Formulation and method for the care of damaged hair

Abstract

A hair care formulation for improving the tensile strength of damage hair is provided, comprising: (a) a dermatogically acceptable vehicle; and (b) a tensile strength improving additive; wherein the tensile strength improving additive comprises: (b1) a (±)-α-tocopherol; and (b2) a carboxy functional organosiloxane compound of formula (I) wherein x is 0 to 25; wherein each R1 is independently selected from an alkylene radical containing 1 to 10 carbon atoms; wherein each R2 is independently selected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbonoxy-functional group of 1 to 18 carbon atoms.

Description

[0001] The present invention relates to a hair care formulation and method for restructuring,strengthening and / or rejuvenating hair. In particular, the present invention relates to a haircare formulation for improving the tensile strength and fatigue resistance of damaged hair,comprising: (a) a dermatologically acceptable vehicle; and (b) a tensile strength improvingadditive; wherein the tensile strength improving additive comprises: (bl) a (±)-a-tocopherol;and (b2) a carboxy functional organosiloxane compound of formula IR²R²R²Ο-R¹-Si-O-Si-O-Si-R¹-OH| | |HOR²R²R²x(I)wherein x is 0 to 25; wherein each R¹ is independently selected from an alkylene radicalcontaining 1 to 10 carbon atoms; wherein each R² is independently selected from the groupconsisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms,an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbonoxy-functional group of 1 to 18carbon atoms. The present invention further relates to a method of improving the Young'smodulus and / or break stress of damaged hair.

[0002] Modifications to the appearance of human hair is a ubiquitous component of personalhygiene. A variety of products and treatments are marketed to consumers to facilitate themodification of the appearance of their hair including chemical treatments for changing thecolor of the hair (e.g., hair dyes, lighteners or bleaches) and for changing the shape of the hair(e.g., straightening or curling). Such chemical treatments tend to be popular amongconsumers because the effects can be dramatic and long lasting. A significant drawback tochemical treatments is the strain and damage exhibited in the treated hair. This derives fromchanges to the chemical and physical structure of the treated hair. Chemical treatments tendto remove barriers from the surface of the hair cuticles, which leads to the hair becomingbrittle, dry and more susceptible to breakage.

[0003] Methods and kits for treating hair are disclosed by Pressly et al. in U.S. Patent No.11,191,707. Pressly et al. disclose a kit comprising: (a) a first formulation comprising one ormore relaxing agents and having an alkaline pH, and (b) a second formulation comprising anactive agent, wherein the active agent has the following structure:(D)s| (A)p---(R)n---(C)r| (B)qwherein A, B, C, and D are reactive moieties containing one or more charges, and whereineach of A, B, C, and D independently contains a moiety selected from the group consisting ofa vinyl sulfone, an acrylate group, a methacrylate group, a styrene group, an acryl amidegroup, a methacryl amide group, a maleate group, a fumarate group, and an itaconate group;R is a linker that contains two or more charges, wherein the charges are opposite to thecharges on the reactive moieties, wherein n=1-10, and wherein R is not a polymer, andwherein the sum of the charges is zero; wherein the reactive moieties are ionically bound tothe linker; and wherein each occurrence of p, q, r, and s is independently an integer from 0 to25, wherein the sum of p+q+r+s is equal to or greater than 2.

[0004] Notwithstanding, there remains a continuing need for hair care formulations whichmay effectively restructure, strengthen and / or rejuvenate hair to prevent or remediate theeffects of damage visited on the hair from chemical, mechanical and environmental insults byimproving the tensile strength of damaged hair (i.e., increasing the Young's modulus and / orbreak stress of the hair).

[0005] The present invention provides a hair care formulation for improving the tensilestrength of damaged hair, comprising: (a) a dermatologically acceptable vehicle; and (b) atensile strength improving additive; wherein the tensile strength improving additivecomprises: (b1) a (±)-a-tocopherol; and (b2) a carboxy functional organosiloxane compoundof formula IR²R²R²Ο-R¹-Si-O-Si-O-Si-R¹-OH| | |HOR²R²R²x(I)wherein x is 0 to 25; wherein each R¹ is independently selected from an alkylene radicalcontaining 1 to 10 carbon atoms; wherein each R² is independently selected from the groupconsisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms,an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbonoxy-functional group of 1 to 18carbon atoms.

