WO2020092032A1

WO2020092032A1 - Hair conditioning compositions

Info

Publication number: WO2020092032A1
Application number: PCT/US2019/057133
Authority: WO
Inventors: Lu Bai; Liang Chen; Yunshen CHEN; Bethany Johnson; Jennifer KOENIG; Lyndsay M. LEAL; Fanwen Zeng
Original assignee: Dow Global Technologies Llc; Rohm And Haas Company; Dow Silicones Corporation
Priority date: 2018-10-30
Filing date: 2019-10-21
Publication date: 2020-05-07

Abstract

Provided are hair conditioning compositions and methods of using the same comprising (a) a polyacrylate oil gel, based on the total weight of the composition, wherein the polyacrylate oil gel comprises (i) at least one cosmetically acceptable hydrophobic ester oil, and (ii) one or more polymers comprising polymerized structural units of (1) 96 to 99.89 weight % of C₄-C₈ (meth)acrylate monomers, (2) 0.1 to 2 weight % of (meth)acrylic acid monomer, and (3) 0.01 to 2 weight % of at least one crosslinker, wherein the polymers are formed by (1) providing a first monomer mixture comprising the C₄-C₈ (meth)acrylate monomers and (meth)acrylic acid monomer, (2) providing a second monomer mixture comprising the crosslinker, and (3) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture, (b) a dermatologically acceptable carrier, and (c) a surface active agent. Also provided are methods of conditioning hair comprising topically administering such compositions to the hair.

Description

HAIR CONDITIONING COMPOSITIONS

FIELD OF THE INVENTION

This invention relates generally to hair conditioning compositions containing

polyacrylate oil gels containing hydrophobic ester oils and acrylic polymers.

BACKGROUND

Personal care hair conditioning compositions contain a variety of components that provide a wide array of benefits to the composition. One class of additives are oil thickeners that provide viscosity enhancements and impart good aesthetics, such as good sensory feel and clarity. Oil thickening agents that are known in the art include, for example, styrene- ethylene/butadiene- styrene copolymers, polyamide polymers, and cellulose-based polymers. These thickeners, however, come with certain drawbacks, including insufficient viscosity enhancement, high formulation temperature, and lack of consistency in viscosity control in consumer product formulations.

To this end, polyacrylate oil gels have been utilized in the art. For example, WO 2017/105957 Al discloses personal care compositions comprising a polyacrylate oil gel containing a cosmetically acceptable hydrophobic ester oil and a polymer including at least two polymerized units. The prior art does not, however, disclose a hair conditioning formulation containing polyacrylate oil gels according to the present invention which achieves the significant conditioning performance such as ease of detangling, smoothness, pliability, slipperiness, and luster.

Accordingly, there is a need to develop hair conditioning compositions that provide significant enhancements to ease of detangling, smoothness, pliability, slipperiness, and luster, while not suffering from the drawbacks of the prior art.

STATEMENT OF INVENTION

One aspect of the invention provides a hair conditioning composition comprising (a) of a polyacrylate oil gel, based on the total weight of the composition, wherein the polyacrylate oil gel comprises (i) at least one cosmetically acceptable hydrophobic ester oil, and (ii) one or more polymers comprising polymerized structural units of (1) 96 to 99.89 weight % of C₄-C₄

(meth)acrylate monomers, (2) 0.1 to 2 weight % of (meth)acrylic acid monomer, and (3) 0.01 to 2 weight % of at least one crosslinker, wherein the polymers are formed by (1) providing a first monomer mixture comprising the C₄-C₄ (meth)acrylate monomers and (meth)acrylic acid monomer, (2) providing a second monomer mixture comprising the crosslinker, and (3) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture, (b) a dermatologically acceptable carrier, and (c) a surface active agent.

Another aspect of the invention provides a method for preparing a hair conditioning composition containing a polyacrylate oil gel, a dermatologically acceptable carrier, and a surface active agent comprising (a) preparing a polymer emulsion by the steps of (i) providing a first monomer mixture comprising (1) 96 to 99.89 weight % of C₄-C₄ (meth) acrylate monomers, based on the total weight of monomers in the polymer emulsion, and (2) 0.1 to 2 weight % of (meth)acrylic acid monomer, based on the total weight of monomers in the polymer emulsion, (ii) providing a second monomer mixture comprising 0.01 to 2 weight % of at least one crosslinker, based on the total weight of monomers in the polymer emulsion, and (iii) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture, (b) spray drying the polymer emulsion to obtain polymer particles, and (c) mixing the polymer particles, the dermatologically acceptable carrier, and the surface active agent at a temperature of from 5 to l50°C.

In another aspect, the invention provides a method for conditioning hair, comprising topically administering to the hair an effective amount of a hair conditioning composition comprising (a) of a polyacrylate oil gel, based on the total weight of the composition, wherein the polyacrylate oil gel comprises (i) at least one cosmetically acceptable hydrophobic ester oil, and (ii) one or more polymers comprising polymerized structural units of (1) 96 to 99.89 weight % of C₄-C₈ (meth) acrylate monomers, (2) 0.1 to 2 weight % of (meth)acrylic acid monomer, and (3) 0.01 to 2 weight % of at least one crosslinker, wherein the polymers are formed by (1) providing a first monomer mixture comprising the C₄-C₄ (meth)acrylate monomers and

(meth)acrylic acid monomer, (2) providing a second monomer mixture comprising the crosslinker, and (3) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture, (b) a dermatologically acceptable carrier, and (c) a surface active agent.

