Hair treatment compositions and methods for treating hair

Information

  • Patent Grant
  • 11419809
  • Patent Number
    11,419,809
  • Date Filed
    Thursday, June 27, 2019
    4 years ago
  • Date Issued
    Tuesday, August 23, 2022
    a year ago
Abstract
The instant disclosure relates to hair treatment compositions that include a unique combination of components that function to impart desirable cosmetic properties to the hair. The hair treatment compositions typically include a first phase containing a non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof, an amine, a cationic polymer, an alkoxysilane, polyols, and water; and a second phase containing a film-forming aminosilicone polymer formed by the reaction between a glycidoxypropyl-terminated dimethyl siloxane polymer, PEG-13 diglycidyl ether, diethylaminopropylamine, and aminopropyltriisopropoxysilane, and at least one silicone oil.
Description
FIELD OF THE DISCLOSURE

The instant disclosure relates to hair treatment compositions that are particularly useful for improving the quality of hair and which can impart beneficial properties such as styling, frizz control, and retention of shape/curl. Also disclosed are methods for using the hair treatment compositions.


BACKGROUND

Many consumers desire to use cosmetic and care compositions that enhance the appearance of keratinous substrates such as hair, e.g., by changing the color, style, and/or shape of the hair, and/or by imparting various cosmetic properties to hair, such as shine and conditioning. Many of the known compositions and processes for enhancing the appearance of hair involve chemical treatments to the hair.


The process of changing the color of hair, for example, can involve depositing an artificial color onto the hair which provides a different shade or color to the hair, and/or lifting the color of the hair, such as lightening the color of dark hair to lighter shades, which m requires the use of oxidizing agents.


Additionally, there are many techniques and compositions for styling or altering the shape of hair. For example, hair care products referred to as “hair relaxers” or “hair straighteners” can relax or straighten curly or kinky hair, including wavy hair. Straightening or relaxing the curls of very curly hair may increase the manageability and ease of styling of such hair. Compositions for permanent waving the hair will impart a curl or a wave to otherwise straight hair. Different types of compositions can be applied onto hair in order to change its shape and make it more manageable, such as alkaline and acidic compositions. Hair relaxers, straighteners, perms, and/or waves may either be applied in a hair salon by a professional or in the home by the individual consumer.


While dyeing or color lifting compositions can effectively alter the color of hair, and relaxing, straightening, perming, and waving compositions can effectively alter the shape of the hair, these chemical treatments can damage the hair fibers and/or irritate the scalp. Thus, in order to reduce or avoid damage to hair, as well as to improve the cosmetic performance of the compositions, different types of hair styling products have been developed by manufacturers that are aimed to help consumers achieve a desired look, including one or more of fuller hair, thicker hair, sleek and straight hair, frizz-free hair, and defined curls. These products are typically provided in forms that are applied after the shampooing and conditioning processes are completed.


In one example, styling products are available that provide protection against external factors such as protection from moisture to minimize or reduce frizziness. To achieve this benefit, a water-resistant film or coating may be applied to the hair using film-forming polymers. Depending on the chemical make-up of the film-forming polymers. Product formulations that include these polymers can tend to be viscous, i.e. as the concentration of the polymer increases its viscosity builds up rapidly. Translated to styling applications, as the solvent evaporates, the polymer solution becomes thicker on the hair surface, leaving a sticky or tacky film residue on the hair. This often leaves hair with a stiff and/or “crunchy” feeling (i.e. the films become hard and brittle and therefore have a crunchy feel or sound when manipulated), which is undesirable to many consumers.


Increasingly, consumers also seek hair products that have a natural look and feel, impart good styling benefits to hair, are durable, and lack the drawbacks of current products, such as the stiff and crunchy effects created by the thick coatings of many styling products. Further, consumers seek products that offer multiple benefits, for example, combining frizz reduction and style hold with softening, straightening and curl definition. Moreover, consumers desire hair products that can protect hair from extreme environmental conditions such as high humidity which causes the hair to become very frizzy, unmanageable, and lose its shape and style.


One important functional element of such products is their ability to style the hair without weighing it down. Many consumers seek hair products which have excellent style memory, cosmeticity, and shine without heavily coating the hair strands, and thereby weighing the hair down and often times exhibiting a brittle or crunchy film. The resulting feel and texture of the hair after the application are important elements of such commodities. While different technologies and products exist in the market for hair styling products, there is still a need for improvement in these areas.


Thus, the object of this invention is related to a composition and method of styling hair utilizing hair compositions which will impart frizz control, and promote curl definition, softness, smoothness, shine and natural feel, but will not result in any product build up or leave the hair feeling heavily coated or weighed down, crunchy, stiff, or brittle. The object of the invention is also to provide these attributes that will last even when hair is exposed to high humidity conditions.


SUMMARY OF THE DISCLOSURE

It has surprisingly been found that compositions and methods of styling hair using a two phase or bi-phase system comprising a first phase which is an aqueous phase and a second phase which is an oily phase impart styling/shaping and other cosmetic benefits to the hair.


One aspect of the invention pertains to a hair treatment composition comprising:

    • (a) a first phase comprising:
      • at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof, and a mixture thereof;
      • at least one amine selected from diamines, polyamines, alkylamines, alkanolamines, and a mixture thereof;
      • at least one cationic polymer;
      • at least one alkoxysilane;
      • at least one polyol; and
      • water; and
    • (b) a second phase comprising:
      • at least one film-forming aminosilicone polymer formed by the reaction between a glycidoxypropyl-terminated dimethyl siloxane polymer, PEG-13 diglycidyl ether, diethylaminopropylamine, and aminopropyltriisopropoxysilane; and
      • at least one silicone oil.


In one embodiment, the first phase is aqueous and the second phase is an oil. In one or more embodiments, the at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof, is a dicarboxylic acid and/or a salt thereof, and a mixture thereof. In some embodiments, the composition comprises at least one dicarboxylic acid and/or a salt thereof, and the at least one dicarboxylic acid and/or a salt thereof is selected from the group consisting of oxalic acid, malonic acid, malic acid, glutaric acid, citraconic acid, succinic acid, adipic acid, tartaric acid, fumaric acid, maleic acid, sebacic acid, azelaic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, and a salt thereof. In one or more embodiments, the at least one dicarboxylic acid and/or a salt thereof is maleic acid, malonic acid, and/or a salt thereof. In some embodiments, the composition comprises at least one tricarboxylic acid and/or a salt thereof, and the at least one tricarboxylic acid and/or a salt thereof is selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and a thereof. In one or more embodiments, the at least one tricarboxylic acid and/or a salt thereof is citric acid, their salts thereof, and a mixture thereof. In some embodiments, the composition comprises at least 0.5 to about 20 wt. % of at least one non-polymeric mono, di, or tricarboxylic acid their salts thereof, and a mixture thereof, based on the total weight of the first phase of the hair treatment composition. In one or more embodiments, the composition comprises maleic acid.


In one or more embodiments, the composition the at least one amine includes one or more alkylamines and/or alkanolamines selected from the group consisting of compounds of formula (II):

NR3R4R5   (II)

wherein R3, R4 and R5 are independently H, C1-C40 alkyl, C1-C40 monohydroxyalkyl or C2-C40 polyhydroxyalkyl, provided that at least one of R3, R4 and R5 is an alkyl or mono or polyhydroxyalkyl. In some embodiments, the composition comprises one or more alkanolamines selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylamino-ethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethylamino)methane, and a mixture thereof. In one or more embodiments, the composition comprises monoethanolamine.


In one or more embodiments, the at least one polyol is selected from hexylene glycol, butylene glycol, propylene glycol, dipropylene glycol, caprylyl glycol, glycerin, and combinations thereof.


In one or more embodiments, the at least one polyol comprises hexylene glycol and butylene glycol.


Any of the above embodiments may be combined. For example, in some embodiments, the hair treatment composition comprises:


(a) a first phase comprising:

    • about 1 to about 5 wt. % of at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof and a mixture thereof selected from oxalic acid, malonic acid, malic acid, glutaric acid, citraconic acid, succinic acid, adipic acid, tartaric acid, fumaric acid, maleic acid, sebacic acid, azelaic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, their salts thereof, and a mixture thereof;
    • about 0.5 to about 5 wt. % of at least one amine including one or more alkanolamines selected from monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylamino-ethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethylamino)methane, and a mixture thereof;
    • about 0.2 to about 3 wt. % of at least one cationic polymer selected from poly(methacryloyloxyethyl trimethylammonium chloride), polyquaternium-37, quaternized cellulose derivatives, polyquaternium-4, polyquaternium-6, polyquaternium-10, polyquaternium-11, cationic alkyl polyglycosides, cationized honey, cationic guar derivatives, polymeric dimethyl diallyl ammonium salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid, copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, vinyl pyrrolidone-vinyl imidazolium methochloride copolymers, quaternized polyvinyl alcohol, polyquaternium-2, polyquaternium-7, polyquaternium-17, polyquaternium-18, polyquaternium-24, polyquaternium-27, polyquaternium-72, and a mixture thereof;
    • about 1.5 to about 8 wt. % of at least one alkoxysilane comprising 3-aminopropyltriethoxysilane;
    • about 1 to about 10 wt. % of at least one polyol comprising hexylene glycol and butylene glycol; and
    • at least 50 wt. % of water;


wherein all weights are based on the total weight of the first phase; and


(b) a second phase comprising:

    • about 0.06 to about 2% wt. % of at least one film-forming aminosilicone polymer selected from Polysilicone-29;
    • at least one silicone oil comprising cyclopentasiloxane;
    • optionally, at least one non-silicone oil; and
    • optionally, at least one organic solvent selected from polyols, C2 to C8 monoalcohols, and a mixture thereof;


wherein all weights are based on the total weight of the second phase.


Another aspect of the invention pertains to methods of treating hair. In some embodiments, the method comprises applying any of the compositions described herein to hair. In one or more embodiments, the composition is applied to hair as part of a shampoo or conditioning routine. In some embodiments, the composition is applied after a chemical relaxer is applied to the hair.





BRIEF DESCRIPTION OF THE DRAWING

Implementation of the present technology will now be described, by way of example only, with reference to the attached figures, wherein:



FIGS. 1a and 1b include pictures of hair swatches at the dry stage after treating the swatches with inventive or comparative bi-phase compositions; and



FIG. 2 includes pictures of a control hair swatch and hair swatches at high humidity condition after treating with an oil phase only, an aqueous phase only, and an inventive bi-phase composition (F); the high humidity condition refers to keeping the swatches for 24 hours at 80% relative humidity and at 25° C.





It should be understood that the various aspects are not limited to the arrangements and instrumentality shown in the drawings.


DETAILED DESCRIPTION OF THE DISCLOSURE

The term “hair treatment composition” encompasses many types of compositions for application to the hair, for example, chemical relaxer compositions, shampoos, conditioners, hair-rinses, hair lotions, hair gels, mouse-type products, sprays, etc. A hair treatment composition is characterized by its ability to provide a cosmetic benefit to the hair. As is well-known, a shampoo provides cleansing benefits to the hair, a conditioner provides conditioning benefits to the hair, and gels can provide styling benefits to the hair. Non-limiting examples of additional benefits that can be imparted to hair include frizz control, curl definition, curl retention, smoothness, softness, suppleness, and natural feel.


The hair treatment compositions of the instant disclosure typically include:

    • (a) a first phase comprising:
    • at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof, and a mixture thereof;
    • at least one amine selected from diamines, polyamines, alkylamines, alkanolamines, and a mixture thereof;
    • at least one cationic polymer;
    • at least one alkoxysilane;
    • at least one polyol; and
    • water; and
    • (b) a second phase comprising:
    • at least one film-forming aminosilicone polymer formed by the reaction between a glycidoxypropyl-terminated dimethyl siloxane polymer, PEG-13 diglycidyl ether, diethylaminopropylamine, and aminopropyltriisopropoxysilane; and
    • at least one silicone oil.


The above compositions, which feature a unique combinations of ingredients, advantageously provide frizz control, curl definition, curl retention, long lasting or humidity-resistant styling and curl care benefits together with natural feel, light-weight feel, softness, and smoothness.


The hair treatment compositions described herein may be in any suitable physical form. Suitable forms include, but are not limited to low to moderate viscosity liquids, lotions, milks, mousses, sprays, gels, creams, pastes, clays, bars, conditioners, and the like. For instance, spray formulations may be dispensed from containers that include aerosol dispensers or pump spray dispensers. Such dispensers are known in the art and are commercially available from a variety of manufacturers. When the spray formulation is dispensed from a pressurized aerosol container, a propellant may be used to force the composition out of the container. Suitable propellants include, but are not limited to, a liquefiable gas or a halogenated propellant. Examples of suitable propellants include dimethyl ether and hydrocarbon propellants such as propane, n-butane, iso-butane, CFCs, and CFC-replacement propellants. The propellants may be used singly or admixed. Furthermore, the hair treatment compositions may be in the form of an emulsion (e.g., water-in-oil or oil-in-water emulsion), wherein the first phase or the second phase or both include an emulsifier.


In an embodiment, the hair treatment composition of the present disclosure is substantially free of emulsifiers.


In an embodiment, the hair treatment composition of the present disclosure is bi-phasic. In an embodiment, the bi-phasic hair treatment composition is shaken up in a container or bottle before the composition is applied onto hair.


In some cases, the hair treatment composition of the present disclosure is in the form of a spray. In one embodiment, when the hair treatment is on the form of a spray, it does not contain a propellant (non-aerosol spray).


The hair treatment compositions may be packaged in a variety of different containers, such as, for example, a ready-to-use container. Non-limiting examples of useful packaging include tubes, jars, caps, unit dose packages, and bottles, including squeezable tubes and bottles and spray bottles.


The first phase and second phase according to the invention may be packaged in separate containers. In an embodiment, the separate containers may be part of a kit, and may be accompanied by instructions on mixing or combining before treating the hair with the mixture or layering the two phases onto hair.


Non-Polymeric Mono, Di, or Tricarboxylic Acid


A non-polymeric mono, di, and/or tricarboxylic acid is an organic compound having one (mono), two (di), or three (tri) carboxylic acid groups (—COOH). The non-polymeric mono, di, and tricarboxylic acids, and/or salts thereof, typically have a molecular weight of less than about 500 g/mol, less than about 400 g/mol, or less than about 300 g/mol.


Non-limiting examples of monocarboxylic acids, or salts thereof, include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, entanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, lactic acid, a salt thereof, and a mixture thereof. In some cases, the hair treatment compositions include at least lactic acid and/or a salt thereof.


Non-limiting examples of dicarboxylic acids and/or salts thereof include oxalic acid, malonic acid, malic acid, glutaric acid, citraconic acid, succinic acid, adipic acid, tartaric acid, fumaric acid, maleic acid, sebacic acid, azelaic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, a salt thereof, and a mixture thereof. In some cases, the hair treatment compositions include oxalic acid, malonic acid, malic acid, maleic acid, a salt thereof, or a mixture thereof.


Non-limiting examples of tricarboxylic acids and salts thereof include citric acid, isocitric acid, aconitric acid, propane-1,2,3-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, a salt thereof, and a mixture thereof. In some instances, the hair treatment compositions include at least citric acid and/or a salt thereof.


In some cases, the hair treatment compositions include at least one or more dicaboxylic acids, and/or a salt thereof, in particular, oxalic acid, malonic acid, malic acid, maleic acid, a salt thereof, or a mixture thereof. A particularly useful dicarboxylic acid is malonic acid and/or a salt thereof. Another particularly useful dicarboxylic acid is maleic acid and/or a salt thereof.


The total amount of the at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof, is at least 0.5 wt. %, based on the total weight of the first phase or the hair treatment composition. In some cases, the total amount of the at least one non-polymeric mono, di, or tricarboxylic acid, and/or salt thereof, is at least 0.5, 0.6, 0.7, 0.8, 0.9, or 1 wt. % up to about 15, 20 wt. %. Furthermore, the total amount of the at least one non-polymeric mono, di, or tricarboxylic acid, and/or salt thereof, may be at least 0.5 wt. % to about 20 wt. %, at least 0.5 wt. % to about 18 wt. %, at least 0.5 wt. % to about 15 wt. %, at least 0.5 wt. % to about 12 wt. %, at least 0.5 wt. % to about 10 wt. %, at least 0.5 wt. % to about 5 wt. %, at least 0.8 wt. % to about 20 wt. %, at least 0.8 wt. % to about 18 wt. %, at least 0.8 wt. % to about 15 wt. %, about 0.8 to about 12 wt. %, about 0.8 to about 10 wt. %, about 0.8 wt. % to about 5 wt. %, about 1 wt. % to about 20 wt. %, about 1 wt. % to about 18 wt. %, about 1 wt. % to about 15 wt. %, about 1 wt. % to about 12 wt. %, about 1 wt. % to about 10 wt. %, about 1 wt. % to about 8 wt. %, about 1 wt. % to about 6 wt. %, about 1 wt. % to about 5 wt. %, based on the total weight of the first phase or the hair treatment composition.


In some embodiments, the total amount of the at least one non-polymeric mono, di, or tricarboxylic acid, and/or salt thereof, may be at least 0.5 wt. % to about 20 wt. %, at least 0.6 wt. % to about 15 wt. %, at least 0.8 wt. % to about 12 wt. %, at least 0.8 wt. % to about 10 wt. %, at least 1 wt. % to about 8 wt. %, at least 1 wt. % to about 6 wt. %, or at least 1 wt. % to about 5 wt. %, based on the total weight of the first phase or the hair treatment composition.


Amines


Non-limiting examples of the types of amines that may be used in the hair treatment compositions are vast, but may include diamines, polyamines, alkylamines, alkanolamines, and mixtures thereof. The one or more amines may be primary, secondary, tertiary amines, and mixtures thereof.


Diamines


Non-limiting examples of diamines that may be useful may be primary amines and secondary amines. The diamine can include both primary and secondary amine groups. Optional diamines may include at least one ethylene oxide group. For example, between 1 and 4 ethylene oxide groups can be present in the diamine. The diamine may optionally include propylene oxide groups. For example, between 1 and 4 propylene oxide groups can be present in the diamine. Non-limiting examples of diamines include 4,9-dioxadodecane-diamine; 4, 7, 10-trioxa-1,13-tridecanediamine; ethylenediamino; polyoxypropylene diamine; polyethylene glycol diamine; triethylene glycol diamine (20E); n-(2-hydroxyethyl)-ethylenediamine; 1,3-diaminopropane; 1,7-diaminoheptane; 1,4-diaminobutane; 1,2-diaminopropane; 1,6-diaminohexane; 1,11-diamino-3,6,9-trioxaundecane; 1,5-diaminopentane; polyoxyethylene diamine; 2,2-dimethyl-1,3-propanediamine; 2,2-bis(aminoethoxy)propane; 4,7,10-trioxa-1,13-tridecanediamine; 1,3-diaminopentane; 4,7,10-trioxa-1,13; 1,5-diamino-2-methylpentane; (3s,4s)-(−)-3,4-hexanediamine dihydrochloride; 1,9-diaminononane, and mixtures thereof.


In some cases, diamines may be selected from the group consisting of 4,9-dioxadodecane-diamine, 4, 7, 10-trioxa-1,13-tridecanediamine, ethylenediamino, polyoxypropylene diamine, polyethylene glycol diamine, triethylene glycol diamine (20E); n-(2-hydroxyethyl)-ethylenediamine; 1,3-diaminopropane, 1,7-diaminoheptane, 1,4-diaminobutane, 1,2-diaminopropane, 1,6-diaminohexane, 1,11-diamino-3,6,9-trioxaundecane, 1,5-diaminopentane, polyoxyethylene diamine, 2,2-dimethyl-1,3-propanediamine, 2,2-bis(aminoethoxy)propane, 4,7,10-trioxa-1,13-tridecanediamine, 1,3-diaminopentane, 4,7,10-trioxa-1,13; 1,5-diamino-2-methylpentane, (3s,4s)-(−)-3,4-hexanediamine dihydrochloride, 1,9-diaminononane, and mixtures thereof.