[0006] The present invention provides a method for improving the tensile strength ofdamaged hair comprising: (a) providing a damaged hair, wherein the damaged hair is selectedfrom the group consisting of chemically damaged hair, thermally damaged hair, mechanicallydamaged hair and combinations thereof; (b) selecting a hair care formulation, comprising:(A) a dermatologically acceptable vehicle; and (B) a tensile strength improving additive;wherein the tensile strength improving additive comprises: (B1) a (±)-a-tocopherol; and (B2)a carboxy functional organosiloxane compound of formula I, wherein x is 0 to 25; whereineach R¹ is independently selected from an alkylene radical containing 1 to 10 carbon atoms;wherein each R² is independently selected from the group consisting of an alkyl group of 1 to18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbonatoms, and a hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and (c) applying thehair care formulation to the damaged hair to provide a treated hair.

[0007] The present invention provides a method for improving the tensile strength ofdamaged hair comprising: (a) providing a damaged hair, wherein the damaged hair is selectedfrom the group consisting of chemically damaged hair, thermally damaged hair, mechanicallydamaged hair and combinations thereof; (b) selecting a hair care formulation, comprising:(A) a dermatologically acceptable vehicle; and (B) a tensile strength improving additive;wherein the tensile strength improving additive comprises: (B1) a (±)-a-tocopherol; and (B2)a carboxy functional organosiloxane compound of formula I, wherein x is 0 to 25; whereineach R¹ is independently selected from an alkylene radical containing 1 to 10 carbon atoms;wherein each R² is independently selected from the group consisting of an alkyl group of 1 to18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbonatoms, and a hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and (c) applying thehair care formulation to the damaged hair to provide a treated hair; wherein the damaged hairis bleached hair and wherein the method comprises improving the Young's Modulus of thetreated hair; wherein the Young's Modulus improvement, YM_Improvement, for the treated hair isat least a 10%; wherein the YM_Improvement is determined according to the formulaYM_Improvement = [ (YM_T - YM_D) / YM_D ] × 100%wherein YM_Improvement is the % improvement in the Young's Modulus for the treated hair;wherein YM_T is the Young's Modulus for the treated hair and wherein YM_D is the Young'sModulus for the damaged hair before treatment with the hair care formulation.

[0008] The present invention provides a method for improving the tensile strength ofdamaged hair comprising: (a) providing a damaged hair, wherein the damaged hair isbleached hair; (b) selecting a hair care formulation, comprising: (A) a dermatologicallyacceptable vehicle; and (B) a tensile strength improving additive; wherein the tensile strengthimproving additive comprises: (B1) a (±)-a-tocopherol; and (B2) a carboxy functionalorganosiloxane compound of formula I, wherein x is 0 to 25; wherein each R¹ isindependently selected from an alkylene radical containing 1 to 10 carbon atoms; whereineach R² is independently selected from the group consisting of an alkyl group of 1 to 18carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbonatoms, and a hydrocarbonoxy-functional group of 1 to 18 carbon atoms; and (c) applying thehair care formulation to the damaged hair to provide a treated hair; wherein the methodcomprises improving the Young's Modulus of the treated hair; wherein the Young's Modulusimprovement, YM_Improvement, for the treated hair is at least a 10%; wherein the YM_Improvement isdetermined according to the formulaYM_Improvement = [ (YM_T - YM_D) / YM_D ] × 100%wherein YM_Improvement is the % improvement in the Young's Modulus for the treated hair;wherein YM_T is the Young's Modulus for the treated hair and wherein YM_D is the Young'sModulus for the damaged hair before treatment with the hair care formulation; and whereinthe method comprises improving the break stress of the treated hair; wherein the break stressimprovement, BS_Improvement, for the treated hair is at least 5%; wherein the BS_Improvement isdetermined according to the formulaBS_Improvement = [ (BS_T - BS_D) / BS_D ] × 100%wherein BS_Improvement is the % improvement in the break stress for the treated hair; whereinBS_T is the break stress for the treated hair and wherein BS_D is the break stress for thedamaged hair before treatment with the hair care formulation.DETAILED DESCRIPTION

