegobetaine L7,

Examples of suitable amidoalkyl sultaines include those compounds of the formula¹⁴ Θ

E — C — NH— (CH₂)_r-lJí — Ri3 ~ SO₃

RlS in which

E is an alkyl or alkenyl group having from about 7 to about 21, for example, from about 7 to about 15 carbon atoms;

Ru and R15 are each independently an alkyl, or hydroxyalkyl group having from about 1 to about 4 carbon atoms;

r is an integer from about 2 to about 6; and

R13 is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms;

In one embodiment, amidoalkyl sultaine is cocamidopropyl hydroxysultaine, commercially available from Rhone-Poulenc Inc. of Cranbury, New Jersey under the trademark, Miratainé CBS.

Examples of suitable amphophosphate compounds include those of the formula:

? © T^{15 16 * * * 20 * * * * 25} ? ©

G — C — NH— (CH₂) —Γ — RnrO — Ρ — OR₁₇ Oh where

G is an alkyl or alkenyl group having about 7 to about

21, for example, from about 7 to about 15 carbon atoms;

s is an integer from about 2 to about 6;

Laugh₆ it is hydrogen or a carboxyalkyl group containing from about 2 to about 3 carbon atoms;

Laugh? is a hydroxyalkyl group containing from about 2 to about carbon atoms or a group of the formula:

R₁₉-O- (CH₂) t-CO₂on what

R19 is an alkylene or hydroxyalkylene group having from about to about 3 carbon atoms and

t is 1 or 2; and

Ria is an alkylene or hydroxyalkylene group having from about 2 to about 53 carbon atoms.

In one embodiment, the amphophosphate compounds are lauroanfo PG-sodium acetate phosphate, commercially available from Mona Industries of Paterson, New Jersey under the trademark, Monateric 1023. and those disclosed in US patent no.^Q 4,380,637, which is incorporated by reference.

Examples of suitable phosphobetaines include those compounds of the formula:

? © í¹ ff ©

E — C-NH— (CH₂)_r-NRO — j³—OR₂ ΌΗ where E, r, R_1f R₂ and R₃, are as defined above.

In one embodiment, the phosphobetaine compounds are those disclosed in US Pat.^Qs 4,215,064, 4,617,414, and 4,233,192, which are all incorporated herein by reference.

Examples of suitable pyrophosphobetaines include those compounds of the formula:

? ®T ·? faith

E — C — NH— (CH₂)_r-N — R — O — P — O — P — OH R₂ O © O © where E, r, R_1; R₂ and R₃. are as defined above.

In one embodiment, the pyrophosphobetaine compounds are those disclosed in US patents no.⁹4,382,036, 4,372,869, and 4,617,414, which are all incorporated herein by reference.

Examples of suitable carboxyalkyl alkyl polyamines include those of the formula:

<img file="BRPI0802407A2_D0008.tif" />

I — y — Rjj-N where

I is an alkyl or alkenyl group containing from about 8 to about 22, for example, from about 8 to about 16 carbon atoms;

R₂₂ θ a carboxyalkyl group having from about 2 to about 3 carbon atoms;

R₂i is an alkylene group having from about 2 to about 3 carbon atoms i is an integer from about 1 to about 4.

Classes of cationic surfactants that are suitable for use in this invention include alkylquaternary (mono, di, or tri), quaternary benzyl, quaternary esters, ethoxylated quaternaries, alkyl amines, and mixtures thereof, in which the alkyl group has about 6 atoms of carbon to about 30 carbon atoms, with about 8 to about 22 carbon atoms being preferred.

Any variety of commercially available pearlescent or opacifying agents that are capable of suspending water-insoluble additives such as silicones and / or that tend to indicate to consumers that the resulting product is a conditioning shampoo are suitable for use in that invention. The pearlescent or opacifying agent can be present in an amount, based on the total weight of the composition, from about 1 percent to about 10 percent, for example, from about 1.5 percent to about 7 percent percent or about 2 percent to about 5 percent. Examples of suitable pearlescent or opacifying agents include, but are not limited to, mono or diesters of (a) fatty acids having from about 16 to about 22 carbon atoms and (b) or ethylene or propylene glycol; mono or diesters of (a) fatty acids having from about 16 to about 22 carbon atoms (b) a polyalkylene glycol of the formula: HO- (JO)_The-H, where J is an alkylene group having from about 2 to about 3 carbon atoms; and a is 2 or 3; fatty alcohols containing from about 16 to about 22 carbon atoms; fatty esters of the formula: KCOOCH2L, where K and L independently contain from about 15 to about 21 carbon atoms; insoluble inorganic solids in the composition of shampoo, and mixtures thereof.