Polyamines


Polyamines have more than two amino groups. In some cases, the composition of the instant disclosure may include one or more polyamines, but in some cases, the compositions are free or essentially free of polyamines. The polyamine may be, for example, aminated polysaccharides comprising multiple amino groups, such as, for example, hydrolysates of aminated polysaccharides.


The polyamine may also be a polymer comprising multiple amino groups including homopolymers, copolymers, and terpolymers.


In some cases, polyamines are chosen from polyethyleneimines. Polyethyleneimines may optionally be substituted. Non-limiting examples of polyethyleneimines which may be used include LUPASOL products commercially available from BASF. Suitable examples of LUPASOL polyethyleneimines include LUPASOL PS, LUPASOL PL, LUPASOL PR8515, LUPASOL G20, LUPASOL G35 as well as LUPASOL SC Polythyleneimine Reaction Products (such as LUPASOL SC-61B, LUPASOL SC-62J, and LUPASOL SC-86X). Other non-limiting examples of polyethyleneimines which may be used in the composition according to the present invention are the EPOMIN products commercially available from Aceto. Suitable examples of EPOMIN polyethyleneimines include EPOMIN SP-006, EPOMIN SP-012, EPOMIN SP-018, and EPOMIN P-1000. Suitable polyamines s also be chosen from polyvinylamines. Examples thereof include LUPAMINES 9095, 9030, 9010, 5095, 1595 from BASF.


The polyamine compounds can also be substituted. An example of such a compound is PEG-15 Cocopolyamine from Cognis.


In some cases, the polyamine is chosen from proteins and protein derivatives. Non-limiting examples of suitable proteins and protein derivatives f include those listed at pages 1701 to 1703 of the C.T.F.A. International Cosmetic Ingredient Dictionary and Handbook, 8th edition, vol. 2, (2000), which is incorporated herein by reference in its entirety. In some cases, the at least one polyamine is chosen from wheat protein, soy protein, oat protein, collagen, and keratin protein.


The polyamine may be an alkoxylated polyamine. The alkoxylated polyamines may be chosen from amine compounds having at least two amino groups and at least one degree of alkoxylation. The alkoxylation is provided by an alkylene oxide group which may be chosen from ethylene oxide and propylene oxide. Non-limiting examples of suitable alkoxylated polyamines include compounds corresponding to the following formula:

NH2R(R′CHCH2O)x(R′CHCH2O)y(R′CHCH2O)z—RNH2


wherein R represents a —CH2-, —CH2CH2—, —CHCH3— or —C(CH3)2— group, or a hydrocarbon radical containing at least 3 carbon atoms that is linear or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted; x, y, and z independently of one another, represent numbers of from 0 to about 100; R′ represents hydrogen, or an alkyl group, preferably a methyl group; and The sum of x+y+z is at least 1. In some cases, R is a linear or branched, acyclic alkyl or alkenyl group or an alkyl phenyl group; x, y, and z independently of one another, preferably represent numbers ranging from 2 to 100.


Non-limiting examples of the alkoxylated polyamines include, for example, tetradecyloxypropyl-1,3-diaminopropane; a C12-14 alkyl oxypropyl-1,3-diaminopropane; a C12-15 alkyloxypropyl amine and other similar materials that are commercially available from Tomah under the tradename of TOMAH DA-17. Other examples of alkoxylated polyamines are diamine compounds belonging to the Jeffamine series such as the JEFFAMINE D and JEFFAMINE ED series available from Huntsman Corporation, Salt Lake City, Utah. Examples of these Jeffamine compounds are JEFFAMINE D230, JEFFAMINE D400, JEFFAMINE D2000, JEFFAMINE D4000, JEFFAMINE HK-511, JEFFAMINE ED600, JEFFAMINE ED900, and JEFFAMINE ED2003. JEFFAMINE D series compounds are amine terminated PPGs (polypropylene glycols) and JEFFAMINE ED series compounds are polyether diamine based with a predominantly PEG (polyethylene glycol) backbone.


Other non-limiting examples of suitable alkoxylated polyamines in the diamine form include compounds corresponding to the following formula:

NH2(CH2)xOCH2CH2O(CH2)xNH2


wherein x is 2 or 3.


Examples of alkoxylated polyamines are diamine compounds belonging to the JEFFAMINE series available from Huntsman Corporation, Salt Lake City, Utah, such as JEFFAMINE EDR148, and JEFFAMINE EDR176.


Additional non-limiting examples of alkoxylated polyamines in the triamine form include compounds corresponding to the following formula:




embedded image


wherein R is hydrogen, —CH2 or —C2H5, n=0 or 1, and x, y, and z independently of one another, represent numbers of from 0 to 100 and the sum of x+y+z is at least 1.


Examples of alkoxylated polyamines are triamine compounds belonging to the JEFFAMINE series such as the JEFFAMINE T series available from Huntsman Corporation, Salt Lake City, Utah. Examples of the JEFFAMINE T series compounds are JEFFAMINE T403, JEFFAMINE T3000, and JEFFAMINE T5000. JEFFAMINE T series compounds are triamines made by reacting PO with a triol initiator followed by aminating the terminal hydroxyl groups.


Alkylamines and Alkanolamines


The one or more alkylamines and/or one or more alkanolamines that may be included in the compositions include compounds of formula (II):

NR3R4R5   (II)


wherein R3, R4 and R5 are independently H, C1-C40 alkyl, C1-C40 monohydroxyalkyl or C2-C40 polyhydroxyalkyl, provided that at least one of R3, R4 and R5 is an alkyl or mono or polyhydroxyalkyl. In some cases, R3, R4 and R5 are independently H, C1-C2 alkyl, C1-C20 monohydroxyalkyl or C2-C20 polyhydroxyalkyl, provided that at least one of R3, R4 and R5 is an alkyl or mono or polyhydroxyalkyl. Finally, R3, R4 and R5 may independently be H, C1-C10 alkyl, C1-C10 monohydroxyalkyl or C2-C10 polyhydroxyalkyl, provided that at least one of R3, R4 and R5 is an alkyl or mono or polyhydroxyalkyl.


Non-limiting examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylamino-ethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethylamino)methane, and mixtures thereof. In some cases, the compositions include at least monoethanol amine. In some cases, the compositions include at least monoethanolamine.


Further non-limiting examples of alkylamines include aliphatic amine compounds corresponding to the following formula and their salts:

RN(R′)2


wherein R is a hydrocarbon radical containing at least 6 carbon atoms. In addition, R can be linear or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted. Typically, R is a linear or branched, acyclic alkyl or alkenyl group or an alkyl phenyl group; and the groups R′, which may be identical or different, represent H or a hydrocarbon radical containing less than 6 carbon atoms. In addition, the groups R′, which may be identical or different, are linear or branched, acyclic or cyclic, saturated or unsaturated, substituted or unsubstituted. In some cases, the groups R′, which may be identical or different, are H or a methyl group.


In some cases, alkylamines include, but are not limited to the following examples: dimethyl lauramine, dimethyl behenamine, dimethyl cocamine, dimethyl myristamine, dimethyl palmitamine, dimethyl stearamine, dimethyl tallowamine, dimethyl soyamine, stearamine, soyamine, cocamine, lauramine, palmitamine, oleamine, tallow amine and mixtures thereof.


Other non-limiting examples of alkyl monoamines include amidoamine compounds corresponding to the following formula and their salts:

RCONHR′N(R″)2


wherein: R is a hydrocarbon radical containing at least 6 carbon atoms. In addition, R can be linear or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted. Typically, R is a linear or branched, acyclic alkyl or alkenyl group or an alkyl phenyl group; and R′ is a divalent hydrocarbon radical containing less than 6 carbon atoms, or 2 or 3 carbon atoms, and R″ is H or a hydrocarbon radical containing less than 6 carbon atoms. In addition, R″ is linear or branched, acyclic or cyclic, saturated or unsaturated, substituted or unsubstituted. Typically, R″ is a linear or branched, acyclic alkyl or alkenyl group. In some cases, R″ is H or a methyl group.


Examples of amidoamines that are useful in the compositions of the instant disclosure include, but are not limited to the following: oleamidopropyl dimethylamine, stearamidopropyl dimethylamine, isostearamidopropyl dimethylamine, stearamidoethyl dimethylamine, lauramidopropyl dimethylamine, myristamidopropyl dimethylamine, behenamidopropyl dimethylamine, dilinoleamidopropyl dimethylamine, palmitamidopropyl dimethylamine, ricinoleamindopropyl dimethylamine, soyamidopropyl dimethylamine, wheat germamidopropyl dimethylamine, sunflowerseedamidopropyl dimethylamine, almondamidopropyl dimethylamine, avocadoamidopropyl dimethylamine, babassuamidopropyl dimethylamine, cocamidopropyl dimethylamine, minkamidopropyl dimethylamine, oatamidopropyl dimethylamine, sesamidopropyl dimethylamine, tallamidopropyl dimethylamine, brassicaamidopropyl dimethylamine, olivamidopropyl dimethylamine, palmitamidopropyl dimethylamine, stearamidoethyldiethylamine, and mixtures thereof.


Additional Amines


Additional amines that may be useful include alkoxylated monoamines. The alkoxylated monoamines are compounds having an amino group and at least one degree of alkoxylation. The alkoxylation is provided by an alkylene oxide group which is often chosen from ethylene oxide and propylene oxide.


Non-limiting examples of suitable alkoxylated monoamines include compounds corresponding to the following formula:

RN[(R′CHCH2O)xH][(R′CHCH2O)yH]


wherein R is a hydrocarbon radical containing at least 6 carbon atoms. R can be linear or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted; x and y, independently of one another, represent numbers of from 0 to 100 provided that the sum of x+y is >0; the groups R′, which may be identical or different, represent hydrogen, or an alkyl group such as a methyl group. Typically, R is a linear or branched, acyclic alkyl or alkenyl group or an alkyl phenyl group; x and y, independently of one another, are each typically a number from 0 to 30. Typically, one R′ group is hydrogen, and the other one is methyl.


Non-limiting examples of alkoxylated monoamines include PEG-2 Cocamine, PEG-3 Cocamine, PEG-5 Cocamine, PEG-10 Cocamine, PEG-15 Cocamine, PEG-20 Cocamine, PEG-2 Lauramine, PEG-12 Palmitamine, PEG-2 Rapeseedamine, PEG-2 Oleamine, PEG-5 Oleamine, PEG-6 Oleamine, PEG-10 Oleamine, PEG-15 Oleamine, PEG-20 Oleamine, PEG-25 Oleamine, and PEG-30 Oleamine. Other examples are alkoxylated derivatives of soyamine, stearamine and tallow amine.


Other non-limiting examples of suitable alkoxylated monoamines include compounds corresponding the following formula:

RNR″[(R′CHCH2O)xH]


wherein R is a hydrocarbon radical containing at least 6 carbon atoms. R can be linear or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted; x represents a number of from 1 to 100; R′ represents hydrogen, or an alkyl group such as in particular a methyl group; and R″ is a hydrogen or a hydrocarbon radical. Typically, R is a linear or branched, acyclic alkyl or alkenyl group or an alkyl phenyl group; x is typically a number from 1 to 30. When R″ is a hydrocarbon radical group, this group may be linear or branched, saturated or unsaturated, substituted or unsubstituted. The hydrocarbon radical represented by R″ may also contain an alkoxylated moiety (as defined by [(R′CHCH2O)yH]), and/or heteroatoms such as nitrogen. When R″ contains at least one alkoxylated moiety, the total number of alkoxylation in the formula may range from 1 to 120. Examples of alkoxylated monoamines include PEG-3 Tallow Aminopropylamine, PEG-10 Tallow Aminopropylamine, PEG-15 Tallow Aminopropylamine, and PEG-105 Behenyl Propylenediamine.


Additional non-limiting examples of alkoxylated monoamines include compounds corresponding to the following formula:

R(R′CHCH2O)x(R′CHCH2O)yNHy


wherein R is a hydrocarbon radical containing at least 6 carbon atoms. R can be linear or branched, acyclic or cyclic, saturated or unsaturated, aliphatic or aromatic, substituted or unsubstituted; x and y, independently of one another, represent numbers of from 0 to 100 with the proviso that the sum of x+y is >0; the groups R′, which may be identical or different, represent hydrogen, or an alkyl group such as in particular a methyl group. Typically, R is a linear or branched, acyclic alkyl or alkenyl group or an alkyl phenyl group; x and y, independently of one another, are each typically a number from 0 to 30. Examples of alkoxylated monoamines include polyetheramines containing a monoamine group. These polyetheramines are commercially available from Hunstman under the tradename JEFFAMINE (M series such as M-600, M-1000, M-2005 and M-2070) and SURFONAMINE series (B-60, B-100, B-200, L-100, L-200, L-207, L-300).


The total amount of the at least one amine may vary, but in some cases, the total amount is about 0.1 to about 20 wt. %, based on the total weight of the first phase or the hair treatment composition. In some cases, the total amount of the at least one amine is about 0.1 to about 20 wt. %, about 0.1 to about 18 wt. %, about 0.1 to about 15 wt. %, about 0.1 to about 12 wt. %, about 0.1 to about 10 wt. %, about 0.1 to about 8 wt. %, about 0.1 to about 5 wt. %, about 0.5 to about 20 wt. %, about 0.5 to about 18 wt. %, about 0.5 to about 15 wt. %, about 0.5 to about 12 wt. %, about 0.5 to about 10 wt. %, about 0.5 to about 8 wt. %, about 0.5 to about 5 wt. %, about 0.8 to about 20 wt. %, about 0.8 to about 18 wt. %, about 0.8 to about 15 wt. %, about 0.8 to about 12 wt. %, about 0.8 to about 10 wt. %, about 0.8 to about 8 wt. %, or about 0.8 to about 5 wt. %.


In some embodiments, the total amount of the at least one amine may be at least 0.1 wt. % to about 20 wt. %, at least 0.2 wt. % to about 15 wt. %, at least 0.4 wt. % to about 10 wt. %, at least 0.5 wt. % to about 10 wt. %, at least 0.5 wt. % to about 8 wt. %, at least 0.5 wt. % to about 6 wt. %, or at least 0.5 wt. % to about 5 wt. %, based on the total weight of the first phase or the hair treatment composition.


Cationic Polymer


Non-limiting examples of cationic polymers include poly(methacryloyloxyethyl trimethylammonium chloride), polyquaternium-37, quaternized cellulose derivatives, polyquaternium-4, polyquaternium-10, cationic alkyl polyglycosides, cationized honey, cationic guar derivatives, polymeric dimethyl diallyl ammonium salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid, copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, vinyl pyrrolidone-vinyl imidazolium methochloride copolymers, quaternized polyvinyl alcohol, polyquaternium-2, polyquaternium-7, polyquaternium-17, polyquaternium-18, polyquaternium-24, polyquaternium-27, and a mixture thereof. In some instances, the one or more cationic polymers may be selected from the group consisting of polyquaternium-4, polyquaternium-10, cationic guar derivatives, and a mixture thereof.


The cationic polymers can be a monoalkyl quaternary amine, such as stearyltrimonium chloride, soyatrimonium chloride or coco-ethyldimonium ethosulfate. Other suitable cationic polymers include, but are not limited to, behentrimonium chloride, dialkyl quaternary amines, such as dicetyldimonium chloride, dicocodimethyl ammonium chloride or distearyldimethyl ammonium chloride; and polyquaternium compounds, such as Polyquaternium-6, Polyquaternium-22 or Polyquaternium-5.


For example, cationic polymers may be chosen from polyquaterium-10 (also called quaternized polyhydroxyethyl cellulose), cetrimonium chloride (also called cetyl trimethyl ammonium chloride, CTAC), behentrimonium chloride (also known as docosyl trimethyl ammonium chloride), behentrimonium methosulfate, steartrimonium chloride, stearalkonium chloride, dicetyldimonium chloride, hydroxypropyltrimonium chloride, cocotrimonium methosulfate, olealkonium chloride, steartrimonium chloride, babassuamidopropalkonium chloride, brassicamidopropyl dimethylamine, Quaternium-91, Salcare/PQ-37, Quaternium-22, Quaternium-87, Polyquaternium-4, Polyquaternium-6, Polyquaternium-11, Polyquaternium-44, Polyquaternium-67, amodimethicone, lauryl betaine, Polyacrylate-1 Crosspolymer, steardimonium hydroxypropyl hydrolyzed wheat protein, behenamidopropyl PG-dimonium chloride, lauryldimonium hydroxypropyl hydrolyzed soy protein, aminopropyl dimethicone, Quaterium-8, and dilinoleamidopropyl dimethylamine dimethicone PEG-7 phosphate.


In some instances, the cationic polymers are cationic conditioning polymers. Examples of cationic conditioning polymers that can be used include, without limitation, cationic cellulose, cationic proteins, and cationic polymers. The cationic polymers can have a vinyl group backbone of amino and/or quaternary ammonium monomers. Cationic amino and quaternary ammonium monomers include, without limitation, dialkylamino alkylmethacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryoloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salts, diallyl quaternary ammonium salts, vinyl compounds substituted with dialkyl aminoalkyl acrylate, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen containing rings such as pyridinium, imidazolium, or quaternized pyrrolidine. Other examples of cationic conditioning polymers that can be used include, without limitation, hydroxypropyltrimonium honey, cocodimonium silk amino acids, cocodimonium hydroxypropyl hydrolyzed wheat or silk protein, polyquaternium-5, polyquaternium-11, polyquaternium-2, polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-14, polyquaternium-16, polyquaternium-22, polyquaternium-10, and guar hydroxypropyltrimonium chloride.


In some cases quaternized polymeric cationic polymers are particularly useful. Particularly preferred are quaternary nitrogen polymers prepared by the polymerization of a dialkyldiallylammonium salt or copolymer thereof in which the alkyl group contains 1 to about 18 carbon atoms, and more preferably where the alkyl group is methyl or ethyl. Details concerning the preparation of these polymers can be found in U.S. Pat. Nos. 3,288,770, 3,412,019 and 4,772,462, incorporated herein by reference. For example, cationic homopolymers and copolymers of polydiallyldimethylammonium chloride are available in aqueous compositions sold under the trademark MERQUAT by the Calgon Corporation, subsidiary of Merck & Co., Pittsburgh, Pa. The homopolymer, which is named Polyquaternium-6 is sold under the trademark MERQUAT-100, and is described as having a weight average molecular weight of approximately 100,000. A copolymer reaction product of dimethyldiallylammonium chloride with acrylamide monomers is named Polyquaternium-7 is described as having a weight average molecular weight of approximately 500,000 and is sold under the trademark MERQUAT-550. Another copolymer reaction product of dimethyldiallylammonium chloride with acrylic acids having a weight average molecular weight from about 50,000 to about 10,000,000 has the name Polyquaternium-22 and is sold under the trademark MERQUAT-280. Polyquaternium-6 is particularly preferred.


Other polymeric conditioners include cationic copolymers of methylvinylimidazolium chloride and vinyl pyrrolidone, sold commercially by BASF Aktiengesellschaft, West Germany under the trademark LUVIQUAT at three comonomer ratios, namely at ratios of 95/5, 50/50 and 30/70 methylvinylimidazolium chloride to polyvinylpyrrolidone. These copolymers at all three comonomer ratios have the name Polyquaternium 16. Polymeric conditioners also include cationic cellulosic polymers of hydroxyethyl cellulose reacted with epichlorohydrin and quaternized with trimethylamine, sold under the trademark POLYMER JR in various viscosity grades and molecular sizes by Union Carbide Corporation, Danbury, Conn. These series of polymers are named Polyquaternium 10. Also useful are quaternized copolymers of hydroxyethylcellulose and dimethyldimethylammonium chloride, having the name Polyquaternium-4, sold in varying molecular weights under the trademark CELQUAT by National Starch and Chemical Corporation, Bridgewater, N.J.