[0009] We have surprisingly found that a tensile strength improving additive comprising acombination of a (+)-a-tocopherol and a carboxy functional organosiloxane compound offormula IR²R²R²Ο-R¹-Si-O-Si-O-Si-R¹-OH| | |HOR²R²R²x(I)wherein x is 0 to 25; wherein each R¹ is independently selected from an alkylene radicalcontaining 1 to 10 carbon atoms; wherein each R² is independently selected from the groupconsisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms,an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbonoxy-functional group of 1 to 18carbon atoms; can significantly improve the tensile strength (i.e., increasing the Young'sModulus and / or the break stress) of damaged hair (preferably, bleached Caucasian scalp hair)treated therewith, while also improving the fatigue resistance of the damaged hair.

[0010] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.

[0011] As used herein, unless otherwise indicated, the phrase "molecular weight" or MWrefers to the weight average molecular weight as measured in a conventional manner with gelpermeation chromatography (GPC) and conventional standards, such as polystyrenemolecular weight standards. GPC techniques are discussed in detail in Modern SizeExclusion Liquid Chromatography - Practice of Gel Permeation and Gel FiltrationChromatography, Second Edition, A.M. Striegel, W. W. Yau, J. J. Kirkland, D. D. Bly; JohnWiley & Sons, Inc. 2009. Molecular weights are reported herein in units of Daltons, orequivalently, g / mol.

[0012] The term "dermatologically acceptable" as used herein and in the appended refers toingredients that are typically used for topical application to the skin and is intended tounderscore that materials that are toxic when present in the amounts typically found in skincare compositions are not contemplated as part of the present invention.

[0013] Preferably, the hair care formulation for improving the tensile strength (i.e., Young'smodulus and / or break stress) of damaged hair of the present invention is for damaged hair(preferably, damaged mammalian hair; more preferably, damaged human hair; mostpreferably, damaged human scalp hair) selected from the group consisting of chemicallydamaged hair (e.g., hair damaged from chemical treatments such as dyeing, bleaching,perming), thermally damaged hair (e.g., hair damaged from exposure to heat via ironing,forced drying, styling), physical damaged hair (e.g., hair damaged from physical abuse suchas friction, pulling, curling) and combinations thereof. More preferably, the hair careformulation for improving the tensile strength of damaged hair of the present invention is forchemically damaged hair (preferably, chemically damaged human scalp hair). Mostpreferably, the hair care formulation for improving the tensile strength of damaged hair of thepresent invention is for bleached hair (preferably, human bleached scalp hair).

[0014] Preferably, the hair care formulation for improving the tensile strength (i.e.,increasing the Young's modulus and / or break stress) of damaged hair (preferably, damagedmammalian hair; more preferably, damaged human hair; most preferably, damaged humanscalp hair) of the present invention is selected from the group consisting of a leave onformulation and a rinse off formulation. More preferably, the hair care formulation forimproving the tensile strength of damaged hair (preferably, damaged mammalian hair; morepreferably, damaged human hair; most preferably, damaged human scalp hair) of the presentinvention is a leave on formulation. Most preferably, the hair care formulation of the presentinvention is for improving the tensile strength of damaged hair (preferably, damagedmammalian hair; more preferably, damaged human hair; most preferably, damaged humanscalp hair) of the present invention is a leave on hair conditioning formulation.