The pearlescent opacifying agent can be introduced into the mild cleaning composition as a preformed, stabilized aqueous dispersion, such as that commercially available from Henkel Corporation of Hoboken, New Jersey under the trademark, Euperlan PK-3000. This material is a combination of glycol distearate (the ethylene glycol diester and stearic acid), Laureth-4 (CH3 (CH2) ioCH₂(OCH2CH2) 40H) and cocamidopropyl betaine and can be in a weight percentage ratio of from about 25 to about 30: about 3 to about 15: about 20 to about 25, respectively.

Any variety of commercially available thickening agents, which are capable of imparting the appropriate viscosity to personal cleaning compositions, are suitable for use in this invention. If used, the thickener would be present in the shampoo compositions in an amount sufficient to raise the Brookfield viscosity of the composition to a value between about 0.5 Pa.s and about 10 Pa.S (500 to about 10,000 centipoise) . Examples of suitable thickening agents not only include: mono- or diesters of 1) polyethylene glycol of the formula: HO- (CH₂CH2O)₂H, where z is an integer from about 3 to about 200; and 2) fatty acids containing from about 16 to about 22 carbon atoms; fatty acid ethoxylated polyol esters; ethoxylated derivatives of mono and diesters of fatty acids and glycerin; hydroxyalkyl cellulose; alkyl cellulose; hydroxyalkyl alkyl cellulose; and their mixtures. Preferred thickeners include polyethylene glycol ester, and most preferably PEG-150 distearate which is available from Stepan Company of Northfield, Illinois or from Comiel, SpA of Bologna, Italy under the trademark, PEG 6000 DS.

Any variety of commercially available secondary conditioners, such as volatile silicones, which impart additional attributes, such as shine to the hair, are suitable for use in this invention. In one embodiment, the volatile silicone conditioning agent has an atmospheric pressure boiling point less than about 220 C. The volatile silicone conditioner can be present in an amount of from about 0 percent to about 3 percent, for example, from about 0.25 percent to about 2.5 percent or about 0, 5 percent to about 1.0 percent, based on the total weight of the composition. Examples of suitable volatile silicones not exclusively include polydimethylsiloxane, polydimethylcyclosiloxane, hexamethyldisiloxane, cyclomethicone fluids such as commercially available polydimethylcyclosiloxane from the trademark Dow Corning Corporation of Midland, Michigan, DC-345 and mixtures thereof, and preferably include cyclomid fluids.

Any variety of commercially available humectants, which are capable of providing conditioning and moisturizing properties to the personal cleaning composition, are suitable for use in the present invention. The humectant can be present in an amount of from about 0 percent to about 10 percent, for example, from about 0.5 percent to about 5 percent or from about 0.5 percent to about 3 percent, based on the total weight of the composition. Examples of suitable wetting agents not only include: 1) water-soluble liquid polyols selected from the group comprising glycerin, propylene glycol, hexylene glycol, butylene glycol, dipropylene glycol, and mixtures thereof; 2) polyalkylene glycol of the formula: HO- (RO)_B-H, where R is an alkylene group having from about 2 to about 3 carbon atoms and b is an integer from about 2 to about 10; 3) methyl glucose polyethylene glycol ether of the formula CH₃-C6H₁₀O5- (OCH₂CH2) c-OH, where c is an integer from about 5 to about 25; 4) urea; and 5) mixtures thereof, with glycerin being the preferred humectant.

Examples of suitable chelating agents include those that are capable of protecting and preserving the compositions of that invention. Preferably, the chelating agent is ethylenediamine tetracetic acid (EDTA), and most preferably it is tetra-sodium EDTA, commercially available22 from the Dow Chemical Company of Midland, Michigan under the trademark, Versene 100XL and is present in an amount, based in the total weight of the composition, from about 0 to about 0.5 percent or from about 0.05 percent to about 0.25 percent.

Suitable preservatives include Quaternium-15, commercially available as Dowicil 200 from Dow Chemical Corporation of Midland, Michigan, and are present in the composition in an amount, based on the total weight of the composition, from about 0 to about 0.2 percent or from about 0.05 percent to about 0.10 percent.