Smaller molecule cationic non-polymeric conditioning agents can also be utilized herein. Exemplary small-molecule conditioning agents can include monofunctional or difunctional quaternary ammonium compounds, such as stearyldimethylbenzylammonium chloride, dimethyldi-(hydrogenated tallow)ammonium chloride, and the like. Non-polymeric conditioning agents can also include the quaternary ammonium salts of gluconamide derivatives, such as gamma-gluconamidopropyldimethyl-2-hydroxyethyl-ammonium chloride and minkamidopropyldimethyl-2-hydroxyethylammonium chloride identified respectively by the names Quaternium 22 and Quaternium 26. Details for the preparation of these materials are found in U.S. Pat. Nos. 3,766,267 and 4,012,398, respectively, and the materials are sold under the trademark CERAPHYL by Van Dyk & Co., Belleville, N.J. Also useful are bis-quaternary ammonium compounds which are dimers, such as 2-hydroxy propylene-bis-1,3-(dimethylstearyl ammonium chloride, designated the name, Hydroxypropyl Bisstearyldimonium chloride. The preparation of these and other bis-quat materials is described in U.S. Pat. No. 4,734,277, and such materials are sold under the trademark JORDAQUAT DIMER by Jordan Chemical Company, Folcroft, Pa.


Exemplary unquaternized polymers having tertiary amino nitrogen groups that become quaternized when protonated can include water-soluble proteinaceous quaternary ammonium compounds. hydrolyzed animal protein, for example, is the name for a chemically-modified quaternary ammonium derivative of hydrolyzed collagen protein having from about 12 to about 18 carbons in at least one aliphatic alkyl group, a weight average molecular weight from about 2500 to about 12,000, and an isoionic point in a range from about 9.5 to about 11.5. This material and structurally related materials are sold under the trademarks CROQUAT and CROTEIN by Croda, Inc., New York, N.Y.


Alkoxysilane


The at least one alkoxysilane often includes at least one solubilizing functional group. As used herein, the term “at least one solubilizing functional group” means any functional chemical group facilitating the bringing into solution of the alkoxysilane in the solvent or in a combination of solvents of the composition, for example, in solvents chosen from water, water-alcoholic mixtures, organic solvents, polar solvents and non-polar solvents. Suitable solubilizing functional groups include, but are not limited to, primary, secondary, and tertiary amine, aromatic amine, alcohol, carboxylic acid, sulfonic acid, anhydride, carbamate, urea, guanidine, aldehyde, ester, amide, epoxy, pyrrole, dihydroimidazole, gluconamide, pyridyle, and polyether groups.


In some cases, the at least one alkoxysilane comprising at least one solubilizing functional group may comprise two or three alkoxy groups. For example, the alkoxy functional groups may be chosen from methoxy and ethoxy functional groups.


In some cases, the at least one alkoxysilane comprising at least one solubilizing functional group may be selected from compounds of the following formula:




embedded image


wherein, R4 is chosen from halogen atoms, OR′ groups, and R11 groups;


R5 is chosen from halogen atoms, OR″ groups, and R12 groups;


R6 is chosen from halogen atoms, OR′″ groups, and R13 groups;


R1, R2, R3, R′, R″, R′″, R11, R12, and R13, which may be identical or different, are chosen from linear and branched, saturated and unsaturated hydrocarbon groups, optionally bearing at least one additional chemical group, wherein R1, R2, R′, R″, and R′″ may also be chosen from hydrogen; provided that at least two groups R4, R5, and R6 are different from R11, R12, and R13, and at least two groups R′, R″, and R′″ are not hydrogen.


The at least one alkoxysilane comprising at least one solubilizing functional group may also be one or more compounds chosen from compounds of the following formula:




embedded image


wherein R9 is chosen from halogen atoms and OR′9 groups;


R10 is chosen from halogen atoms and OR′1 groups;


R′9 and R′10, which may be identical or different, are chosen from hydrogen, and linear and branched, saturated and unsaturated C1-C14 hydrocarbon groups


R7 is a non hydrolyzable functional group providing a cosmetic effect; and


R8 is a non hydrolyzable functional group bearing at least one function chosen from amines, carboxylic acids and salts thereof, sulfonic acids and salts thereof, polyols such as glycol, polyethers such as polyalkylene ether, and phosphoric acids and salts thereof; and provided that at least one of R9 and R10 is not a halogen.


In some cases, the at least one alkoxysilane comprising at least one solubilizing functional group may be chosen from compounds of the following formula:




embedded image


wherein R12 is chosen from halogen atoms, OR′12 groups, and RO groups;


R13 is chosen from halogen atoms, OR′13 groups, and R′O groups;


R14 is chosen from halogen atoms, OR′14 groups, and R″O groups;


R11 is chosen from groups bearing at least one function chosen from carboxylic acids and salts thereof, sulfonic acids and salts thereof, and polyalkylethers;


Ro, R′o, R″o, R′12, R′13, and R′14, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C1-C14 hydrocarbon groups optionally bearing at least one additional chemical functional group chosen from carboxylic acids and salts thereof, sulfonic acids and salts thereof, and polyalkylether functions, and wherein R′12, R′13, and R14 may also be chosen from hydrogen; provided that at least two groups from R12, R13 and R14 are different from RO, R′O, and R″O groups; and provided further that at least two of the groups R′12, R′13, and R′14 are not hydrogen.


According to another embodiment, the at least one alkoxysilane comprising at least one solubilizing functional group may be chosen from compounds of the following formula:

(R21O)x(R22)ySi-(A)p-[NR23-(A′)p′]q-[NR′23-(A″)p″]q′-Si—(R′22)y′(OR′21)x


wherein R21, R22, R′21, and R′22, which may be identical or different, are chosen from linear and branched, saturated and unsaturated hydrocarbon chains, optionally comprising at least one heteroatom, optionally interrupted by or substituted with at least one group chosen from ether, ester, amine, amide, carboxyl, hydroxyl, and carbonyl groups;


x is an integer ranging from 1 to 3;


y is 3-x;


x′ is an integer ranging from 1 to 3;


y′ is 3-x′,


p, p′, p″, q, and q′ can each be 0 or 1, wherein at least one of q or q′ is not equal to zero;


A, A′, and A″, which may be identical or different, are chosen from linear and branched C1-C20 alkylene divalent radicals; and R23 and R′23, which may be identical or different, are chosen from hydrogen and linear and branched, saturated and unsaturated hydrocarbon chains, optionally comprising at least one heteroatom, optionally interrupted by or substituted with at least one entity chosen from ether, C1-C20 alcohol ester, amine, carboxyl, alkoxysilane, C6-C30 aryl, hydroxyl, and carbonyl groups, and aromatic, heterocyclic, and non-heterocyclic rings, optionally substituted with at least one group chosen from C3-C20 alcohol ester, amine, amide, carboxyl, alkoxysilane, hydroxyl, carbonyl, and acyl groups.


The at least one alkoxysilane comprising at least one solubilizing functional group may also be chosen from compounds of the following formula:




embedded image



wherein R24 and R25, which may be identical or different, are chosen from linear and branched, saturated and unsaturated hydrocarbon chains, optionally comprising at least one heteroatom, optionally interrupted by or substituted with at least one group chosen from ether, ester, amine, amide, carboxyl, hydroxyl, and carbonyl groups;


x″ is 2 or 3; [0170] y″ is 3-x″;


n′ is 0 or 1;


n″ is 0 or 1;


E and E′, which may be identical or different, are chosen from linear and branched C1-C20 alkylene divalent radicals;


R26 and R27, which may be identical or different, are chosen from hydrogen and linear and branched, saturated and unsaturated hydrocarbon chains, optionally comprising at least one heteroatom, optionally interrupted by or substituted with at least one entity chosen from ether, C1-C20 alcohol ester, amine, carboxyl, alkoxysilane, C6-C30 aryl, hydroxyl, and carbonyl groups, and aromatic, heterocyclic, and non-heterocyclic rings, optionally substituted with at least one group chosen from C1-C20 alcohol ester, amine, amide, carboxyl, alkoxysilane, hydroxyl, carbonyl, and acyl groups;


r is an integer ranging from 0 to 4;


r′=0 or 1; and


R28 is chosen from hydrogen and linear and branched, saturated and unsaturated hydrocarbon chains, comprising, optionally at least one heteroatom, optionally interrupted by or substituted with at least one entity chosen from ether, alkyl alcohol ester, amine, carboxyl, alkoxysilane, alkyl aryl, hydroxyl, and carbonyl groups, and aromatic, heterocyclic, and non-heterocyclic rings.


According to a further exemplary embodiment, the at least one alkoxysilane comprising at least one solubilizing functional group may be chosen from compounds of the following formula:

(R29O)x1(R30)y1-Si-(A1)s-CH═O


wherein R29 and R30, independently, are chosen from linear and branched, saturated and unsaturated hydrocarbon chains, optionally comprising at least one heteroatom, optionally interrupted by or substituted with at least one group chosen from ether, ester, amine, amide, carboxyl, hydroxyl, and carbonyl groups;


x1 is 2 or 3;


y1 is 3-x1;


A1 is chosen from linear and branched C1-C20 alkylene divalent radicals, optionally interrupted by or substituted with at least one group chosen from C1-C30 alcohol ester, amine, carboxyl, alkoxysilane, C6-C30 aryl, hydroxyl, and carbonyl groups; and


s is 0 or 1.


In some instances, the at least one alkoxysilane comprising at least one solubilizing functional group is chosen from compounds of the following formula:




embedded image


wherein the R radicals, which may be identical or different, are chosen from C1-C6 alkyl radicals and n is an integer ranging from 1 to 6, for example, from 2 to 4.


The alkoxysilanes useful in the present disclosure can be chosen from alkoxysilanes comprising a silicon atom in a formula R(4-n)SiXn, wherein X is a hydrolysable group such as methoxy, ethoxy or 2-methoxyethoxy, R is a monovalent organic radical which contains 1 to 12 carbon atoms and may contain groups such as mercapto, epoxy, acrylyl, methacrylyl, amino or urea, and n is an integer from 1 to 4, and according to at least one embodiment is 3. Exemplary alkoxysilanes include, but are not limited to, 3-mercaptopropyltriethoxysilane and aminoalkyltrialkoxysilanes such as 3-aminopropyltriethoxysilane, as described in French Patent Application No. FR2789896, incorporated by reference herein. Other useful alkoxysilanes are cited, for example, in EP1216022, incorporated by reference herein, which describes alkoxysilanes comprising at least one hydrocarbon chain containing a non-basic solubilizing chemical function. In this respect, non-limiting mention may be made of the HCl-neutralized sodium N-[(3-trimethoxysilyl)propyl]ethylenediaminetriacetate supplied by GELEST. In some cases, the alkoxysilanes may comprise at least one hydrocarbon chain containing fluorine atoms. Non-limiting examples include but are not limited to the 3,3,3-trifluoropropyltriethoxysilane or tridecafluorooctyltriethoxysilane compounds described in EP1510197, incorporated by reference herein.


It is also contemplated that these alkoxysilanes may carry a solubilizing, non-hydrolysable group such as amino groups, carboxylic acids, sulphonic acids, sulphates, quaternary ammoniums, polyalcohols, polyether and phosphates. One possible example of the foregoing types of alkoxysilanes is aminopropyl-N-(4,2-dinitrophenyl)aminopropyldiethoxysilane. Additional exemplary compounds of this type are described, for example, in EP1216023, which is herein incorporated by reference. Non-limiting examples of useful alkoxysilanes include 3-mercaptopropyltriethoxysilane and aminoalkyltrialkoxysilanes such as 3-aminopropyltriethoxysilane (“APTES”, described in French Patent Application No. FR 2 789 896, incorporated herein by reference), and mixtures thereof. In some cases, the hair-treatment compositions include 3-aminopropyltriethoxysilane.


The total amount of the at least one alkoxysilane may vary, but in some cases, the total amount is about 0.1 to about 20 wt. %, based on the total weight of the first phase or the hair treatment composition. In some cases, the total amount of the at least one alkoxysilane is about 0.1 to about 20 wt. %, about 0.1 to about 18 wt. %, about 0.1 to about 15 wt. %, about 0.1 to about 12 wt. %, about 0.1 to about 10 wt. %, about 0.1 to about 8 wt. %, about 0.1 to about 5 wt. %, about 0.5 to about 20 wt. %, about 0.5 to about 18 wt. %, about 0.5 to about 15 wt. %, about 0.5 to about 12 wt. %, about 0.5 to about 10 wt. %, about 0.5 to about 8 wt. %, about 0.5 to about 5 wt. %, about 0.8 to about 20 wt. %, about 0.8 to about 18 wt. %, about 0.8 to about 15 wt. %, about 0.8 to about 12 wt. %, about 0.8 to about 10 wt. %, about 0.8 to about 8 wt. %, about 0.8 to about 5 wt. %, about 1 to about 20 wt. %, about 1 to about 18 wt. %, about 1 to about 15 wt. %, about 1 to about 12 wt. %, about 1 to about 10 wt. %, about 1 to about 8 wt. %, about 1 to about 5 wt. %, about 1.5 to about 20 wt. %, about 1.5 to about 18 wt. %, about 1.5 to about 15 wt. %, about 1.5 to about 12 wt. %, about 1.5 to about 10 wt. %, about 1.5 to about 8 wt. %, or about 1.5 to about 5 wt. %.


In some embodiments, the total amount of the at least one alkoxysilane may be at least 0.1 wt. % to about 20 wt. %, at least 0.5 wt. % to about 15 wt. %, at least 1 wt. % to about 10 wt. %, at least 1.5 wt. % to about 10 wt. %, at least 1.5 wt. % to about 8 wt. %, at least 1.5 wt. % to about 5 wt. %, or at least 1.5 wt. % to about 3 wt. %, based on the total weight of the first phase or the hair treatment composition.


Polyols


In one or more embodiments, the at least one polyol comprises one or more glycol compounds. In further embodiments, the glycol compounds are selected from the group consisting of hexylene glycol, butylene glycol, propylene glycol, dipropylene glycol, and combinations thereof. In other embodiments, the at least one polyol comprises glycerin.


In one or more embodiments, the at least one polyol comprises a mixture of two ingredients in a ratio ranging from about 1:2 to about 2:1, or more specifically about 1:1. In some embodiments, the at least one comprises hexylene glycol and butylene glycol. In one or more embodiments, the at least one polyol comprises propylene glycol in addition to hexylene glycol and butylene glycol.


While not wishing to be bound to any particular theory, it is thought that the presence of the polyol increases the efficacy of penetrating actives such as maleic acid. The polyol may also act as a surfactant and assists in stabilizing the emulsion. Emulsion stability is a particularly important effect when low pH ingredients are present (e.g., maleic acid) because such low pH ingredients can have a negative effect on emulsion stability. Thus, it is thought that the at least one polyol works to counteract the negative effect of low pH ingredients on emulsion stability as well as assisting active penetration to the cortex.


In some embodiments, the total amount of the at least one polyol may be at least 0.1 wt. % to about 20 wt. %, at least 0.5 wt. % to about 15 wt. %, at least 1 wt. % to about 12 wt. %, at least 1.5 wt. % to about 10 wt. %, at least 1.5 wt. % to about 8 wt. %, at least 1.5 wt. % to about 5 wt. %, based on the total weight of the first phase or the hair treatment composition.


Water


The amount of water in the first phase or hair treatment compositions may be at least 50 wt. %, or from about 50 to about 95 wt. %, about 50 to about 90 wt. %, about 50 to about 85 wt. %, about 60 to about 80 wt. %.


Film-Forming Aminosilicone Polymer


In accordance with some embodiments, the at least one film-forming aminosilicone polymer comprises Polysilicone-29, which is a film-forming aminosilicone polymer formed by the reaction between a glycidoxypropyl-terminated dimethyl siloxane polymer, PEG-13 diglycidyl ether, diethylaminopropylamine, and aminopropyltriisopropoxysilane sold under the tradename SILSOFT CLX-E emulsion (Momentive Performance Materials).


In accordance with the various embodiments, the amount of each of the at least one film-forming aminiosilicone polymer is from about 0.01 to about 5 wt. %, or from about 0.03 to about 4 wt. %, or from about 05 to about 3 wt. %, or from about 0.06% to about 2% or any suitable combination, sub-combination, range, or sub-range thereof by weight, based on the weight of the composition. One of ordinary skill in the art, however, will appreciate that other ranges are within the scope of the invention.


Thus, any one of the at least one film-forming aminiosilicone polymer is present, by weight, based on the total weight of the second phase of the hair treatment composition, from about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3 to about 5 wt. %, including increments and ranges therein and there between.


Silicone Oil


The at least one silicone oil of the present disclosure may be selected from polyalkylsiloxanes, polyarylsiloxanes, polyalkarylsiloxanes, polyestersiloxanes, polyphenylsilicones, and a mixture thereof.


The term “silicone oil” is interchangeable with the terms “polysiloxane” and “polysiloxane oil.” For purposes of the instant disclosure, “amino silicones” are not considered a “silicone oil.” Instead, amino silicones form an independent category of component that may optionally be included in the hair treatment compositions. A more detailed definition and non-limiting examples of amino silicones are provided later, under the heading “Amino Silicone.”


Non-limiting examples of silicone oils include polyalkylsiloxanes, polyarylsiloxanes, polyalkarylsiloxanes, polyestersiloxanes, polyphenylsiloxanes and a mixture thereof. In some instances, the silicone oil is preferably water insoluble at room temperature.


Representative examples of non-volatile, non-phenyl silicone oils which may be mentioned include cyclopentasiloxane, polydimethylsiloxanes; alkyl dimethicones; vinylmethyl methicones; and also silicones modified with aliphatic groups. It should be noted that “dimethicone” (INCI name) corresponds to a poly(dimethylsiloxane) (chemical name), which is particularly preferred in some instances.


The silicone oils are preferably chosen from non-volatile dimethicone oils. In particular, these oils can be chosen from the following non-volatile oils:

    • polydimethylsiloxanes (PDMSs),
    • PDMSs comprising aliphatic groups, in particular alkyl or alkoxy groups, which are pendent and/or at the end of the silicone chain, these groups each comprising from 2 to 24 carbon atoms. By way of example, mention may be made of the cetyl dimethicone sold under the commercial reference Abil Wax 9801 from Evonik Goldschmidt,
    • PDMSs comprising aliphatic groups, or functional groups such as hydroxyl, thiol and/or amine groups,
    • polyalkylmethylsiloxanes substituted with functional groups such as hydroxyl and thiol groups,
    • polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, and mixtures thereof.


Preferably, non-volatile and non-phenyl silicone oils are chosen from polydimethylsiloxanes; alkyl dimethicones and also PDMSs comprising aliphatic groups, in particular C2-C24 alkyl groups.


The silicone oil may be chosen from silicones of the following formula:




embedded image


in which:


R1, R2, R5 and R6 are, together or separately, an alkyl radical containing 1 to 6 carbon atoms,


R3 and R4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical, or a hydroxyl radical,


X is an alkyl radical containing from 1 to 6 carbon atoms, or a hydroxyl radical,


n and p are integers chosen so as to have a fluid compound, in particular of which the viscosity at 25° C. is between 1 centistokes (cSt) and 1,000,000 (cSt).