DETAILED DESCRIPTION

The inventors have now surprisingly found that hair conditioning compositions comprising a polyacrylate oil gel containing one or more polymers having a high weight percent of polymerized structural units of C₄-C₄ (meth) acrylate monomer, a small weight percent of (meth)acrylic acid monomer, and a small weight percent of crosslinker, in which the polymer is prepared by adding a first monomer mixture containing the C₄-C₄ (meth) acrylate monomer and (meth)acrylic acid monomer to a polymerization reactor while simultaneously adding a second monomer mixture containing the crosslinker to the first monomer mixture, a dermatologically acceptable carrier, and a surface active agent, provide significant conditioning enhancements such as ease of detangling, smoothness, pliability, slipperiness, and luster, while avoiding the greasiness associated with oil-containing hair conditioning formulations. Accordingly, the present invention provides in one aspect a conditioning composition comprising (a) a polyacrylate oil gel comprising (i) a hydrophobic ester oil, (1) 96 to 99.89 weight % of C₄-C₄ (meth)acrylate monomers, (2) 0.1 to 2 weight % of (meth)acrylic acid monomer, and (3) 0.01 to 2 weight % of at least one crosslinker, wherein the polymers are formed by (1) providing a first monomer mixture comprising the C₄-Cx (meth)acrylate monomers and (meth)acrylic acid monomer, (2) providing a second monomer mixture comprising the crosslinker, and (3) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture, (b) a dermatologically acceptable carrier, and (c) a surface active agent.

In the present invention,“hair conditioning” is intended to refer to cosmetic

compositions for application to hair, including, for example, leave-on conditioners and rinse-off conditioners. Preferably, the personal care composition is cosmetically acceptable.

“Cosmetically acceptable” refers to ingredients typically used in personal care compositions, and is intended to underscore that materials that are toxic when present in the amounts typically found in personal care compositions are not contemplated as part of the present disclosure. The compositions of the invention may be manufactured by processes well known in the art, for example, by means of conventional mixing, dissolving, granulating, emulsifying, encapsulating, entrapping or lyophilizing processes.

As used herein, the term“polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term“polymer” includes the terms“homopolymer,”“copolymer,” and“terpolymer.” As used herein, the term “polymerized structural units” of a given monomer refers to the remnant of the monomer after polymerization. As used herein, the term“(meth)acrylate” refers to either acrylate or methacrylate, and the term“(meth) acrylic” refers to either acrylic or methacrylic. As used herein, the term“substituted” refers to having at least one attached chemical group, for example, alkyl group, alkenyl group, vinyl group, hydroxyl group, carboxylic acid group, other functional groups, and combinations thereof. The inventive hair conditioning compositions include polyacrylate oil gels containing one or more polymers and one or more hydrophobic ester oils. In certain embodiments, the polyacrylate oil gels are present in the hair conditioning composition in an amount of from 0.1 to 20 weight %, preferably from 0.5 to 10, and more preferably from 1 to 6 weight %, based on the total weight of the hair conditioning composition

The polyacrylate oil gels of the invention contain one or more polymers comprising structural units of C₄-Cs (meth)acrylate monomers and (meth)acrylic acid monomers. Suitable C₄-C₈ (meth)acrylate monomers include, for example, n-butyl (meth)acrylate, i-butyl

(meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, phenyl (meth) acrylate, benzyl (meth)acrylate, and 2-phenylethyl (meth)acrylate. Preferably, the C4-C8 (meth)acrylate monomers comprise one or more of i-butyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. In certain embodiments, the polymer comprises polymerized structural units of C4-C8 (meth) acrylate monomers in an amount of from 96 to 99.89, preferably from 97.5 to 99.5 weight %, more preferably from 98.2 to 99.3 weight %, and more preferably from 98.9 to 99.1 weight %, based on the total weight of the polymer. In certain embodiments, the C4-C8 (meth)acrylate monomers comprise i-butyl methacrylate and 2- ethylhexyl methacrylate in a ratio of from 9:1 to 2:3, preferably from 3:2 to 2:3, and more preferably from 1:1 to 2:3.

The polymers of the inventive hair conditioning compositions also comprise structural units of (meth)acrylic acid monomer. In certain embodiments, the polymer comprises polymerized structural units of (meth)acrylic acid monomer in an amount of from 0.1 to 2 weight %, preferably from 0.5 to 1.5 weight %, and more preferably from 0.75 to 1.25 weight %, based on the total weight of the polymer.

The polymers of the inventive hair conditioning composition also comprise polymerized structural units of at least one crosslinker. Crosslinkers are monomers having two or more non- conjugated ethylenically unsaturated groups. Suitable crosslinkers include, for example, di- or trl-allyl ethers and di- or tri- (meth) aery lyl esters of diols or polyols (e.g., trimethylolpropane diallyl ether (TMPDE), trimethylolpropane trimethacrylate (TMPTMA), and ethylene glycol dimethacrylate (EGDMA)), di- or tri-allyl esters of di- or tri-acids (e.g., diallyl phthalate), allyl (meth)acrylate, divinyl sulfone, triallyl phosphate, and divinylaromatics (e.g., divinylbenzene).

In certain embodiments, the polymer comprises polymerized structural units of crosslinker in an amount of from 0.01 to 2 weight %, preferably from 0.5 to 1.25 weight %, and more preferably from 0.1 to 0.5 weight %, based on the total weight of the polymer. In certain embodiments, the polymers have an average particle size of from 50 to 2,000 nm, preferably of from 75 to 1,100 nm, and more preferably of from 100 to 200 nm. Polymer molecular weights can be measured by standard methods such as, for example, size exclusion chromatography or intrinsic viscosity. In certain embodiments, the polymers are present in the polyacrylate oil gel in an amount of from 0.05 to 15 weight %, preferably from 0.2 to 10, and more preferably from 1 to 7 weight %, based on the total weight of the polyacrylate oil gel. In certain other embodiments, the polymers are present in the hair conditioning composition in an amount of from 0.05 to 10 weight %, preferably from 0.10 to 5 weight %, and more preferably from 0.15 to 1.5 weight %, based on the total weight of the composition.