Compositions produced via the present invention are preferably used as or in personal care products such as shampoos, lotions, baths, gels, and the like. As discussed above, applicants have unexpectedly revealed that the present methods allow the formulation of such personal care products having improved color retention for dyed hair and, optionally, desirable foaming characteristics.

Any conventional means for contacting dyed hair can be used in accordance with the present invention. The cleaning methods of the present invention may further comprise any of a variety of optional, additional steps conventionally associated with cleaning hair and skin including, for example, rinsing, foaming and the like.

EXAMPLES

The following Examples are intended to be illustrative and not to be limited in any way.

Example 1

Two compositions according to embodiments of the present invention (E1-E2) and a comparative composition (C1) are produced by combining the ingredients in the amounts listed in table 1 below as follows:

Each of the compositions in Table 1 was independently prepared as follows:

Water (50.0 parts) was added to a pipette. The polymer, (Inutec SP-1 in E15 and E16, and Carbopol Aqua SF1 in C9) was added to the mixed water. The following ingredients were added to it independently with mixing until each respective resulting mixture was homogeneous: Te5 gobetaine L7V, Cedepal TD403LD, Tween 20, Promidium LTS, Celquat 230 M, Pheononip and Versene 100XL. The pH of the resulting solution was then adjusted either with a solution of 20% citric acid or 20% sodium hydroxide.

Table 1

<td>Trademark</td><td>INCI name</td><td>C1</td><td>E1</td><td>E2</td>

<td></td><td></td><td>w / the polymer</td><td>PA-18</td><td>hm- inulin</td>

<td>PA-18 (23%)</td><td>octadecene / MA polymer</td><td> —</td><td> 7,826</td><td> —</td>

<td>Inutec SP-1 (100%)</td><td>mouse lauryl carbamate lina</td><td> —</td><td> —</td><td> 1,8</td>

<td>Tegobetaine L-7V (30%)</td><td>cocamidopropyl betaine</td><td> 22,50</td><td> 22,50</td><td> 22,50</td>

<td>Cedepal TD403LD</td><td>sodium trideceth sulfate</td><td> 16,00</td><td> 16,00</td><td> 16,00</td>

<td>Tween 20</td><td>polysorbate-20</td><td> 0,500</td><td> 0,500</td><td> 0,500</td>

<td>Promidium LTS</td><td>distearate PEG 150 &amp; PPG-2 hydroethyl cocamide</td><td> 0,750</td><td> 0,750</td><td> 0,750</td>

<td>Celquat 230M</td><td></td><td> 0,1425</td><td> 0,1425</td><td> 0,1425</td>

<td>Fragrance</td><td>fragrance</td><td> 0,2750</td><td> 0,2750</td><td> 0,2750</td>

<td>Phenonip XB</td><td>phenoxyethanol and parabens</td><td> 0,600</td><td> 0,600</td><td> 0,600</td>

<td>Versene 100XL</td><td>EDTA tetrasodium</td><td> 0,250</td><td> 0,250</td><td> 0,250</td>

<td>solution of NaOH (30%)</td><td>sodium hydroxide</td><td>what</td><td>what</td><td>what</td>

<td>Water</td><td>Water</td><td>what</td><td>what</td><td>what</td>

Delta CMC

Delta CMC associated with compositions E1, E2, and C1 were measured via the Reverse Titration Tensiometry Test described below and listed in Table 2.

A well-known method for measuring the surface tension of surfactant solutions is the Wilhelmy plate method (Holmberg, K .; Jonsson, B .; Kronberg, B .; Lindman, B. Surfactants and Polymers in Aqueous Solution, Wiley &amp; Sons , p. 347). In the method, the plate is submerged into a liquid and the downward force exerted by the liquid on the plate is measured. The surface tension of the liquid can then be determined based on the strength of the plate and the dimensions of the plate. It is also well known that by measuring a surface tension over a range of concentrations the critical micelle concentration (CMC) can then be determined.

There are commercially available plate method instruments. In the following examples, a Kruss K12 Tensiometer (Kruss USA, Mathews, NC) with a Wilhelmy platinum plate used to determine the surface tension of each sample over a range of concentrations. The test can be performed either forward or reverse. In any case, a sample container contains some initial solution in which Wilhelmy's Wilhelmy plate measures surface tension. Then a second solution is dosed into the sample container, stirred, and then probed again with the Wilhelmy plate. The solution initially in the sample container before the titration begins, in which the second solution is administered meteredly, will be called here after the initial solution, and the solution which is dosed in the sample container during the metering will be called hereinafter dosage solution, according to the convention used by Kruss USA.