As non-volatile non-phenyl silicone oils which can be used according to the invention, mention may be made of those for which:

    • the substituents R1 to R6 and X represent a methyl group, and p and n are such that the viscosity is 500 000 cSt, for example the product sold under the name SE30 by the company General Electric, the product sold under the name AK 500000 by the company Wacker, the product sold under the name Mirasil DM 500 000 by the company Bluestar, and the product sold under the name Dow Corning 200 Fluid 500 000 cSt by the company Dow Corning,
    • the substituents R1 to R6 and X represent a methyl group, and p and n are such that the viscosity is 60 000 cSt, for example the product sold under the name Dow Corning 200 Fluid 60 000 CS by the company Dow Corning, and the product sold under the name Wacker Belsil DM 60 000 by the company Wacker,
    • the substituents R1 to R6 and X represent a methyl group, and p and n are such that the viscosity is 100 cSt or 350 cSt, for example the products sold respectively under the names Belsil DM100 and Dow Corning 200 Fluid 350 CS by the company Dow Corning,
    • the substituents R1 to R6 represent a methyl group, the group X represents a hydroxyl group, and n and p are such that the viscosity is 700 cSt, for example the product sold under the name Baysilone Fluid T0.7 by the company Momentive.


In some embodiments, it is preferable that the hair treatment compositions include two or more silicone oils, for example, two or more silicone oils selected from polyalkylsiloxanes, polyarylsiloxanes, polyalkarylsiloxanes, polyestersiloxanes, and a mixture thereof. In some instances, the two or more silicone oils are preferably two or more silicone oils selected from polyalkylsiloxanes (e.g., dimethicones) and cyclopentasiloxane. It is especially useful to include two or more silicone oils wherein at least one silicone oil has a viscosity of about 1 to 1000 centistokes and at least one silicone oil has a viscosity greater than 1000 to about 1,000,000 centistokes at 25° C. Centistokes is a standard unit used in the silicone industry for characterizing silicone oils because it is a representation of cinematic viscosity, which provides a better description of the behavior of silicone oils, as opposed to a dynamic viscosity (often represented by mPa·s). The viscosity of the silicone oils can be determined by methods known in the art, for example, using the Stokes viscosity or even a rotational viscometer.


The silicone oils having a viscosity of about 5 to 1000 cSt, may also have a viscosity of about 50 to about 1000 cSt, about 100 to about 1000 cSt, about 50 to about 750 cSt, about 100 to about 750 cSt, about 50 to about 500 cSt, about 100 to about 500 cSt, about 150 to about 500 cSt, about 200 to about 500 cSt, or about 350 cSt, including all ranges and subranges there between.


The total amount of all silicone oil(s) (except for the optional aminosilicone, which is not considered a silicone oil according to the instant disclosure) in the second phase of the hair treatment compositions can vary but is typically about 60 to about 99 wt. %, based on the total weight of the second phase or hair treatment composition. In some instances, the total amount of silicone oil(s) may be about 70 to about 98 wt. %, about 80 to about 98 wt. %, about 80 to about 98 wt. %, about 85 to about 98 wt. %, or about 90 to about 98 wt. %, based on the total weight of the second phase, including all ranges and subranges there between.


The total amount of all silicone oil(s) (except for the optional aminosilicone, which is not considered a silicone oil according to the instant disclosure) in the hair treatment compositions can vary but is typically about 10 to about 50 wt. %, based on the total weight of the hair treatment composition. In some instances, the total amount of silicone oil(s) may be about 12 to about 45 wt. %, about 15 to about 40 wt. %, about 15 to about 35 wt. %, about 15 to about 30 wt. %, about 15 to about 28 wt. %, about 15 to about 25 wt. %, or about 18 to about 25 wt. %, based on the total weight of the hair treatment composition, including all ranges and subranges there between.


Non-Silicone Oils


The at least one non-silicone oil includes, for example, fluoro oils, hydrocarbon-based oils, etc. The term “oil” means any fatty substance which is in liquid form at room temperature (20-25° C.) and at atmospheric pressure (760 mmHg). Often, at least one of the oils in the cosmetic composition is part of an oily phase. An “oily phase” is a phase comprising at least one oil that may include additional liposoluble and lipophilic ingredients and the fatty substances. The oily phase can be combined with an aqueous phase in an emulsion. Oil that is suitable for use herein may be volatile or non-volatile. The term “volatile oil” relates to oil that is capable of evaporating on contact with the skin or a keratin fiber in less than one hour, at room temperature and atmospheric pressure. The volatile oil(s) are liquid at room temperature and have a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 0.13 Pa to 40 000 Pa (10-3 to 300 mmHg). The term “non-volatile oil” relates to oil which remains on the skin or the keratin fiber, at room temperature and atmospheric pressure, for at least several hours and which in particular has a vapor pressure of less than 10-3 mmHg (0.13 Pa).


The term “fluoro oil” relates to oil comprising at least one fluorine atom. The term “hydrocarbon-based oil” relates to oil comprising mainly hydrogen and carbon atoms. Hydrocarbon-based oil may be animal hydrocarbon-based oil, plant hydrocarbon-based oil, mineral hydrocarbon-based oil or a synthetic hydrocarbon-based oil. Further, suitable oil may be a mineral hydrocarbon-based oil, a plant hydrocarbon-based oil, or a synthetic hydrocarbon-based oil.


Fluoro Oils


The one or more fluoro oil may be selected from the group consisting of perfluoromethylcyclopentane, perfluoro-1,3-dimethylcyclohexane, dodecafluoropentane, tetradecafluorohexane, bromoperfluorooctyl, nonafluoromethoxybutane, nonafluoroethoxyisobutane and 4-trifluoromethylperfluoromorpholine. Volatile fluoro oils, such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, may also be used.


Hydrocarbon-Based Oils


The one or more hydrocarbon-based oils may be a saturated hydrocarbon, an unsaturated hydrocarbon, lipids, triglycerides, a natural oil, and/or a synthetic oil. In some embodiments, the compositions include a synthetic oil selected from the group consisting of hydrogenated polyisobutene and hydrogenated polydecene.


The hydrocarbon-based oil may be a non-volatile hydrocarbon-based, such as:


(i) hydrocarbon-based oils of plant origin, such as glyceride triesters, which are generally triesters of fatty acids and of glycerol, the fatty acids of which can have varied chain lengths from C4 to C24, it being possible for these chains to be saturated or unsaturated and linear or branched; these oils are in particular wheat germ oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin seed oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, and musk rose oil.


(ii) synthetic ethers containing from 10 to 40 carbon atoms;


(iii) linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, and 4 0 squalane;


(iv) synthetic esters, for instance oils of formula RCOOR′ in which R represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R′ represents a hydrocarbon-based chain that is especially branched, containing from 1 to 40 carbon atoms on condition that R+R′ is 10, for instance Purcellin oil (cetearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoate, such as the product sold under the trade name Finsolv TN® or Witconol TN® by Witco or Tegosoft TN® by Evonik Goldschmidt, 2-ethylphenyl benzoate, such as the commercial product sold under the name X-Tend 226 by ISP, isopropyl lanolate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate, such as the product sold under the name of “Dub Dis” by Stearinerie Dubois, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, such as propylene glycol dioctanoate; hydroxylated esters, such as isostearyl lactate or diisostearyl malate; and pentaerythritol esters; citrates or tartrates, such as di(linear C12-C13 alkyl) tartrates, such as those sold under the name Cosmacol ETI by Enichem Augusta Industriale, and also di(linear C14-C15 alkyl) tartrates, such as those sold under the name Cosmacol ETL® by the same company; or acetates;


(v) fatty alcohols that are liquid at room temperature, containing a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol or 2-undecylpentadecanol;


(vi) higher fatty acids, such as oleic acid, linoleic acid or linolenic acid;


(vii) carbonates, such as dicaprylyl carbonate, such as the product sold under the name Cetiol CC by Cognis;


(viii) fatty amides, such as isopropyl N-lauroyl sarcosinate, such as the product sold under the trade name Eldew SL 205@ from Ajinomoto; and


(ix) essential oils selected from the group consisting of sunflower oil, sesame oil, peppermint oil, macadamia nut oil, tea tree oil, evening primrose oil, sage oil, rosemary oil, coriander oil, thyme oil, pimento berries oil, rose oil, anise oil, balsam oil, bergamot oil, rosewood oil, cedar oil, chamomile oil, sage oil, clary sage oil, clove oil, cypress oil, eucalyptus oil, fennel oil, sea fennel oil, frankincense oil, geranium oil, ginger oil, grapefruit oil, jasmine oil, juniper oil, lavender oil, lemon oil, lemongrass oil, lime oil, mandarin oil, marjoram oil, myrrh oil, neroli oil, orange oil, patchouli oil, pepper oil, black pepper oil, petitgrain oil, pine oil, rose otto oil, rosemary oil, sandalwood oil, spearmint oil, spikenard oil, vetiver oil, wintergreen oil, and ylang ylang.


In certain instances, the non-volatile hydrocarbon-based oils are glyceride triesters and in particular to caprylic/capric acid triglycerides, synthetic esters and in particular isononyl isononanoate, oleyl erucate, C12-C15 alkyl benzoate, 2-ethylphenyl benzoate and fatty alcohols, such as octyldodecanol.


As volatile hydrocarbon-based oils, mention is made of hydrocarbon-based oils containing from 8 to 16 carbon atoms and in particular of branched C8-C16 alkanes, such as C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, the oils sold under the Isopar or Permethyl trade names, branched C C8-C16 esters, and isohexyl neopentanoate.


Organic Solvents


The hair-treatment compositions or second phase of the hair treatment compositions may optionally include at least one organic solvent (non-silicone solvents).


Non-limiting examples of organic solvents include, for example, glycerin, alcohols (for example, C1-15, C1-10, or C1-6 alcohols), organic solvents, polyols (polyhydric alcohols), glycols (e.g., butylene glycol, caprylyl glycol, etc.), and a mixture thereof.


Non-limiting examples of organic solvents include monoalcohols and polyols such as ethyl alcohol, isopropyl alcohol, propyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof such as, for example, monomethyl ether of propylene glycol, butylene glycol, hexylene glycol, dipropylene glycol as well as alkyl ethers of diethylene glycol, for example monoethyl ether or monobutyl ether of diethylene glycol. Other suitable examples of organic solvents are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propane diol, and glycerin. The organic solvents can be volatile or non-volatile compounds.


Further non-limiting examples of organic solvents include alkanediols such as glycerin, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, (caprylyl glycol), 1,2-hexanediol, 1,2-pentanediol, and 4-methyl-1,2-pentanediol; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-iso-propyl ether; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetine, diacetine, triacetine, sulfolane, and a mixture thereof.


Polyhydric alcohols are useful. Examples of polyhydric alcohols include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and a mixture thereof. Polyol compounds may also be used. Non-limiting examples include the aliphatic diols, such as 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1,2-diol, and 2-ethyl-1,3-hexanediol, and a mixture thereof.


The total amount organic solvent(s) in the second phase or hair treatment composition, if present, can vary but is typically about 0.1 to about 10 wt. %, based on the total weight of the second phase or hair treatment composition. In some cases, the total amount of water-soluble solvent(s) is about 0.1 to about 8 wt. %, about 0.1 to about 6 wt. %, about 0.1 to about 0.5 to about 10 wt. %, about 0.5 to about 8 wt. %, about 0.5 to about 6 wt. %, about 0.5 to about 5 wt. %, about 1 wt. %, about 2 wt. %, about 3 wt. %, or about 4 wt. %, including all ranges and subranges there between.


In an embodiment, the second phase is substantially free of water.


Other Components


In one or more embodiments, the hair treatment compositions and first and second phases described herein may contain one or more additional ingredients. Examples include, but are not limited to oils (natural or plant-based or synthetic, non-silicone oils), surfactants, emulsifiers, cationic conditioning agents, aminosilicones, non-silicone organic solvents, film formers, other polymers, fragrance and preservatives. Additional details regarding such additional ingredients follows below.


Preservatives


One or more preservatives may be included in the compositions and phases described herein for treating hair. Suitable preservatives include, but are not limited to, glycerin containing compounds (e.g., glycerin or ethylhexylglycerin or phenoxyethanol), benzyl alcohol, parabens (methylparaben, ethylparaben, propylparaben, butylparaben, isobutylparaben, etc.), sodium benzoate, ethylenediamine-tetraacetic acid (EDTA), potassium sorbate, and/or grapefruit seed extract, or combinations thereof. More than one preservative may be included in the composition. Other preservatives are known in the cosmetics industries and include salicylic acid, DMDM Hydantoin, Formaldahyde, Chlorphenism, Triclosan, Imidazolidinyl Urea, Diazolidinyl Urea, Sorbic Acid, Methylisothiazolinone, Sodium Dehydroacetate, Dehydroacetic Acid, Quaternium-15, Stearalkonium Chloride, Zinc Pyrithione, Sodium Metabisulfite, 2-Bromo-2-Nitropropane, Chlorhexidine Digluconate, Polyaminopropyl biguanide, Benzalkonium Chloride, Sodium Sulfite, Sodium Salicylate, Citric Acid, Neem Oil, Essential Oils (various), Lactic Acid, and Vitamin E (tocopherol).


The total amount of the one or more preservatives, when present, may vary. In some cases, the total amount of the one or more preservatives is about 0.01 to about 5 wt. %, about 0.01 to about 4 wt. %, about 0.15 to about 1 wt. %, or about 1 to about 3 wt. %, based on the total weight of the composition.


Emulsifiers


Emulsifiers as referred to herein, may also include co-emulsifiers. Emulsifiers may be chosen from nonionic surfactants such as alkoxylated fatty alcohols, fatty alcohols, polygylcerol esters of fatty acids, alkyl polyglycosides, polysorbates, amino acid emulsifiers, and alkyl amine oxides.


Suitable components, such as those listed in the instant disclosure (including those listed above), may be included or excluded from the hair styling compositions depending on the specific combination of other components, the form of the compositions, and/or the use of the formulation (e.g., hair spray, cream, paste, conditioner, etc.).


Ratio of First Phase to Second Phase


In forming the hair treatment composition or system, the first phase (aqueous) can be combined with the second phase (oil) in a weight ratio ranging from about 2:0.5 to about 5:1 or from about 2:1 to about 4:1 or from about 2:1 to about 3:1, including all ranges and sub-ranges therebetween.


Methods


Another aspect of the invention pertains to methods of using the hair treatment compositions described herein. The methods generally comprise applying any of the hair treatment compositions described to hair. The hair treatment compositions may be useful in a variety of settings, and either for treated or untreated hair. Use on treated hair can include chemically relaxed hair. The hair treatment composition may be applied post relaxer but before neutralizing shampoo, after neutralizing shampoo, in or as a conditioner, or as a leave in treatment after the relaxation process. Use on untreated hair may include as part of a shampoo, part of a conditioner, as a pre-treatment, or after washing the hair as a leave-in treatment.


Methods of treating hair according to the disclosure may include applying a hair treatment composition of the instant disclosure to the hair (wet, damp, or dry hair), allowing the hair treatment to remain on the hair for a sufficient amount of time, and rinsing the hair treatment composition from the hair. The hair treatment composition may be applied to the hair before, during, or after other hair treatment compositions (e.g., a chemical relaxer composition, a shampoo, a conditioner, a lotion, a gel, etc.).


As mentioned previously, the hair treatment compositions are particularly useful for treating chemically treated hair. In some cases, a hair treatment composition is applied to the hair shortly after a chemical treatment composition is rinsed from the hair (e.g., within about 5, 10, 15, 20, or 30 minutes from when the chemical treatment composition is rinsed from the hair), while the hair is still wet or damp. The hair treatment composition may be allowed to remain on the hair for a period of time, for example from about a few seconds (1, 3, 5, or 10 seconds) to about 10, 20, or 30 minutes, or longer. In some cases, the hair treatment composition is applied to the chemically treated hair shortly after a chemical treatment composition is rinsed from the hair; and after applying the hair treatment composition, the hair is subsequently treated with a shampoo and/or a conditioner, or a conditioning shampoo (all-in-one shampoo/conditioner). The hair treatment composition may be rinsed from the hair prior to application of a shampoo and/or a conditioner, or a conditioning shampoo, or it may be allowed to remain on the hair during shampooing and/or conditioning and rinsed from the hair with the shampoo or the conditioner, or with the conditioning shampoo. For example, the hair treatment composition may be applied to the hair and without rinsing the hair treatment from the hair, a shampoo (or conditioner or conditioning shampoo) is subsequently applied to the hair (layered onto the hair treatment composition already applied to the hair). Both compositions (the hair treatment composition and the shampoo, conditioner, or conditioning shampoo) are rinsed from the hair together.


Moreover, the hair treatment composition may be combined with a shampoo and/or a conditioner, or with a conditioning shampoo, prior to application to the hair. Combining the hair treatment compositions with one or more additional hair treatment compositions (e.g., a shampoo, a conditioner, a conditioning shampoo, a rinse, etc.). For instance, the hair treatment composition may be mixed with a shampoo (or conditioner or conditioning shampoo) prior to application to the hair. In this case, the mixture of the shampoo (or conditioner or conditioning shampoo) and the hair treatment composition are simultaneously applied to the hair during the cleansing and/or conditioning process and simultaneously rinsed from the hair. Alternatively, the hair treatment composition may be layered on top of (or lathered into) hair to which a shampoo (or conditioner or conditioning shampoo) has already been applied or vice versa. In this case, the hair treatment composition may be applied to the hair first and without rinsing it from the hair, a shampoo (or conditioner or conditioning shampoo) is then subsequently applied to the hair. Alternatively, the shampoo (or conditioner or conditioning shampoo) may be first applied to the hair and without rinsing the shampoo (or conditioner or conditioning shampoo) from the hair, the hair treatment composition is also applied to the hair. Then, the compositions are simultaneously rinsed from the hair.


Described above is the individual application of a hair treatment composition or the combined or layered application of a hair treatment composition with another composition (e.g., a shampoo, conditioner, conditioning shampoo, etc.). In some cases, a hair treatment composition is individually applied to the hair and also combined or layered with another composition (e.g., a shampoo, conditioner, conditioning shampoo, etc.) that is also applied to the hair. For example, a hair treatment composition may be applied to the hair. Subsequently, with or without rinsing the hair treatment composition from the hair, another composition (e.g., a shampoo, conditioner, conditioning shampoo, etc.) in which the hair treatment composition has been mixed may be applied to the hair.


When combined with another composition (e.g., a shampoo, conditioner, conditioning shampoo, etc.), the hair treatment composition may be mixed with or used with in a ratio of about 1:10 to about 10:1, about 1:5 to about 5:1, about 1:3 to about 3:1, about 1:2 to about 2:1, about 1:1 to about 4:1, about 1:1 to about 3:1, or about 1:1 to about 2:1 (hair treatment composition of the instant disclosure:another composition).


The hair treatment compositions may be allowed to remain on the hair for a minimum amount of time before being rinsed from the hair, but allowing the hair treatment composition to remain on the hair for an extended period of time is not needed. Conveniently, the hair treatment compositions can be applied and allowed to remain on the hair for a period of time that is typical for regular shampooing and/or conditioning. For example, the hair treatment composition (whether combined with another hair treatment composition such as a shampoo or conditioner) may be applied to the hair and allowed to remain on the hair for a few seconds (1, 2, 3, 5, or 10 seconds) up to about 1, 2, 5, 10, 20, or 30 minutes, or longer.


When the hair treatment composition is not applied to the hair, simultaneously with another composition (e.g., a shampoo, conditioner, conditioning shampoo, etc.), the hair treatment composition may be applied to the hair immediately after or before the hair is treated with another composition (e.g., a shampoo, conditioner, conditioning shampoo, etc.). For example, the hair treatment compositions may be applied to the hair within about 1, 2, 5, 10, or 20 minutes before or after another composition is applied to the hair.