Suitable polymerization techniques for preparing the polymers contained in the inventive personal care compositions include, for example, emulsion polymerization. Aqueous emulsion polymerization processes typically are conducted in an aqueous reaction mixture, which contains at least one monomer and various synthesis adjuvants, such as the free radical sources, buffers, and reductants in an aqueous reaction medium. In certain embodiments, a chain transfer agent may be used to limit molecular weight. The aqueous reaction medium is the continuous fluid phase of the aqueous reaction mixture and contains more than 50 weight % water and optionally one or more water miscible solvents, based on the weight of the aqueous reaction medium. Suitable water miscible solvents include, for example, methanol, ethanol, propanol, acetone, ethylene glycol ethyl ethers, propylene glycol propyl ethers, and diacetone alcohol. In certain embodiments, the aqueous reaction medium contains more than 90 weight % water, preferably more than 95 weight % water, and more preferably more than 98 weight % water, based on the weight of the aqueous reaction medium.

The polymer emulsions of the present invention are prepared using a“power feed” of monomers. Polymer emulsions made using power feed of monomers are known (see, e.g., US 9,587,057). In certain embodiments, the polymers are formed by providing a first monomer mixture comprising (1) 96 to 99.89 weight % of C₄-C₄ (meth) acrylate monomers (as described above), based on the total weight of monomers in the polymer emulsion, and (2) 0.1 to 2 weight % of (meth)acrylic acid monomer, based on the total weight of monomers in the polymer emulsion, (ii) providing a second monomer mixture comprising 0.01 to 2 weight % of at least one crosslinker, based on the total weight of monomers in the polymer emulsion, and (iii) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture. In certain embodiments, the C₄-C₄

(meth)acrylate monomers are selected from the group consisting of ethylhexyl (meth)acrylate, butyl (meth) acrylate, and combinations thereof. In certain embodiments, the crosslinker is selected from the group consisting of trimethylolpropane trimethacrylate, trimethylolpropane diallyl ether, ethylene glycol dimethylacrylate, and combinations thereof.

In certain embodiments, less than 10 weight % of the monomers is in the polymerization reactor prior to addition of the first monomer mixture, preferably less than 7 weight %, and more preferably less than 5 weight %. In certain embodiments, the monomers are added to the reactor over a period of time from 60 to 240 minutes, preferably from 70 to 170 minutes, and more preferably 80 to 100 minutes. In certain embodiments, the time of addition of the second monomer mixture to the first monomer mixture is from 50 to 120% of the time of addition of the first monomer mixture to the polymerization reactor, preferably from 70 to 100%, and more preferably from 85 to 100%. In certain embodiments, addition of the second monomer mixture to the first monomer mixture begins no later than addition of the first monomer mixture to the polymerization reactor, preferably at the same time.

The polymers of the present invention may be isolated by a spray drying process. While spray drying is one preferred embodiment of how to produce the dry powder, other suitable methods include, for example, freeze drying, a two-step process including the steps of (i) pan drying the emulsion and then (ii) grinding the pan dried material into a fine powder, coagulation of the acrylic emulsion and collection of the powder by filtration followed by washing and drying, fluid bed drying, roll drying, and freeze drying. Suitable techniques for spray drying the polymer beads of the present invention are known in the art, for example, as described in US 2014/0113992 Al. In certain embodiments, anti-caking agents are used when spray drying the polymer beads. Suitable anti-caking agents include, for example, mineral fillers (e.g., calcium carbonate, kaolin, titanium oxide, talc, hydrated alumina, bentonite, and silica), solid polymer particles with a 77 or T_m greater than 60°C (e.g., polymethylmethacrylate, polystyrene, and high density polyethylene), and water soluble polymers with a T_g greater than 60°C (e.g., polyvinyl alcohol and methylcellulose). The anti-caking agent can be mixed in the acrylic suspension prior to spray drying or introduced as a dry powder in the spray drying process. In certain embodiments, the anti-caking agent coats the polymer beads to prevent the beads from sticking to each other inner wall of the dryer. In certain embodiments, the anti-caking agent is present in an amount of from 0 to 20 weight %, and more preferably from 0.01 to 10 weight %, based on the total weight of the polymer beads.

The polyacrylate oil gels of the present invention also contain a cosmetically acceptable hydrophobic ester oil. In general, any hydrophobic ester oil or mixtures thereof which are toxicologically safe for human or animal use may constitute the oil base of the present invention. In certain embodiments, the hydrophobic ester oil comprises aliphatic C8-C24 alkyl triglycerides. Suitable hydrophobic ester oils include, for example, caprylic/capric triglycerides, saturated fatty esters and diesters (e.g., isopropyl palmitate, octyl palmitate, butyl stearate, isocetyl stearate, octadodecyl stearate, octadodecyl stearoyl stearate, diisopropyl adipate, and dioctyl sebacate), and animal oils and vegetable oils (e.g., mink oil, coconut oil, soybean oil, palm oil, corn oil, cocoa butter, sesame oil, sunflower seed oil, jojoba oil, olive oil, lanolin oil, almond oil, and argan oil). In certain embodiments, the hydrophobic ester oil is diffused in an oil base. Suitable oil bases include any oil or mixture of oils which are conventionally used in personal care products including, for example, paraffin oils, paraffin waxes, and fatty alcohols (e.g., stearyl alcohol, isostearyl alcohol, and isocetyl alcohol). In certain preferred embodiments, the hydrophobic ester oil comprises one or more of caprylic/capric triglycerides and sunflower seed oil. In certain embodiments, the hydrophobic ester oils are present in the poly acrylate oil gel in an amount of from 85 to 99.95 weight %, preferably from 90 to 99.8 weight %, and more preferably from 93 to 99 weight %, based on the total weight of the polyacrylate oil gel. In certain other embodiments, the hydrophobic ester oils are present in the hair conditioning composition in an amount of from 0.25 to 40 weight %, preferably from 0.9 to 15 weight %, and more preferably from 2.85 to 8.5 weight %, based on the total weight of the composition.

