# Patent

## Title
Personal care composition for a keratin substrate comprising conditioning and/or styling polymer

## Abstract

A personal care conditioning and/or styling composition for a keratin substrate comprising: (i) about 50 wt. % to 95 wt. % of at least one cationic or pseudo-cationic monomer selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC) and/or Vinylpyrrolidone (VP); (ii) about 1 wt. % to 30 wt. % of at least one anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS), and/or (c) sodium methyl allyl sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of at least one hydrophobic monomer selected from the group consisting of (a) polyoxyethylene (PEG)-18-behenylether-methacrylate (BEM) (b) Lauryl-ethoxylated-methacrylate (LEM), (c) stearyl acrylate (SA), (d) Stream-10-allyl-ether, (e) Vinylcaprolactam (V-cap), and/or (f) Hydroxyethyl-pyrrolidone-methacrylate (M06). Also described is a process of preparing said polymer, and its method of use.

## Background
FIELD OF THE INVENTION
The present application relates to a personal care composition, and, more particularly, to a personal care composition comprising a conditioning and/or styling copolymer for a keratin substrate of hair and/or skin origin.
BACKGROUND OF THE INVENTION
Undamaged virgin hair is smooth and shiny; its cuticles on the surface of the hair lie down smoothly making the combing easy. The hair surface is also hydrophobic in nature preventing excessive water absorption during washing. When the hair is either mechanically or chemically damaged through bleaching, perming or coloring, the hair surface becomes rough and frizzy and difficult to detangle and comb. As the hair surface becomes more hydrophilic, the resulting hair fibers swell during washing, making the hair even more difficult to comb.
Current conditioning and/or styling systems for regular and damaged hair generally use one or more combinations of cationic surfactants, amphoteric surfactants, silicones, fatty alcohols, polyquatemiums, amino acids, proteins, lipids and humectants. Wet conditioning of regular or damaged hair is accomplished by neutralizing the anionic charge of the hair by positively charged surfactants and polymers and creating a hydrophobic layer from surfactant and polymers. This hydrophobic layer results in a reduction of the swelling of the hair fibers by making the hair more hydrophobic and reducing friction of the hair fibers. An overall result of wet conditioning is improved detangling, manageability and soft feel of the hair. Upon treatment with cleansing systems like shampoos. 2/1 shampoos, body washes or shower gels, the combing performance, detangling properties, hydrophobicity of the hair and lubricity are not maintained sufficiently.
U.S. Pat. No. 6,110,451 assigned to Calgon Coporation discloses a keratin conditioning composition comprising: (a) about 5% to about 50%, by weight, of a surfactant component selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants; (b) about 0.05% to about 10%, by weight, of a water soluble, organic, ampholytic polymer; (c) about 0.05% to about 10%, by weight, of a water soluble, organic, cationic polymer; (d) zero to about 70%, by weight, of a water insoluble liquid; and (e) an aqueous carrier. The method for treating keratin based substrates according to the present invention comprises contacting the substrate with such composition.
U.S. Pat. No. 6,482,776 assigned to Calgon Corporation discloses a composition comprising a branched or crosslinked ampholyte polymer wherein the polymer consists essentially of: (a) from 1 to about 99 mol % of a monomer selected from the group consisting of acrylamidopropyltrimethyl ammonium halide and methacrylamidoproplytrimethyl ammonium halide; (b) from 1 to about 80 mol % of a monomer selected from the group consisting of acrylic acid, methacrylic acid and 2-acrylamido-2-methylpropane sulfonic acid; (c) from about 0.0001 to about 1 mol % of a monomer selected from the group consisting of N,N′-methylenebisacrylamide, triallyl methyl ammonium chloride, allyl methacrylate, n-methylol acrylamide, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate and allyl sucrose; and (d) from 0.1 to about 70 mol % of a monomer selected from the group consisting of C4-C22 straight or branched chain alkyl acrylate or alkyl methacrylate monomers; wherein the mol ratio of (a): (b) ranges from about 20:80 to about 95:5 and the weight average molecular weight of the polymer is at least about 1,000.
PCT Publication No.: WO2000057847A2 assigned to Calgon Corporation discloses a hair conditioning shampoo composition that contains (a) a surfactant component that can contain anionic surfactants and/or amphoteric surfactants (optionally including zwitterionic and nonionic surfactants), (b) a dispersed, insoluble, nonionic silicone hair conditioning agent, (c) a water soluble, organic, ampholytic polymer hair conditioning agent; and (d) an aqueous carrier. The conditioning shampoo composition optionally contains an organic, water insoluble, liquid component.
U.S. Pat. No. 7,737,237 assigned to Phodia Chimie discloses a controlled structure copolymer comprising a (block A)-(block B) diblock copolymer, a (block A)-(block B)-(block A) triblock copolymer or a (block B)-(block A)-(block B) triblock copolymer.
U.S. Pat. No. 6,451,756 B2 discloses hydrophobically modified polycarboxylate polymers that are useful for promoting soil release from fabrics, particularly cotton and cotton-containing fabrics, by contacting the fabrics with compositions comprising the polymers.
US Publication No. 20110271460A1 discloses compositions for household care which include a cationic nanogel, particularly for treating and/or modifying hard or textile surfaces. The composition particularly enables a hydrophilisation of hard surfaces, particularly useful in cleaning or rinsing operations.
U.S. Pat. No. 7,115,254 B1 assigned to Nalco Company discloses a method of treating hair, skin or nails comprising applying a cosmetically acceptable composition comprising from about 0.01 to about 40 weight percent, based on polymer solids, of a stable solution of a cationic copolymer composed of about 1 to about 99 mole percent diallyl-N,N-disubstituted ammonium halide and about 99 to about 1 mole percent N-vinylpyrollidone, wherein the solution as a RSV of about 0.4 to about 10 dL/g to said hair, skin or nails.
U.S. Pat. No. 6,110,451 assigned to Calgon Corporation discloses a keratin conditioning composition is disclosed that contains (a) a surfactant component that can contain anionic surfactants, amphoteric surfactants, cationic surfactants, nonionic surfactants and/or zwitterionic, (b) a water soluble, organic, ampholytic polymer conditioning agent, (c) a water soluble, organic, cationic polymer conditioning agent; (d) optionally a water insoluble liquid; and (e) an aqueous carrier. The conditioning composition optionally contains a silicone and/or an organic, water insoluble, liquid. The conditioning composition according to the present invention is useful in cleaning and/or conditioning keratin based substrates, such as hair, skin, and nails.
US Publication No. 20050226838 assigned to Wella AG discloses a hair treatment composition contains preferably from 0.01 to 20 percent by weight of at least one N-hydroxyalkyl-O-benzyl chitosan and from 0.01 to 20 percent by weight of at least one other hair treatment effective ingredient. Various methods of treating hair with hair treatment compositions containing one or more of the N-hydroxyalkyl-0-benzyl chitosans are described.
Therefore, there is an increasing demand for hair care products designed to retain the properties of “virgin hair” and to prevent possible damage during the chemical and mechanical treatment. In the present application, the limitations set forth above are addressed by a personal care conditioning and/or styling composition for a keratin substrate comprising:
(A) at least one conditioning and/or styling copolymer obtained by polymerizing (i) about 50 wt. % to 95 wt. % of at least one cationic or pseudo-cationic monomer; (ii) about 1 wt. % to 30 wt. % of at least one anionic monomer; and (iii) about 0.1 wt. % to 20 wt. % of at least one hydrophobic monomer; (B) at least one cosmetically acceptable excipient; and (C) optionally, at least one effective amount of personal care active ingredient.
SUMMARY OF THE INVENTION
The present application provides a personal care conditioning and/or styling composition for a keratin substrate comprising: (A) at least one conditioning and/or styling polymer obtained by polymerizing (i) about 50 wt. % to 95 wt. % of at least one cationic or pseudo-cationic monomer selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC) and/or Vinylpyrrolidone (VP); (ii) about 1 wt. % to 30 wt. % of at least one anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS), and/or (c) sodium methyl allyl sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of at least one hydrophobic monomer selected from the group consisting of (a) polyoxyethylene (PEG)-18-behenylether-methacrylate (BEM) (b) Lauryl-ethoxylated-methacrylate (LEM), (c) stearyl acrylate (SA), (d) Streath-10-allyl-ether (BRIJ), (e) vinylcaprolactam (V-Cap), and/or (f) Hydroxyethyl-pyrrolidone-methacrylate (MO6); (B) at least one cosmetically acceptable excipient; and (C) optionally, at least one effective amount of personal care active ingredient.
An important embodiment of the present application is to provide a personal care composition which is capable of fixing or treating hair conditioning and/or styling properties comprising detangling, wet combability, wet feel, dry combability, dry feel, sheen, static flyaway control, hydrophobicity, surface smoothening, improved deposition, no build-up, color protection, and/or curl retention. Moreover, the composition is able to provide “virgin feel condition” to the hair after multiple washes particularly with respect to (1) increased hydrophobicity, (2) improved detangling and wet combability, (3) improved deposition, and/or (4) no build-up.
Yet another aspect of the present application is to provide a method for treating or fixing regular/damaged keratin substrate comprising contacting the keratin substrate with an effective amount of personal care composition comprising a conditioning and/or styling copolymer of (i) about 50 wt. % to 95 wt. % of at least one cationic or pseudo-cationic monomer selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC) and/or Vinylpyrrolidone (VP); (ii) about 1 wt. % to 30 wt. % of at least one anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS), and/or (c) sodium methyl allyl sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of at least one hydrophobic monomer selected from the group consisting of (a) polyoxyethylene-18-behenylether-methacrylate (BEM) (b) Lauryl-ethoxylated-methacrylate (LEM), (c) stearyl acrylate (SA), (d) Streath-10-allyl-ether (BRIJ), (e) vinylcaprolactam (V-cap) and/or (f) Hydroxyethyl-pyrrolidone-methacrylate (MO6); (B) at least one cosmetically acceptable excipient; and (C) optionally, at least one effective amount of personal care active ingredient; and wherein the copolymer is preferably a terpolymer or tetrapolymer having a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about lmeq/g to about 6 meq/g.
Still another aspect of the present application is to provide a process for preparing a conditioning and/or styling copolymer comprising polymerizing: (i) about 50 wt. % to 95 wt. % of at least one cationic or pseudo-cationic monomer selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC) and/or Vinylpyrrolidone (VP); (ii) about 1 wt. % to 30 wt. % of at least one anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS), and/or (c) sodium methyl allyl sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of at least one hydrophobic monomer selected from the group consisting of (a) polyoxyethylene (PEG)-18-behenylether-methacrylate (BEM) (b) Lauryl-ethoxylated-methacrylate (LEM), (c) stearyl acrylate (SA), or (d) Streath-10-allyl-ether (BRIJ), (e) vinylcaprolactam (V-cap), and/or (f) Hydroxyethyl-pyrrolidone-methacrylate (MO6); and wherein said co-polymer is a terpolymer or tetrapolymer having a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about lmeq/g to about 6 meq/g.



BRIEF DESCRIPTION OF THE FIGURES
Further embodiments of the present invention can be understood with the appended figures.
FIG. 1 is a picture of Texture Analyzer employed for measuring wet combability
FIG. 2 shows a wet comb energy on bleached hair for conditioner
FIG. 3 shows a wet comb energy on bleached hair for conditioner
FIG. 4 shows a wet comb energy on bleached hair for shampoos
FIG. 5 shows a hydrophobicity evaluation of terpolymers
FIG. 6 shows a wet stage sensory evaluation after 5 washing cycles
FIG. 7 shows a dry stage sensory evaluation after 5 washings cycles
FIG. 8 shows a wet comb energy on bleached hair for sulfate free shampoos
FIGS. 9 to 12 shows durable styling properties of hair tresses
FIG. 13 shows curl retention study of homo/terpolymers on hair tresses
FIG. 14 shows curl retention demonstration of Homo/Terpolymer at 50%±2% humidity, 25° C.±2° C.
FIG. 15 shows curl retention demonstration in absence of homo/terpolymer at 50% 2% humidity, 25° C.±2° C.
FIG. 16 shows distribution of shine of curve of APTAC Homopolymer
FIG. 17 shows distribution of shine of curve of APTAC Terpolymer
FIG. 18 shows distribution of shine of curve of a commercial mousse
FIG. 19 shows distribution of shine of curve of copolymer VC713 mousse