Kits


The hair treatment compositions of the instant disclosure may be incorporated into a kit. For example, the kits may include at least one hair treatment composition according to the instant disclosure or the aqueous phase and the oil phase according to the instant disclosure as separate components and one or more additional hair treatment compositions, for example, a hair relaxer composition, a shampoo, a conditioner, etc.


The various hair treatment compositions and/or the aqueous phase and oil phase according to the instant disclosure are separately contained in the kits. In some instances, the kits include one or more hair treatment compositions (according to the instant disclosure) or the aqueous phase and the oil phase according to the instant disclosure, a shampoo, and/or a conditioner, all of which are separately contained. The kits may also include one or more hair treatment compositions (according the instant disclosure) or the aqueous phase and the oil phase according to the instant disclosure, a chemical relaxer composition, and optionally a shampoo and/or a conditioner. Instructions, mixing components, brushes, gloves, measuring tools, etc., may also be included in the kits.


Implementation of the present disclosure is provided by way of the following examples. The examples serve to illustrate the technology without being limiting in nature.


EXAMPLES

The following Examples are intended to be non-restrictive and explanatory only. The ingredient amounts in the compositions/formulas described below are expressed in % by weight, based on the total weight of the composition.


Several formulas were produced having the ingredients as listed in the tables below. The balance of all formulas was water.


Example I: Composition










TABLE 1






US INCI NAME OF
Formula X



INGREDIENTS
Wt. % (Active)

















First Phase A
MALEIC ACID
1.3


(aqueous)
ETHANOLAMINE
0.68



AMINOPROPYL
1.88



TRIETHOXYSILANE




POLYQUATERNIUM-6
0.3



DIPROPYLENE GLYCOL
0.23



HEXYLENE GLYCOL
1.13



BUTYLENE GLYCOL
1.13



CAPRYLYL GLYCOL
0.4



PHENOXYETHANOL
0.6



WATER
67.8


Second Phase B (oil)
POLYSILICONE-29
0.08



CYCLOPENTASILOXANE
21.5



DIMETHICONOL
1.7



OLEA EUROPAEA (OLIVE)
1.3



FRUIT OIL









Example II: In Viva Testing (on Hair Swatches)

Samples of various formulations of the aqueous phase, the oil phase, and the aqueous and oil phases together were tested on hair swatches to. The samples were applied onto hair swatches and the treated swatches were then placed in a humidity chamber for 24 hours at 25° C. and 80% relative humidity. Each swatch was visually and sensorially assessed and the width of each swatch at the middle and bottom (cm) using a digital caliper was measured. The width measurements can be correlated with the degree of frizziness. The measurements can also be correlated to the spread of the hair which could indicate the volumized or poofy (puffed up) appearance of the hair. However, it should be noted that the hair can have less spread or width but at the same time, visually exhibit frizziness.


Example IIA: Phases








TABLE 2







Aqueous (Water) Phases










US INCI NAME OF



Aqueous Phase
INGREDIENTS
Wt. % (Active)





A
Polyquaternium-6
0.40%



Aminopropyl triethoxysilane
2.50%



Deionized Water
QS 100%


B
Hexylene Glycol
1.50%



Butylene Glycol
1.50%



Deionized Water
QS 100%


C
Maleic Acid
 1.8%



Ethanolamine
0.90%



Deionized Water
QS 100%


D
Polyquaternium-6
0.40%



Aminopropyl triethoxysilane
2.50%



Hexylene Glycol
1.50%



Butylene Glycol
1.50%



Deionized Water
QS 100%


E
Polyquaternium-6
0.40%



Aminopropyl triethoxysilane
2.50%



Maleic Acid (30% Solution)
 1.8%



Ethanolamine
0.90%



Deionized Water
QS 100%


F
Polyquaternium-6
0.40%



Aminopropyl triethoxysilane
2.50%



Maleic Acid
1.80%



Ethanolamine
0.90%



Hexylene Glycol
1.50%



Butylene Glycol
1.50%



Deionized Water
Q.S. 100% 


G
Maleic Acid
1.80%



Ethanolamine
0.90%



Hexylene Glycol
1.50%



Butylene Glycol
1.50%



Deionized Water
QS 100%










The process of making the aqueous phase was as follows:


a. Add water to beaker; begin mixing using a Rayneri mixer with propeller blade attachment.


b. Add each raw material or ingredient, one at a time. Mix well between each addition.









TABLE 3







Oil Phases









Oil Phase
US INCI NAME OF INGREDIENTS
Wt. % (Active)





H1
DIMETHICONOL
6.8%



CYCLOPENTASILOXANE
86.2% 



(100% active)




Polysilicone-29
0.3%



Olive Oil (100% active)
  5%



Dipropylene glycol
0.9%



Water
0.8%



Total
100.00%  


H2
DIMETHICONOL
7.2%



CYCLOPENTASILOXANE
90.8% 



Polysilicone-29
0.15% 



Olive Oil
  1%



Dipropylene glycol
0.45% 



Water
0.4%



Total
100% 


H3
DIMETHICONOL
7.2%



CYCLOPENTASILOXANE
90.8% 



Olive Oil
  2%



Total
100% 










The process of making the oil phase was as follows:


a. Add each RM one at a time while mixing using a Rayneri mixer with propeller blade attachment.


Example IIB: Assessments of Hair Swatches

Hair Treatment Protocol:


Each test swatch (Caucasian Curl Type 4) was treated according to the following:






    • 1. The swatch was shampooed with a convention cleansing shampoo by lathering the shampoo on the hair for 30 seconds (1 ml per 2.5 gram hair swatch); the swatch was then rinsed with water.

    • 2. Excess water was removed by running the fingers through the hair.

    • 3. Each treatment was applied on the shampooed swatch and carefully worked through the hair (bi-phase treatment=1 g/2.5 g swatch; aqueous phase treatment=0.75 g/2.5 g swatch; oil phase treatment=0.25 g/2.5 g swatch.

    • 4. The swatches were allowed to air dry.












TABLE 4







Assessment of Hair Treated with Oil Phase and Control









BEFORE HUMIDITY

%


EXPOSURE(DRY)
AFTER HUMIDITY EXPOSURE*
CHANGE**










Oil Phase only, Control H2









1.6 cm (m)
2.4 cm (m)
50.0%


1.9 cm (b)
2.7 cm (b)
42.1%







Hair appeared and felt greasy


Control, Z (cleansed swatch; no treatment)









5.7 cm (m)
7.1 cm (m)
24.6%


4.9 cm (b)
8.1 cm (b)
65.3%







Very frizzy





*All swatches were placed in humidity chamber for 24 hours, at 25° C. and 80% relative humidity


**percent change is calculated by taking the difference in width measurements of each swatch before and after humidity exposure divided by the width measurement before humidity exposure













TABLE 5







Assessment of Hair Treated with Aqueous Phase Only


(from Table 2); Comparison of Various


formulations of the Aqueous Phase and to Control









BEFORE HUMIDITY
AFTER HUMIDITY
%


EXPOSURE(DRY)
EXPOSURE*
CHANGE**










I (Aqueous Phase A)









2.6 cm (m)
4.5 cm (m)
73.1%


2.7 cm (b)
4.0 cm (b)
48.1%


A little crunchy; sealed ends
A little stiff; sealed




ends and less poofy***




than Z/J/K








J (Aqueous Phase B)









3.9 cm (m)
5.7 cm (m)
46.2%


4.6 cm (b)
5.9 cm (b)
28.3%


Frizzy, poofy***; ends not
Natural feel but frizzy



sealed









K (Aqueous Phase C)









4.2 cm (m)
5.2 cm (m)
23.8%


3.3 cm (b)
4.8 cm (b)
45.5%


A little stiff; I better
Sealed ends and natural



than K and K better
feel but frizzy



than J (frizz-wise).









L (Aqueous Phase D)









2.5 cm (m)
3.0 cm (m)
20.0%


2.0 cm (b)
4.1 cm (b)
100+% 


A little crunchy; very
A little stiff



sleek; sealed ends









M (Aqueous Phase E)









2.6 cm (m)
4.9 cm (m)
88.5%


2.6 cm (b)
5.4 cm (b)
100+% 


A little crunchy; ends




are almost sealed; good




visual appearance









N (Aqueous Phase F)









2.6 cm (m)
3.0 cm (m)
15.3%


2.5 cm (b)
3.4 cm (b)
36.0%


A little crunchy;
Least frizzy and poofy;



sealed ends.
sealed ends; nice



Best visual appearance -
curl pattern



good frizz control with
Best visual appearance;



nice curl pattern and
gave the best shine



volume









O (Aqueous Phase G)









3.7 cm (m)
6.1 cm (m)
64.8%


4.2 cm (b)
6.4 cm (b)
52.3%


More natural feel;
Very frizzy



sealed ends; less




frizz control than N





*All swatches were placed in humidity chamber for 24 hours, at 25° C. and 80% relative humidity


**percent change is calculated by taking the difference in width measurements of each swatch before and after humidity exposure divided by the width measurement before humidity exposure


***poofy means puffed up or having too much volume or more spread out







Summary of Table 5 results: Treatment N (aqueous phase F) resulted in the lowest percent change in the width of the middle section of the swatch compared to the other treatments. Also, Treatment N (aqueous phase F) resulted in the lowest percent change in the width of the bottom section of the swatch compared to the other treatments, except for Treatment J. Treatment J had the lowest percent change in width but the treated swatch exhibited more frizziness compared to the swatch treated with Treatment N.









TABLE 6







Assessment of Hair Treated with Bi-phase (Oil Phase, H2, and Aqueous


Phase from Table 2; (25% oil phase, 75% Aqueous Phase)


Comparison of Various Combinations of the Aqueous Phase and the Oil Phase









BEFORE HUMIDITY
AFTER HUMIDITY
%


EXPOSURE(DRY)
EXPOSURE*
CHANGE**










Bi-Phase A









2.9 cm (m)
3.7 cm (m)
27.6%


1.4 cm (b)
2.6 cm (b)
85.7%


crunchy
crunchy








Bi-Phase B









4.2 cm (m)
5.6 cm (m)
33.3%


4.5 cm (b)
5.7 cm (b)
26.7%


Ends are not sealed
Very frizzy, poofy and with




fly-aways)








Bi-Phase C









4.6 cm (m)
5.0 cm (m)
 8.7%


3.4 cm (b)
4.1 cm (b)
20.6%



Less poofy than B but frizzy








Bi-Phase D









1.6 cm (m)
2.5 cm (m)
56.3%


1.2 cm (b)
2.6 cm (b)
100+% 


Crunchy
A little crunchy; ends are apart








Bi-Phase E









4.1 cm (m)
5.0 cm (m)
21.9%


3.5 cm (b)
4.5 cm (b)
28.6%


Stiff
A little stiff; poofy








Bi-Phase F (invention)









2.8 cm (m)
3.8 cm (m)
35.7%


2.7 cm (b)
4.1 cm (b)
51.9%


A little stiff.
Still has shine; nice curl



Best visual appearance;
pattern.



more shine
Best visual appearance; more




shine








Bi-Phase G









5.1 cm (m)
5.8 cm (m)
13.7%


5.3 cm (b)
6.8 cm (b)
28.3%


Ends not sealed
Seems to be the most poofy





*All swatches were placed in humidity chamber for 24 hours, at 25° C. and 80% relative humidity


**percent change is calculated by taking the difference in width measurements of each swatch before and after humidity exposure divided by the width measurement before humidity exposure


***poofy means puffed up or having too much volume or more spread out







Summary of Table 6 results: Treatment with the bi-phase treatment F resulted in a best visual appearance of the hair, more shine, very good curl pattern, and curl definition as compared to the hair treated with the other treatments, even if the percent change in width could have been higher compared to some of the other treatments which produced one or more of the less desirable effects such as stiffness, crunchiness, unsealed ends of the hair, more frizziness, too much volume and/or fly-aways at the ends, even when the percent change in width was less. This is evident from the images presented in FIGS. 1A and 1B and in FIG. 2 which shows swatches treated with Treatments H2 (oil phase), N (aqueous phase), and F (biphase—combination of oil phase H2 and aqueous phase N).


In particular, while some of the treatments showed lower percent changes in the width of the swatches compared to bi-phase treatment F, the swatches visually appeared to be very frizzy. For example, the percent changes for the swatches treated with the combination of the aqueous phase C, with an oil phase, H2, (Bi-Phase Treatment C) were lower compared to other percent changes but the swatches were visually found to be very frizzy.


Conclusion: It was found that while some swatches treated with the aqueous phases alone had less poofiness or less width, the treatments with the aqueous phases did not provide enough shine to the hair and the hair swatches generally felt more dry to the touch. On the other hand, while the treatment with the oil phase alone (Control H2) could provide shine to hair, treatment with the oil phase alone did not necessarily reduce the width of the swatches (% changes of 42 to 50%) and made the hair feel and look greasy. By combining the oil phase H with the aqueous phase N to form the bi-phase treatment F, the inventors discovered that the bi-phase treatment reduced the hair crunchiness, smoothened the flyaways, and provided shine, a very good curl pattern, curl definition, and the best visual appearance among all the swatches treated with the bi-phase compositions. At the same time, it was found that bi-phase treatment F provided softness to the hair. When swatch treated with the invention (bi-phase treatment F) exhibited the best visual appearance with respect to curl patterns, curl definition, and frizz control as compared to the swatches treated with Control, Z, oil phase H2 alone, and aqueous phase N alone (see FIG. 2).


In addition, the inventors surprisingly discovered that the cosmetic attributes provided by bi-phase treatment F such as frizz control and curl pattern and curl definition lasted even after exposing the hair to high humidity conditions, thereby conferring humidity-resistant properties to hair.


Thus, the combination of ingredients in the aqueous phase and in the oil phase to form bi-phase treatment F plus the right balance of the amount of the aqueous phase and of the oil phase resulted in the best overall performance by bi-phase treatment F with respect to the visual and sensorial attributes.


Example IV Performance Testing on Hair Swatches

Comparison of Swatches after 24 Hours at 80% Relative Humidity













TABLE 7







Oil Phase,
Aqueous
Oil + Aqueous Phases


Attributes
Untreated
H2
Phase, F
(Bi-Phase F)







Anti-Frizz

+++
++
+++


Long-Lasting

++
++
+++


Natural Feel
+++
+
+
+++


Shine

+++
++
+++


Smoothness

+++
++
+++


Curl

++
+++
+++


Definition






Lightweight

+
+++
+++





Key


− Unfavorable


+ Ok


++ Good


+++ Very good






The results in Table 7 above show that the swatches treated with the bi-phase treatment F had very good ratings with respect to all the attributes tested, which include visual and sensorial attributes, even after exposing the hair to high humidity conditions.


The foregoing description illustrates and describes the invention. The disclosure shows and describes only the preferred embodiments but it should be understood that the invention is capable to use in various other combinations, modifications, and environments and is capable of changes or modifications within the scope of the inventive concepts as expressed herein, commensurate with the above teachings and/or the skill or knowledge of the relevant art. The embodiments described herein above are further intended to explain best modes known by applicant and to enable others skilled in the art to utilize the disclosure in such, or other, embodiments and with the various modifications required by the particular applications or uses thereof. Accordingly, the description is not intended to limit the invention to the form disclosed herein.


As used herein, the terms “comprising,” “having,” and “including” (or “comprise,” “have,” and “include”) are used in their open, non-limiting sense. The phrase “consisting essentially of” limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristics of the claimed invention.


The terms “a,” “an,” and “the” are understood to encompass the plural as well as the singular.


Thus, the term “a mixture thereof” also relates to “mixtures thereof.” Throughout the disclosure, if the term “a mixture thereof” is used, following a list of elements as shown in the following example where letters A-F represent the elements: “one or more elements selected from the group consisting of A, B, C, D, E, F, or mixtures thereof.” The term, “a mixture thereof” does not require that the mixture include all of A, B, C, D, E, and F (although all of A, B, C, D, E, and F may be included). Rather, it indicates that a mixture of any two or more of A, B, C, D, E, and F can be included. In other words, it is equivalent to the phrase “one or more elements selected from the group consisting of A, B, C, D, E, F, and a mixture of any two or more of A, B, C, D, E, and F.”


Likewise, the term “a salt thereof” also relates to “salts thereof.” Thus, where the disclosure refers to “an element selected from the group consisting of A, B, C, D, E, F, a salt thereof, or mixtures thereof,” it indicates that that one or more of A, B, C, D, and F may be included, one or more of a salt of A, a salt of B, a salt of C, a salt of D, a salt of E, and a salt of F may be included, or a mixture of any two of A, B, C, D, E, F, a salt of A, a salt of B, a salt of C, a salt of D, a salt of E, and a salt of F may be included.


The salts referred to throughout the disclosure may include salts having a counterion such as an alkali metal, alkaline earth metal, or ammonium counterion. This list of counterions, however, is non-limiting.


The expression “one or more” means “at least one” and thus includes individual components as well as mixtures/combinations.


The term “plurality” means “more than one” or “two or more.”


Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions can be modified in all instances by the term “about,” meaning within +/−1%, 2%, 3%, 4%, or 5% of the indicated number.


Some of the various categories of components identified for the hair-treatment compositions may overlap. In such cases where overlap may exist and the composition/product includes two overlapping components (or more than two overlapping components), an overlapping component does not represent more than one component. For example, a fatty acid may be defined as both a “fatty compound” and a “surfactant/emulsifier.” If a particular composition/product includes both a fatty compound component and an emulsifier component, a single fatty acid can serve as only a fatty compound or a surfactant/emulsifier (a single fatty acid does not serve as both the fatty compound and the surfactant/emulsifier).


All percentages, parts and ratios herein are based upon the total weight of the compositions of the present invention, unless otherwise indicated.


All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc. Furthermore, all ranges provided are meant to include every specific range within, and combination of sub-ranges between, the given ranges. Thus, a range from 1-5, includes specifically points 1, 2, 3, 4 and 5, as well as sub-ranges such as 2-5, 3-5, 2-3, 2-4, 1-4, etc.; and points of 1, 2, 3, 4, and 5 includes ranges and sub-ranges of 1-5, 2-5, 3-5, 2-3, 2-4, 1-4, etc.


All numbers herein are understood to be modified by “about,” whether or not expressly stated. Additionally, all numbers are intended to represent exact figures as additional embodiments, whether or not modified by “about.” For example, “an amount of about 1%” includes an amount of exactly 1%. As a further example, “an amount of 1%” includes an amount of about 1%. The term “about” is generally understood to encompass a range of +/−10% from the stated number, and is intended to cover amounts of +/−1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, and 10%.


The term “surfactants” includes salts of the surfactants even if not explicitly stated. In other words, whenever the disclosure refers to a surfactant, it is intended that salts of the surfactant are also encompassed to the extent such salts exist, even though the specification may not specifically refer to a salt (or may not refer to a salt in every instance throughout the disclosure), for example, by using language such as “a salt thereof” or “salts thereof.” Sodium and potassium are common cations that form salts with surfactants. However, additional cations such as ammonium ions, or alkanolammonium ions such as monoethanolammonium or triethanolammonium ions, may also form salts of surfactants.


The term “substantially free” or “essentially free” as used herein means the specific material may be present in small amounts that do not materially affect the basic and novel characteristics of the claimed invention. For instance, there may be less than 2% by weight of a specific material added to a composition, based on the total weight of the compositions (provided that an amount of less than 2% by weight does not materially affect the basic and novel characteristics of the claimed invention. Similarly, the compositions may include less than 2 wt %, less than 1.5 wt %, less than 1 wt %, less than 0.5 wt %, less than 0.1 wt %, less than 0.05 wt %, or less than 0.01 wt %, or none of the specified material. Furthermore, all components that are positively set forth in the instant disclosure may be negatively excluded from the claims, e.g., a claimed composition may be “free,” “essentially free” (or “substantially free”) of one or more components that are positively set forth in the instant disclosure.