The hair conditioning compositions of the present invention also include a

dermatologically acceptable carrier. Such material is typically characterized as a carrier or a diluent that does not cause significant irritation to the skin and does not negate the activity and properties of active agent(s) in the composition. Examples of dermatologically acceptable carriers that are useful in the invention include, without limitation, water, such as deionized or distilled water, emulsions, such as oil-in-water or water-in-oil emulsions, alcohols, such as ethanol, isopropanol or the like, glycols, such as propylene glycol, glycerin or the like, creams, aqueous solutions, oils, ointments, pastes, gels, lotions, milks, foams, suspensions, powders, or mixtures thereof. The aqueous solutions may contain cosolvents, e.g., water miscible cosolvents. Suitable water miscible cosolvents include, for example, ethanol, propanol, acetone, ethylene glycol ethyl ethers, propylene glycol propyl ethers, and diacetone alcohol. In some embodiments, the composition contains from about 50 to about 99.7 percent by weight of the dermatologically acceptable carrier, based on the total weight of the composition.

The hair conditioning compositions of the present invention also contain at least one surface active agent. Suitable surface active agents include, for example, glyceryl esters, fatty alcohols, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Suitable glyceryl esters include, for example, glyceryl distearate, PEG- 100 Stearate, 2- ethyl hexyl oleate, glycerol trioleate, glyceryl monooleate, glyceryl monotallate, n-butyl stearate, neopentylglycol dioleate, pentaerythritol monooleate, pentaerythritol tetraoleate, and tmp- trioleate. Suitable fatty aclohols include, for example, decyl alcohol, decyl lauryl alcohol, lauryl alcohol, lauryl myristyl alcohol, lauryl cetyl alcohol, lauryl stearyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, octyl decyl alcohol, cetearyl alcohol, and octyldodecanol. Suitable nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkylglucosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Suitable nonionic surfactants also include

poly(oxyethylene)-poly(oxypropylene)-poly (oxy ethylene) tri -block copolymers .

Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are also commonly known as Poloxamers. Other suitable nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, and polyoxyalkylene glycol modified polysiloxane surfactants.

Alternatively, the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides.

Suitable cationic surfactants include, for example, ester quat, dodecyltrimethyl ammonium chloride/lauryltrimethyl ammonium chloride (LTAC), cetyltrimethyl ammonium chloride (CTAC), didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, and didocosyldimethyl ammonium chloride, and fatty acid amines and amides and their salts and derivatives (e.g., as aliphatic fatty amines and their derivatives).

Suitable anionic surfactants include, for example: (i) sulfonic acids and their salt derivatives, including alkyl, aralkyl, alkyl naphthalene, alkyl diphenyl ether sulfonic acids, and their salts, having at least 6 carbon atoms in the alkyl substituent (e.g., dodecyl benzene sulfonic acid, and its sodium salt or its amine salt); (ii) alkyl sulfates having at least 6 carbon atoms in the alkyl substituent (e.g., sodium lauryl sulfate); (iii) the sulfate esters of polyoxyethylene monoalkyl ethers; (iv) long chain carboxylic acid surfactants and their salts (e.g., lauric acid, steric acid, oleic acid, and their alkali metal and amine salts). Some other examples of anionic surfactants are alkali metal sulfosuccinates, sulfonated glyceryl esters of fatty acids (e.g., sulfonated monoglycerides of coconut oil acids), salts of sulfonated monovalent alcohol esters (e.g., sodium oleyl isothionate), amides of amino sulfonic acids (e.g., the sodium salt of oleyl methyl tauride), sulfonated products of fatty acid nitriles (e.g., palmitonitrile sulfonate), sulfonated aromatic hydrocarbons (e.g., sodium alpha-naphthalene monosulfonate),

condensation products of naphthalene sulfonic acids with formaldehyde, sodium octahydro anthracene sulfonate, alkali metal alkyl sulfates, ether sulfates having alkyl groups of eight or more carbon atoms (e.g., sodium lauryl ether sulfate), and alkylaryl sulfonates having one or more alkyl groups of eight or more carbon atoms (e.g., neutral salts of hexadecylbenzene sulfonic acid and C20 alkylbenzene sulfonic acid).

Suitable amphoteric surfactants include, for example, betaines (e.g.,

cocamidopropylbetaine), sultaines (e.g., cocamidopropylhydroxysultaine), lecithin, and hydrogenated lecithin.

In certain embodiments, the hair conditioning compositions include surface active agents in an amount of from 0.1 to 20 weight %, preferably 1 to 10 weight %, and more preferably from 2 to 5 weight %, based on the total weight of the hair conditioning composition.

In certain embodiments, the hair conditioning compositions further contain a conditioning agent. Suitable conditioning agents include, for example, cationic polymers, proteins, natural oils, silicones, waxes, and hydrocarbon oils. Suitable cationic polymers include, for example, cationically charge-modified polymers derived from various animal and plant sources, e.g., guar gum and guar gum derivatives, cellulose, proteins, polypeptides, chitosan, lanolin, starches, silicones, and cationically charge-modified cellulose polymers (e.g., polyquaternium-lO and polyquaternium-67). Suitable proteins include, for example, cocodimonium hydroxypropyl hydrolyzed casein, cocodimonium hydroxypropyl hydrolyzed collagen, cocodimonium hydroxypropyl hydrolyzed hair keratin, cocodimonium hydroxypropyl hydrolyzed keratin, cocodimonium hydroxypropyl hydrolyzed rice protein, cocodimonium hydroxypropyl hydrolyzed silk, cocodimonium hydroxypropyl hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl silk amino acids, cocoyl hydrolyzed collagen, cocoyl hydrolyzed keratin, hydrolyzed keratin, hydrolyzed oat flour, hydrolyzed silk, hydrolyzed silk protein, hydrolyzed soy protein, hydrolyzed wheat protein, hydrolyzed wheat protein, keratin, potassium cocoyl hydrolyzed collagen, TEA-cocoyl hydrolyzed collagen, and TEA-cocoyl hydrolyzed soy protein. Suitable natural oils include, for example, castor oil, triisocetyl citrate, sorbitan sesquioleate, Cio-is triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil, cottonseed oil, glyceryl triacetyl hydroxystearate, glyceryl triacetyl ricinoleate, glyceryl trioctanoate, hydrogenated castor oil, linseed oil, mink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, sunflower seed oil, tricaprin, trihydroxystearin, triisostearin, trilaurin, trilinolein, trimyristin, triolein, tripalmitin, tristearin, walnut oil, wheat germ oil, and cholesterol, perhydrosqualene or arara oil, and sweet almond, calophyllum, palm, castor, avocado, jojoba, argan, olive, and cereal germ oil. Suitable silicones include, for example, silicone fluids, gums, resins, elastomers, silicone surfactants and emulsifiers (e.g., silicone poly ethers), organofunctional silicones (e.g., aminofunctional silicones and alkylmethylsiloxanes). Suitable waxes include, for example, synthetic wax, ceresin, paraffin, ozokerite, illipe butter, beeswax, carnauba, microcrystalline, lanolin, lanolin derivatives, candelilla, cocoa butter, shellac wax, spermaceti, bran wax, capok wax, sugar cane wax, montan wax, whale wax, bayberry wax, animal waxes (e.g, beeswax), vegetable waxes (e.g., camauba, candelilla, ouricury or japan wax or cork fibre or sugarcane waxes), mineral waxes (e.g., paraffin or lignite wax or microcrystalline waxes), synthetic waxes (e.g., polyethylene waxes, waxes obtained by the Fischer-Tropsch synthesis, silicone waxes (e.g., polymethylsiloxane alkyls, alkoxys, and/or esters). In certain embodiments, the hair