[0015] Preferably, the hair care formulation for improving the tensile strength (i.e.,increasing the Young's modulus and / or break stress) of damaged hair (preferably, wherein thedamaged hair is selected from the group consisting of chemically damaged hair, thermallydamaged hair, mechanically damaged hair and combinations thereof)(preferably, wherein thedamaged hair is damaged mammalian hair (more preferably, damaged human hair; mostpreferably, damaged human scalp hair)) of the present invention, comprises: (a) adermatologically acceptable vehicle (preferably, 25 to 99.9 wt% (more preferably, 45 to99.75 wt%; still more preferably, 79 to 99.5 wt%; most preferably, 84 to 99.25 wt%), basedon weight of the hair care formulation, of a dermatologically acceptable vehicle); and (b) atensile strength improving additive (preferably, 0.1 to 10 wt% (more preferably, 0.25 to 7wt%; still more preferably, 0.5 to 6 wt%; most preferably, 0.75 to 1.25 wt%) based on weightof the hair care formulation, of the tensile strength improving additive); wherein the tensilestrength improving additive comprises: (b1) a (±)-a-tocopherol (preferably, 0.001 to 1 wt%(more preferably, 0.01 to 0.5 wt%; still more preferably, 0.02 to 0.2 wt%; most preferably,0.05 to 0.15 wt%), based on weight of the tensile strength improving additive, of the(±)-a-tocopherol); and (b2) a carboxy functional organosiloxane compound of formula I(preferably, 99 to 99.999 wt% (more preferably, 99.5 to 99.99 wt%; still more preferably,99.8 to 99.98 wt%; most preferably, 99.85 to 99.95 wt%), based on weight of the tensilestrength improving additive, of the carboxy functional organosiloxane compound of formulaI)R²R²R²Ο-R¹-Si-O-Si-O-Si-R¹-OH| | |HOR²R²R²x(I)wherein x is 0 to 25 (preferably, 2 to 20; more preferably, 4 to 15; still more preferably, 5 to10; most preferably, 7); wherein each R¹ is independently selected from an alkylene radicalcontaining 1 to 10 carbon atoms (preferably, an alkylene radical containing 1 to 4 carbonatoms; more preferably, an alkylene radical containing 1 to 3 carbon atoms; most preferablya -CH₂CH₂- group and a -CHCH₃- group); wherein each R² is independently selected fromthe group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbonoxy-functionalgroup of 1 to 18 carbon atoms (preferably, an alkyl group of 1 to 18 carbon atoms, an arylgroup of 6 to 18 carbon atoms and a hydrocarbonoxy-functional group of 1 to 18 carbonatoms; more preferably, an alkyl group of 1 to 4 carbon atoms and an aryl group of 6 to 12carbon atoms; still more preferably, an alkyl group of 1 to 4 carbon atoms; most preferably, amethyl group).