DETAILED DESCRIPTION OF THE INVENTION
While this specification concludes with claims particularly pointing out and distinctly claiming that which is regarded as the invention, it is anticipated that the invention can be more readily understood through reading the following detailed description of the invention and study of the included examples
The singular forms “a,” “an,” and “the” include plural forms unless the context clearly dictates otherwise specified or clearly implied to the contrary by the context in which the reference is made. The term “Comprising” and “Comprises of” includes the more restrictive claims such as “Consisting essentially of” and “Consisting of”.
The term “about” can indicate a difference of 10 percent of the value specified. Numerical ranges as used herein are meant to include every number and subset of numbers enclosed within that range, whether particularly disclosed or not. Further, these numerical ranges should be construed as providing support for a claim directed to any number or subset of numbers in that range.
All percentages, parts, proportions and ratios as used herein, are by weight of the total composition, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore; do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified.
All references to singular characteristics or limitations of the present invention shall include the corresponding plural characteristic or limitation, and vice-versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made.
As used herein, the words “preferred” or “preferably” and variants refer to embodiments of the invention that afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
References herein to “one embodiment” or “one aspect” or “one version” or “one objective” of the invention include one or more such embodiment, aspect, version or objective, unless the context clearly dictates otherwise.
All publications, articles, papers, patents, patent publications, and other references cited herein are hereby incorporated herein in their entirety for all purposes to the extent consistent with the disclosure herein.
The term “polymer” refers to a compound comprising repeating structural units (monomers) connected by covalent chemical bonds. Polymers may be further derivatized, crosslinked, grafted or end-capped. Non-limiting examples of polymers include copolymers, terpolymers, quaternary polymers, and homologues. The term “copolymer” refers to a polymer consisting essentially of two or more different types of monomers polymerized to obtain said copolymer, for example, a terpolymer or tetrapolymer and the like.
The term “conditioning agents”, and grammatical variations thereof, as it relates to compositions for hair care includes cosmetically and pharmaceutically useful materials that can function as humectants, moisturizers, and emollients. It is recognized that some conditioning agents can serve more than one function in a composition, such as an emulsifying agent, a lubricant, and/or a solvent. Conditioning agents include any material which is used to give a particular conditioning benefit to hair. In hair treatment compositions, suitable conditioning agents are those which deliver one or more benefits relating to shine, softness, combability, antistatic properties, wet-handling, damage repair, manageability, detangling, body, and lubricity.
What is described herein is a personal care conditioning and/or styling composition for keratin substrate comprising: (A) at least one conditioning and/or styling co-polymer obtained by polymerizing (i) about 50 wt. % to 95 wt. % of at least one cationic or pseudo-cationic monomer selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC) and/or Vinylpyrrolidone (VP); (ii) about 1 wt. % to 30 wt. % of at least one anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS), and/or (c) sodium methyl allyl sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of at least one hydrophobic monomer selected from the group consisting of (a) polyoxyethylene-18-behenylether-methacrylate (BEM) (b) Lauryl-ethoxylated-methacrylate (LEM), (c) stearyl acrylate (SA), (d) Streath-10-allyl-ether (BRIJ), (e) vinylcaprolactam (V-Cap), and/or (f) Hydroxyethyl-pyrrolidone-methacrylate (MO6); (B) at least one cosmetically acceptable excipient; and (C) optionally, at least one effective amount of personal care active ingredient.
The preferred range of cationic or pseudo-cationic polymer (APTAC/VP) for preparing a desired copolymer of present application include but not limited to 50 wt. % to 55 wt. %; 56 wt. % to 60 wt. %; 61 wt. % to 65 wt. %; 66 wt. % to 70 wt. %; 71 wt. % to 75 wt. %; 76 wt. % to 80 wt. %; 81 wt. % to 85 wt. %; 86 wt. % to 90 wt. %; 91 wt. % to 95 wt. %. Most preferred range is 86 wt. % to 95 wt. % of the terpolymer.
The preferred range of an anionic monomer employed for preparing desired copolymer of present application includes but is not limited to lwt. % to 5 wt. %; 6 wt. % to 10 wt. %; 11 wt. % to 15 wt. %; 16 wt. % to 20 wt. %; 21 wt. % to 25 wt. %; 26 wt. % to 30 wt. %. Most preferred range is lwt. % to 10 wt. % of the terpolymer.
The preferred range of a hydrophobic monomer employed for preparing a desired copolymer of present application includes but is not limited to 0.01 wt. % to 5 wt. %; 6 wt. % to 10 wt. %; 11 wt. % to 15 wt. %; 16 wt. % to 20 wt. %. Most preferred range is 0.01 wt. % to 5 wt. % of the terpolymer.
The term “keratin substrate” as used herein includes skin, nails and “keratin fibers”, and wherein the “keratin fibers” means hair on head, eyelashes, eyebrows and other mammalian bodily hair.
The weight average molecular weight of said copolymer of the present application, as determined by gel permeation chromatography (GPC), is at least about 10,000, preferably about 100,000 to about 2,000,000, more preferably from about 200,000 to about 500,000 g/mol, alternatively, viscometry can also be used to determine the average molecular weight of the present application.
The copolymer of use in the personal care composition of the invention has a cationic degree of substitution (Cat-DS) of greater than about 0.001 units. Preferably, the copolymer is a terpolymer or tetrapolymer having a cationic degree of substitution in the range of 0.001 to about 5.0, preferably in the range of from about 0.2 to about 3.0, more preferably in the range of about 0.4 to about 3.0.
Further, the terpolymer or tetrapolymer of the present invention has a cationic charge density in the range of from about lmeq/g to about 8 meq/g. Preferable cationic charge density is in the range of from about 3.5 to about 7 meq/g, more preferably in the range of about 3.5 to about 5.5 meq/g.
A conditioning and/or styling terpolymer/tetrapolymer of the present application is obtained by polymerizing: (i) about 50 wt. % to 95 wt. % of at least one cationic or pseudo-cationic monomer selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC) and/or Vinylpyrrolidone (VP); (ii) about 1 wt. % to 30 wt. % of at least one anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS), and/or (c) sodium methyl ally! sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of at least one hydrophobic monomer selected from the group consisting of (a) polyoxyethylene (PEG)-18-behenylether-methacrylate (BEM) (b) Lauryl-ethoxylated-methacrylate (LEM), (c) stearyl acrylate (SA), or (d) Streath-10-allyl-ether (BRIJ), (e) vinylcaprolactam (V-cap), and/or (f) Hydroxyethyl-pyrrolidone-methacrylate (MO6); and wherein said co-polymer is a terpolymer or tetrapolymer having a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about lmeq/g to about 6 meq/g.
Non-limiting terpolymers or tetrapolymers of the present application include but are not limited to:

    
    
        A. a terpolymer of (i) about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 1 wt. % to 30 wt. % of acrylamido methylpropyl sulfonate (AMPS), an anionic monomer; and (iii) about 0.1 wt. % to 20 wt. % polyoxyethylene (PEG)-18-behenylether methacrylate (BEM), a hydrophobic monomer.
        B. a terpolymer of (i) about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 1 wt. %−30 wt. % of acrylamido methylpropyl sulfonate (AMPS), an anionic monomer; and (iii) about 0.1 wt. % to 20 wt. % stearyl acrylate (SA), a hydrophobic monomer.
        C. a terpolymer of (i) about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 1 wt. % to 30 wt. % of sodium methyl allyl sulfonate (SMAS), an anionic monomer; and (iii) about 0.1 wt. % to 20 wt. % polyoxyethylene (PEG)-18-behenylether methacrylate (BEM), a hydrophobic monomer.
        D. a terpolymer of (i) about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 1 wt. % to 30 wt. % of sodium methyl allyl sulfonate (SMAS), an anionic monomer; and (iii) about 0.1 wt. % to 20 wt. % stearyl acrylate (SA). a hydrophobic monomer.
        E. a terpolymer of (i) about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 1 wt. % to 30 wt. % of acrylic acid (AA), an anionic monomer; and (iii) about 0.1 wt. % to 20 wt. % polyoxyethylene (PEG)-18-behenylether methacrylate (BEM), a hydrophobic monomer.
        F. a tetrapolymer of (i) about 50 wt. % to 95 wt. % of acrylic acidamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 1 wt. % to 30 wt. % of acrylic acid (AA), an anionic monomer; (iii) about 0.1 wt. % to 20 wt. % polyoxyethylene (PEG)-18-behenylether methacrylate (BEM), a hydrophobic monomer; and (iv) about 0.1 wt. % to 20 wt. % vinylcaprolactam (V-cap), a hydrophobic monomer.
        G. a tetrapolymer of (i) about 50 wt. % to 95 wt. % of acrylic acidamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 50 wt. % to 95 wt. % of Vinylpyrrolidone (VP), a pseudo-cationic monomer; (iii) about 1 wt. % to 30 wt. % of acrylic acid (AA), an anionic monomer; and (iv) about 0.1 wt. % to 20 wt. % polyoxyethylene (PEG)-18-behenylether methacrylate (BEM), a hydrophobic monomer.
    
    