conditioning compositions include conditioning agents in an amount of from 0.1 to 10 weight %, preferably 0.2 to 5 weight %, and more preferably from 0.3 to 2 weight %, based on the total weight of the hair conditioning composition.

In certain embodiments, the hair conditioning compositions further contain a thickener. Suitable thickeners include, for example, acrylates copolymers (e.g., ACULYN™ 33 available from The Dow Chemical Company), acrylates cross-polymers, urethanes (e.g., ACULYN™

46N available from The Dow Chemical Company), sodium alginate, gum arabic,

polyoxyethylene, guar gum, hydroxypropyl guar gum, ethoxylated alcohols, such as laureth-4 or polyethylene glycol 400, cellulose derivatives (e.g., hydroxy ethylcellulose, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, and polypropylhydroxy ethylcellulose), starch, and starch derivatives (e.g., hydroxyethylamylose and starch amylose), locust bean gum, electrolytes (e.g., sodium chloride and ammonium chloride), and saccharides (e.g., fructose and glucose), and derivatives of saccharides (e.g., PEG- 120 methyl glucose diolate). In certain embodiments, the thickeners are selected from the group consisting of acrylates copolymers, acrylates cross-polymers, urethanes, cellulose derivatives, saccharide derivatives, electrolytes, and mixtures thereof. In certain embodiments, the thickener is used in an amount sufficient to provide a viscosity in the hair conditioner composition of 500 mm²/s to 25,000 mm²/s. In certain embodiments, the hair conditioning compositions include thickeners in an amount of from 0.05 to 10 weight %, and preferably 0.05 to 5 weight %, based on the total weight of the hair conditioning composition. The hair conditioning compositions according to the present invention may be formulated by conventional mixing processes known to those skilled in the art. In certain embodiments, the formulation temperature is from 5 to l50°C, preferably from 25 to 70°C. The order of addition of the polymer particles, hydrophobic ester oil, surface active agent, and dermatologically acceptable carrier is not consequential, and thus can be mixed in any order of addition. In certain embodiments, polymer particles are pre-mixed with hydrophobic ester oil, and then emulsified into the dermatologically acceptable carrier.

Other additives may be included in the compositions of the invention such as, but not limited to, abrasives, absorbents, aesthetic components such as fragrances, pigments, colorings/colorants, essential oils, skin sensates, astringents (e.g., clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate), preservatives, anti-caking agents, a foam building agent, antifoaming agents, antimicrobial agents (e.g., iodopropyl butylcarbamate), antioxidants, binders, biological additives, buffering agents, bulking agents, chelating agents, chemical additives, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, external analgesics, film formers or materials, e.g., polymers, for aiding the film forming properties and substantivity of the composition (e.g., copolymer of eicosene and vinyl pyrrolidone), opacifying agents, pH adjusters, propellants, reducing agents, sequestrants, skin conditioning agents (e.g., humectants, including miscellaneous and occlusive), skin soothing and/or healing agents (e.g., panthenol and derivatives (e.g., ethyl panthenol), aloe vera, pantothenic acid and its derivatives, allantoin, bisabolol, and dipotassium glycyrrhizinate), skin treating agents, vitamins (e.g., Vitamin C) and derivatives thereof, silicones, and thickeners (e.g., hydroxyethyl cellulose). The amount of optional ingredients effective for achieving the desired property provided by such ingredients can be readily determined by one skilled in the art.

The hair conditioning compositions of the present invention are useful for the conditioning of hair, including, for example, ease of detangling, smoothness, pliability, slipperiness, and luster. Thus, in one aspect the present invention provides that the hair conditioning compositions may be used in a method for conditioning hair comprising topically administering to the hair a composition comprising (a) a polyacrylate oil gel, based on the total weight of the composition, wherein the polyacrylate oil gel comprises (i) at least one cosmetically acceptable hydrophobic ester oil, and (ii) one or more polymers comprising polymerized structural units of (1) 97 to 99.5 weight % of C₄-Cs (meth)acrylate monomers, and (2) 0.5 to 3 weight % of (meth)acrylic acid monomer, (b) a dermatologically acceptable carrier; and (c) a surface active agent. In practicing the methods of the invention, the hair conditioning compositions are generally administered topically by applying or spreading the compositions onto the hair. A person of ordinary skill in the art can readily determine the frequency with which the compositions should be applied. The frequency may depend, for example, on the level of dryness an individual is likely to encounter in a given day and/or the sensitivity of the individual to humidity. By way of non- limiting example, administration on a frequency of at least once per day may be desirable.