[0016] More preferably, the hair care formulation for improving the tensile strength ofdamaged hair (preferably, wherein the damaged hair is selected from the group consisting ofchemically damaged hair, thermally damaged hair, mechanically damaged hair andcombinations thereof)(preferably, wherein the damaged hair is damaged mammalian hair(more preferably, damaged human hair; most preferably, damaged human scalp hair)) of thepresent invention, comprises: (a) a dermatologically acceptable vehicle (preferably, 25 to99.9 wt% (more preferably, 45 to 99.75 wt%; still more preferably, 79 to 99.5 wt%; mostpreferably, 84 to 99.25 wt%), based on weight of the hair care formulation, of adermatologically acceptable vehicle); and (b) a tensile strength improving additive(preferably, 0.1 to 10 wt% (more preferably, 0.25 to 7 wt%; still more preferably, 0.5 to 6wt%; most preferably, 0.75 to 1.25 wt%), based on weight of the hair care formulation, of thetensile strength improving additive); wherein the tensile strength improving additivecomprises: wherein the tensile strength improving additive comprises: (bl) a (±)-α-tocopherol (preferably, 0.001 to 1 wt% (more preferably, 0.01 to 0.5 wt%; still morepreferably, 0.02 to 0.2 wt%; most preferably, 0.05 to 0.15 wt%), based on weight of thetensile strength improving additive, of the (±)-a-tocopherol); and (b2) a carboxy functionalorganosiloxane compound of formula I (preferably, 99 to 99.999 wt% (more preferably, 99.5to 99.99 wt%; still more preferably, 99.8 to 99.98 wt%; most preferably, 99.85 to 99.95 wt%),based on weight of the tensile strength improving additive, of the carboxy functionalorganosiloxane compound of formula I)R²R²R²Ο-R¹-Si-O-Si-O-Si-R¹-OH| | |HOR²R²R²x(I)wherein x is 0 to 25 (preferably, 2 to 20; more preferably, 4 to 15; still more preferably, 5 to10; most preferably, 7); wherein each R¹ is independently selected from an alkylene radicalcontaining 1 to 10 carbon atoms (preferably, an alkylene radical containing 1 to 4 carbonatoms; more preferably, an alkylene radical containing 1 to 3 carbon atoms; most preferablya -CH2CH2- group and a -CHCH3- group); wherein each R² is independently selected fromthe group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbonoxy-functionalgroup of 1 to 18 carbon atoms (preferably, an alkyl group of 1 to 18 carbon atoms, an arylgroup of 6 to 18 carbon atoms and a hydrocarbonoxy-functional group of 1 to 18 carbonatoms; more preferably, an alkyl group of 1 to 4 carbon atoms and an aryl group of 6 to 12carbon atoms; still more preferably, an alkyl group of 1 to 4 carbon atoms; most preferably, amethyl group); and with any one or more of the following provisos (i)-(v) (i.e., all provisostaken individually, all possible combinations of two or more provisos and all of the provisostogether are contemplated):(i) with the proviso that the hair care formulation comprises less than 0.01 wt%(preferably, < 0.005 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%;yet more preferably, < 0.00001 wt%; most preferably, 0 wt%), based on weight of the haircare formulation, of a cationic polymer;(ii) with the proviso that the hair care formulation comprises less than 0.05 wt%(preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%;yet more preferably, < 0.00001 wt%; most preferably, 0 wt%), based on weight of the haircare formulation, of a polymer selected from the group consisting of an anionic polymer, anonionic polymer and mixtures thereof;(iii) with the proviso that the hair care formulation comprises less than 0.05 wt%(preferably, < 0.01 wt%; more preferably, < 0.001 wt%; still more preferably, < 0.0001 wt%;yet more preferably, < 0.00001 wt%; most preferably, 0 wt%), based on weight of the haircare formulation, of an oxazoline functionalized polymer; wherein the oxazolinefunctionalized polymer is a molecule having repeating units and at least one oxazoline group(preferably having a molecular weight of > 5,000 g / mol (more preferably, > 10,000 g / mol);and(iv) with the proviso that the hair care formulation comprises less than 0.005 wt%(preferably, < 0.001 wt%; more preferably, < 0.0005 wt%; still more preferably, < 0.0001wt%; yet more preferably, < 0.00001 wt%; most preferably, 0 wt%), based on weight of thehair care formulation, of a polycarbodiimide compound; wherein the polycarbodiimidecompound has at least two carbodiimide groups per molecule and wherein the carbodiimidegroups are linear triatomic moieties depicted by the formula -(N=C=N)-.

[0017] Preferably, the hair care formulation for improving the tensile strength (i.e.,increasing the Young's modulus and / or break stress) of damaged hair of the presentinvention, comprises: 25 to 99.9 wt% (preferably, 45 to 99.75 wt%; more preferably, 79 to99.5 wt%; most preferably, 84 to 99.25 wt%), based on weight of the hair care formulation,of a dermatologically acceptable vehicle. More preferably, the hair care formulation forimproving the tensile strength of damaged hair of the present invention, comprises: 25 to99.9 wt% (preferably, 45 to 99.75 wt%; more preferably, 79 to 99.5 wt%; most preferably, 84to 99.25 wt%), based on weight of the hair care formulation, of a dermatologically acceptablevehicle; wherein the dermatologically acceptable vehicle comprises water. Still morepreferably, the hair care formulation for improving the tensile strength of damaged hair forimproving the tensile strength of damaged hair of the present invention, of the presentinvention, comprises: 25 to 99.9 wt% (preferably, 45 to 99.75 wt%; more preferably, 79 to99.5 wt%; most preferably, 84 to 99.25 wt%), based on weight of the hair care formulation,of a dermatologically acceptable vehicle; wherein the dermatologically acceptable vehicle isselected from the group consisting of water and an aqueous C₁₋₄ alcohol mixture. Mostpreferably, the hair care formulation for improving the tensile strength of damaged hair forimproving the tensile strength of damaged hair of the present invention, of the presentinvention, comprises: 25 to 99.9 wt% (preferably, 45 to 99.75 wt%; more preferably, 79 to99.5 wt%; most preferably, 84 to 99.25 wt%), based on weight of the hair care formulation,of a dermatologically acceptable vehicle; wherein the dermatologically acceptable vehicle iswater.

[0018] Preferably, the water used in the hair care formulation of the present invention is atleast one of distilled water and deionized water. More preferably, the water used in the haircare formulation of the present invention is distilled and deionized.