A process for preparing a conditioning and/or styling copolymer comprising polymerizing: (i) about 50 wt. % to 95 wt. % of at least one cationic or pseudo-cationic monomer selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC) and/or Vinylpyrrolidone (VP); (ii) about 1 wt. % to 30 wt. % of at least one anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS), and/or (c) sodium methyl allyl sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of at least one hydrophobic monomer selected from the group consisting of (a) polyoxyethylene (PEG)-18-behenylether-methacrylate (BEM) (b) Lauryl-ethoxylated-methacrylate (LEM), (c) stearyl acrylate (SA), (d) Streath-10-allyl-ether (BRIJ), or (e) vinylcaprolactam (V-cap), and/or (f) Hydroxyethyl-pyrrolidone-methacrylate (MO6); and wherein said co-polymer is a terpolymer or tetrapolymer having a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about lmeq/g to about 6 meq/g.
According to one important aspect of the present application, the above disclosed terpolymers and tetrapolymers of the present application can advantageously be combined and formulated with (1) at least one anionic, cationic, nonionic and/or zwitter-ionic/amphoteric polymers or mixtures thereof, (2) at least one personal care active ingredient, and/or (3) at least one cosmetically acceptable excipient.
The cationic polymers that can be used along with conditioning and/or styling copolymer of this application are those known to improve the cosmetic properties of hair which may be normal or damaged in nature. The expression “cationic polymer” as used herein, indicates any polymer containing cationic groups and/or ionizable groups in cationic groups. The cationic polymers used generally have a molecular weight the average number of which falls between about 500 and 5,000,000 and preferably between 1000 and 3,000,000. The preferred cationic polymers are chosen from among those containing units including primary, secondary, tertiary, and/or quaternary amine groups that may either form part of the main polymer chain or a side chain. Useful cationic polymers include known polyamine, polyaminoamide, and quaternary polyammonium types of polymers, such as:
(1) Homopolymers and copolymers derived from acrylic or methacrylic esters or amides. The copolymers can contain one or more units derived from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides, acrylic or methacrylic acids or their esters, vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters. Specific examples include: copolymers of acrylamide and dimethyl amino ethyl methacrylate quaternized with dimethyl sulfate or with an alkyl halide; copolymers of acrylamide and methacryloyl oxyethyl trimethyl ammonium chloride; the copolymer of acrylamide and methacryloyl oxyethyl trimethyl ammonium methosulfate; copolymers of vinyl pyrrolidone/dialkylaminoalkyl acrylate or methacrylate, optionally quaternized, such as the products sold under the name GAFQUAT by Ashland; the dimethyl amino ethyl methacrylate/vinyl caprolactam/vinyl pyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by Ashland; the vinyl pyrrolidone/methacrylamidopropyl dimethylamine copolymer, marketed under the name STYLEZE CC 10 by Ashland; the vinyl pyrrolidone/quaternized dimethyl amino propyl methacrylamide copolymers such as the product sold under the name GAFQUAT HS 100 by Ashland; and the vinyl pyrrolidone/dimethylaminopropyl methacrylamide/C9-C24 alkyldimethylaminopropyl methacrylic acid quaternized terpolymers described in U.S. Pat. No. 6,207,778 and marketed under the name STYLEZE-W20 by Ashland.
(2) Derivatives of cellulose ethers containing quaternary ammonium groups, such as hydroxy ethyl cellulose quaternary ammonium that has reacted with an epoxide substituted by a trimethyl ammonium group.
(3) Derivatives of cationic cellulose such as cellulose copolymers or derivatives of cellulose grafted with a hydrosoluble quaternary ammonium monomer, as described in U.S. Pat. No. 4,131,576, such as the hydroxy alkyl cellulose, and the hydroxymethyl-, hydroxyethyl- or hydroxypropyl-cellulose grafted with a salt of methacryloyl ethyl trimethyl ammonium, methacrylamidopropyl trimethyl ammonium, or dimethyl diallyl ammonium.
(4) Cationic polysaccharides such as described in U.S. Pat. Nos. 3,589,578 and 4,031,307, guar gums containing cationic trialkyl ammonium groups, guar gums modified by a salt, e.g., chloride of 2,3-epoxy propyl trimethyl ammonium, Cassia, Chitosan, Chitin and the like.
(5) Polymers composed of piperazinyl units and alkylene or hydroxy alkylene divalent radicals with straight or branched chains, possibly interrupted by atoms of oxygen, sulfur, nitrogen, or by aromatic or heterocyclic cycles, as well as the products of the oxidation and/or quaternization of such polymers.
(6) Water-soluble polyamino amides prepared by polycondensation of an acid compound with a polyamine. These polyamino amides may be reticulated.
(7) Derivatives of polyamino amides resulting from the condensation of polyalcoylene polyamines with polycarboxylic acids followed by alcoylation by bi-functional agents.
(8) Polymers obtained by reaction of a polyalkylene polyamine containing two primary amine groups and at least one secondary amine group with a dioxycarboxylic acid chosen from among diglycolic acid and saturated dicarboxylic aliphatic acids having 3 to 8 atoms of carbon. Such polymers are described in U.S. Pat. Nos. 3,227,615 and 2,961,347.
(9) The cyclopolymers of alkyl dialyl amine or dialkyl diallyl ammonium such as the homopolymer of dimethyl diallyl ammonium chloride and copolymers of diallyl dimethyl ammonium chloride and acrylamide.
(10) Quaternary diammonium polymers such as hexadimethrine chloride. Polymers of this type are described particularly in U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945, and 4,027,020.
(11) Quaternary polyammonium polymers, including, for example, Mirapol® A 15, Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175 products sold by Miranol.
(12) The quaternary polymers of vinyl pyrrolidone and vinyl imidazole such as the products sold under the names Luviquat® FC 905, FC550, and FC 370 by BASF.
(13) Quaternary polyamines.
(14) Reticulated polymers known in the art.
Suitable Polyquaternium type of cationic polymers for the present application would include but not limited to Polyquaternium 4, Polyquaternium 5, Polyquaternium 6, Polyquatemium 7, Polyquaternium 10, Polyquaternium 11, Polyquaternium 15, Polyquatemium 16, Polyquaternium 22, Polyquatemium 28, Polyquaternium 32, Polyquatemium 37, Polyquaternium 39, Polyquatemium 46, Polyquaternium 47, Polyquatemium 53, Polyquaternium 55, Polyquaternium 67, and/or Polyquatemium 87. Other polymers known by their CTFA category name “Quaternium” are suitable for the present application would include but not limited to Quatemium-8, Quaternium-14, Quaternium-15, Quaternium-18, Quaternium-22, Quaternium-24, Quaternium-26, Quaternium-27, Quaternium-30, Quaternium-33, Quaternium-53, Quaternium-60, Quaternium-61, Quaternium-72, Quaternium-78, Quaternium-80, Quaternium-81, Quaternium-81, Quaternium-82, Quaternium-83 and Quaternium-84.
Other cationic polymers that may be used within the context of the invention are cationic proteins or hydrolyzed cationic proteins, polyalkyleneimines such as polyethyleneimines, polymers containing vinyl pyridine or vinyl pyridinium units, condensates of polyamines and epichlorhydrins, quaternary polyurethanes, and derivatives of chitin.
The anionic polymers that can be employed along with a conditioning and/or styling copolymer of this application would include but are not limited to carboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), crotonic acid, styrene sulfonic acid, itconic acid, and the like.
Preferred anionic homo and copolymer of the present application would include but are not limited to (a) Homo- or copolymers of acrylic or methacrylic acid or salts thereof; (b) Copolymers of acrylic or methacrylic acids with a mono-ethylenic monomer such as ethylene, styrene, vinyl esters, acrylic acid esters or methacrylic acid esters. These copolymers can be grafted onto a polyalkylene glycol and optionally crosslinked; (c) Copolymers comprising: (i) one or more maleic, fumaric or itaconic acids or anhydrides and (ii) at least one monomer selected from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers optionally being monoesterified or monoamidated; (d) Copolymers comprising: (i) one or more maleic, citraconic or itaconic anhydrides and (ii) one or more monomers selected from allylic or methallylic esters optionally containing one or more acrylamide, methacrylamide, alpha-olefin, acrylic or methacrylic ester, acrylic or methacrylic acid or vinylpyrrolidone groups in their chain, the anhydride functions of these copolymers optionally being monoesterified or monoamidated; (e) Polyacrylamides containing carboxylate groups; (f) The polymers comprising sulphonic groups are polymers containing vinylsulphonic, styrenesulphonic, naphthalenesulphonic or acrylamidoalkylsulphonic units.
Other preferred anionic copolymers are selected from the group consisting of but not limited to vinyl acetate/crotonic acid copolymer, vinyl acetate/acrylate copolymer, vinyl acetate/vinyl neodecanoate/crotonic acid copolymer, sodium acrylate/vinyl alcohol copolymer, sodium polystyrene sulphate, ethyl acrylate/N-tert-Butyl acrylamide/acrylic acid copolymer, vinylpyrrolidone/vinyl acetate/itaconic acid copolymer, acrylic acid/acrylamide copolymer and sodium salts thereof, homo and copolymers of acrylic acid and/or methacrylic acid and/or salts thereof, acrylate/hydroxyacrylate copolymer, octylacrylamide/acrylate copolymer, octylacrylamide/methacrylic ester copolymer, butyl acrylate/N-vinylpyrrolidone copolymer, methyl vinyl ether/maleic acid copolymer and the ethyl, isopropyl and butyl esters, silicone/acrylic acid or methacrylic acid copolymer, polyurethanes based on diisocyanates with terminal acid groups.
The amphoteric polymers cab be selected from the following polymers: (1) Polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamides and acrylamides. (2) Polymers containing units derived from: a) at least one monomer selected from acrylamides and methacrylamides substituted on the nitrogen with an alkyl radical, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as esters containing primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulphate.
Further, the exemplary amphoteric polymer can selected from the group N-Octylacrylamid/Acrylsaure/tertiary-Butylaminoethylmethacrylat-Copolymer, N-Octylacrylamld/Methacrylsaure/tertiary-butylaminoethylmethacrylat-Copolymer group and copolymers of Methacryloylbetain/alkyl methacrylates, copolymers of monomers having carboxyl- and/or sulfonic groups, particularly acrylic acid, methacrylic acid, itaconic acid, and monomers containing amino groups, especially Monoalkylaminoalkylacrylate, dialkylaminoalkyl, Monoalkylaminoalkylmethacrylate, dialkylaminoalkyl, Mono-alkylaminoalkylacrylamide, dialkylamino-alkylacrylamides, Mono-alkylaminoalkylmethacrylamide, Dialkylaminoalkylmethacrylamide, and copolymers of N-octyl acrylamide, methyl methacrylate, hydroxypropyl methacrylate.
Nonionic polymers having at least one fatty chain and at least one hydrophilic unit, are preferably chosen from: (1) celluloses modified with groups containing at least one fatty chain such as, for example: hydroxyethyl celluloses modified with groups containing at least one fatty chain such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof, and in which the alkyl groups are preferably C8-C22; (2) hydroxypropyl guars modified with groups containing at least one fatty chain; (3) polyether urethanes containing at least one fatty chain such as a C8-C30 alkyl or alkenyl group; (4) copolymers of C1-C6 alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain; (5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain; (6) polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences; and (7) polymers with an aminoplast ether backbone containing at least one fatty chain. Other relevant nonionic polymers which are disclosed in US Patent Application No's. 20070134191 and 20110165108 may be employed for the purposes of the present application.
The polymerization of the polymer useful herein is carried out by any appropriate method known in the prior art by a person skilled in the art. Particularly, the polymerization is carried out by any one of the methods disclosed in “Principles of Polymerization” 4th edition, 2004, Wiley by George Odian and is referred and disclosed herein in its entirety. Further, the polymerization of terpolymer of the present application may contain a suitable catalyst or initiators such as amines, bases, organic acids and/or photo-initiators. However, the preferred polymerization technique employed to prepare a conditioning polymer would include but not limited to radical polymerization, emulsion polymerization, ionic chain polymerization, bulk polymerization, suspension polymerization or precipitation polymerization.
It is contemplated to employ at least one personal care active ingredient for preparing a personal care composition of the present application comprising a conditioner terpolymer and at least one cosmetically acceptable agent, wherein, the preferred personal care active ingredient of the present application would include but not limited to Carnitine, Betain Aminoacids as i.e. valine, glycine, arginine, allantoin, tocopherol nicotinate, niacinamide, retinyl propionate, palmitoyl-gly-his-lys, phytosterol, polyphenolic compounds, flavonoids, flavones, flavonols, isoflavone, dexpanthenol, panthenol, bisabolol, farnesol, phytantriol, salicylic acid, zinc/sodium pyridinethione salts, piroctone olamine, selenium disulfide, tetrahydrocurcumin, glucosamine, N-acteyl glucosamine, vitamin B3, retinoids, peptides, phytosterol, dialkanoyl hydroxyproline, hexamidine, salicylic acid, N-acyl amino acids, escolols, sunscreen actives, UV-A/UV-B protecting agent, UV filters, water soluble vitamins, oil soluble vitamins, hesperedin, mustard seed extract, glycyrrhizic acid, glycyrrhetinic acid, carnosine, Butylated Hydroxytoluene (BHT) and Butylated Hydroxyanisole (BHA), ergothioneine, vanillin, vanillin derivatives, diethylhexyl syrinylidene malonate, melanostatine, sterol esters, fatty acids, poly-unsaturated fatty acids, anti-fungal agents, thiol compounds, N-acetyl cysteine, glutathione, thioglycolate, β-carotene, ubiquinone, amino acids, idebenone, dehydroacetic acid, Licohalcone A, creatine, creatinine, feverfew extract, yeast extract, beta glucans, alpha glucans, alone or in combination.
The preferred polyphenolic compounds include flavonoids such as those broadly disclosed in U.S. Pat. No. 5,686,082. Exemplary flavonoids include at least one flavones, flavanols, isoflavones, coumarins, chromones, dicoumarols, chromanones, chromanols, and/or isomers (e.g., cis/trans isomers). Suitable flavones and isoflavones include unsubstituted flavone, unsubstituted isoflavone, daidzein (7,4′-dihydroxy isoflavone), genistein (5,7,4′-trihydroxy isoflavone), equol (7,4′-isoflavandiol), 5,7-dihydroxy-4′-methoxy isoflavone, 7,2′-dihydroxy flavone, 3′,4′-dihydroxy naphthoflavone, 7,8-benzoflavone, 4′-hydroxy flavone, 5,6-benzoflavone, soy isoflavones (e.g., isoflavones extracted from soy) and other plant sources of such mixtures (e.g. red clover), and mixtures thereof. Other suitable flavonoids include hesperitin, hesperidin, quercetin and mixtures thereof. Other polyphenolic compounds include tetrahydrocurcuminoids. Tetrahydrocurcuminoids include tetrahydrocurcumin, tetrahydrodemethoxycurcumin, and tetrahydrobismethoxycurcumin.
The effective amount of personal care active ingredient employed in the present application is in the range of from about 0.01 wt. % to about 10 wt. %, preferably about 0.1 wt. % to about 5.0 wt. % and more preferably in the range of 0.05 wt. % to about 3.0 wt. % of the total composition.
The personal care composition of present application is capable of fixing or treating hair and features conditioning and/or styling properties such as detangling, wet combability, wet feel, dry combability, dry feel, sheen, static flyaway control, hydrophobicity, surface smoothening, improved deposition, no build-up, color protection, and/or curl retention. Further, the personal care composition comprising a terpolymer of present application is able to provide “virgin feel condition” to the hair after multiple washes.
The personal care composition of present application can be an appropriate product selected from the group consisting of hair-care products, shampoos, hair conditioners, 2 in 1 shampoos, leave in and rinse off conditioners, hair treatments including intensive treatments, styling and treating hair compositions, hair perming products, hair straightners, hair relaxants, hair sprays and lacquers, permanent hair dyeing systems, hair styling mousses, hair gels, semi-permanent hair dyeing systems, temporary hair dyeing systems, hair bleaching agents, permanent hair wave systems, hair setting formulations, non-coloring hair preparations, hair-frizz-control gels, hair leave-in conditioners, hair pomades, hair de-tangling products, hair fixatives, hair conditioning mists, hair care pump sprays and other non-aerosol sprays, skin-care products, hair cuticle coats, skin care moisturizing mists, skin wipes, pore skin wipes, pore cleaners, blemish reducers, skin exfoliators, skin desquamation enhancers, skin towelettes, skin protection ointments, skin powders, skin pads, paste masks and muds, face masks, facial cleansing products, anti-acne preparations, bath products, shower products, liquid soaps, bar soaps, body oils, body lotions, body gels, body and hand preparations, face and body washes, bath salts, bath and body milks, foam baths, synthetic and non-synthetic soap bars, hand liquids, shaving lotions, shaving and aftershave preparations, pre-shaves and pre-electric shaves, nail varnishes, nail polish, nail polish remover, nail creams and lotions, cuticle softeners, nail conditioners, eye shadows, mascaras, eye liners, eye shadows, blushes, makeup, eye shadow sticks, baby lotions, baby baths and shampoos, baby conditioners, fragrances and/or odoriferous ingredients consisting preparations, dentifrices, deodorizing and antiperspirant preparations, decorative preparations, light protection formulations, treatment creams, lipsticks. dry and moist make-up, rouge, powders, depilatory agents, sun care products, compositions comprising UV blockers or UV protectors, anti-aging products, foundations, face powders, moisturizing preparations, tanning preparations, nose strips, make-up removers, cold creams, mousses, shower gels, personal care rinse-off products, gels, scrubbing cleansers, astringents, lip balms, lip glosses, anhydrous creams and lotions, oil/water, water/oil, multiple and macro and micro emulsions, water-resistant creams and lotions, mouth-washes, massage oils, toothpastes, clear gels and sticks, ointment bases, topical wound-healing products, aerosol talc, barrier sprays, vitamin, herbal-extract preparations, and/or controlled-release personal care products.
The personal care composition of present invention can be formulated in several required forms according to their necessity, and the non-limiting forms include emulsion, lotion, gel, vesicle dispersion, paste, cream, solid stick, mousse, shampoo, spray, balm, wipe, milk, foam, jellies, liquid, tonics, and/or enamel.
As used herein, the term “cosmetically acceptable excipient” means any ingredient/compound or mixture of ingredients/compounds or compositions that are typically employed to produce other desirable effects in personal care compositions. The preferred cosmetically acceptable excipients include but not limited to preservatives, antioxidants, chelating agents, sunscreen agents, proteins, amino acids, vitamins, dyes, hair coloring agents, plant extracts, plant derivatives, plant tissue extracts, plant seed extracts, plant oils, botanicals, botanical extracts, humectants, fragrances, perfumes, oils, emollients, lubricants, butters, penetrants, thickeners, viscosity modifiers, thickeners, polymers, resins, hair fixatives, film formers, surfactants, detergents, emulsifiers, opacifying agents, volatiles, propellants, liquid vehicles, carriers, salts, pH adjusting agents, neutralizing agents, buffers, hair conditioning agents, anti-static agents, anti-frizz agents, anti-dandruff agents, hair waving agents, hair straightening agents, relaxers, absorbents, fatty substances, gelling agents, moisturizers, hydrophilic or lipophilic active agent, preserving agents, fillers, dyestuffs, reducing agents, cosmetic oils, perfumes, liquid vehicles, solvents, carriers, silicones, and combinations thereof.