In reverse titration, the concentration of the initial solution is higher than the concentration of the dosed administration solution. During the reverse titration tests of the following examples, the dosed delivery solution was HLPC grade water (Fischer Scientific, NJ), which had no surfactant, 0 mg / L. The total concentration formulas (for example, those in Table 5) were diluted with HLPC grade water (Fischer

Scientific, NJ) at a dilution of about 5% by weight. This diluted 5% solution was then added to the sample container and was the initial solution. The surface tension of this initial solution was measured, and then a volume of the dosed administration solution was added to the sample container. The solution was stirred for at least 5 minutes, before the next surface tension was removed. This dosed administration, stirring and then measurement were repeated until the dilution reached at least 0.0008%. A test experiment according to this procedure is hereinafter called the Reverse Titration Tensiometry Test.

From the raw tensiometry data, CMC was determined for each sample in the following ways. First, the equation for a horizontal line was adjusted for the portion of the data at high concentrations above, that is, concentrations above the lowest point of the graph and well within the region where the surface tension is essentially constant, as shown, for example, in Figure 4 as line 41. Then, the equation for a straight line is fitted to the data at lower concentrations having a surface tension above the horizontal line derived previously, as shown, for example, in Figure 4 as line 42. The intersection of these two lines / equations 43 was then defined as the CMC for that sample.

Table 2

<td>Composition</td><td>hm-polymer (mg / L)</td><td>CMC (mg / L)</td><td>CMC (mg / L)</td>

<td>C1</td><td> 0</td><td> 54</td><td>at</td>

<td>E1</td><td>PA-18</td><td> 986</td><td> 932</td>

<td>E2</td><td>Inutec SP-1</td><td> 613</td><td> 559</td>

Color Retention

Compositions E1, E2, and C1 were tested for color retention when used for washing dyed hair as follows, along with just water and a comparative commercial product marketed as Pantene Pro-V (hereinafter C2) containing the ingredients as listed on the label: water, sodium laureth sulfate, sodium lauryl sulfate, cocamidopropyl betaine, sodium chloride, patenol, pantenyl ethyl ester, lysine HCI, Methyl Tyrosinate HCI, Histidine, Fragrance, Cocamide MEA, Citric Acid, Sodium Benzoate, EDTA Tetrasodium, Methylchloristiazolinone, Methylisothiazolinone, Sodium Citrate, Sodijm Xylenesulfonate.

Curls of blond human hair (25.4 cm (10 in length) and 10.16 cm (4 in width) were obtained from DeMeo brothers Inc. (New York, NY). The hair curls were dried with LOREAL Paris ®color pulse concentrated color mousse # 50 Lively Auburn, after instructions on the container, after at least 24 h, the initial (dyed) color of the bunch was measured for the colorimeter.

The original curl was then separated into 5 curls (each 1.90 cm (% wide), and then each curl was washed with a different cleaning formula (water, C1, C2, E1, or E2) according to the washing procedure that follows: First, the curl of hair was rinsed with tap water for 10 seconds (5.67 l / min @ 37.7 ° C (1.5 gal / min @ 100 ° F). Then 0.2 g of the particular formula (water, C1, C2, E1, or E2) was applied to each 1.0 g of hair, and then it was lathered for 30 s, rinsed for 60 s. The curl of hair was combed and blown dry with a Vidal Sassoon® 1250 watt set on hi blow dryer. The washing procedure was repeated and color was quantified with the spectrophotometer after 0.1.4, 9.14, and 28 washes.

A Hunter Ultra Pro Vis Spectrophotometer® was used to quantify the color of the hair curls. The spectrophotometer was calibrated to an industrial standard; D65 Northern Noon Daylight which is 6226.85 ° C (6500 Kelvin), the spectrum is 470-680 nm. With the spectrophotometer, measurements were taken twice at each of the three locations in the curl; top, middle, and bottom end of each curl of hair. The quantification of hair color at each stage by the spectrophotometer provided CIE L, a, b, color information. For each washing condition, all values ​​collected in each curl of hair were then averaged to provide L, a, b data for the particular washing formula and condition. Observation showed that the data were also analyzed non-aggregated, that is, each of the three positions in the hair curls were compared between formula, and the same trends were observed.