[0019] Preferably, the hair care formulation for improving the tensile strength (i.e.,increasing the Young's modulus and / or break stress) of damaged hair of the presentinvention, comprises: 0.1 to 10 wt% (preferably, 0.25 to 7 wt%; more preferably, 0.5 to 6wt%; most preferably, 0.75 to 1.25 wt%), based on weight of the hair care formulation, of atensile strength improving additive; wherein the tensile strength improving additivecomprises: (b1) 0.001 to 1 wt% (preferably, 0.01 to 0.5 wt%; more preferably, 0.02 to 0.2wt%; most preferably, 0.05 to 0.15 wt%), based on weight of the tensile strength improvingadditive, of a (±)-a-tocopherol; and (b2) 99 to 99.999 wt% (preferably, 99.5 to 99.99 wt%;more preferably, 99.8 to 99.98 wt%; most preferably, 99.85 to 99.95 wt%), based on weightof the tensile strength improving additive, of a carboxy functional organosiloxane compoundof formula IR²R²R²Ο-R¹-Si-O-Si-O-Si-R¹-OH| | |HOR²R²R²xwherein x is 0 to 25 (preferably, 2 to 20; more preferably, 4 to 15; still more preferably, 5 to10; most preferably, 7); wherein each R¹ is independently selected from an alkylene radicalcontaining 1 to 10 carbon atoms (preferably, an alkylene radical containing 1 to 4 carbonatoms; more preferably, an alkylene radical containing 1 to 3 carbon atoms; most preferablya -CH₂CH₂- group and a -CHCH₃- group); and wherein each R² is independently selectedfrom the group consisting of an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and a hydrocarbonoxy-functionalgroup of 1 to 18 carbon atoms (preferably, an alkyl group of 1 to 18 carbon atoms, an arylgroup of 6 to 18 carbon atoms and a hydrocarbonoxy-functional group of 1 to 18 carbonatoms; more preferably, an alkyl group of 1 to 4 carbon atoms and an aryl group of 6 to 12carbon atoms; still more preferably, an alkyl group of 1 to 4 carbon atoms; most preferably, amethyl group). More preferably, the hair care formulation for improving the tensile strengthof damaged hair of the present invention, comprises: 0.1 to 10 wt% (preferably, 0.25 to 7wt%; more preferably, 0.5 to 6 wt%; most preferably, 0.75 to 1.25 wt%), based on weight ofthe hair care formulation, of a tensile strength improving additive; wherein the tensilestrength improving additive comprises: (b1) 0.001 to 1 wt% (preferably, 0.01 to 0.5 wt%;more preferably, 0.02 to 0.2 wt%; most preferably, 0.05 to 0.15 wt%), based on weight of thetensile strength improving additive, of a (±)-a-tocopherol; and (b2) 99 to 99.999 wt%(preferably, 99.5 to 99.99 wt%; more preferably, 99.8 to 99.98 wt%; most preferably, 99.85 to99.95 wt%), based on weight of the tensile strength improving additive, of a carboxyfunctional organosiloxane compound of formula I; wherein x is 0 to 25 (preferably, 2 to 20;more preferably, 4 to 15; still more preferably, 5 to 10; most preferably, 7); wherein each R¹is independently selected from a -CH₂CH₂- group and a -CHCH₃- group; and wherein eachR² is independently selected from the group consisting of an alkyl group of 1 to 4 carbonatoms and an aryl group of 6 to 12 carbon atoms (preferably, an alkyl group of 1 to 4 carbonatoms; most preferably, a methyl group). Still more preferably, the hair care formulation forimproving the tensile strength of damaged hair of the present invention, comprises: 0.1 to 10wt% (preferably, 0.25 to 7 wt%; more preferably, 0.5 to 6 wt%; most preferably, 0.75 to 1.25wt%), based on weight of the hair care formulation, of a tensile strength improving additive;wherein the tensile strength improving additive comprises: (b1) 0.001 to 1 wt% (preferably,0.01 to 0.5 wt%; more preferably, 0.02 to 0.2 wt%; most preferably, 0.05 to 0.15 wt%), basedon weight of the tensile strength improving additive, of a (±)-a-tocopherol; and (b2) 99 to99.999 wt% (preferably, 99.5 to 99.99 wt%; more preferably, 99.8 to 99.98 wt%; mostpreferably, 99.85 to 99.95 wt%), based on weight of the tensile strength improving additive,of a carboxy functional organosiloxane compound of formula I; wherein x is 5 to 10 (mostpreferably, 7); wherein each R¹ is independently selected from a -CH₂CH₂- group anda -CHCH₃- group; and wherein each R² is independently selected from the group consistingof an alkyl group of 1 to 4 carbon atoms; most preferably, a methyl group). Most preferably,the hair care formulation for improving the tensile strength of damaged hair of the presentinvention, comprises: 0.1 to 10 wt% (preferably, 0.25 to 7 wt%; more preferably, 0.5 to 6wt%; most preferably, 0.75 to 1.25 wt%), based on weight of the hair care formulation, of atensile strength improving additive; wherein the tensile strength improving additivecomprises: (b1) 0.001 to 1 wt% (preferably, 0.01 to 0.5 wt%; more preferably, 0.02 to 0.2wt%; most preferably, 0.05 to 0.15 wt%), based on weight of the tensile strength improvingadditive, of a (±)-a-tocopherol; and (b2) 99 to 99.999 wt% (preferably, 99.5 to 99.99 wt%;more preferably, 99.8 to 99.98 wt%; most preferably, 99.85 to 99.95 wt%), based on weightof the tensile strength improving additive, of a carboxy functional organosiloxane compoundof formula I; wherein x is 7; and wherein each R¹ is independently selected froma -CH₂CH₂- group and a -CHCH₃- group; and wherein each R² is a methyl group.