Suitable rheology modifiers and thickeners include synthetic and semi-synthetic rheology modifiers. Exemplary synthetic rheology modifiers include acrylic based polymers and copolymers. One class of acrylic based rheology modifiers are the carboxyl functional alkali-swellable and alkali-soluble thickeners (ASTs) produced by the free-radical polymerization of acrylic acid alone or in combination with other ethylenically unsaturated monomers. The polymers can be synthesized by solvent/precipitation as well as emulsion polymerization techniques. Exemplary synthetic rheology modifiers of this class include homopolymers of acrylic acid or methacrylic acid and copolymers polymerized from one or more monomers of acrylic acid, substituted acrylic acid, and salts and C1-C30 alkyl esters of acrylic acid and substituted acrylic acid. As defined herein, the substituted acrylic acid contains a substituent positioned on the alpha and/or beta carbon atom of the molecule wherein the substituent is preferably and independently selected from C1-4 alkyl, —CN, and —COOH. Optionally, other ethylenically unsaturated monomers such as, for example, styrene, vinyl acetate, ethylene, butadiene, acrylonitrile, as well as mixtures thereof can be copolymerized into the backbone. The foregoing polymers are optionally crosslinked by a monomer that contains two or more moieties that contain ethylenic unsaturation. In one aspect, the crosslinker is selected from a polyalkenyl polyether of a polyhydric alcohol containing at least two alkenyl ether groups per molecule. Other Exemplary crosslinkers are selected from allyl ethers of sucrose and allyl ethers of pentaerythritol, and mixtures thereof. These polymers are more fully described in U.S. Pat. No. 5,087,445; U.S. Pat. No. 4,509,949; and U.S. Pat. No. 2,798,053 herein incorporated by reference in its entirety.
Commercially available Carbomers include Carbopol® polymers 934, 940, 941, 956, 980 and 996 available from Lubrizol Advanced Materials, Inc. In another embodiment the AST rheology modifier is selected from a crosslinked copolymer polymerized from a first monomer selected from one or more monomers of (meth)acrylic acid, substituted acrylic acid, and salts of (meth)acrylic acid and substituted acrylic acid and a second monomer selected from one or more C1-C5 alkyl acrylate esters of (meth)acrylic acid. These polymers are designated under the INCI name of Acrylates Copolymer. Acrylates Copolymers are commercially available under the trade names Aculyn® 33 from Rohm and Haas and Carbopol® Aqua SF-1 from Lubrizol Advanced Materials, Inc. In a further aspect the rheology modifier is selected from a crosslinked copolymer polymerized from a first monomer selected from one or more monomers of acrylic acid, substituted acrylic acid, salts of acrylic acid and salts of substituted acrylic acid and a second monomer selected from one or more C10-C30 alkyl acrylate esters of acrylic acid or methacrylic acid. In one aspect, the monomers can be polymerized in the presence of a steric stabilizer such as disclosed in U.S. Pat. No. 5,288,814 which is herein incorporated by reference. Some of the forgoing polymers are designated under INCI nomenclature as Acrylates/C10-30 Alkyl Acrylate Crosspolymer and are commercially available under the trade names Carbopol® 1342 and 1382, Carbopol® Ultrez 20 and 21, Carbopol® ETD 2020 and Pemulen® TR-1 and TR-2 from Lubrizol Advanced Materials, Inc. Any vinyl or acrylic based rheology modifiers are suitable.
Another class of synthetic rheology modifiers and thickeners suitable for use in accordance with an embodiment of the present invention includes hydrophobically modified ASTs commonly referred to as hydrophobically modified alkali-swellable and alkali-soluble emulsion (HASE) polymers. Typical HASE polymers are free radical addition polymers polymerized from pH sensitive or hydrophilic monomers (e.g., acrylic acid and/or methacrylic acid), hydrophobic monomers (e.g., C1-C30 alkyl esters of acrylic acid and/or methacrylic acid, acrylonitrile, styrene), an “associative monomer”, and an optional crosslinking monomer. The associative monomer comprises an ethylenically unsaturated polymerizable end group, a non-ionic hydrophilic midsection that is terminated by a hydrophobic end group. The non-ionic hydrophilic midsection comprises a polyoxyalkylene group, e.g., polyethylene oxide, polypropylene oxide, or mixtures of polyethylene oxide/polypropylene oxide segments. The terminal hydrophobic end group is typically a C8-C40 aliphatic moiety. Exemplary aliphatic moieties are selected from linear and branched alkyl substituents, linear and branched alkenyl substituents, carbocyclic substituents, aryl substituents, aralkyl substituents, arylalkyl substituents, and alkylaryl substituents. In one aspect, associative monomers can be prepared by the condensation (e.g., esterification or etherification) of a polyethoxylated and/or polypropoxylated aliphatic alcohol (typically containing a branched or unbranched C8-C40 aliphatic moiety) with an ethylenically unsaturated monomer containing a carboxylic acid group (e.g., acrylic acid, methacrylic acid), an unsaturated cyclic anhydride monomer (e.g., maleic anhydride, itaconic anhydride, citraconic anhydride), a monoethylenically unsaturated monoisocyanate (e.g., α,α-dimethyl-m-isopropenyl benzyl isocyanate) or an ethylenically unsaturated monomer containing a hydroxyl group (e.g., vinyl alcohol, allyl alcohol). Polyethoxylated and/or polypropoxylated aliphatic alcohols are ethylene oxide and/or propylene oxide adducts of a monoalcohol containing the C8-C40 aliphatic moiety. Non-limiting examples of alcohols containing a C8-C40 aliphatic moiety are capryl alcohol, iso-octyl alcohol (2-ethyl hexanol), pelargonic alcohol (1-nonanol), decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetyl alcohol, cetearyl alcohol (mixture of C16-C18 monoalcohols), stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, melissyl, lacceryl alcohol, geddyl alcohol, and C2-C20 alkyl substituted phenols (e.g., nonyl phenol), and the like.
Exemplary HASE polymers are disclosed in U.S. Pat. No. 3,657,175; U.S. Pat. No. 4,384,096; U.S. Pat. No. 4,464,524; U.S. Pat. No. 4,801,671; and U.S. Pat. No. 5,292,843, which are herein incorporated by reference. In addition, an extensive review of HASE polymers is found in Gregory D. Shay, Chapter 25, “Alkali-Swellable and Alkali-Soluble Thickener Technology A Review”, Polymers in Aqueous Media—Performance Through Association, Advances in Chemistry Series 223, J. Edward Glass (ed.), ACS, pp. 457-494, Division Polymeric Materials, Washington, D.C. (1989), the relevant disclosures of which are incorporated herein by reference. The HASE polymers are commercially available from Rohm & Haas under the trade designations Aculyn® 22 (INCI Name: Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn® 44 (INCI Name: PEG-150/Decyl Alcohol/SMDI Copolymer), Aculyn 46® (INCI Name: PEG-150/Stearyl Alcohol/SMDI Copolymer), and Aculyn® 88 (INCI Name: Acrylates/Steareth-20 Methacrylate Crosspolymer).
Another class of synthetic and semi-synthetic rheology modifiers and thickeners suitable for use in accordance with an embodiment of the present invention includes cationically modified acrylic polymers and copolymers and cationically modified cellulose ethers. The acrylic polymers and copolymers and cellulose ethers are cationically modified via quaternization. For the acrylic polymers and copolymers, quaternization can occur by polymerizing a quaternized monomer into the acrylic polymer backbone or by post functionalizing the acrylic polymer with a quaternizing agent. An exemplary quaternary acrylic polymer is designated under INCI nomenclature as Polyquaternium-37 and is commercially available under the trade names Synthalen CR21 and Synthalen CN, from 3V Inc. The quaternized celluloses are prepared by post functionalizing the desired cellulosic backbone (e.g., hydroxyethyl cellulose) with a quaternizing agent such as a quaternary ammonium salt (e.g., diallyldimethyl ammonium chloride, trimethyl ammonium chloride substituted epoxide). Exemplary quaternary cellulosic polymers are designated under the INCI names Polyquaternium-4, Polyquaternium-10, and Polyquaternium-67.
Other rheology modifiers suitable for use in the personal care compositions of the invention are disclosed in U.S. Pat. No. 7,205,271 the disclosure of which is herein incorporated by reference.
Suitable surfactants or surfactant systems for preparing a personal care composition comprising a conditioning and/or styling copolymer of the present application can be selected from anionic, non-ionic, amphoteric, cationic and mixtures thereof. The contemplated surfactants for use herein are as follows:
(A) Anionic Surfactants: Anionic surfactants are particularly useful in accordance with certain embodiments of the present application. Surfactants of the anionic type that may be useful include:
(1) Sulfonates and Sulfates: Suitable anionic surfactants include sulfonates and sulfates such as alkyl sulfates, alkylether sulfates, alkyl sulfonates, alkylether sulfonates, alkylbenzene sufonates, alkylbenzene ether sulfates, alkylsulfoacetates, secondary alkane sulfonates, secondary alkylsulfates, alkyl sulfosuccinates and the like. Further, examples of anionic surfactants include water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of the monosulfated monoglyceride of hydrogenated coconut oil fatty acids, higher alkyl sulfates such as sodium lauryl sulfate, alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate, higher alkyl sulfoacetates, higher fatty acid esters of 1,2-dihydroxy propane sulfonate, and the substantially saturated higher aliphatic acyl amides of lower aliphatic amino carboxylic acid compounds, such as those having 12 to 16 carbons in the fatty acid, alkyl or acyl radicals, and the like.
(2) Phosphates and Phosponates: Suitable anionic surfactants also include phosphates such as alkyl phosphates, alkylether phosphates, aralkylphosphates, and aralkylether phosphates. Examples include a mixture of mono-, di- and tri-(alkyltetraglycolether)-o-phosphoric acid esters generally referred to as trilaureth-4-phosphate commercially available under the trade designation HOSTAPHAT 340KL from Clariant Corp., as well as PPG-5 ceteth 10 phosphate available under the trade designation CRODAPHOS SG from Croda Inc., Parsipanny, N.J.
(3) Amine Oxides: Suitable anionic surfactants also include amine oxides. Examples of amine oxide surfactants include lauryldimethylamine oxide, laurylamidopropyldimethylamine oxide, and/or cetyl amine oxide.
(B) Amphoteric Surfactants: Surfactants of the amphoteric type include surfactants having tertiary amine groups which may be protonated as well as quaternary amine containing zwitterionic surfactants. Those that may be useful include:
(1) Ammonium Carboxylate Amphoterics: Examples of such amphoteric surfactants include, but are not limited to: certain betaines such as cocobetaine and cocamidopropyl betaine; monoacetates such as sodium lauroamphoacetate; diacetates such as disodium lauroamphoacetate; amino- and alkylamino-propionates such as lauraminopropionic acid.
(2) Ammonium Sulfonate Amphoterics: These classes of amphoteric surfactants are often referred to as “sultaines” or “sulfobetaines” for example, cocamidopropylhydroxysultaine.
(C) Nonionic Surfactants: Surfactants of the nonionic type that may be particularly useful include:
(1) Polyethylene oxide extended sorbitan monoalkylates (i.e. Polysorbates); (2) Polyalkoxylated alkanols; (3) Polyalkoxylated alkylphenols include polyethoxylated octyl or nonyl phenols having HLB values of at least about 14, which are commercially available under the trade designations ICONOL and TRITON; (4) Polaxamers. Surfactants based on block copolymers of ethylene oxide (EO) and propylene oxide (PO) may also be effective. Both EO-PO-EO blocks and PO-EO-PO blocks are expected to work well as long as the HLB is at least about 14, and preferably at least about 16. Such surfactants are commercially available under the trade designations PLURONIC and TETRONIC from BASF; (5) Polyalkoxylated esters—Polyalkoxylated glycols such as ethylene glycol, propylene glycol, glycerol, and the like may be partially or completely esterified, i.e. one or more alcohols may be esterified, with a (C8 to C22) alkyl carboxylic acid. Such polyethoxylated esters having an HLB of at least about 14, and preferably at least about 16, may be suitable for use in compositions of the present invention; (6) Alkyl Polyglucosides. This includes glucopon 425, which has a (C8 to C16) alkyl chain length.
(D) Cationic Surfactants: Surfactants of the cationic type that may be useful include but are not limited to, primary amines, secondary amines, tertiary amines, quaternary amines, alkanolamines, mono-alkyl alkanolamines, di-alkyl alkanolamines, tri-alkyl alkanolamines, alkyl mono alkanolamines, alkyl di-alkanolamines, alkylamines, mono-alkyl amines, di-alkyl amines, tri-alkylamines, alkoxylated amines, alkyl and aryl amine alkoxylates, methoxylated alkylamines, ethoxylated alkylamines, alkoxylated alkanolamines, alkyl alkanolamines, alkoxylated ethylene diamine derivatives, alkyl/aryl/arylalkyl amine oxides. Preferred cationic surfactants of the present invention include, but are not limited to, (a) alkyl alkanolamines; and (b) alkyl tertiary amines. Additional information on useful cationic surfactants for the purpose of present invention is set forth in McCutcheon's Detergents and Emulsifiers, North American Ed., 1982 and Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 346-387, the contents of which are incorporated herein by reference.
Suitable emulsifiers include the following classes of ethers and esters: ethers of polyglycols and of fatty alcohols, esters of polyglycols and of fatty acids, ethers of polyglycols and of fatty alcohols which are glycosylated, esters of polyglycols and of fatty acids which are glycosylated, ethers of C12-30 alcohols and of glycerol or of polyglycerol, esters of C12-30 fatty acids and of glycerol or of polyglycerol, ethers of oxyalkylene-modified C12-30 alcohols and of glycerol or polyglycerol, ethers of C12-30 fatty alcohols comprising and of sucrose or of glucose, esters of sucrose and of C12-30 fatty acids, esters of pentaerythritol and of C12-30 fatty acids, esters of sorbitol and/or of sorbitan and of C12-30 fatty acids, ethers of sorbitol and/or of sorbitan and of alkoxylated sorbitan, ethers of polyglycols and of cholesterol, esters of C12-30 fatty acids and of alkoxylated ethers of sorbitol and/or sorbitan, and combinations thereof. Linear or branched type silicone emulsifiers may also be used. Particularly useful polyether modified silicones include KF-6011, KF-6012, KF-6013, KF-6015, KF-6015, KF-6017, KF-6043, KF-6028, and KF-6038 from Shin-Etsu. Also particularly useful are the polyglycerolated linear or branched siloxane emulsifiers including KF-6100, KF-6104, and KF-6105 from Shin-Etsu. Emulsifiers also include emulsifying silicone elastomers. Suitable emulsifying silicone elastomers may include at least one polyalkyl ether or polyglycerolated unit.
The personal care composition of present application can be preserved by adding minor quantity of preservatives to the compositions. Such preservatives can be selected from, but are not limited to triazoles, imidazoles, naphthalene derivatives, benzimidazoles, morphline derivatives, dithiocarbamates, benzisothiazoles, benzamides, boron compounds, formaldehyde donors, isothiazolones, thiocyanates, quaternary ammonium compounds, iodine derivates, phenol derivatives, micobicides, pyridines, dialkylthiocarbamates, nitriles, parabens, alkyl parabens and salts thereof.
Suitable antioxidants may be added to facilitate the enhanced shelf-life of the personal care composition. Exemplary antioxidants that can be used include vitamins such as vitamin E, vitamin E acetate, vitamin C, vitamin A, and vitamin D, and derivatives thereof. Additional exemplary antioxidants include but are not limited to propyl, octyl and dodecyl esters of gallic acid, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and nordihydroguaiaretic acid. In general, the required amount of antioxidant for the present composition is in the range of about 0.2 wt. % to about 2 wt. %, and can be provided in an amount of about 0.5 wt. % to about 1.5 wt. %, based on the total weight of the composition.
The preferred fatty substance based excipient for the present application include fatty alcohols, natural and synthetic waxes, ceramides, mineral oils, vegetable oils, animal oils, synthetic oils. The other preferred fatty substance are isododecane, hydrogenated polyisobutene, squalane, isononyl isononanoate, cyclotetra- and -pentadimethicones, phenyltrimethicone, ethylene homopolymers, ethoxylated fats and oils, fluoroalkanes, seracite, shea butter, arachidyl propionate alone or in combination. For the definition of waxes, mention may be made, for example, of P. D. Dorgan, Drug and Cosmetic Industry, December 1983, pp. 30-33.
The preferred waxes of the present application would include microcrystalline waxes, carnauba wax, candelilla wax, esparto wax, paraffin wax, ozokerite. It is also considered to use plant waxes such as olive tree wax, rice wax, fruit waxes, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax of blackcurrant flower sold by the company Bertin (France), animal waxes such as beeswaxes, or modified beeswaxes; other waxes or waxy starting materials which can be used according to this application are, in particular, marine waxes and polyethylene waxes or polyolefins.
The animal or plant oils are preferably chosen from sunflower oil, corn oil, soybean oil, avocado oil, jojoba oil, marrow oil, Argan oil, grapeseed oil, sesame oil, hazelnut oil, fish oils, glyceryl tricaprocaprylate, or plant or animal oils of formula R1COOR2 in which R1 represents a higher fatty acid residue containing from 7 to 29 carbon atoms and R2 represents a linear or branched hydrocarbon-based chain containing from 3 to 30 carbon atoms, particularly alkyl or alkenyl, for example purcellin oil or liquid jojoba wax. Further, it is also possible to use natural or synthetic essential oils such as, for example, eucalyptus oil, lavandin oil, lavender oil. vetiver oil, Litsea cubeba oil, lemon oil, sandalwood oil, rosemary oil, camomile oil, savory oil, nutmeg oil, cinnamon oil, hyssop oil, caraway oil, orange oil, geraniol oil, cade oil, almond oil, argan oil, avocado oil, olive oil, sun flower oil, cedar oil, wheat germ oil and bergamot oil.
The compounds of ceramide type are natural or synthetic ceramides and/or glycoceramides and/or pseudoceramides and/or neoceramides. The ceramide based type of compounds are described in detail in various patent prior arts, for example, DE4424530, DE 4424533, DE4402929, DE4420736, WO95/23807, WO94/07844, EP-A-0646572, WO 95/16665, FR-2673179, EP-A-0227994, WO94/07844, WO94/24097 and WO94/10131, the teachings of which are included herein by way of reference in its entirety.
Moisturizers employed in the present invention would include glycols, glycerols, propylene glycol, diethylene glycol monoethyl ether, sorbitol, sodium salt of pyroglutamic acid, glycerol, glycerol derivatives, glycerin, trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, sodium hyaluronate, and the like.
Further, it is known that moisturizers that bind well with water, thereby retaining it on the hair surface is called humectants. Examples of humectants which can be incorporated into a product of the present application are glycerine, propylene glycol, polypropylene glycol, polyethylene glycol, lactic acid, sodium lactate, pyrrolidone carboxylic acid, urea, phospholipids, collagen, elastin, ceramides, lecithin sorbitol, PEG-4, and mixtures thereof. Additional suitable moisturizers are polymeric moisturizers that belong to water soluble and/or water swellable in nature. Polysaccharides such as hyaluronic acid, chitosan can also be employed along with moisturizers of the present application as binder to enhance their property.
The preferred solvent of the present application may consist of water, a cosmetically acceptable solvent, or a blend of water and a cosmetically acceptable solvent, such as a lower alcohol composed of C1 to C4, such as ethanol, isopropanol, t-butanol, n-butanol, alkylene glycols such as propylene glycol, and glycol ethers. However, the compositions of the invention can be anhydrous. The most preferred solvents of the present application would include water, ethanol and/or iso-propanol.