All publications and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. In the event of an inconsistency between the present disclosure and any publications or patent application incorporated herein by reference, the present disclosure controls.

Claims
  • 1. A hair treatment composition comprising: (a) a first phase comprising: at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof, and a mixture thereof;at least one amine selected from diamines, polyamines, alkylamines, alkanolamines, and a mixture thereof;at least one cationic polymer;at least one alkoxysilane selected from 3-mercaptopropyltriethoxysilane and/or 3-aminopropyltriethoxysilane;at least one polyol; andwater;and(b) a second phase comprising: Polysilicone-29; andat least one silicone oil;wherein the weight ratio of the first phase (a) to the second phase (b) ranges from about 2:0.5 to about 5:1.
  • 2. The hair treatment composition of claim 1, wherein the at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof, is a dicarboxylic acid and/or a salt thereof.
  • 3. The hair treatment composition of claim 2, comprising at least one dicarboxylic acid and/or a salt thereof, selected from oxalic acid, malonic acid, malic acid, glutaric acid, citraconic acid, succinic acid, adipic acid, tartaric acid, fumaric acid, maleic acid, sebacic acid, azelaic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, their salts thereof, and a mixture thereof.
  • 4. The hair treatment composition of claim 3, wherein the at least one dicarboxylic acid and/or a salt thereof is maleic acid, malonic acid, and/or a salt thereof, and a mixture thereof.
  • 5. The hair treatment composition of claim 2, comprising at least one tricarboxylic acid and/or a salt thereof, wherein the at least one tricarboxylic acid and/or a salt thereof is selected from citric acid, isocitric acid, aconitric acid, propane-1,2,3-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, their salts thereof, and a mixture thereof.
  • 6. The hair treatment composition of claim 5, wherein the at least one tricarboxylic acid and/or a salt thereof is citric acid, and a mixture thereof.
  • 7. The hair treatment composition of claim 1 the at least one non-polymeric mono, di, or tricarboxylic acid and/or a salt thereof, is present in an amount of at least 0.5 to about 20 wt. % based on the total weight of the first phase of the hair treatment composition.
  • 8. The hair treatment composition of claim 1 comprising at least one amine including one or more alkylamines and/or alkanolamines selected from the compounds of formula (II): NR3R4R5   (II)wherein R3, R4 and R5 are independently H, C1-C40 alkyl, C1-C40 monohydroxyalkyl or C2-C40 polyhydroxyalkyl, provided that at least one of R3, R4 and R5 is an alkyl or mono or polyhydroxyalkyl.
  • 9. The hair treatment composition of claim 8 comprising one or more alkanolamines selected from monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylamino-ethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethylamino)methane, and a mixture thereof.
  • 10. The hair treatment composition of claim 9 comprising monoethanolamine.
  • 11. The hair treatment composition of claim 1, wherein the at least one amine is present in an amount of about 0.1 to about 20 wt. %, based on the total weight of the first phase of the hair treatment composition.
  • 12. The hair treatment composition of claim 1, wherein the at least one cationic polymer is selected from poly(methacryloyloxyethyl trimethylammonium chloride), polyquaternium-37, quaternized cellulose derivatives, polyquaternium-4, polyquaternium-6, polyquaternium-10, polyquaternium-11, cationic alkyl polyglycosides, cationized honey, cationic guar derivatives, polymeric dimethyl diallyl ammonium salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid, copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, vinyl pyrrolidone-vinyl imidazolium methochloride copolymers, quaternized polyvinyl alcohol, polyquaternium-2, polyquaternium-7, polyquaternium-17, polyquaternium-18, polyquaternium-24, polyquaternium-27, polyquaternium-72, and a mixture thereof.
  • 13. The hair treatment composition of claim 12, wherein the at least one cationic polymer is polyquaternium-6.
  • 14. The hair treatment composition of claim 1, wherein the at least one cationic polymer is present in an amount of about 0.01 to about 10 wt. %, based on the total weight of the first phase of the hair treatment composition.
  • 15. The hair-treatment composition of claim 1, wherein the at least one alkoxysilane is present in an amount of about 0.1 to about 20 wt. %, based on the total weight of the first phase of the hair-treatment composition.
  • 16. The hair treatment composition of claim 1, wherein the at least one polyol is selected from hexylene glycol, butylene glycol, propylene glycol, dipropylene glycol, caprylyl glycol, glycerin, and a mixture thereof.
  • 17. The hair treatment composition of claim 1, wherein the at least one polyol is present in an amount of about 0.1 to about 20 wt. %, based on the total weight of the first phase of the hair-treatment composition.
  • 18. The hair treatment composition of claim 1, wherein the Polysilicone-29 is present in an amount from about 0.01% to about 5% by weight, based on the total weight of the second phase of the hair treatment composition.
  • 19. The hair treatment composition of claim 1, wherein the at least one silicone oil is selected from polyalkylsiloxanes, polyarylsiloxanes, polyalkarylsiloxanes, polyestersiloxanes, polyphenylsiloxanes and a mixture thereof.
  • 20. The composition of claim 1, wherein the weight ratio of the first phase (a) to the second phase (b) ranges from about 2:1 to about 4:1.
  • 21. The composition of claim 1, wherein the composition has a bi-phasic appearance.
  • 22. The composition of claim 1, wherein the composition is in a spray form.
  • 23. The composition of claim 1, wherein the first phase or the second phase or both first and second phases are substantially free of emulsifiers.
  • 24. A hair treatment composition comprising: (a) a first phase comprising: about 0.6 to about 15 wt. % of at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof and a mixture thereof, including at least one dicarboxylic acid and/or a salt thereof;about 0.2 to about 15 wt. % of at least one amine including one or more alkanolamines selected from monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylamino-ethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethylamino)methane, and a mixture thereof;about 0.05 to about 8 wt. % of at least one cationic polymer selected from poly(methacryloyloxyethyl trimethylammonium chloride), polyquaternium-37, quaternized cellulose derivatives, polyquaternium-4, polyquaternium-6, polyquaternium-10, polyquaternium-11, cationic alkyl polyglycosides, cationized honey, cationic guar derivatives, polymeric dimethyl diallyl ammonium salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid, copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, vinyl pyrrolidone-vinyl imidazolium methochloride copolymers, quaternized polyvinyl alcohol, polyquaternium-2, polyquaternium-7, polyquaternium-17, polyquaternium-18, polyquaternium-24, polyquaternium-27, polyquaternium-72, and a mixture thereof;about 0.5 to about 15 wt. % of at least one alkoxysilane selected from 3-mercaptopropyltriethoxysilane and/or 3-aminopropyltriethoxysilane;about 0.5 to about 15 wt. % of at least one polyol selected from hexylene glycol, butylene glycol, and a mixture thereof; andat least 50 wt. % of water;and(b) a second phase comprising: Polysilicone-29;at least one silicone oil selected from cyclopentasiloxane, polydimethylsiloxane, and a mixture thereof;optionally, at least one non-silicone oil; andoptionally, at least one organic solvent selected from polyols, C2 to C8 monoalcohols, and a mixture thereof;wherein the weight ratio of the first phase (a) to the second phase (b) ranges from about 2:0.5 to about 5:1.
  • 25. A method of treating hair, the method comprising applying the composition of claim 1 to hair.
  • 26. A method of treating hair, the method comprising applying the composition of claim 24 to hair.
  • 27. A hair treatment system comprising: (a) a first phase comprising: at least one non-polymeric mono, di, or tricarboxylic acid, and/or a salt thereof, and a mixture thereof;at least one amine selected from diamines, polyamines, alkylamines, alkanolamines, and a mixture thereof;at least one cationic polymer;at least one alkoxysilane selected from 3-mercaptopropyltriethoxysilane and/or 3-aminopropyltriethoxysilane;at least one polyol; andwater;and(b) a second phase comprising: Polysilicone-29; andat least one silicone oil;wherein the first phase and the second phase are combined as one component, orwherein the first phase and the second phase are separate components;wherein the weight ratio of the first phase (a) to the second phase (b) ranges from about 2:0.5 to about 5:1.
US Referenced Citations (372)
Number Name Date Kind
2261002 Ritter Oct 1941 A
2271378 Searle Jan 1942 A
2273780 Dittmar Feb 1942 A
2375853 Kirby et al. May 1945 A
2388614 Kirby et al. Nov 1945 A
2454547 Bock et al. Nov 1948 A
2674580 Henkin Apr 1954 A
2850351 Moore et al. Sep 1958 A
2961347 Floyd Nov 1960 A
3142623 Zviak et al. Jul 1964 A
3193464 Edman et al. Jul 1965 A
3206462 McCarty Sep 1965 A
3227615 Korden Jan 1966 A
3288770 Butler Nov 1966 A
3412019 Hoover et al. Nov 1968 A
3472243 Wall et al. Oct 1969 A
3472840 Stone et al. Oct 1969 A
3589978 Kamal et al. Jun 1971 A
3632559 Matter et al. Jan 1972 A
3766267 Zak et al. Oct 1973 A
3840656 Kalopissis et al. Oct 1974 A
3874870 Green et al. Apr 1975 A
3917817 Vanlerberghe et al. Nov 1975 A
3929990 Green et al. Dec 1975 A
3966904 Green et al. Jun 1976 A
4001432 Green et al. Jan 1977 A
4003699 Rose et al. Jan 1977 A
4005193 Green et al. Jan 1977 A
4012398 Conner et al. Mar 1977 A
4013787 Vanlerberghe et al. Mar 1977 A
4025617 Green et al. May 1977 A
4025627 Green et al. May 1977 A
4025653 Green et al. May 1977 A
4026945 Green et al. May 1977 A
4027020 Green et al. May 1977 A
4031307 DeMartino et al. Jun 1977 A
4075136 Schaper Feb 1978 A
4131576 Iovine et al. Dec 1978 A
4166894 Schaper Sep 1979 A
4172887 Vanlerberghe et al. Oct 1979 A
RE30199 Rose et al. Jan 1980 E
4189468 Vanlerberghe et al. Feb 1980 A
4197865 Jacquet et al. Apr 1980 A
4217914 Jacquet et al. Aug 1980 A
4240450 Grollier et al. Dec 1980 A
4277581 Vanlerberghe et al. Jul 1981 A
4348202 Grollier et al. Sep 1982 A
4349532 Vanlerberghe et al. Sep 1982 A
4381919 Jacquet et al. May 1983 A
4412943 Hirota et al. Nov 1983 A
4422853 Jacquet et al. Dec 1983 A
4425132 Grollier et al. Jan 1984 A
4532950 Lang et al. Aug 1985 A
4579732 Grollier et al. Apr 1986 A
4591610 Grollier May 1986 A
4608250 Jacquet et al. Aug 1986 A
4734277 Login Mar 1988 A
4761273 Grollier et al. Aug 1988 A
4770873 Wolfram et al. Sep 1988 A
4772462 Boothe et al. Sep 1988 A
4777040 Grollier et al. Oct 1988 A
4793992 Mathews et al. Dec 1988 A
4793993 Siuta-Mangano et al. Dec 1988 A
4812307 Siuta-Mangano Mar 1989 A
4834971 Klenk et al. May 1989 A
4855130 Konrad et al. Aug 1989 A
4906460 Kim et al. Mar 1990 A
4948579 Jacquet et al. Aug 1990 A
4970066 Grollier et al. Nov 1990 A
5061289 Clausen et al. Oct 1991 A
5085860 Junino et al. Feb 1992 A
5091171 Yu et al. Feb 1992 A
5143518 Madrange et al. Sep 1992 A
5196189 Jacquet et al. Mar 1993 A
5221286 Singleton et al. Jun 1993 A
5293885 Darkwa et al. Mar 1994 A
5350572 Savaides et al. Sep 1994 A
5356438 Kim et al. Oct 1994 A
5380340 Neunhoeffer et al. Jan 1995 A
5534267 Neunhoeffer et al. Jul 1996 A
5565216 Cowsar et al. Oct 1996 A
5593662 Deckner et al. Jan 1997 A
5616150 Moeller et al. Apr 1997 A
5628991 Samain et al. May 1997 A
5635168 Burns et al. Jun 1997 A
5651960 Chan et al. Jul 1997 A
5656265 Bailey et al. Aug 1997 A
5663366 Neunhoeffer et al. Sep 1997 A
5688291 Said et al. Nov 1997 A
5708151 Möckli Jan 1998 A
5750099 Yoshihara et al. May 1998 A
5766576 Lowe et al. Jun 1998 A
5785962 Hinz et al. Jul 1998 A
5811085 Halloran Sep 1998 A
5833966 Samain Nov 1998 A
5853707 Wells et al. Dec 1998 A
5869068 De Lacharriere et al. Feb 1999 A
5951969 Golinski et al. Sep 1999 A
5972322 Rath et al. Oct 1999 A
5985803 Rizvi et al. Nov 1999 A
6013250 Cannell et al. Jan 2000 A
6015574 Cannell et al. Jan 2000 A
6036966 Youssefyeh Mar 2000 A
6090762 Clapperton et al. Jul 2000 A
6099592 Vidal et al. Aug 2000 A
6173717 Schonert et al. Jan 2001 B1
6231843 Hoelzel et al. May 2001 B1
6241971 Fox et al. Jun 2001 B1
6284003 Rose et al. Sep 2001 B1
6309426 Dias et al. Oct 2001 B1
6338741 Vidal et al. Jan 2002 B1
6348189 Tanabe et al. Feb 2002 B1
6348200 Nakajima et al. Feb 2002 B1
6358502 Tanabe et al. Mar 2002 B1
6398821 Dias et al. Jun 2002 B1
6458906 Torgerson et al. Oct 2002 B1
6488945 Sato Dec 2002 B2
6515050 Mitsuzuka et al. Feb 2003 B1
6537532 Torgerson et al. Mar 2003 B1
6562327 Nguyen et al. May 2003 B1
6569412 Yamaguchi et al. May 2003 B2
6645258 Vidal et al. Nov 2003 B2
6645478 Rollat et al. Nov 2003 B2
6669933 Duffer et al. Dec 2003 B2
6706258 Gallagher et al. Mar 2004 B1
6730789 Birault et al. May 2004 B1
6767875 Snyder et al. Jul 2004 B1
6979439 Sakai et al. Dec 2005 B1
6984250 Legrand et al. Jan 2006 B1
7041142 Chan et al. May 2006 B2
7044986 Ogawa et al. May 2006 B2
7135167 Legrand et al. Nov 2006 B2
7147843 Koshida et al. Dec 2006 B2
7151079 Fack et al. Dec 2006 B2
7204861 Marsh et al. Apr 2007 B2
7390479 Sockel et al. Jun 2008 B2
7427656 Decarolis et al. Sep 2008 B2
7495037 Moszner et al. Feb 2009 B2
7598213 Geary et al. Oct 2009 B2
7612141 Sakai et al. Nov 2009 B2
7815901 Mathonneau et al. Oct 2010 B2
7905926 DeGeorge et al. Mar 2011 B2
7915208 Roso et al. Mar 2011 B2
7931698 Simonet et al. Apr 2011 B2
7972388 Hamilton et al. Jul 2011 B2
7981405 Ueyama et al. Jul 2011 B2
8163861 Puerta et al. Apr 2012 B2
8241370 Legrand et al. Aug 2012 B2
8288329 Hata et al. Oct 2012 B2
8298519 Adams et al. Oct 2012 B2
8357356 Zaeska et al. Jan 2013 B2
8388701 Uellner et al. Mar 2013 B2
8513200 Dixon et al. Aug 2013 B2
8613913 Chang et al. Dec 2013 B2
8632758 Terada Jan 2014 B2
8642021 Brautigam et al. Feb 2014 B2
8642659 Springer et al. Feb 2014 B2
8921292 Fujita et al. Dec 2014 B2
9006162 Rizk Apr 2015 B1
9044409 Carola et al. Jun 2015 B2
9095518 Pressly et al. Aug 2015 B2
9114088 Konno et al. Aug 2015 B2
9144537 Pressly et al. Sep 2015 B1
9175114 Puerta et al. Nov 2015 B2
9180086 Cabourg et al. Nov 2015 B2
9283156 Savaides et al. Mar 2016 B2
9326926 Pressly et al. May 2016 B2
9402796 Briggs et al. Aug 2016 B2
9498419 Pressly et al. Nov 2016 B2
9597273 Pressly et al. Mar 2017 B2
9610241 Cabourg et al. Apr 2017 B2
9849071 Fack et al. Dec 2017 B2
9918923 Naiberk et al. Mar 2018 B1
9993406 Manneck et al. Jun 2018 B2
10004673 Elsen-Wahrer et al. Jun 2018 B1
10085931 Baghdadli et al. Oct 2018 B2
10219994 Lechner et al. Mar 2019 B2
10231915 Dreher et al. Mar 2019 B2
10561599 Patterson et al. Feb 2020 B2
10576307 Patterson Mar 2020 B2
20010029637 Nakashimada et al. Oct 2001 A1
20010042276 Kawasoe et al. Nov 2001 A1
20010052354 Nishibe et al. Dec 2001 A1
20020029429 Dias et al. Mar 2002 A1
20020032933 Dias et al. Mar 2002 A1
20020050013 Vidal et al. May 2002 A1
20020053110 Dias et al. May 2002 A1
20020155081 Coope Oct 2002 A1
20020189034 Kitabata et al. Dec 2002 A1
20030012761 Koshida et al. Jan 2003 A1
20030019051 Vidal et al. Jan 2003 A9
20030049222 Akhter et al. Mar 2003 A1
20030072962 Matsuzaki et al. Apr 2003 A1
20030083380 Yu et al. May 2003 A1
20030152543 Legrand et al. Aug 2003 A1
20030215415 Mitsumatsu et al. Nov 2003 A1
20040034944 Legrand et al. Feb 2004 A1
20040034946 Legrand et al. Feb 2004 A1
20040067212 Tokuyama et al. Apr 2004 A1
20040086475 Boswell et al. May 2004 A1
20040088800 Cotteret May 2004 A1
20040156877 Tokuyama et al. Aug 2004 A1
20040181883 Legrand et al. Sep 2004 A1
20040202689 Subramanyan et al. Oct 2004 A1
20040216244 Cotteret et al. Nov 2004 A1
20040228580 Lee et al. Nov 2004 A1
20040241114 Gupta Dec 2004 A1
20040256598 Plos et al. Dec 2004 A1
20040258652 Pascaly et al. Dec 2004 A1
20050015894 Cottard et al. Jan 2005 A1