Some embodiments of the invention will now be described in detail in the following Examples.

EXAMPLES

Example 1

Preparation of Exemplary Polymer and Comparative Polymers

Exemplary polymers in accordance with the present invention and comparative polymers contain the components recited in Table 1.

Table 1. Exemplary and Comparative Polymers

Comparative

iBMA = Ao-butyl methacrylate

EHMA = 2-ethylhexyl methacrylate

MAA = methacrylic acid

TMPDE = trimethylolpropane diallyl ether

TMPTMA = trimethylolpropane trimethacrylate

⁺ Available from PolymerExpert

⁺⁺ Available from Kraton Performance Polymers, Inc.

Synthesis of Exemplary Polymers Using Power Feed Method Synthesis of exemplary P-El was carried out as follows. A three liter round bottom flask was equipped with a mechanical overhead stirrer, heating mantle, thermocouple, condenser and inlets for the addition of monomer, initiator and nitrogen. The kettle was charged with 470 grams deionized water and 7.46 grams of DS-4 (Polystep A-16-22: sodium dodecylbenzene sulfonate from Stepan). The kettle contents were set to stir with a nitrogen flow and heated to 87-89 °C. To a plastic lined vessel, 7.00 grams of DS-4 and 181.65 grams deionized water was added and mixed with overhead stirring. 410.22 grams of Ao-butyl methacrylate, 100.62 grams of 2-ethylhexyl methacrylate, and 5.16 grams of methacrylic acid was charged to the vessel and allowed to form a smooth, stable monomer emulsion. A power feed solution of 34.98 grams of Ao-butyl methacrylate, 8.58 grams of 2-ethylhexyl methacrylate, 0.44 grams of methacrylic acid, and 0.56 grams of TMPDE was prepared and set aside. An initial catalyst charge of 0.28 grams of ammonium persulfate and 12.71 grams of deionized water was prepared and set aside. A kettle buffer solution of 1.92 grams of ammonium bicarbonate and 12.71 grams of deionized water was prepared and set aside. A preform seed of 22.38 grams was removed from the stable monomer emulsion and put into a small beaker. A rinse of 16.8 grams of deionized water was prepared. A co-feed catalyst charge of 0.28 grams of ammonium persulfate and 49.22 grams of deionized water was prepared and set aside.

When the kettle was at temperature, the kettle buffer solution and initial catalyst solution were added to the reactor, followed by the perform seed and rinse. The reaction was monitored for a small exotherm. After the exotherm, the temperature control was adjusted to 83-85 °C.

The powerfeed solution was set up to feed directly into the monomer emulsion vessel at a rate of 0.55 grams/minute over 80 minutes and was started at the same time as the monomer emulsion feed. The monomer emulsion feed was added to the kettle, sub-surface, at a rate of 4.40 grams/minute for 15 minutes. After 15 minutes, the rate was increased to 8.80 grams/minutes for 75 minutes, giving a total feed time of 90 minutes. While the monomer emulsion feed was added to the kettle, the co-feed catalyst solution was also added over 90 minutes at a rate of 0.55 grams/minute. At the completion of the feeds, 16.8 grams of deionized water was added as a rinse. The reaction was then held for 20 minutes at 83-85 °C.

During the hold, a chase promoter of 3.77 grams of a 0.15% iron sulfate heptahydrate solution was prepared. A chase activator solution of 1.12 grams of Ao-ascorbic acid dissolved in 36.40 grams of deionized water was prepared. A chase catalyst solution of 2.14 grams of 70% ieri-butyl hydroperoxide in 35.40 grams of deionized water was prepared.

After the 20 minute hold, the reaction was cooled to 80 °C. At 80 °C, the chase promoter solution was added as a shot to the kettle. The kettle contents were then cooled to 70 °C, while adding the chase activator and chase catalyst solutions separately by syringe over 60 minutes at a feed rate of 0.7 grams/minute. The reaction was held for 10 minutes, and then cooled to room temperature. At room temperature, the emulsion was filtered through a 100 mesh bag.

All other exemplary polymers were prepared substantially as described above, with the appropriate changes in monomer and monomer amounts as recited in Table 1.

Example 2

Particle Size Characterization of Exemplary Polymers

Exemplary polymers as prepared in Example 1 were evaluated for particle size as shown in Table 2.

Table 2. Particle Size Characterization

The particle size distributions was determined by light scattering using a Malvern Mastersizer 2000 Analyzer equipped with a 2000uP module. Approximately 0.5 g of polymer emulsion samples were pre-diluted into 5 mL of 0.2 weight % active Triton 405 in degassed, DI water (diluents). The pre-diluted sample was added drop-wise to the diluent filled 2000uP module while the module was pumped at 1100 rpm. Red light obscurations were targeted to be between 4 and 8%. Samples were analyzed using a Mie scattering module (particle real refractive index of 1.48 and absorption of zero: Diluent real refractive index of 1.330 with absorption of zero).

A general purpose (spherical) analysis model with“normal sensitivity” was used to analyze the diffraction patterns and convert them into particle size distributions.

Example 3

Spray Drying of Exemplary Polymers

Exemplary polymers as prepared in Example 1 were spray dried according to the following procedure. A two-fluid nozzle atomizer was equipped on a Mobile Minor spray dryer (GEA Process Engineering Inc.). The spray drying experiments were performed under an inert atmosphere of nitrogen. The nitrogen supplied to the atomizer at ambient temperature was set at 1 bar and 50% flow, which is equivalent to 6.0 kg/hour of flow rate. The polymer emulsion was fed into the atomizer at about 30 mL/min using a peristaltic pump (Masterflex L/S). Heated nitrogen was used to evaporate the water. The inlet temperature was set at l40°C, and the outlet temperature was equilibrated at 40-50°C by fine tuning the emulsion feed rate. The resulting polymer powder was collected in a glass jar attached to the cyclone and subsequently vacuum dried at room temperature to removed residual moisture.