It is contemplated to employ other suitable solvents for preparing products of the present application would include but not limited to linear and branched C1-C6 alcohols, such as ethanol, propanol, isopropanol, butanol, hexanol, and mixtures thereof; aromatic alcohols, such as benzyl alcohol, cycloaliphatic alcohols, such as cyclohexanol, and the like; saturated C12-C30 fatty alcohol, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like. Non-limiting examples of polyols include polyhydroxy alcohols, such as glycerin, propylene glycol, butylene glycol, hexylene glycol, C2-C4 alkoxylated alcohols and C2-C4 alkoxylated polyols, such as ethoxylated, propoxylated, and butoxylated ethers of alcohols, diols, and polyols having about 2 to about 30 carbon atoms and 1 to about 40 alkoxy units, polypropylene glycol, polybutylene glycol, and the like. Non-limiting examples of non-aqueous auxiliary solvents include silicones, and silicone derivatives, such as cyclomethicone, and the like, aliphatic solvents such as cyclohexane and heptane, ketones such as acetone and methyl ethyl ketone, and mixtures thereof; ethers such as diethyl ether, dimethoxymethane, and mixtures thereof, natural and synthetic oils and waxes, such as vegetable oils, plant oils, animal oils, essential oils, mineral oils, C7-C40 isoparaffins, alkyl carboxylic esters, such as ethyl acetate, amyl acetate, ethyl lactate, and the like, jojoba oil, shark liver oil, and the like.
The preferred neutralizing agents that can be included in the product of the present application to neutralize components such as e.g. an emulsifier or a foam builder/stabilizer include but are not limited to alkali hydroxides such as a sodium and potassium hydroxide; organic bases such as methylethylamine (MEA), ammonia, aminoalcohols, lithium hydroxide, diethanolamine (DEA); triethanolamine (TEA), aminomethyl propanol, and mixtures thereof; amino acids such as arginine and lysine and any combination of any foregoing. The neutralizing agent can be present in an amount of about 0.01 wt. % to about 8 wt. %, preferably, 1 wt. % to about 5 wt. %.
Other preferred pH adjusting agents would include alkaline pH adjusting agents include alkali metal hydroxides, such as sodium hydroxide, and potassium hydroxide; ammonium hydroxide; organic bases, such as triethanolamine, diisopropylamine, dodecylamine, diisopropanolamine, aminomethyl propanol, cocamine, oleamine, morpholine, triamylamine, triethylamine, tromethamine (2-amino-2-hydroxymethyl)-1,3-propanediol), and tetrakis(hydroxypropyl)ethylenediamine; and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like, and mixtures thereof. Acidic pH adjusting agents can be organic acids, including amino acids, and inorganic mineral acids. Non-limiting examples of acidic pH adjusting agents include acetic acid, citric acid, fumaric acid, glutamic acid, glycolic acid, hydrochloric acid, lactic acid, nitric acid, phosphoric acid, sodium bisulfate, sulfuric acid, tartaric acid, and the like, and mixtures thereof.
Suitable buffering agents include but are not limited to alkali or alkali earth carbonates, phosphates, bicarbonates, citrates, borates, acetates, acid anhydrides, succinates and the like, such as sodium phosphate, citrate, borate, acetate, bicarbonate, and carbonate.
Examples of anti-dandruff agents that can be used are cimbazole, octopirox and zinc pyrithione, salicylic acid, elemental sulfur, selenium dioxide, and the azole antimycotics.
According to one important embodiment of the present application, it is contemplated to employ natural plant extracts showing hair conditioning, restructuring effects, growing effects, can be used in the conditioners. Those are preferably the extracts from almond, coconut, mango, peach, lemon, wheat, rosemary, apricot, algae, grapefruit, sandalwood, lime orange, Acacia concinna, Butea parviflora, Butea superb, Butea frondosa and/or Aloe Vera. The extracts of these plants are obtained from seeds, roots, stem, leaves, flowers, bark, fruits, and/or whole plant.
According to one important embodiment of the present application, it is contemplated to employ at least one organic UV filters which can filter out UV rays can be selected from hydrosoluble or liposoluble filters, whether siliconated or nonsiliconated, and mineral oxide particles, the surface of which may be treated.
Hydrosoluble organic UV filters can be chosen from para-amino benzoic acid and its salts, anthranilic acid and its salts, salicylic acid and its salts, hydroxy cinnamic acid and its salts, sulfonic derivatives of benzothiazoles, benzimidizoles, benzoxazoles and their salts, sulfonic derivatives of benzophenone and their salts, sulfonic derivatives of benzylidene camphor and their salts, derivatives of benzylidene camphor substituted by a quaternary amine and their salts, derivatives of phthalydene-camphosulfonic acids and their salts, sulfonic derivatives of benzotriazole, and mixtures thereof.
Hydrophilic polymers which have light-protective qualities against UV rays can be used. These include polymers containing benzylidene camphor and/or benzotriazole groups.
Suitable liposoluble organic UV filters would include but are not limted to derivatives of para-aminobenzoic acid, such as the esters or amides of para-aminobenzoic acid; derivatives of salicylic acid; derivatives of benzophenone; derivatives of dibenzoyl methane; derivatives of diphenyl acrylates; derivatives of benzofurans; UV filter polymers containing one or more silico-organic residues; esters of cinnamic acid; derivatives of camphor; derivatives of trianilino-s-triazine; the ethylic ester urocanic acid; benzotriazoles; derivatives of hydroxy phenyl triazine; bis-resorcinol-dialkyl amino triazine; and mixtures thereof.
The liposoluble (or lipophilic) organic UV filter according to the invention can be chosen from octyl salicylate; 4-tert-butyl-4′-methoxy dibenzoyl methane; octocrylene; 4-methoxy cinnamate; 2-ethylhexyl [2-ethylhexyl 4-methoxycinnamate]; and 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethyl silyl)oxy]disiloxanyl]propynyl]phenol.
Other UV filters particularly preferred for use herein are derivatives of benzophenones such as 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid, 2-hydroxy-4-methoxy benzophenone, derivatives of benzalmalonates such as poly dimethyl/methyl (3(4-(2.2-bis-ethoxy carbonyl vinyl)-phenoxy)-propenyl) siloxane, derivatives of benzylidene camphor such as b-b′camphosulfonic-[1-4 divinylbenzene] acid and derivatives of benzimidazole such as 2-phenyl-benzimidazol-5-sulfonic acid.
Water-insoluble UV filters also include various mineral oxides. The mineral oxides can be selected from among titanium oxides, zinc oxides, and cerium oxides. The mineral oxides can be used in the form of ultrafine nanoparticles.
Preferred UV filters include Escalol HP-610 (dimethylpabamido propyl laurdimonium tosylate and propylene glycol stearate) and Crodasorb HP (polyquaternium 59).
The coloring agents, colorants or dyes used herein include natural foods colors and dyes suitable for food, drug and cosmetic applications. These colorants are also known as FD & C, and D&C dyes and lakes and are preferably water-soluble in nature. A full recitation of all FD&C and D&C dyes and their corresponding chemical structures may be found in the Kirk-Othmer Encyclopedia of Chemical Technology, Volume 5, pages 857-884, which text is accordingly incorporated herein by reference. These coloring agents may be incorporated in amount up to about 3%, more particularly up to about 2%, and in some cases less than about 1% by weight of the personal care compositions.
In preparing personal care composition herein, it is preferred to add suitable thickening agents wherever required to provide a desirable consistency to the appropriate formulation. Examples of useful thickening agents include carboxyvinyl polymers, carrageenan, hydroxyethyl cellulose, hydrophobically modified hydroxy-ethyl-cellulose, laponite and water soluble salts of cellulose ethers such as sodium carboxymethylcellulose and sodium carboxymethyl hydroxyethyl cellulose, copolymers of lactide and glycolide monomers, carbomers. Natural gums such as gum karaya, xanthan gum, gum arabic, Guars, HP Guars, and gum tragacanth can also be used. Some thickening agents, however, except polymeric polyether compounds, e.g., polyethylene or polypropylene oxide (MW 300 to 1,000,000), capped with alkyl or acyl groups containing 1 to about 18 carbon atoms. Carbomers are commercially available from Lubrizol as the Carbopol Series. Particularly preferred carbopols include Carbopol 934, 940, 941, 956, 980, 981, 1342, 1382, 2984, 5984, Aqua, Ultrez, ETD polymers, Pemulen polymers, and mixtures thereof. Thickening agents are usually present in an amount from about 0.1% to about 25% by weight of the disinfectant/cleaning concentrate composition. However, the preferred amount of thickening agent for the present composition is the range of about 0.01-5.0% by weight, preferably about 0.05-2.0%.
The term “sequestering agent” or “chelating agent” as used herein relates to a compound which is capable of bonding or complexing a metal ion between two or more atoms of the compound, thereby neutralizing or controlling harmful effects of such metal ions. Wherein holding or bonding of a metal ion is through combination of one or more different types of bonds including coordination and/or ionic bonds. The suitable organic or inorganic sequestering or chelating for the purposes of the present application is selected from the group comprising polyols, gluconates, sorbitals, mannitols, carbonates, hydroxamates, catechols, α-amino carboxylates, alkanolamines, metal-ion sequestrants, hydroxy-carboxylic acids, aminocarboxylic acids, amino polycarboxylic acids, polyamines, polyphosphates, phosphonic acids, crown ethers, amino acids, polycarboxylic acids, cyclodextrin, phosphonates, polyacrylates or polymeric polycarboxylates, condensed phosphates. Further, the information on sequestering and chelating agents is disclosed in T. E. Furia, CRC Handbook of Food Additives, 2nd Edition, pp. 271-294 (1972), and M. S. Peterson and A. M. Johnson (Eds.), Encyclopedia of Food Science, pp. 694-699 (1978) are incorporated herein by reference in its entirety.
The pH of the composition can be controlled within any desired range according to the type and purpose of the formulation. In order to attain the desired pH range, various pH modifiers may be employed in the present composition. Specific examples of basic pH modifiers are ammonia; sodium, potassium, and lithium hydroxide; sodium, potassium, and lithium meta silicates; monoethanolamine; triethylamine; isopropanolamine; diethanolamine; and triethanolamine. The suitable acidic pH modifying agents that can be employed in the present application include, but are not limited to, mineral acids, carboxylic acids and polymeric acids. Specific examples for mineral acids are hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid. Examples for appropriate carboxylic acids are citric acid, glycolic acid, lactic acid, maleic acid, malic acid, succinic acid, glutaric acid, benzoic acid, malonic acid, salicylic acid, gluconic acid, and mixtures thereof. Examples for suitable polymeric acids include straight-chain poly(acrylic) acid and its copolymers (e.g., maleic-acrylic, sulfonic-acrylic, and styrene-acrylic copolymers), cross-linked polyacrylic acids having a molecular weight of less than about 250,000, poly(methacrylic) acid, and naturally occurring polymeric acids such as carageenic acid, carboxymethyl cellulose, and alginic acid.
The desired pH of the personal care composition is in the range of from about 3 to about 13, and in some embodiment, it is preferably between about 4 to about 8. The utility levels of the pH modifying agent may be present in an effective amount required to achieve the desired pH level.
A perfume or fragrance obtained from natural or synthetic source can be employed in the present personal care composition. The fragrance may be used along with a suitable solvent, diluents or carrier. Fragrances may be added in any conventionally known method, for example, admixing to a composition or blending with other ingredients used to form a composition, in amounts which are found to be useful to increase or impart the desired scent characteristics to the disinfectant or cleaning compositions. Fragrances for the present application can be one or more selected from the following non-limiting group of compounds such as essential oils, absolutes, resinoids, resins, concretes, hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, including saturated and unsaturated compounds and aliphatic, carbocyclic and heterocyclic compounds.
According to one embodiment of the present application, the conditioning and/or styling composition optionally comprises any silicones which are known to a person skilled in the art, such silicones may be present in the form of oils, waxes, resins, or gums. Silicones for the present invention can be selected from Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp 204-308, John Wiley & Sons, Inc. (1989), is incorporated herein by reference. Non-limiting examples of suitable silicone conditioning agents, and optional suspending agents for the silicone, are described in detail in U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646, and U.S. Pat. No. 5,106,609 and can be readily referred for the purposes of the invention.
Suitable silicones for the present application are duly disclosed in U.S. Pat. No. 2,826,551, U.S. Pat. No. 3,964,500, U.S. Pat. No. 4,364,837, British Patent No. 849433, EP-A-0 582152, WO 93/23009, and Silicon Compounds, Petrarch Systems, Inc. (1984), all of which are incorporated herein by reference
The suitable silicones of the present application would include but are not limited to polyorganosiloxanes, polyalkyl siloxanes, polyaryl siloxanes, polyalkyl aryl siloxanes, silicone gums and resins, and polyorgano siloxanes modified by organofunctional groups, and mixtures thereof. Suitable polyalkyl siloxanes include polydimethyl siloxanes with terminal trimethyl silyl groups or terminal dimethyl silanol groups (dimethiconol) and polyalkyl (C1-C25) siloxanes. Suitable polyalkyl aryl siloxanes include polydimethyl methyl phenyl siloxanes and polydimethyl diphenyl siloxanes, linear or branched. The silicone gums suitable for use herein include polydiorganosiloxanes preferably having a number-average molecular weight between 200,000 and 1,000,000, used alone or mixed with a solvent. Examples include polymethyl siloxane, polydimethyl siloxane/methyl vinyl siloxane gums, polydimethyl siloxane/diphenyl siloxane, polydimethyl siloxane/phenyl methyl siloxane and polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxanes. Suitable silicone resins include silicones with a dimethyl/trimethyl siloxane structure and resins of the trimethyl siloxysilicate type. The organo-modified silicones suitable for use in the invention include silicones such as those previously defined and containing one or more organofunctional groups attached by means of a hydrocarbon radical and grafted siliconated polymers. Particularly preferred are amino functional silicones. The silicones may be used in the form of emulsions, nano-emulsions, or micro-emulsions.
Another embodiment of the present application provides a method for treating or fixing damaged keratin substrate comprising contacting said keratin substrate with an effective amount of personal care composition comprising a conditioning and/or styling terpolymer/tetrapolymer of (i) about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 1 wt. % to 30 wt. % of an anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS) or (c) sodium methyl allyl sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of a hydrophobic monomer selected from the group consisting of (a) polyoxyethylene (PEG)-18-behenylether methacrylate (BEM) or (b) stearyl acrylate (SA), and wherein, said terpolymer has a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about 1 meq/g to about 6 meq/g.
Yet another embodiment of the present application provides a method for washing or caring damaged or undamaged keratin substrate comprising applying an effective amount of composition comprising a conditioning and/or styling terpolymer/tetrapolymer of (i) about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC), a cationic monomer; (ii) about 1 wt. % to 30 wt. % of an anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS) or (c) sodium methyl allyl sulfonate (SMAS); and (iii) about 0.1 wt. % to 20 wt. % of a hydrophobic monomer selected from the group consisting of (a) polyoxyethylene (PEG)-18-behenylether methacrylate (BEM) or (b) stearyl acrylate (SA), and wherein, the terpolymer has a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about lmeq/g to about 6 meq/g.
According to one important embodiment of the is application, there is provided a method of protecting dyed hair color from fading or wash-out during exposure to air and/or shampooing which comprising contacting/treating said dyed hair with an effective amount of personal care composition of claim 1 comprising: (a) a conditioning and/or styling terpolymer of (i) about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC); (ii) about 1 wt. % to 30 wt. % of an anionic monomer selected from the group consisting of (a) acrylic acid (AA), (b) acrylamido methylpropyl sulfonate (AMPS) or (c) sodium methyl allyl sulfonate (SMAS); and (iii)cabout 0.1 wt. % to 20 wt. % of a hydrophobic monomer selected from the group consisting of (a) polyoxyethylene (PEG)-18-behenylether methacrylate (BEM) or (b) stearyl acrylate (SA); and wherein said terpolymer has a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about lmeq/g to about 6 meq/g. The above disclosed method is capable of protecting hair dyes that are disclosed in US 20050226838 and which included herein in its entirety.
The effective amount of terpolymer or tetrapolymer required for a personal care composition to treat, fix or wash a damaged keratin substrate is in the range of from about 0.01 wt. % to about 5.0 wt. %, and preferably in the range of from about 0.2 wt. % to about 3.0 wt. % of the total composition.
According to one embodiment of the present application, it is contemplated to employ at least one terpolymer of present application and at least one commercially available conditioning polymer. Suitable commercially available conditioning polymers are selected from the following non-limiting group of examples which include polymeric quaternary ammonium salts such as, without being limited thereto, polyquaternium-7, a polymeric quaternary ammonium salt of acrylamide and dimethyl diallylammonium chloride monomers (such as MACKERNIUMTM-007, McIntyre Group, Ltd.); polyquatemium-10, a polymeric quaternary ammonium salt of hydroxyethylcellulose reacted with a trimethylammonium substituted epoxide (such as the UCARE® Polymers JR, LK, LR, SR series, Amerchol and CELQUAT® SC series, Akzo Nobel); polyquaternium-39, a polymeric quaternary ammonium salt of acrylic acid, diallyl dimethylammonium chloride and acrylamide (such as the MERQUAT® and MERQUAT® Plus polymers, Ondeo Nalco); quaternized derivatives of natural gums, e.g., guar hydroxypropyltrimonium chloride (such as the N-HANCE® and Supercol® polymers, Ashland Inc.), and the like.
Further, certain aspects of the present invention are illustrated in detail by way of the following examples. The examples are given herein for illustration of the invention and are not intended to be limiting thereof.
EXAMPLE 1
Wet Combability
The combing measurement of the hair tresses treated with conditioner was done on a texture analyzer (FIG. 1) without manually detangling the hair. The energy needed to comb the tress was listed as gf-mm. For every measurement, 3 bleached hair tresses were used and the average was calculated. To measure durable conditioning the tress was first treated with 0.2 g/g hair conditioner, which is then rinsed off and the comb energy is measured. After the measurement the hair is washed with non-conditioning shampoo once, comb energy was measured then 3 and 5 times. No conditioner was applied in between.
From FIG. 2, it is demonstrated that chassis is provided good initial conditioning properties, but it is also evident that cationic surfactants do not provide long-lasting conditioning. The Chassis consist of cationic surfactant and fatty alcohol. Adding 1% homopolymer PolyAPTAC to chassis has provided excellent long-lasting conditioning. It has outperformed commercial example containing cationic polymers.
EXAMPLE 2
Wet Combability after Multiple Washings
The Terpolymers provided even improved durability compared to homopolymer/s. Also the initial wet comb energy values right after the application was much lower. There was no significant difference between the different types of terpolymers. From the results (FIG. 3), it is apparent that the conditioning performance of terpolymers after several washes with silicone-free shampoo is even improved compared to cationic homopolymer (PolyAPTAC). The conditioners were applied on damaged hair 0.2 g grams per gram of bleached hair (1 hour bleached) and wet comb energies were measured after 1, 3 and 5 times of washing with 0.1 grams per gram hair shampoo (shampoo: 12/2 SLES/CAPB).