20050036970 Sabbagh et al. Feb 2005 A1
20050087718 Okada Apr 2005 A1
20050095215 Popp May 2005 A1
20050176615 Kinoshita et al. Aug 2005 A1
20050186164 Akyuz Aug 2005 A1
20050191263 Ueyama et al. Sep 2005 A1
20050193501 Chan et al. Sep 2005 A1
20050201966 Ueyama et al. Sep 2005 A1
20060024257 Chang et al. Feb 2006 A1
20060062751 Sato et al. Mar 2006 A1
20060075580 Chan et al. Apr 2006 A1
20060093571 Glinski May 2006 A1
20060135397 Bissey-Beugras et al. Jun 2006 A1
20060166845 Terada Jul 2006 A1
20060182702 Kitabata et al. Aug 2006 A1
20060198807 Morioka Sep 2006 A1
20060228316 Cannell et al. Oct 2006 A1
20060251673 Hwang et al. Nov 2006 A1
20060276369 Levecke et al. Dec 2006 A1
20070041921 Neill et al. Feb 2007 A1
20070067924 Beck et al. Mar 2007 A1
20070107142 Nguyen et al. May 2007 A1
20070116661 Mata May 2007 A1
20070160560 Laurent et al. Jul 2007 A1
20070161543 Yu et al. Jul 2007 A1
20070190008 Campain et al. Aug 2007 A1
20070261594 Vaskelis et al. Nov 2007 A1
20070264208 Mougin et al. Nov 2007 A1
20080025937 Cassier Jan 2008 A1
20080025939 Cassier et al. Jan 2008 A1
20080066773 Anderson et al. Mar 2008 A1
20080118458 Giesen et al. May 2008 A1
20080124295 Duranton et al. May 2008 A1
20080138309 Malle et al. Jun 2008 A1
20080141468 Cotteret Jun 2008 A1
20080187506 Carballada et al. Aug 2008 A1
20080226576 Benabdillah et al. Sep 2008 A1
20080233072 Bureiko et al. Sep 2008 A1
20080306025 Yu et al. Dec 2008 A1
20090022681 Carballada et al. Jan 2009 A1
20090041699 Molenda Feb 2009 A1
20090053165 Brown et al. Feb 2009 A1
20090071493 Nguyen et al. Mar 2009 A1
20090074683 Nguyen et al. Mar 2009 A1
20090126756 Syed et al. May 2009 A1
20090208499 Yu et al. Aug 2009 A1
20090214628 de Rijk Aug 2009 A1
20090252697 Barbarat et al. Oct 2009 A1
20090274677 Isaacs et al. Nov 2009 A1
20100004391 Haddleton et al. Jan 2010 A1
20100015079 Schrader Jan 2010 A1
20100081716 Matsunaga et al. Apr 2010 A1
20100119468 Garcia Castro et al. May 2010 A1
20100154140 Simonet et al. Jun 2010 A1
20100158845 Ellington et al. Jun 2010 A1
20100158964 Cunningham et al. Jun 2010 A1
20100178267 Puerta et al. Jul 2010 A1
20100189795 Dreher Jul 2010 A1
20100202998 Ramos-Stanbury et al. Aug 2010 A1
20100247463 Yu et al. Sep 2010 A1
20100303748 Hercouet Dec 2010 A1
20110056508 Gross et al. Mar 2011 A1
20110061671 Neplaz et al. Mar 2011 A1
20110142778 Hloucha et al. Jun 2011 A1
20110150804 Nojiri et al. Jun 2011 A1
20110213033 Tokuyama et al. Sep 2011 A1
20110256084 Dixon et al. Oct 2011 A1
20110311463 Diamond et al. Dec 2011 A1
20120015894 Terada Jan 2012 A1
20120022037 Terada Jan 2012 A1
20120064137 Kawai Mar 2012 A1
20120114583 Giesen et al. May 2012 A1
20120118316 Uellner et al. May 2012 A1
20120121706 Paus et al. May 2012 A1
20120180807 Flohr Jul 2012 A1
20120230935 Kim et al. Sep 2012 A1
20120244082 Sulzbach et al. Sep 2012 A1
20120288459 Burg et al. Nov 2012 A1
20120329650 Lopez-Cervantes Dec 2012 A1
20130016246 Hatanaka et al. Jan 2013 A1
20130034515 Stone et al. Feb 2013 A1
20130102513 Terada Apr 2013 A1
20130118996 Kaplan May 2013 A1
20130149274 Nguyen et al. Jun 2013 A1
20130152959 Genain et al. Jun 2013 A1
20130156716 Yontz Jun 2013 A1
20130164240 Schrott Jun 2013 A1
20130172518 Huang et al. Jul 2013 A1
20130216491 Ogihara et al. Aug 2013 A1
20130233331 Khenniche et al. Sep 2013 A1
20130233332 Khenniche et al. Sep 2013 A1
20130266529 Deconinck et al. Oct 2013 A1
20130280199 Albert et al. Oct 2013 A1
20130309190 Dimotakis et al. Nov 2013 A1
20130315852 Streuli Nov 2013 A1
20140120047 Krueger May 2014 A1
20140158150 Schoepgens et al. Jun 2014 A1
20140170105 Chen et al. Jun 2014 A1
20140171354 Miralles et al. Jun 2014 A1
20140186283 Cabourg et al. Jul 2014 A1
20140196741 Cabourg et al. Jul 2014 A1
20140246041 Krueger Sep 2014 A1
20140256885 Puerta et al. Sep 2014 A1
20150004117 Tan et al. Jan 2015 A1
20150004119 Tan et al. Jan 2015 A1
20150034117 Pressly et al. Feb 2015 A1
20150034119 Pressly et al. Feb 2015 A1
20150037270 Pressly et al. Feb 2015 A1
20150037271 Pressly et al. Feb 2015 A1
20150053228 Bonauer et al. Feb 2015 A1
20150053230 Myatt Feb 2015 A1
20150090285 Worner et al. Apr 2015 A1
20150157544 Briggs et al. Jun 2015 A1
20150252302 Rieth et al. Sep 2015 A1
20150283041 Benn et al. Oct 2015 A1
20150290101 Pressly et al. Oct 2015 A1
20150297496 Kroon et al. Oct 2015 A1
20150313816 Daubresse Nov 2015 A1
20150328102 Pressly et al. Nov 2015 A1
20160058688 Anderheggen et al. Mar 2016 A1
20160081899 Pressly et al. Mar 2016 A1
20160166479 Chiou Jun 2016 A1
20160175238 Shin et al. Jun 2016 A1
20160193129 Pressly et al. Jul 2016 A1
20160235649 Streuli Aug 2016 A1
20160263003 Pressly et al. Sep 2016 A1
20160310394 Pressly et al. Oct 2016 A1
20160331664 Anderheggen et al. Nov 2016 A1
20160348037 Findlay et al. Dec 2016 A1
20170007518 Everaert et al. Jan 2017 A1
20170112740 Schoepgens et al. Apr 2017 A1
20170112743 Schoepgens et al. Apr 2017 A1
20170113071 Schoepgens et al. Apr 2017 A1
20170119122 Rautenberg-Groth et al. May 2017 A1
20170128334 Schoepgens et al. May 2017 A1
20170128342 Schoepgens et al. May 2017 A1
20170143611 Hippe et al. May 2017 A1
20170151143 Scheunemann et al. Jun 2017 A1
20170151144 Scheunemann et al. Jun 2017 A1
20170151146 Scheunemann et al. Jun 2017 A1
20170151147 Scheunemann et al. Jun 2017 A1
20170151156 Scheunemann et al. Jun 2017 A1
20170157011 Punyani et al. Jun 2017 A1
20170165161 Manneck et al. Jun 2017 A1
20170202763 Manneck et al. Jul 2017 A1
20170246094 Dreher Aug 2017 A1
20170252291 Lechner et al. Sep 2017 A1
20170360658 Ferrari et al. Dec 2017 A1
20180055751 Gevgilili et al. Mar 2018 A1
20180116942 Mahadeshwar et al. May 2018 A1
20180140531 Singer et al. May 2018 A1
20180140532 Singer et al. May 2018 A1
20180280267 Rughani et al. Oct 2018 A1
20180280269 Rughani et al. Oct 2018 A1
20180280270 Rughani et al. Oct 2018 A1
20180280271 Fack et al. Oct 2018 A1
20180338895 Patterson et al. Nov 2018 A1
20180338901 Patterson et al. Nov 2018 A1
20180339175 Patterson et al. Nov 2018 A1
20190160000 Herrlein May 2019 A1
20190201309 Machover et al. Jul 2019 A1
20200129405 Mitchell et al. Apr 2020 A1
Foreign Referenced Citations (234)
Number Date Country
1383377 Dec 2002 CN
1423548 Jun 2003 CN
1424016 Jun 2003 CN
1454074 Nov 2003 CN
1678281 Oct 2005 CN
1717215 Jan 2006 CN
1778289 May 2006 CN
1798539 Jul 2006 CN
101282705 Oct 2008 CN
101495087 Jul 2009 CN
101686920 Mar 2010 CN
101843561 Sep 2010 CN
101966136 Feb 2011 CN
102056896 May 2011 CN
102166163 Aug 2011 CN
102231974 Nov 2011 CN
102281864 Dec 2011 CN
102361627 Feb 2012 CN
102397232 Apr 2012 CN
102451117 May 2012 CN
103356395 Oct 2013 CN
103998099 Aug 2014 CN
104066419 Sep 2014 CN
104159567 Nov 2014 CN
104519962 Apr 2015 CN
105267066 Jan 2016 CN
105902403 Aug 2016 CN
105902404 Aug 2016 CN
106265109 Jan 2017 CN
1220969 Jul 1966 DE
2225541 Dec 1973 DE
2359399 Jun 1975 DE
3843892 Jun 1990 DE
4133957 Apr 1993 DE
4300320 Jul 1994 DE
19543988 May 1997 DE
10051773 Apr 2002 DE
10051774 Apr 2002 DE
20208254 Aug 2002 DE
102004052480 May 2006 DE
10 2007 039745 Feb 2009 DE
202015104742 Oct 2015 DE
102014213317 Jan 2016 DE
102015223828 Sep 2016 DE
102015221460 May 2017 DE
102016200688 Jul 2017 DE
202017001430 Jul 2017 DE
0122324 Oct 1984 EP
0159628 Oct 1985 EP
0286261 Oct 1988 EP
0298684 Jan 1989 EP
0299764 Jan 1989 EP
0437114 Jul 1991 EP
0512879 Nov 1992 EP
0636358 Feb 1995 EP
0714954 Jun 1996 EP
0770375 May 1997 EP
0855178 Jul 1998 EP
0978272 Feb 2000 EP
1118319 Jul 2001 EP
1174112 Jan 2002 EP
1216023 Apr 2005 EP
1541117 Jun 2005 EP
1570832 Sep 2005 EP
1216022 Apr 2006 EP
1690524 Aug 2006 EP
1779896 May 2007 EP
1810657 Jul 2007 EP
2123250 Nov 2009 EP
2165697 Mar 2010 EP
2229933 Sep 2010 EP
2295029 Mar 2011 EP
2460511 Jun 2012 EP
2471504 Jul 2012 EP
2478892 Jul 2012 EP
1510197 Mar 2016 EP
1492597 Aug 1967 FR
1583363 Oct 1969 FR
2162025 Jul 1973 FR
2252840 Jun 1975 FR
2270846 Dec 1975 FR
2280361 Feb 1976 FR
2316271 Jan 1977 FR
2320330 Mar 1977 FR
2336434 Jul 1977 FR
2368508 May 1978 FR
2413907 Aug 1979 FR
2505348 Nov 1982 FR
2542997 Sep 1984 FR
2733749 Nov 1996 FR
2789895 Aug 2000 FR
2789896 Aug 2000 FR
2801308 May 2001 FR
2841129 Dec 2003 FR
2886136 Dec 2006 FR
2939030 Jun 2010 FR
2944441 Oct 2010 FR
2966352 Apr 2012 FR
2975899 Dec 2012 FR
2975900 Dec 2012 FR
713675 Aug 1954 GB
741307 Nov 1955 GB
773559 Apr 1957 GB
1026978 Apr 1966 GB
1125794 Aug 1968 GB
1153196 May 1969 GB
1260451 Jan 1972 GB
1546809 May 1979 GB
1584364 Feb 1981 GB
63-154611 Jun 1988 JP
S63-255214 Oct 1988 JP
02-019576 Jan 1990 JP
H02-138110 May 1990 JP
05-163124 Jun 1993 JP
H07-069847 Mar 1995 JP
08-198732 Aug 1996 JP
H08-509478 Oct 1996 JP
2000-229821 Aug 2000 JP
2001-081013 Mar 2001 JP
2002-097115 Apr 2002 JP
2002-105493 Apr 2002 JP
2002-121121 Apr 2002 JP
2002-356408 Dec 2002 JP
2002-363048 Dec 2002 JP
2003-095876 Apr 2003 JP
2003-516335 May 2003 JP
2004-026976 Jan 2004 JP
2005-060398 Mar 2005 JP
2005-154348 Jun 2005 JP
2006-2194593 Aug 2006 JP
2006-327994 Dec 2006 JP
2008-189686 Aug 2008 JP
2009-007283 Jan 2009 JP
2009-536619 Oct 2009 JP
2010-155823 Jul 2010 JP
2012-515218 Jul 2012 JP
2013-500328 Jan 2013 JP
2015-086211 May 2015 JP
2016-003185 Jan 2016 JP
2017-095451 Jun 2017 JP
2018-514570 Jun 2018 JP
10-2001-0039848 Jul 2001 KR
2003-0003970 Jan 2003 KR
10-2004-0098688 Nov 2004 KR
10-2006-0059564 Jun 2006 KR
10-2012-0062511 Jun 2012 KR
10-2016-0064420 Jun 2016 KR
2144945 Jan 2000 RU
2229281 May 2004 RU
9300882 Jan 1993 WO
9308787 May 1993 WO
9408969 Apr 1994 WO
9408970 Apr 1994 WO
9501152 Jan 1995 WO
9501772 Jan 1995 WO
9515144 Jun 1995 WO
9615765 May 1996 WO
9724106 Jul 1997 WO
9856333 Dec 1998 WO
9911226 Mar 1999 WO
9966793 Dec 1999 WO
0135912 May 2001 WO
0147486 Jul 2001 WO
0152005 Jul 2001 WO
0219976 Mar 2002 WO
0232383 Apr 2002 WO
0232386 Apr 2002 WO
02055034 Jul 2002 WO
2004002411 Jan 2004 WO
2004019858 Mar 2004 WO
2016058749 Apr 2005 WO
2005058258 Jun 2005 WO
2006011771 Feb 2006 WO
2006134051 Dec 2006 WO
2007003307 Jan 2007 WO
2007038733 Apr 2007 WO
2009024936 Feb 2009 WO
2010015517 Feb 2010 WO
2010023559 Mar 2010 WO
2010049434 May 2010 WO
2011134785 Nov 2011 WO
2012033813 Mar 2012 WO
2012080321 Jun 2012 WO
2012084532 Jun 2012 WO
2012084876 Jun 2012 WO
2012164064 Dec 2012 WO
2013092080 Jun 2013 WO
2013136480 Sep 2013 WO
2014016407 Jan 2014 WO
2014072490 May 2014 WO
2014118212 Aug 2014 WO
2014125452 Aug 2014 WO
2014144076 Sep 2014 WO
2014167508 Oct 2014 WO
2014207097 Dec 2014 WO
2015017768 Feb 2015 WO
2015026994 Feb 2015 WO
2015033351 Mar 2015 WO
2015058942 Apr 2015 WO
2015069823 May 2015 WO
2015075064 May 2015 WO
2015118357 Aug 2015 WO
2015175986 Nov 2015 WO
2016005114 Jan 2016 WO
2016005144 Jan 2016 WO
2016069877 May 2016 WO
2016091492 Jun 2016 WO
2016098870 Jun 2016 WO
2016100885 Jun 2016 WO
2016102543 Jun 2016 WO
2016120642 Aug 2016 WO
2016161360 Oct 2016 WO
2016179017 Nov 2016 WO
2016198203 Dec 2016 WO
2017041903 Mar 2017 WO
2017041905 Mar 2017 WO
2017041906 Mar 2017 WO
2017041907 Mar 2017 WO
2017041908 Mar 2017 WO
2017041909 Mar 2017 WO
2017041910 Mar 2017 WO
2017059646 Apr 2017 WO
2017085117 May 2017 WO
2017091794 Jun 2017 WO
2017091796 Jun 2017 WO
2017091797 Jun 2017 WO
2017091800 Jun 2017 WO
2017102855 Jun 2017 WO
2017102936 Jun 2017 WO
2017116465 Jul 2017 WO
2017196299 Nov 2017 WO
2017207198 Dec 2017 WO
2018081399 May 2018 WO
2018085478 May 2018 WO
Non-Patent Literature Citations (212)
Entry
Translation of Chinese Office Action for counterpart Application No. 201680079800.4, dated Aug. 24, 2020.
Search Report for Chinese Application No. 201680079800.4, dated Aug. 24, 2020.
Translation of Chinese Office Action for counterpart Application No. 201680079773.0, dated Aug. 21, 2020.
Search report for counterpart Chinese Application No. 201680079773.0, dated Aug. 21, 2020.
Translation of Japanese Office Action for counterpart Application No. 2018-546409, dated Sep. 7, 2020.
Translation of Chinese Office Action for counterpart Application No. 201680079774.5, dated Sep. 1, 2020.
Fridman, R.A., “Technology of Cosmetics,” publ. of “Food Industry,” 1964, pp. 3-6, 297-308, 411-428 and 441-466 (translation).
Zefirova, N.S., “Big Russian Encyclopedia,” Chemical Encylopedia, 1995, vol. 4, pp. 183-185 (translation).
Third Party Submission for U.S. Appl. No. 16/712,326 with attachments, filed Sep. 8, 2020.
Mexican Office Action for counterpart Application No. MX/a/2017/013983, dated Sep. 15, 2020.
Non-Final Office Action for copending U.S. Appl. No. 15/778,807, dated Oct. 9, 2020.
Japanese Notice of Reasons for Refusal for counterpart Application No. 2019-553190, dated Oct. 27, 2020.
Translation of Korean Notice of Last Preliminary Rejection for counterpart Application No. 10-2018-7017668, dated Oct. 21, 2020.
Non-Final Office Action for copending U.S. Appl. No. 15/942,042, dated Nov. 12, 2020.
Final Office Action for copending U.S. Appl. No. 15/356,967, dated Nov. 17, 2020.
Final Office Action for copending U.S. Appl. No. 15/357,056, dated Nov. 19, 2020.
Japanese Office Action for counterpart Application No. 2018-546408, dated Dec. 7, 2020.
Japanese Notice of Reasons for Rejection of counterpart Application No. 2019-553559, dated Dec. 1, 2020.
Japanese Notice of Reasons for Rejection for counterpart Application No. 2019-564945, dated Dec. 1, 2020.
Mintel: “Conditioner,” Unilever, XP055576893, Database accession No. 3014885, Mar. 2, 2015.
“Olaplex Alleges Patent Infringement by L'OREAL re Hairbond-Building Prior to Colouring,” Focus on Pigments, vol. 2017, No. 3, Mar. 31, 2017, p. 7.
Final Office Action for copending U.S. Appl. No. 15/339,035, dated May 2, 2019.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2017/058495, dated May 9, 2019.
Notice of Allowance for copending U.S. Appl. No. 15/778,803, dated Jun. 3, 2019.
Extended European Search Report for counterpart Application No. 16869327.3-1114, dated Jun. 4, 2019.
Mintel: “Detox 7 Day Cure Purifying Serum,” XP055593471, Jeanne Gatineau, Feb. 11, 2013.
Extended European Search Report for counterpart Application No. 16869330.7-1114, dated Jul. 5, 2019.
Extended European Search Report for counterpart Application No. 16869326.5-1114, dated Jun. 26, 2019.
Translation of Mexican Office Action for counterpart Application No. MX/a/2018/005829, dated Jun. 13, 2019.
Non-Final Office Action for copending U.S. Appl. No. 15/339,035, dated Aug. 20, 2019.
Mexican Office Action for counterpart Application No. MX/a/2017/013983, dated Jul. 2, 2019.
Notice of Allowance for copending U.S. Appl. No. 16/042,478, dated Sep. 25, 2019.
Non-Final Office Action for copending U.S. Appl. No. 15/778,807, dated Sep. 30, 2019.
Brazilian Office Action for counterpart Application No. BR112017023380-0, dated Oct. 10, 2019.
Brazilian Office Action for counterpart Application No. BR112018010381-0, dated Nov. 25, 2019.
Brazilian Office Action for counterpart Application No. BR112018010357-8, dated Nov. 25, 2019.
Mexican Office Action for counterpart Application No. MX/a/2018/005829, dated Oct. 5, 2019.
Brazilian Office Action for counterpart Application No. BR112018010344, dated Nov. 25, 2019.
Mexican Office Action for counterpart Application No. MX/a/2017/013983, dated Dec. 16, 2019.
Japanese Office Action for counterpart Application No. 2018-526844, dated Dec. 23, 2019.
Japanese Office Action for counterpart Application No. 2018-526845, dated Dec. 23, 2019.
Japanese Office Action for counterpart Application No. 2018-546409, dated Dec. 23, 2019.
Brazilian Written Opinion for counterpart Application No. BR112018010341, dated Nov. 25, 2019.
Non-Final Office Action for counterpart Japanese Application No. 2018-546408, dated Jan. 6, 2020.
Mintel: “Tonic,” Dr. Kurt Wolff, Dr. Wolff Plantur 39, ID# 3133037, Apr. 2015.
Mintel: “Conditioner,” LG Household & Health Care, Beyond Professional, ID# 3240637, Jun. 2015.
Russian Office Action for counterpart Application No. 2018114758/04, dated Dec. 13, 2019.
Translated Notification of Reasons for Refusal for counterpart KR Application No. 10-2018-7017668, dated Jan. 21, 2020.
Translated Office Action for counterpart RU Application No. 2017134681/04(0060925), dated Dec. 30, 2019.
Non-Final Office Action for copending U.S. Appl. No. 15/778,805, dated Feb. 12, 2020.