In order to quantify the color fading that occurred during 5 washing before dC values, how much dE were calculated from the data of L, a, b for each condition according to the equations:

A.D_x = Aa² + Áb² = (a0 - ax)² + (b0 - b_x)² in_x = AL² + Aa²+ Ab² = (l_o - Lx)² + (a0 - a_x)² + (b₀ - B_x)² where x is the number of wash cycles, L_O is the initial L after drying,

L_x is the L x number of washes, ao is the initial one after drying, the_x is the a in x number of washes, bo is the initial ob after drying, and b_x is the b in x number of washes. The results, both dC and dE, are shown in table 2 after the various washing conditions and are illustrated in Figure 2.

Table 2

<td>n^and of washes</td><td>WATER</td><td>C2</td><td>C1</td><td>E1</td><td>E2</td>

<td> 1</td><td> 1,0±0,6</td><td> 3,1 ±0,6</td><td> 2,9 ±0,6</td><td> 3,0 ±0,8</td><td> 1,9 ± 1,0</td>

<td> 4</td><td> 2,0 ±0,5</td><td> 7,4 ±0,3</td><td> 6,7 ±1,4</td><td> 5,8 ±1,0</td><td> 5,3 ±0,7</td>

<td> 9</td><td> 4,2 ±1,4</td><td> 9,3 ± 0,5</td><td> 9,9 ±0,0</td><td> 6,1 ±01,0</td><td> 6,7 ±0,1</td>

<td> 14</td><td> 7,5 ± 0,5</td><td> 12,4 ±0,6</td><td> 12,1 ±0,4</td><td> 9,7 ±0,6</td><td> 8,5 ±0,4</td>

<td> 21</td><td> 9,7 ±0,1</td><td> 14,0 ±0,7</td><td> 13,2 ±0,3</td><td> 10,9 ± 0,7</td><td>10.9 V 0.6</td>

<td colspan="3">A.D_x</td><td></td><td></td><td></td>

<td>N^Q of washes</td><td>Water</td><td>C2</td><td>C1</td><td>E1</td><td>E2</td>

<td> 1</td><td> 0,9 ±0,6</td><td> 1,7±0,4</td><td> 1,4 ± 0,5</td><td> 1,6 ±0,6</td><td> 1,0 ±0,3</td>

<td> 4</td><td> 1,7 ±0,4</td><td> 4,0 ±0,8</td><td> 3,6 ±0,5</td><td> 2,9 ±0,5</td><td> 2,7 ±0,4</td>

<td> 9</td><td> 3,1 ±0,9</td><td> 5,4 ±0,5</td><td> 6,0 ±0,1</td><td> 3,6 ±0,5</td><td> 3,9 ±0,2</td>

<td> 14</td><td> 5,0 ±0,4</td><td> 6,9 ±0,6</td><td> 6,9 ±0,2</td><td> 5,5 ±0,2</td><td> 4,9 ±0,1</td>

<td> 21</td><td> 7,0 ±0,1</td><td> 7,9 ±0,4</td><td> 8,1 ±0,2</td><td> 5,8 ±0,3</td><td> 5,8 ±0,3</td>

As shown, trends in color change are similar for both AD and dE. In the curl of hair washed only with water, there is a significant increase in both DE and AD. Hair curls washed with or with Example C1 or C2 have increases in both dE and dC that are significantly greater than that of just water. This increase in dE and dC displayed in C1 and C2 is due to the addition dye removed by the surfactant. Surprisingly, the dE and dC value for E1 and E2 in each washing condition was similar to water and significantly lower than the corresponding C1 and dE and dC value.

C2. E1 and E2 contain the same amount of surfactants as C1 and a similar amount of surfactant as C2, however E1 and E2 also contain a low molecular weight hm-polymer in addition to the surfactant.

Exam Data, Color Retention

In addition to instrumental quantification of color change, after the total washing cycle (21 cycles) the hair curls were evaluated by 10 people. All curls were placed on a sheet of white cardboard and people were asked to assess the color fading of each hair curl with a rating between 1 and 4 (1 less fade and 4 more fade).

Table 3

<td></td><td>Water</td><td>C2</td><td>C1</td><td>E1</td><td>E2</td>

<td>21 washes</td><td> 1,1 ±0,3</td><td> 3,7 ± 0,5</td><td> 3,3 ±0,5</td><td> 1,6 ±0,5</td><td> 1,7 ±0,9</td>

The results of the examination, shown in Table 3, correspond well with the result of color fading of the spectrophotometer. Again the water exhibits the least fading, and significantly more fading was observed from C1 and C2. E1 and E2 exhibited unexpectedly low fade.