TABLE 1







Comparison of Wet Comb energy of copolymers and terpolymers













Persistency, 



Anionic
Hydrophobic
wet comb energy 


APTAC
monomer, 
Monomer, 
(no TAS)











Mw 500,000 Da
5 wt %
1.5 wt %
Initial 
5 Washes














Chassis TAS/FA
—
—
1348
116,000


Homopolymer,
—
—
12,000
4000


PolyAPTAC






Copolymer
—
Stearyl acrylate
4500
3500


Copolymer
—
BEM 2.5 %
3900
2500


Copolymer
SMAS

13,000
50,000


Terpolymer
SMAS
Stearyl Acrylate
8,500
41,000



Acrylic Acid
Stearyl acrylate
4900
2500


Terpolymer
AMPS
Stearyl acrylate
4000
2500


(MW.500,000 Da)
Acrylic Acid
BEM
6000
2500



AMPS
BEM
6000
2500









Terpolymers can be applied to shampoo applications, as well. FIG. 4 presents the wet comb energy after 1 and 3 shampooing. Terpolymer has clearly outperformed commercial referencing sample and shampoo containing cationic Guar, which is typically used conditioning polymer in various shampoos. The wet combability test results are provided in Table 1.
EXAMPLE 3
Hydrophobicity Determination by Contact Angle Measurement
Contact angle is the indication of the surface hydrophobicity of hair. The immediate and long-lasting hydrophobicity of the terpolymers were studied by measuring the contact angle after several washes with a clarifying shampoo. The method is as follows: (i) A portion of the hair tress was stretched on a specially designed plate so that the fibers were suspended together in space to form a “single” surface (ii) A droplet of Deionized water was delivered from a syringe onto the fiber surface. Droplet mass is  ̃0.008 g, (iii) Images were collected at intervals of is or 10 s.
The higher the contact angle the more hydrophobic is the surface. The undamaged virgin brown hair is naturally hydrophobic, but all the chemical treatments such as bleaching reduce the hydrophobicity of the hair. Contact angle of virgin hair is about 110 which is reduced to 85 by bleaching. Also the water droplet applied to the hair surface is absorbed in 60 s. On virgin hair, the droplet can stay several hours. The results demonstrates (FIG. 5) the influence of different (1 wt %) terpolymers supplied from a conditioner on the contact angle. It is concluded that the treatment with terpolymer containing conditioners were able to retain the hydrophobicity of the damaged hair close to the level of virgin hair. The hydrophobicity test results are provided in Table 2.







TABLE 2







Hydrophobicity Evaluation by contact angle measurement















hydrophobicity
Contact



APTAC
Anionic
Hydrophobic
initial contact
angle
Shampoo (0.2%)


Mw 500,000 Da
5 wt. %
1.5 wt. %
angle
(10 min)
1 wash/3 washes

















Chassis TAS/FA
—
—
86
76
0
0
—


Homopolymer
—
—
88
94
38
27
—


Copolymer
—
Stearyl acrylate
101
—
26
—
—


Copolymer
—
BEM 2.5%
—
—
—
—
37,000/10,000


Copolymer
SMAS
—
—
—
—
—
58,000/50,000


Terpolymer
SMAS
Stearyl Acrylate
—
—
—
—
62,000/57,000


Terpolymer
AMPS
Stearyl acrylate
99
107
55
45
33,000/9,000 


(MW. 500,000 Da)
Acrylic
BEM
99
94
34
49
21,000/4500 



Acid



AMPS
BEM
102
103
87
18
50,000/15,000









EXAMPLE 4
Sensory Evaluation
A trained panel of experts has evaluated the sensory properties of the treated hair tresses and the results were very much correlating with measured values e.g. comb energy values. Sensory properties are essential part of consumer acceptance. With the help of the sensory evaluation the long-term properties after multiple uses can be determined.
Terpolymers were used at 0.2 wt % active in conjunction with 12 wt % SLE2S, 2 wt % CAPB with water added to 100%. The simple shampoo formula was then applied to the hair at 0.3 g/g bleached Caucasian hair and washed and rinsed off. After drying at RT, it was evaluated. Then the procedure was repeated 4 more times and the samples were evaluated. The following test shampoos and market reference shampoos were compared with terpolymers of the present application for the sensory evaluation (Table 3).







TABLE 3







Test Shampoos used for sensory evaluation











Formulations
Code
Z304-16C
Z298-16D
Z290-16E





Aqua
—
q.s.
q.s.
q.s.