Final Office Action for copending U.S. Appl. No. 15/778,807, dated Mar. 13, 2020.
Final Office Action for copending U.S. Appl. No. 15/339,035, dated Apr. 10, 2020.
Non-Final Office Action for copending U.S. Appl. No. 16/273,787, dated Apr. 9, 2020.
International Search Report and Written Opinion for counterpart Application No. PCT/US2017/059827, dated Jun. 28, 2018.
“Lamesoft® PO 65 Datasheet,” Retrieved from the internet on Jun. 7, 2018, http://e-applications.basf-ag.de/data/basf-pcan/pds2/pds2-web.nsf.
Non-Final Office Action for copending U.S. Appl. No. 15/356,967, dated May 3, 2017.
Final Office Action for copending U.S. Appl. No. 15/356,967, dated Dec. 4, 2017.
Non-Final Office Action for copending U.S. Appl. No. 15/356,967, dated Aug. 24, 2018.
Final Office Action for copending U.S. Appl. No. 15/356,967, dated Apr. 11, 2019.
Non-Final Office Action for copending U.S. Appl. No. 15/356,967, dated Feb. 21, 2020.
Notice of Allowance for copending U.S. Appl. No. 15/604,152, dated Oct. 2, 2019 (now U.S. Pat. No. 10,561,599).
Non-Final Office Action for copending U.S. Appl. No. 15/604,152, dated Jun. 13, 2019.
Non-Final Office Action for copending U.S. Appl. No. 15/942,042, dated Jan. 24, 2020.
ALS “Cocamidopropyl betaine,” printed 2020; http://www.caslab.com/Cocamidopropyl_betaine_CAS_61789-40-0.
Notice of Allowability for copending U.S. Appl. No. 15/604,152, dated Dec. 10, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/US2018/025466, dated Jul. 9, 2018.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2018/025466, dated Oct. 1, 2019.
Corrected Notice of Allowability for copending U.S. Appl. No. 15/604,189, dated Dec. 11, 2019 (now U.S. Pat. No. 10,576,307).
Notice of Allowance for copending U.S. Appl. No. 15/604,189, dated Oct. 22, 2019.
Copending U.S. Appl. No. 15/484,625, filed Apr. 11, 2017 (WO 2016/179017).
Copending U.S. Appl. No. 15/484,663, filed Apr. 11, 2017 (WO 2017/091794).
Copending U.S. Appl. No. 15/339,035, filed Oct. 31, 2016 (WO 2018/081399).
International Search Report and Written Opinion for counterpart Application No. PCT/US2016/030172, dated Sep. 19, 2016.
International Search Report and Written Opinion for counterpart Application No. PCT/US2016/063724, dated Feb. 2, 2017.
International Search Report and Written Opinion for counterpart Application No. PCT/US2016/063727, dated Feb. 8, 2017.
International Search Report and Written Opinion for counterpart Application No. PCT/US2016/063732, dated Feb. 6, 2017.
International Search Report and Written Opinion for counterpart Application No. PCT/US2016/063728, dated Feb. 1, 2017.
Mintel: “Abundant Volume Conditioner,” Alterna Professional Haircare, Database Record No. 2177147, Sep. 2013.
Mintel: “Hair Colourant,” Catzy Hair Colourant, Database Record ID 743114, Jul. 2007, 4 pages.
Mintel: “Combing Cream,” Devintex Cosmeticos, Database Record No. 1595490, Jul. 2011.
Mintel: “Combing Cream,” Devintex Cosmeticos, Database Record No. 1595658, Jul. 2011.
Mintel: “Conditioner,” Devintex Cosmeticos, Database Record No. 1595545, Jul. 2011.
Mintel: “Conditioner,” Laperle Haircare, Database Record No. 3645337, Feb. 2016.
Mintel: “Conditioner,” Laperle Haircare, Database Record No. 3790215, Feb. 2016.
Mintel: “Conditioner,” Liqwd, Database Record No. 1172691, Sep. 2009.
Mintel: “Conditioner,” TIGI, Database Record No. 1442418, Nov. 2010.
Mintel: “Conditioner,” TIGI International, Database Record No. 1445427, Nov. 2010.
Mintel: “Conditioner,” TGI International, Database Record No. 3280151, Jul. 2015.
Mintel, “Masque for Beautiful Color,” Oribe Hair Care, Database Record No. 1522953, Mar. 2011.
Mintel: “Moisturizing Conditioner,” Frederic Fekkai, Database Record No. 1507159, Mar. 2011.
Mintel: “Post-Service Perfector,” Redken, Database Record No. 4326453, Nov. 2016.
Mintel: “Step 3-Conditioner,” L'OREAL, Database Record No. 4353779, Oct. 2016.
Mintel: “Step 3-Conditioner,” L'OREAL, Database Record No. 4609117, Feb. 2017.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2016/30172, dated Jun. 19, 2017.
Petition for Post-Grant Review of U.S. Pat. No. 9,498,419, filed Jan. 31, 2017, with Exhibits.
Non-Final Office Action for copending U.S. Appl. No. 15/484,625, dated Jun. 21, 2017 (now U.S. Pat. No. 10,231,915).
Final Office Action for copending U.S. Appl. No. 15/484,625, dated Nov. 14, 2017 (now U.S. Pat. No. 10,231,915).
Non-Final Office Action for copending U.S. Appl. No. 15/484,663, dated Jun. 21, 2017 (now U.S. Pat. No. 10,058,494).
Final Office Action for copending U.S. Appl. No. 15/484,663, dated Nov. 28, 2017 (now U.S. Pat. No. 10,058,494).
Non-Final Office Action for copending U.S. Appl. No. 15/339,035, dated Jan. 10, 2018.
International Search Report for counterpart Application No. PCT/US2017/058495, dated Jan. 5, 2018.
Third Party Submission for U.S. Appl. No. 15/484,663, filed Feb. 28, 2018, with attachments.
Pressly, Eric et al., U.S. Appl. No. 61/994,709, filed May 16, 2014 and became publicly available on Nov. 19, 2015.
Estetica: the hairstyling professional magazine, (http://estetica.it/int/a/schwarzkopf-professional-launches-fibreplex), “Schwarzkopf Professional Launches Fibreplex®,” published Sep. 23, 2015 reporting that Fibreplex was launched during Sep. 2015.
Fibreplex® No. 1 Product Label.
Fibreplex® No. 1 Material Safety Data Sheet.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2016/063727, dated Jun. 7, 2018.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2016/063732, dated Jun. 7, 2018.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2016/063728, dated Jun. 7, 2018.
Non-Final Office Action for copending U.S. Appl. No. 15/484,625, dated Jun. 20, 2018 (now U.S. Pat. No. 10,231,915).
International Preliminary Report on Patentability for counterpart Application No. PCT/US2016/063724, dated Jun. 7, 2018.
Non-Final Office Action for copending U.S. Appl. No. 15/339,035, dated Oct. 5, 2018.
Notice of Allowance for copending U.S. Appl. No. 15/484,625, dated Oct. 31, 2018.
Bayraktar, V.N., “Organic Acids Concentration in Wine Stocks After Saccharomyces cerevisiae Fermentation,” Biotechnologia Acta, vol. 6, No. 2, Jan. 1, 2013, pp. 97-106.
Supplementary European Search Report for counterpart Application No. EP16789846, dated Oct. 30, 2018.
Communication Pursuant to Rules 70(32) and 70a(2) EC for counterpart Application EP16789846, dated Jan. 23, 2019.
Written Opinion for counterpart Application EP16789846, dated Jan. 23, 2019.
Supplementary Extended Search Report and Written Opinion for counterpart European Application No. 16869324, dated Apr. 25, 2019.
Mintel: “Conditioner,” Unilever, XP-55576888, Database accession No. 1419415, Oct. 21, 2010.
Non-Final Office Action for copending U.S. Appl. No. 15/604,189, dated Apr. 8, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/US2018/034371, dated Nov. 16, 2018.
Mintel: “Hydrating Hair Colour,” Garnier, Jan. 2017, pp. 1-6.
Final Office Action for copending U.S. Appl. No. 15/603,889, dated Jul. 12, 2019.
Non-Final Office Action for copending U.S. Appl. No. 15/603,889, dated Jan. 2, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/US2018/034378, dated Jul. 24, 2018.
Final Office Action for copending U.S. Appl. No. 16/234,883, dated Mar. 11, 2020.
Final Office Action for copending U.S. Appl. No. 16/176,350, dated Apr. 8, 2020.
Non-Final Office Action for copending U.S. Appl. No. 16/176,350, dated Nov. 14, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/US2019/059002, dated Feb. 4, 2020.
Korean Notification of Reasons for Refusal of counterpart Application No. KR10-2017-7034789, dated May 19, 2020.
Non-Final Office Action for copending U.S. Appl. No. 16/176,350, dated Sep. 30, 2020.
Non-Final Office Action for copending U.S. Appl. No. 16/234,883, dated Sep. 16, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/US2018/067814, dated Feb. 25, 2019.
Final Office Action for copending U.S. Appl. No. 15/942,042, dated Jun. 1, 2020.
Japanese Notice of Reasons for Refusal for Application No. 2017-557074, dated Jun. 1, 2020.
Non-Final Office Action for copending U.S. Appl. No. 15/942,085, dated Jun. 19, 2020.
Mintel, “Masque Force Architecte Reconstructing Masque,” L'Oreal, Feb. 2012, pp. 1-6.
Shiseido Super Mild Hair Care—Shampoo and Conditioner Refill Set. https://web.archive.org/web/20160326190615/nttp://www.truenu.com/TR/Shiseido-Super-Mild-Hair-Care-Shampoo-Conditioner-Refill-Set-Two-400ml-Refill-Pouches-Details.html. Published Mar. 26, 2016.
Non-Final Office Action for copending U.S. Appl. No. 15/941,916, dated Jun. 24, 2020.
Non-Final Office Action for copending U.S. Appl. No. 15/941,965, dated Jul. 15, 2020.
Third Party Observation for counterpart Application No. EP20160869330, dated Jun. 26, 2020.
Third Party Observation for counterpart Application No. EP20160869326, dated Jul. 2, 2020.
Third Party Observation for counterpart Application No. EP20160869327, dated Jul. 2, 2020.
International Search Report and Written Opinion for counterpart Application No. PCT/US2018/025448, dated Jul. 9, 2018.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2018/025448, dated Oct. 1, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/US2018/025431, dated Jun. 20, 2018.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2018/025431, dated Oct. 1, 2019.
International Search Report and Written Opinion for counterpart Application No. PCT/US2018/025418, dated Jun. 21, 2018.
International Preliminary Report on Patentability for counterpart Application No. PCT/US2018/025418, dated Oct. 1, 2019.
Translated Japanese Office Action for counterpart Application No. 2018-526844, dated Aug. 3, 2020.
Translation of Mexican Office Action for counterpart Application No. MX/a/2018/005829, dated Jul. 13, 2020.
Non-Final Office Action for copending U.S. Appl. No. 16/234,883 dated Aug. 26, 2020.
Mascolo Group, label.m Anti-Frizz Mist, Mintel Gnpd, record ID5618119, published Apr. 2018, p. 1-5.
Federici Brands, Color WOW Dream Coat Supernatural Spray, Mintel GNPD, record ID5637153, published Apr. 2018, p. 1-2.
Garnier, Gamier Fructis Sleek & Shine Moroccan Sleek Oil Treatment, Mintel GNPD, record ID1876023, published Sep. 2012, p. 1-2.
Duai, Leave-In Conditioner, Mintel GNPD, record ID5781323, published Jun. 2018, p. 1-2.
Redken, Redken Pillow Proof Express Treatment Primer, Mintel Gnpd, record ID5117339, published Sep. 2017, p. 1-4.
Redken, Redken Pillow Proof Express Primer Time-Saving Blowdry Primer with Heat Protection, Mintel GNPD, record ID6117357, published Nov. 2018, p. 1-2.
Redken, Redken Pillow Proof Time-Saving Blowdry Primer with Heat Protection, Mintel GNPD, record ID4537755, published Jan. 2017, p. 1-3.
International Search Report and Written Opinion for counterpart Application No. PCT/US2017/059817, dated Feb. 6, 2018.
Non-Final Office Action for copending U.S. Appl. No. 15/357,056, dated Apr. 16, 2020.
Olaplex with relaxers, Olaplex™, pp. 1-2, Apr. 11, 2017, https://olaplex.es/olaplex-with-relaxers/.
Relaxers, resource Library, Olaplex Education, pp. 1-2, Apr. 11, 2017, https://help.olaplex.com/detail/relaxers.
International Search Report and Written Opinion for counterpart Application No. PCT/US2018/034366, dated Jul. 25, 2018.
Anonymous: “Curly Hair Conditioner,” Mintel, GNPD, XP002782449, 2015, pp. 1-2.
Translation of Chinese Office Action for counterpart Application No. 201680079110.9, dated Aug. 11, 2020.
Ruiming, Li, “Hairdressing Technology,” China Railway Publishing House, Jun. 30, 2015, pp. 112-113.
Copending U.S. Appl. No. 16/455,139, “Hair Treatment Compositions and Methods for Treating Hair,” filed Jun. 27, 2019.
Translation of Russian Office Action for counterpart Application No. 2017134681-04, dated Aug. 17, 2020.
Final Office Action for copending U.S. Appl. No. 16/234,883, dated Dec. 24, 2020.
Translation of Third Party Observation for Application No. 2018-546408, dated Sep. 11, 2020.
European Office Action for counterpart Application No. 16869327.3-1 112, dated Dec. 18, 2020.
Translation of Russian Office Action for counterpart Application No. 218114758/04, dated Dec. 21, 2020.
Final Office Action for copending U.S. Appl. No. 15/941,916, dated Mar. 10, 2021.
Final Office Action for copending U.S. Appl. No. 15/941,965, dated Apr. 5, 2021.
Translation of Chinese Office Action for counterpart Application No. 201880021603.6, dated Mar. 2, 2021.
Translation of Chinese Office Action for counterpart Application No. 201680039105.5, dated Feb. 4, 2021.
European Office Action for counterpart Application No. 16869330.7-1112, dated Feb. 4, 2021.
European Office Action for counterpart Application No. 16869324.0-1112, dated Feb. 18, 2021.
Translation of Chinese Office Action for counterpart Application No. 201680079800.4, dated Feb. 24, 2021.
Supplemental Search Report for Chinese counterpart Application No. 201680079800.4, dated Feb. 18, 2021.
Final Office Action for copending U.S. Appl. No. 15/942,042, dated May 12, 2021.
Non-Final Office Action for copending U.S. Appl. No. 15/942,085, dated Jun. 8, 2021.
Tetrasodium Etidronate, https://uk.lush.com/ingredients/tetrasodium-etidronate. Published Mar. 28, 2020.
Shoup, F.K., et al., “Amino Acid Composition of Wheat Varieties and Flours Varying Widely in Bread-Making Potentialities,” Journal of Food Science, vol. 31, Issue 1, published Jan. 1966, pp. 94-101.
“Oxy Cream,” Makki Cosmetics, https://www.makkicosmetics.com/makki/showProductjsp?productID=Oxy25030&brandID=Makki, published Jun. 30, 2016.
Non-Final Office Action for copending U.S. Appl. No. 15/339,035, dated Jun. 25, 2021.
Non-Final Office Action for copending U.S. Appl. No. 15/603,889, dated Jun. 25, 2021.
Partial Translation of Office Action for copending MX Application No. MX/a/2017/013983, dated Apr. 4, 2021.
Translation of Chinese Office Action for counterpart Application No. 201680079773, dated Apr. 14, 2021.
Translation of Japanese Office Action for counterpart Application No. 2017-557074, dated May 31, 2021.
Translation of Japanese Notice of Reasons for Refusal for counterpart Application No. 2019-553190, dated Jun. 12, 2021.
Non-Final Office Action for copending U.S. Appl. No. 16/234,883, dated Sep. 17, 2021.
Final Office Action for copending U.S. Appl. No. 15/942,085, dated Sep. 21, 2021.
Final Office Action for copending U.S. Appl. No. 15/778,807, dated Jul. 21, 2021.
Non-Final Office Action for copending U.S. Appl. No. 15/356,967, dated Jul. 22, 2021.
Copending U.S. Appl. No. 17/403,327, titled: “Hair Treatment Compositions, Methods, and Kits for Treating Hair,” Inventors: Barbara Mitchell et al., filed Aug. 16, 2021.
Final Office Action for copending U.S. Appl. No. 15/603,889, dated Jan. 6, 2022.
Translation of Chinese Office Action for counterpart Application No. 201680039105.5, dated Jan. 14, 2022.
Translation of Chinese Office Action for counterpart Application No. 201880034056.5 dated Dec. 28, 2021.
Communication Pursuant to Rule 114(2) EPC (Third Party Observation) for EP Application No. 20160869324, dated Apr. 22, 2022.
U.S. Appl. No. 61/994,709 for “Hair Treatment Compositions and Methods,” Inventors: Eric D. Pressly and Craig J. Hawker, filed May 16, 2014.
“Practical Modern Hair Science,” Chapter 4, Edited by Trefor Evans and R. Randall Wickett, Allured Business Media, 2012, pp. 1065-1-1065-45.
Third Party Submission for counterpart Application No. EP 20160869330, dated May 6, 2022.
Translation of Second Chinese Office Action for counterpart Application No. 201880034056.5, dated May 30, 2022.
Chinese Office Action for counterpart Application No. 201880084390.1, dated Jun. 30, 2022 (translation unavailable).
EP Office Action for counterpart Application No. 16789846.9-1109, dated Jul. 6, 2022.
Final Office Action for copending U.S. Appl. No. 15/339,035, dated Apr. 14, 2022.
Third Party Submission and Concise Description of Relevance for U.S. Appl. No. 17/356,132, dated Apr. 20, 2022.
Third Party Submission for copending U.S. Appl. No. 17/379,405, filed May 10, 2022.
Non-Final Office Action for copending U.S. Appl. No. 15/942,042, dated May 23, 2022.
Third Party Submission and Concise Description of Relevance for copending U.S. Appl. No. 17/403,327, dated Jun. 27, 2022.
Related Publications (1)
Number Date Country
20200405618 A1 Dec 2020 US