Example 4

Preparation of Exemplary Conditioning Oil Formulations

Exemplary conditioning oil formulations according to the present invention including exemplary polymers as prepared in Example 3, comparative conditioning oil formulations, and control leave-in hair conditioning formulations, contain the components recited in Tables 3(a)- (d).

Table 3(a). Exemplary and Control Conditioning Oil Formulations

Table 3(b). Exemplary, Comparative, and Control Conditioning Oil Formulations

Table 3(c). Exemplary and Control Conditioning Oil Formulations

Table 3(d). Exemplary and Control Conditioning Oil Formulations

Exemplary conditioning oil formulations were formulated by mixing the exemplary polymers as prepared in Example 3 together with the other components in the amounts specified in Tables 3(a)-(d) under stirring at 500 rpm at 50°C for 1 hour.

Example 5

Conditioning Effect of Conditioning Oil Formulations

The conditioning effect of exemplary conditioning oil formulations as prepared in Example 4 was measured using the INSTRON Dry Combing Method. Medium bleached European human hair from International Hair Importers was used for testing the conditioning oil formulations prepared herein. Each tress weighed about 2.0 grams. Each tress was rinsed for 15 seconds under a stream of 40°C tap water. Using a pipette, 0.4 grams (0.2 ml per gram of hair) of a solution containing nine percent of sodium lauryl sulfate was applied and lathered through the tress for 30 seconds. The tress was rinsed for 30 seconds under running water. Excess water was removed from the tress by passing the tress between the index and middle fingers of the hand. The tresses were clipped to vertical racks and dried. Once dry, the conditioning oil formulations were applied to the tresses in the amount of 0.3 grams (0.15 ml per gram of hair), and the tresses were stroked 10 times with fingers to distribute evenly on hair.

For formulations prepared in Tables 3(a), 3(b), and 3(d), after 16 hours, 0.18 grams (0.4 ml per gram of hair) grams of EverSleek Sulfate-Free shampoo (available from L’ Oreal) were applied to the tresses and lathered through the tresses for 30 seconds. For formulations prepared in Table 3(c), after 1 hour, 0.18 grams (0.4 ml per gram of hair) grams of EverSleek Sulfate-Free shampoo (available from L’Oreal) were applied to the tresses and lathered through the tresses for 30 seconds. The tresses were then rinsed for 30 second under running water. Excess water was removed from the tresses by passing the tresses between the index and middle fingers of the hand. The tresses were clipped to vertical racks and dried.

The tresses were combed once before performing an INSTRON study. INSTRON combing is used for determining conditioning performance by the ease of dry combing. The test employs an INSTRON strain gauge, which is equipped to measure the force required to comb the hair. The conditioning performance is based on the ability of a particular hair treatment formulation, such as a shampoo or a hair conditioner, to reduce the force required to comb the hair with the INSTRON strain gauge. The force is reported as an Average Combing Load (“ACL”). The lower the ACL value, the better the conditioning effect imparted by the formulation being tested. Three tresses per treatment and 5 measurements per tress were averaged to generate the combing data. According to the INSTRON Dry Combing method, hair is detangled by combing the tress 3 times. Then hair is retangled by swirling the tress clockwise 3 times and swirling it counter clockwise 3 times. The tress is then placed on a hanger and INSTRON combed. Retangle and INSTRON combing are repeated until all data points are collected. An ACL for three tresses is measured for each treatment. The effectiveness of a treatment can then be expressed as an ACL of the treated tress or percent reduction in ACL, calculated using the relationship:

ACL Reduction % =

((Sample hair ACL - Control hair ACL) x 100) / Control hair ACL

The ACL and percent reduction in ACL for exemplary oil conditioning formulations against the Controls are shown in Tables 4(a)-(d).

Table 4(a). ACL of Exemplary and Control Conditioning Oil Formulations

Table 4(b). ACL of Exemplary. Comparative, and Control Conditioning Oil Formulations

Table 4(c). ACL of Exemplary, Comparative, and Control Conditioning Oil Formulations

Table 4(d). ACL of Exemplary and Control Conditioning Oil Formulations

provide a significant improvement in the dry conditioning properties of hair.

Example 6

Preparation of Exemplary Hair Conditioner Formulations

Exemplary hair conditioner formulations according to the present invention including exemplary polymers as prepared in Example 3, and control leave-in hair conditioning formulations, contain the components recited in Tables 5(a)-(b).

Table 5(a). Exemplary and Control Hair Conditioner Formulations

²VERSENE™ 220 available Dow Chemical

³Crodacol™ CS50 available from Croda

⁴Arlacel™ 165 available from Croda

⁵NEOLONE™ PE available from Dow Chemical Table 5(b). Exemplary and Control Hair Conditioner Formulations

²VERSENE™ 220 available Dow Chemical

³Crodacol™ CS50 available from Croda

4Arlacel™ 165 available from Croda

⁵NEOLONE™ PE available from Dow Chemical

Deionized water was added to the mixing vessel and heated to 70°C. With moderate agitation, the hydroxyethyl cellulose was dispersed until fully dissolved. Heat was decreased to 60°C and cetearyl alcohol, PEG- 100 stearate, glyceryl stearate, and silicone fluid were added. The hair conditioner was mixed for 3 minutes and then tetrasodium EDTA was added and mixed for 3 minutes. When temperature was below 40°C, the phenoxyethanol and

methylisothiazolinone were added. The water loss was compensated for and the formulation was mixed for an additional 5 minutes. The final pH of the conditioner formulations were all approximately 5.