APTAC/AA/BEM
A16522
1
—
—


APTAC/AMPS/SA
A16530
—
1
—


APTAC/AMPS/BEM
A16541
—

1


Sodium Laureth
—
12
12
12


ether sulfate, solids %






Cocamidopropyl
—
2
2
2


Betaine, % solids






Preservative
—
0.5
0.5
0.5


Sodium Chloride
—
2
2
2








Commercial Shampoo 
Aqua, ALS, CAPB, Sodium Chloride, 


Nordic hair care pure
Niacinamide, sugar cane extract, 


volume
Hydroxypropyl guar 



hydroxypropyltrimonium Chloride 



(Jaguar C162), Camellia Sinensis Extract



Thermo-active formula, no silicone, 



texturizing agent for 48 h lasting volume
















TABLE 4







Sensory Evaluation Wet Stage Summary















Garnier



Z304-16C
Z304-16D
Z304-16E
fructis shampoo









Washing cycles
















Parameter
Description
1
5
1
5
1
5
1
5





Combability
Ease of
2.75
4.33
2.50
3.58
2.25
3.583
1.92
2.33


Difficult-easy
detangling


Combability
Ease of combing
2.83
4.33
2.25
3.67
2.08
3.333
1.75
2.00


Difficult-easy
down hair shaft









At wet state all the tested terpolymers in the shampoo clearly outperformed commercial non-silicone containing shampoo and efficacy got improved after several washes. At the dry-state after multiple washes shampoos based on the terpolymers outperformed the commercial example. The wet and dry stage sensory evaluations are provided in Table 4 and Table 5; FIG. 6 and FIG. 7.







TABLE 5







Sensory Evaluation Dry Stage Summary















Commercial silicon



Z304-16C
Z304-16D
Z304-16E
free shampoo









Washing Cycles
















Parameter
Description
1
5
1
5
1
5
1
5





Sheen
Amount of
3.58
3.83
3.58
3.83
3.33
3.833
3.50
3.58


dull-shiny
reflected light


Combability
Ease of
3.50
4.33
3.75
3.83
3.25
4.083
3.25
3.08


Difficult-easy
detangling


Combability
Ease of combing
3.42
4.25
3.50
4.00
3.33
3.917
3.08
3.08


Difficult-easy
down hair shaft


Fly away
Tendency of
2.42
3.67
2.67
3.58
2.75
3.500
3.75
3.50


Much-none
individual hairs



to rebel each



after 3 strokes of



combing


Volume
Extend to which
3.92
3.50
3.50
3.67
3.50
3.583
3.08
3.83


Low volume-full
the hair appears



full


Slipperiness
Lack of drag or
3.75
3.92
4.00
3.75
3.92
3.750
3.83
3.75


Drags-slips
resistance as



moving along



hairs between



fingers


Roughness
A rough, brittle
3.42
4.00
3.50
4.00
3.17
4.000
3.17
3.75


Drag-smooth
texture


Dryness
Feel devoid of
3.33
4.00
3.58
4.00
3.42
4.083
3.58
3.83


Very dry-not dry
moisture









EXAMPLE 5
Procedure for Determining the Cationic Charge Density of Polymers
To determine the cationic charge of polymers, a Mütek charge analyzer was used. The aqueous sample was placed in the measuring cell. Once the PCD was turned on, the piston of the cell oscillates and causes a high flow rate. Any charged material adsorbed to the cell wall was separated from its counter-ions by the flow to create a streaming current. Two electrodes in the cell pick up this current and display it. The titration module automatically selects the titrant which is charged oppositely to the sample (cationic sample—anionic titrant) and adds it to the sample until 0 mV was reached. As a result the consumption of titrant in ml was indicated on the display as well as the charge demand in meq/l.
EXAMPLE 6
Wet Combability of Sulfate Free Shampoo Composition
The combing measurement of the hair tresses treated with sulfate-free shampoo was done on Instron device. The energy needed to comb the tress was listed as gf-mm. For every measurement 3 bleached hair tresses were used and the average was calculated. To measure durable conditioning the tress is first treated with 0.1 g/g hair shampoo, which is then rinsed off and the comb energy is measured. The tress was washed 2 more times and the comb energy was again measured. The results of wet comb energy after 1 and 3 washes are disclosed in FIG. 8 for sulfate free shampoo compositions of Table 6.
From the results of wet combability of Sulfate free shampoo compositions, it is evident that the conditioning performance of terpolymers in sulfate-free shampoo is even better as compared to PoIyAPTAC, a cationic homopolymer. The shampoos were applied on damaged hair 0.1 g grams per gram of bleached hair (1 hour bleached) and wet comb energies were measured after 1 and 3 and 5 times of washing with 0.1 grams per gram hair experimental shampoo. Both homopolymer and terpolymer containing sulfate-free shampoos were outperforming commercial silicone-free shampoo. When compared to the silicone-containing commercial sulfate-free shampoo, the experimental shampoo was performing on the same level even without silicones.







TABLE 6







Sulfate free shampoo compositions comprising 


Homopolymers/Terpolymers












Solids (%)
Solids (%)



INCI
Formula 1
Formula 2







Aqua
qs 100
qs 100



PolyAPTAC
0.2
—



APTAC/AA/BEM
—
0.2



Disodium Laureth Sulfosuccinate
8.16
8.16



Cocamidopropyl Betaine/
3.85
3.85



Alkylamidopropyl Betaine





Sodium Lauroyl Sarcosinate
2.70
2.70



Methylisothiazolinone and Phenyl- 
0.2
0.2



propanol and Propylene Glycol





Sodium hydroxide





Citric acid










EXAMPLE 7
Durable Styling Properties of Conditioning Polymers on Frizzy Hair
The durable styling properties of following conditioning polymers were evaluated on frizzy hair:
i. APTAC Homopolymer: (Poly-APTAC)
ii. APTAC based terpolymer: A 16522 (APTAC/AA/BEM)
iii. Hair spray containing Styleze XT3
iv. Commercial Available hair spray (heat activated)
v. 3% polymer solution of each polymer is prepare and is tested.
The Hair tresses treated with above mentioned formulations are evaluated according to the protocol which is presented below. Originally it was developed to study styling durability of Styleze XT3. Wherein, the use of Styleze XT3 in hairstyling products provides benefits for different hair types such as curly, wave and frizzy hair. The polymer is activated after heating by a hair straightener and concentrates on the damaged parts of hair to improve the softness, frizz and shine. With the same technology, commercially available hairspray is a heat-activated formula with keratin protein. This semi-permanent styling spray is claimed to transform curly, frizzy hair into a straight, smooth style that lasts up to 3 washes.
Tress Treatment Method:
Materials Required:

    
    
        i. Shampoo; Normal—non care/conditioning
        ii. Conditioner: Normal
        iii. Tress type: 1′′ or 1.5′′ width×6.5′′ length mulatto (2 g and 3.5 g, respectively).
        iv. Blow dryer: Professional.
        v. Vent brush
        vi. Flat Iron: 1′′ wide, high temp setting (>1=205° C.)− preferably need to deliver sustained heat (>145° C.) to the hair fiber assembly (it has been observed that the temperature realized on the hair is approximately 40-50° C. lower than the iron setpoint—dependant on the rate of movement). Iron setpoint of 232 C preferred for optimal results.
    
    


Method:
Hair tress was washed with warm water (35-40° C.)−30 second wetting, 30 sec wash, 30 sec rinse. The excess water is removed and blot with towel—tress in damp state. Approximately, 0.30 g of product/gram of hair was applied; worked through from root to tip with fingers until uniformly distributed—remove excess with fingers or comb. The tress was straightened by Blow dry (high heat) with slow uniform motion from root to tip with vent brush. It was ensured for alignment of fibers prior to next step. Flat iron root to tip with 4 to 5 passes,  ̃1.25 in/sec. Wherein, the hair should feel smooth and natural with good shine, and if there is any raspy polymeric feel, additional passes were allowed. Tress was allowed to equilibrate to lab conditions for 30-45 min at 25° C./40% RH. Tresses were evaluated for their straightness. Hair tresses were washed with warm water of 35-40° C. with 30 seconds wetting, 30 seconds wash (normal shampoo), and 30 seconds rinse. Further, condition the hair for 30 seconds, followed by 30 seconds rinse. The hair was dried with diffuse hot air (dome dryer). The hair tresses were allowed to equilibrate to lab conditions for 30-45 min at 25° C./40% RH. The tress was evaluated after one wash. In the similar manner, repeat steps for 7 to10 times as desired.
From durable styling experimental results (FIGS. 9 to 12), it is very evident that the polymer solutions containing either homopolymer or terpolymer (A16522) outperformed commercial hair sprays designed to provide durable styling. Both test products showed visibly a good performance. Frizzy hair is transformed into a straight, smooth hair. The frizz was thus reduced significantly. For long lasting effect (durability) the composition of this invention is better than commercially available analogous after multiple washes.
EXAMPLE 8
Stiffness/Flexibility Evaluation of Conditioning Polymers on Hair
Stiffness is defined as the resistance to being crushed. A stiff styling product would be one that requires a high force in order to cause a deformation. The stiffness/flexibility of the homo and terpolymers were measured at 50% RH. A set of 6 tresses were used for every sample. It is observed that the homo and terpolymer containing APTAC provided significantly lower stiffness as compared to that of references products or polymer (Table 7). The higher stiffness is associated with stronger hold.







TABLE 7







Stiffness/Flexibility of Homopolymers/Terpolymers









Product
Average Stiffness (F1)
Std. Dev.












APTAC Homopolymer
86.49
27.43


Terpolymer A 16522
74.80
8.15


Commercial Mousse A
188.65
55.59


Commercial Mousse B
316.78
61.28


(Reference)











EXAMPLE 9
Resilience Evaluation of Conditioning Polymers on Hair
Resilience is the maintenance of stiffness on repeated deformations. So when looking at the stiffness data, the closer the ratio is to one for a sample, the more resilient the product. It means that the duration of a curl hold stiffness of a product is better. Hence, the developmental polymers showed a better result than the references and it is significant (Table 8). The stiffness retention of both test polymers is almost the same.







TABLE 8







The average resilience of Homopolymers/Terpolymers









Product
Average Resilience
Std. Dev.












APTAC Homopolymer
1.05
0.01


Terpolymer A 16522
1.05
0.04


Commercial Mousse A
0.86
0.02


Commercial Mousse B
0.69
0.06


(Reference)









EXAMPLE 10
Plasticity Evaluation of Conditioning Polymers on Hair
Plasticity is defined as the ability of a material to bend without breaking. The plasticity of the homo and terpolymers of present application is as good as the references products (Table 9).







TABLE 9







The average plasticity of Homopolymers/Terpolymers









Product
Average Plasticity
Std. Dev.












APTAC homopolymer
1.10
0.02


Terpolymer A 16522
1.11
0.02


Commercial Curl Power Mousse A
1.10
0.02


Commercial Mousse B
1.10
0.02


(Reference)









EXAMPLE 11
Elasticity Evaluation of Conditioning Polymers on Hair
Elasticity is defined as the ability of a material to bend without breaking and return to the original shape without using an external force. Test polymers performed better than reference, i.e. Commercial Mousse. Terpolymer A16522 is slightly better than APTAC Homopolymer, but there was no significant difference in the performance (Table 9A).







TABLE 9A







The average elasticity of Homopolymers/Terpolymers











Product
Average Elasticity
Std. Dev.















APTAC Homopolymer
0.78
0.09



Terpolymer A 16522
0.87
0.07



Commercial Mousse
0.54
0.12



Commercial Mousse
0.19
0.02



(Reference)










EXAMPLE 12
Curl Retention Evaluation of Conditioning Polymers on Hair
This analysis indicates the holding power of a styling product. A set of 8 tresses is used for every sample. The curl retention of the test polymers is measured based on following parameters:
i. Temperature: 25° C.±2°
ii. Humidity: 50%±2%
iii. Time: 4.5 hours
Wherein, the test polymers showed better results than reference group wherein no polymer was employed but the results were not better than Commercial Curl Power mousse. Curl retention of Poly-APTAC was better than terpolymer A16522 with the confidence interval at 95%. After 4.5 hours, the curl retention of Poly-APTAC is 70% and terpolymer A 16522 60%.
EXAMPLE 13
Shine Evaluation of Conditioning Polymers on Hair
Shiny hair is a healthy sign. Therefore use of polymers in hair styling products is available to increase the shine of hair by forming a film around the surface of hair. Such polymers increases the luster values of hair after treatment and it can be calculated as the difference between specular and diffuse reflectance. The shine capability of products was measured. Set of 4 very dark European Caucasian virgin brown hair tresses was used for every sample. The luster calculation is given below:




  
    L
    Stamm
  
  =
  
    
      
        
          S
          -
          
            D
            stamm
          
        
        S
      
      ⁢
      
        
      
      ⁢
      
        L
        Robbins
      
    
    =
    
      S
      
        
          D
          Stamm
        
        ×
        W
        ⁢
        
          1
          2
        
      
    
  




S=Area under Specular reflectance curve
DStamm=Area under Stamm type Diffuse reflectance curve
W1⁄2=Width of Specular peak at 1⁄2 its maximum intensity
The Lustre value is comparing the contrast between the dark region and the light region. The Peak Maxima is an indication of the brightness of the light portion of the tress. W1⁄2 is the width of the specular peak at half of its maximum intensity or the light area. Further the shine is evaluated and described by the Intensity, Stamm Luster and Robbins Luster values. Studies were conducted for (i) homo and terpolymer of APTAC; (ii) A commercial reference polymer; (iii) VC713 based mousse, a reference polymer. From our results, it is observed that the use of APTAC based polymers is better than reference polymer in providing gloss for hair stresses. The results are discussed in below Table 10-13 and FIG. 16-19.







TABLE 10







Shine evaluation of APTAC Homopolymer











APTAC
Peak
W1/2
Stamm
Robbins


homopolymer
Maxima
(mm)
Lustre
Lustre














Untreated
214.22
7.02
0.81
0.76


Treated
193.28
7.94
0.89
1.22


% Average Increase
−11.2
11.6
9.3
36.0


Standard Deviation
7.7
2.2
3.1
15.1
















TABLE 11







Shine evaluation of APTAC Terpolymer











APTAC
Peak
W1⁄2
Stamm
Robbins


terpolymer A16522
Maxima
(mm)
Lustre
Lustre














Untreated
213.86
7.33
0.80
0.70


Treated
196.33
8.45
0.87
0.91


% Average Increase
−9.2
13.1
7.5
22.5


Standard Deviation
7.9
8.0
1.0
6.0
















TABLE 12







Shine evaluation of Commercial Mousse (Reference)











Commercial
Peak
w1⁄2
Stamm
Robbins


mousse
Maxima
(mm)
Lustre
Lustre














Untreated
203.70 
7.24
0.82
0.76


Treated
191.14 
7.47
0.86
0.99


% Increase
−6.56
2.83
5.00
21.02


Standard Deviation
1.74
4.17
2.30
14.20
















TABLE 13







Shine evaluation of VC713 based mousse (Reference)











VC 713
Peak
w1⁄2
Stamm
Robbins


based mousse
Maxima
(mm)
Lustre
Lustre














Untreated
194.81
7.43
0.83
0.79


Treated
180.90
7.62
0.86
0.95


% Increase
−7.77
2.40
3.60
15.88


Standard Deviation
3.36
2.40
1.89
9.95









EXAMPLE 14
Shampoo for Protecting Dyed Hair Color













12472-79
12472-107


Ingredients
Weight %
Weight %

















Deionized Water
QS
QS


APTAC/AMPS/PEG-BEM 
2.50
—


(40% active)




Sodium Laureth Sulfate 
17.15
17.15


(2M, 70% active)




Cocamidopropyl Betaine (30% active)
6.67
6.67


Methylisothiazolinone & 
0.20
0.20


Phenylpropanol &




Propylene Glycol & water




Citric Acid (10% solution)
1.10
0.56


Sodium Chloride
1.42
2.49


Sodium Hydroxide (10% solution)
0.60




pH = 5.63,
pH = 5.70,



Viscosity = 4380 
Viscosity = 6600 



cps
cps









EXAMPLE 15
Conditioner for Protecting Dyed Hair Color













12472-76
12472-75


Ingredients
Weight %
Weight %

















Deionized Water
QS
QS


APTAC/AMPS/PEG-BEM 
2.50
—


(40% active)




Cetrimonium Chloride (25% active)
4.00
4.00


Cetyl Alcohol
5.00
5.00


Cetyl Hydroxyethyl Cellulose
0.50
0.50


Dimethicone
1.00
1.00


Propylene Glycol
0.50
0.50


Propylene Glycol & Diazolidinyl 
0.50
0.50


Urea & Iodorpropynyl 




Butylcarbamate




Citric Acid (10% solution)
0.17




pH = 4.85
pH = 3.92



Viscosity = 86000 
Viscosity 133000 



cps
cps









Materials: The medium density platinum bleached hair (6′′ length) from International Hair Importers was procured. The hair tresses were cut to 0.5 inches in width and weight approximately 2.97 grams. Wherein, textures and tones permanent hair color (Shade 4R, Red Hot Red) was measured using HunterLab Colorimeter.
Hair dyeing procedure: Dye 1′′ hair tresses for 45 minutes at 71F; rinse each hair tress for 2 minutes under running water. The APTAC/AMPS/PEG-BEM terpolymer was employed for evaluate its ability to protect the dyed hair color with various evaluation parameters that are known in the prior art for a person skilled in the art.
Interpreting the results: Color measurements (L*, a*, b*) were taken on each tress right after dyeing. L*, a*, b* values were measured on each tress after one, three, five and ten wash/treatment cycles. These values were compared to the initial L*, a*, b* values for the tress, and ΔE* was calculated for each tress. Each tress served as its own control. 10 measurements were taken for each tress. ΔE* was calculated based on the initial value of the tress. The ΔE* reported is the average ΔE* for 3 tresses. The smaller the ΔE* value, the smaller the color change, and better the color protection.

ΔE*√{square root over (ΔL*+Δa*+Δb*)}

Where: ΔL*=L*T−L*initial; Δa*=a*T−a*initial; Δb*=b*T−b*initial 




  
    %
    ⁢
    
      
    
    ⁢
    Color
    ⁢
    
      
    
    ⁢
    protection
  
  =
  
    
      
        
          Δ
          ⁢
          
            
          
          ⁢
          
            E
            sample
            *
          
        
        -
        
          Δ
          ⁢
          
            
          
          ⁢
          
            E
            control
            *
          
        
      
      
        Δ
        ⁢
        
          
        
        ⁢
        
          E
          control
          *
        
      
    
    ×
    100
  




It should be noted that the terpolymers are meant to be used in combination with other cationic ingredients. For that reason, we tried the color protection performance in conditioner bases that are mimic finished formulas and also tried the performance of the terpolymer in finished commercial formulas. Commercial available compositions typically comprise a combination of alkyl quaternary compounds such as cetrimonium chloride, behentrimonium chloride to provide conditioning benefit, and silicones such as dimethicone to provide conditioning and color protection benefit. Therefore, it is important to assess the effect of the terpolymer in the presence of cationic polymers and silicones, as this will be a good indicator of its performance in finished products.
EXAMPLE 16
Rinse-Off Conditioner (1 Application) with Shampoo Procedure
Step 1: (a) The conditioner (0.5 mL) of example 16 was applied to freshly dyed/rinsed hair. (b) The hair was left as such for 1 minute, and then (c) rinsed for 30 seconds followed by hair is air dried.
Step 2: (a) Further, the above hair was rinsed for 30 seconds under running water (38° C. 4 L/min), (b) massaged with 0.5 mL shampoo into hair for 30 seconds, and then, (c) rinsed for 30 seconds. (d) Air dry tress was performed. Repeat step 2a-d for ten times.
The result of rinse-off conditioner (1 application) is summarized in Table 14.







TABLE 14







Results for one time application of rinse-off conditioner











With
Without




PolyAPTAC/AMPS/
PolyAPTAC/AMPS/ 
% Color


Rinse-off
PEG-BEM
PEG-BEM
Protection













ΔE* 1x
6.24
6.88
9.30


ΔE* 3x
12.65
14.12
10.41


ΔE* 5x
14.38
16.04
10.35


ΔE* 10x
16.11
19.39
16.92









EXAMPLE 17
Shampoo with Leave-On Conditioner Regimen Procedure
Step 1: (a) The leave-on conditioner (0.5 mL) was applied to wet, freshly dyed/rinsed hair, and (b) then remove the excess conditioner from hair. (c) Hair was dried with air.
Step 2: (a) Further, the above hair was rinsed for 30 seconds, (b) then massage the with 0.5 mL shampoo into hair for another 30 seconds followed by (c) the hair was again rinsed for 30 seconds, (d) 0.5 mL of leave-on conditioner was applied to the hair and remove the excess amount, (e) then, air dry hair. Repeat steps 2a-e for 10 times.
The result of shampoo with leave-on conditioner is summarized in Table 15.







TABLE 15







Results for shampoo with leave-on conditioner regimen











With
Without




Po1yAPTAC/
PolyAPTAC/ 




AMPS/PEG-
AMPS/PEG-
% Color


Leave-on
BEM (12472-76 & 79)
BEM (12472-107 &75)
Protection













ΔE* 1x
5.61
5.9
4.92


ΔE* 3x
9.08
11.47
20.84


ΔE* 5x
9.43
12.66
25.51


ΔE* 10x
11.2
14.74
24.02









EXAMPLE 18
Shampoo with Conditioner and Leave-On Conditioner Regimen Procedure
Step 1: (a) The leave-on conditioner (0.5 mL) was applied to wet, freshly dyed/rinsed hair, and (b) then remove the excess conditioner from hair. (c) Hair was dried with air.
Step 2: (a) Further, the above hair was rinsed for 30 seconds, (b) massage with 0.5 mL shampoo into hair for another 30 seconds followed by (c) the hair was again rinsed for 30 seconds, (d) massage with 0.5 mL conditioner into hair and leave on for 30 seconds (e) the hair was rinsed again for 30 seconds (f) 0.5 mL leave on conditioner was applied to hair (g) hair was air dried, and (h) repeat the step 2 a-g for ten times.
The result of shampoo with conditioner and leave-on conditioner is duly summarized in Table 16.







TABLE 16







Results for shampoo with conditioner and leave-on conditioner regimen











With
Without



Conditioner
PolyAPTAC/
PolyAPTAC/
% 


and
AMPS/PEG- 
AMPS/PEG-
Color


Leave-on
BEM (12472-76 & 79)
BEM (12472-107 &75)
Protection













ΔE* 1x
6.28
7.8
19.49


ΔE* 3x
9.5
11.31
16.00


ΔE* 5x
10.45
12.15
13.99


ΔE* 10x
12.9
15.04
14.23









EXAMPLE 19
Commercial Shampoo with Conditioner Regimen Procedure
Steps: (a) The hair was rinsed for 30 seconds under running water, (b) massaged with 0.5 mL commercial shampoo into hair for another 30 seconds followed by (c) the hair was rinsed again for 30 seconds, (d) again massaged with 0.5 mL conditioner into hair and leave on for 30 seconds (e) then, hair was rinsed again for 30 seconds (f) air dry tress was performed, and (g) repeat the step a-f for ten times.
The result of commercial shampoo with conditioner is duly summarized in Table 17.







TABLE 17







Results for commercial shampoo with conditioner regimen











Without
With




PolyAPTAC/AMPS/ 
PolyAPTAC/AMPS/
% Color


Conditioner
PEG-BEM
PEG-BEM
Protection













1x wash
9.12
6.22
31.83


3x wash
17.14
15.45
9.82


5x wash
21.22
18.34
13.56


10x wash
24.36
21.11
13.34









EXAMPLE 20
Commercial Shampoo with Leave on Conditioner Regimen Procedure
Steps: (a) The leave on conditioner (0.5 mL) was applied to wet, freshly dyed/rinsed hair and removed excess conditioner from hair (b) then hair was air dried (c) hair was rinsed for 30 seconds (d) massaged with 0.5 mL commercial shampoo into hair for another 30 seconds followed by (e) the hair was rinsed again for 30 seconds, (f) again massaged with 0.5 mL leave-on conditioner into hair and remove the excess application, (g) the hair was air dried (h) repeat the steps a-f for ten times.
The result of commercial shampoo with leave-on conditioner is duly summarized in Table 18.







TABLE 18







Results for commercial shampoo with leave-on conditioner regimen











Without
With



Leave-on
PolyAPTAC/AMPS/ 
PolyAPTAC/AMPS/
% Color


Conditioner
PEG-BEM
PEG-BEM
Protection













1x wash
7.80
4.79
38.66


3x wash
17.71
15.07
14.93


5x wash
21.35
18.99
11.04


10x wash
22.64
21.11
6.77









EXAMPLE 21
Commercial Shampoo with Conditioner and Leave-On Conditioner Regimen
Step 1: (a) The conditioner (0.5 mL) was applied to wet, freshly dyed/rinsed hair, and (b) then remove the excess conditioner from hair. (c) Hair was dried with air.
Step 2: (a) The above hair was rinsed for 30 seconds (b) massaged with 0.5 mL commercial shampoo into hair for another 30 seconds followed by (c) the hair was rinsed again for 30 seconds, (d) again massaged with 0.5 mL conditioner into hair and leave-on for 30 seconds, (e) then hair was rinsed for 30 seconds (f) the leave-on conditioner (0.5 mL) was applied to the previously rinsed hair, (g) the hair was air dried, and (h) repeat the step 2a-g for ten times.
The result of commercial shampoo with conditioner and leave-on conditioner is duly summarized in Table 19.







TABLE 19







Results for commercial shampoo with conditioner and leave-on conditioner











Without
With



Leave-on
PolyAPTAC/AMPS/
Po1yAPTAC/AMPS/
% Color


Conditioner
PEG-BEM
PEG-BEM
Protection













1x wash
10.76
7.30
32.16


3x wash
20.16
16.97
15.81


5x wash
23.69
20.03
15.44


10x wash
25.44
21.84
14.16









While this invention has been described in detail with reference to certain preferred embodiments, it should be appreciated that the present invention is not limited to those precise embodiments. Rather, in view of the present disclosure, which describes the current best mode for practicing the invention, many modifications and variations would present themselves to those skilled in the art without departing from the scope and spirit of this invention.

## Claims

1. A conditioning and/or styling terpolymer for a keratin substrate obtained by polymerizing:
i. about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC), a cationic monomer;
ii. about 1 wt. % to 30 wt. % of acrylamido methylpropyl sulfonate (AMPS), an anionic second monomer; and
iii. about 0.1 wt. % to 20 wt. % polyoxyethylene (PEG)-18-behenylether methacrylate (BEM), a hydrophobic third
wherein said terpolymer has a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about 1 meq/g to about 6 meq/g.

2. The composition according to claim 1, wherein the average molecular weight of said terpolymer is in the range of from about 100,000 to 1000,000 g/mol as determined by gel permeation chromatography.

3. The composition according to claim 1, wherein the average molecular weight of said terpolymer ranges from about 200,000 to 500,000 g/mol as determined by gel permeation chromatography.

4. A conditioning and/or styling terpolymer for a keratin substrate obtained by polymerizing:
i. about 50 wt. % to 95 wt. % of acrylamidopropyl trimethylammonium chloride (APTAC);
ii. about 1 wt. % to 30 wt. % of acrylic acid (AA), an anionic monomer; and
iii. about 0.1 wt. % to 20 wt. % polyoxyethylene (PEG)-18-behenylether methacrylate (BEM);
wherein said terpolymer has a cationic degree of substitution (Cat-DS) of greater than about 0.001 units, and wherein the cationic charge density is in the range of about 1 meq/g to about 6 meq/g.

5. The composition according to claim 4, wherein the average molecular weight of said terpolymer is in the range of from 100,000 to 100,000 g/mol as determined by gel permeation chromatography.

6. The composition according to claim 4, wherein the average molecular weight of said terpolymer ranges from 200,000 to 500,000 g/mol as determined by gel permeation chromatography.