Example 7

Conditioning Effect of Hair Conditioner Formulations

The conditioning effect of exemplary hair conditioner formulations as prepared in Example 6 were measured using the INSTRON Dry Combing Method. Medium bleached European human hair from International Hair Importers was used for testing the conditioning oil formulations prepared herein. Each tress weighed about 2.0 grams. Each tress was rinsed for 15 seconds under a stream of 40°C tap water. Using a pipette, 0.4 grams of a solution containing nine percent of sodium lauryl sulfate was applied and lathered through the tress for 30 seconds. The tress was rinsed for 30 seconds under running water. Excess water was removed from the tress by passing the tress between the index and middle fingers of the hand. The tresses were clipped to vertical racks and dried. Once dry, hair tresses were rinsed with tap water for 30 seconds at 40°C. The test conditioner was applied to the tresses in the amount of 0.8 grams, and the tresses were stroked for 60 seconds. The tress were rinsed for 30 seconds under tap water at 40°C. Excess water was removed by pulling the tress through the index and middle fingers of the hand. The tresses were allowed to dry separately on a paper towel overnight at room temperature.

The tresses were combed once before performing an INSTRON study as described in Example 5. The ACL and percent reduction in ACL for exemplary hair conditioner

formulations against the Controls are shown in Tables 6(a)-(b).

Table 6(a). ACL of Exemplary and Control Hair Conditioner Formulations

Table 6(b). ACL of Exemplary and Control Hair Conditioner Formulations

The results show that the exemplary hair conditioner formulations of the present invention provide a significant improvement in the dry conditioning properties of hair.

Claims

WHAT IS CLAIMED IS:

1. A hair conditioning composition comprising:

(a) a polyacrylate oil gel, based on the total weight of the composition, wherein the polyacrylate oil gel comprises

(i) at least one cosmetically acceptable hydrophobic ester oil, and

(ii) one or more polymers comprising polymerized structural units of

(1) 96 to 99.89 weight % of C₄-Cx (meth) acrylate monomers,

(2) 0.1 to 2 weight % of (meth)acrylic acid monomer, and

(3) 0.01 to 2 weight % of at least one crosslinker, wherein the polymers are formed by (1) providing a first monomer mixture comprising the C₄- C₈ (meth)acrylate monomers and (meth)acrylic acid monomer, (2) providing a second monomer mixture comprising the crosslinker, and (3) adding the first monomer mixture to a

polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture;

(b) a dermatologically acceptable carrier; and

(c) a surface active agent.

2. The hair conditioning composition of claim 1, wherein the surface active agent is selected from the group consisting of glyceryl esters, fatty alcohols, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and mixtures thereof.

3. The hair conditioning composition of claim 1 further comprising (d) a conditioning agent selected from the group consisting of cationic polymers, proteins, natural oils, silicones, waxes, and mixtures thereof.

4. The hair conditioning composition of claim 1 further comprising (e) a thickener selected from the group consisting of a thickener selected from the group consisting of acrylates copolymers, acrylates cross-polymers, urethanes, cellulose derivatives, saccharide derivatives, electrolytes, and mixtures thereof.

5. The hair conditioning composition of claim 1, wherein the hydrophobic ester oil comprises one or more aliphatic C8-C24 alkyl triglycerides.

6. The hair conditioning composition of claim 1, wherein the C₄-Cs (meth)acrylate monomers are selected from the group consisting of ethylhexyl (meth)acrylate, butyl

(meth)acrylate, and mixtures thereof.

7. The composition of claim 1, wherein the crosslinker is selected from the group consisting of trimethylolpropane trimethacrylate, trimethylolpropane diallyl ether, ethylene glycol dimethylacrylate, and mixtures thereof.

8. The hair conditioning composition of claim 1,

wherein the polyacrylate oil gel is present in an amount of from 0.1 to 20 weight %, based on the total weight of the composition,

wherein the at least one cosmetically acceptable hydrophobic ester oil comprises one or more aliphatic C8-C24 alkyl triglycerides,

wherein the C₄-Cs (meth)acrylate monomers are selected from the group consisting of ethylhexyl (meth)acrylate, butyl (meth)acrylate, and mixtures thereof,

wherein the crosslinker is selected from the group consisting of trimethylolpropane trimethacrylate, trimethylolpropane diallyl ether, ethylene glycol dimethylacrylate, and mixtures thereof,

wherein the dermatologically acceptable carrier is present in an amount of from 50 to 99.7 weight %, based on the total weight of the composition,

wherein the surface active agent is present in an amount of from 0.1 to 20 weight %, based on the total weight of the composition,

wherein the surface active agent is selected from the group consisting of glyceryl esters, fatty alcohols, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and mixtures thereof,

wherein the composition further comprises (d) 0.1 to 10 weight % of a conditioning agent, based on the total weight of the composition, and

wherein the conditioning agent is selected from the group consisting of cationic polymers, proteins, natural oils, silicones, waxes, and mixtures thereof.

9. A method for preparing a hair conditioning composition comprising a polyacrylate oil gel, a dermatologically acceptable carrier, and a surface active agent comprising:

(a) preparing a polymer emulsion by the steps of

(i) providing a first monomer mixture comprising (1) 96 to 99.89 weight % of C₄- C₈ (meth)acrylate monomers, based on the total weight of monomers in the polymer emulsion, and (2) 0.1 to 2 weight % of (meth)acrylic acid monomer, based on the total weight of monomers in the polymer emulsion,

(ii) providing a second monomer mixture comprising 0.01 to 2 weight % of at least one crosslinker, based on the total weight of monomers in the polymer emulsion, and

(iii) adding the first monomer mixture to a polymerization reactor while simultaneously adding the second monomer mixture to the first monomer mixture;

(b) spray drying the polymer emulsion to obtain polymer particles; and (c) mixing the polymer particles, the dermatologically acceptable carrier, and the surface active agent at a temperature of from 5 to l50°C.

10. A method for conditioning hair, comprising topically administering to the hair an effective amount of a hair conditioning composition comprising

(i) at least one cosmetically acceptable hydrophobic ester oil, and

(ii) one or more polymers comprising polymerized structural units of

(1) 96 to 99.89 weight % of C₄-Cs (meth) acrylate monomers,

(2) 0.1 to 2 weight % of (meth)acrylic acid monomer, and

(b) a dermatologically acceptable carrier; and

(c) a surface active agent.