[0020] Preferably, the hair care formulation for improving the tensile strength of damagedhair of the present invention, optionally further comprises at least one additional ingredientselected from the group consisting of an antimicrobial agent / preservative (e.g., benzoic acid,sorbic acid, phenoxyethanol, methylisothiazolinone, ethylhexyl glycerin); an antioxidant(e.g., butylated hydroxytoluene); a chelating agent (e.g., tetrasodium ethylene diaminetetraacetic acid); a conditioning agent (e.g., guar hydroxypropyltrimonium chloride, PQ-10,PQ-7); an emulsifying agent (e.g., glyceryl stearate, PEG-100 stearate, cetrimoniumchloride); a foaming agent; a fragrance; a humectant (e.g., glycerin, sorbitol, monoglycerides,lecithins, glycolipids, fatty alcohols (e.g., cetyl alcohol, stearyl alcohol), fatty acids,polysaccharides, sorbitan esters, polysorbates (e.g., Polysorbate 20, Polysorbate 40,Polysorbate 60, and Polysorbate 80), diols (e.g., propylene glycol), diol analogs, triols, triolanalogs, cationic polymeric polyols); a lubricating agent; a natural oil or ester emollient (e.g.,mono-, di-, tri-glycerides such as sunflower seed oil, coconut oil, cottonseed oil, borage oil,borage seed oil, primrose oil, castor and hydrogenated castor oils, rice bran oil, soybean oil,olive oil, safflower oil, shea butter, jojoba oil and combinations thereof); an opacifier; apenetrant; a pearlizing agent; pH adjusting agent (e.g., citric acid); a pigment; a plant extract;a protein / amino acid; a rheology modifier (e.g., PEG-150 pentaerythrityl tetrastearate;hydroxyethylcellulose); a salt; a sensory modifier; a sunscreen additive; a surfactant; and awax. More preferably, the hair care formulation for improving the tensile strength ofdamaged hair of the present invention, optionally further comprises at least one additionalingredient selected from the group consisting of an antimicrobial agent / preservative (e.g.,benzoic acid, sorbic acid, phenoxyethanol, methylisothiazolinone, ethylhexyl glycerin); achelating agent (e.g., tetrasodium ethylene diamine tetraacetic acid); an emulsifying agent(e.g., glyceryl stearate, PEG-100 stearate, cetrimonium chloride); a humectant (e.g., glycerin,sorbitol, monoglycerides, lecithins, glycolipids, fatty alcohols (e.g., cetyl alcohol, stearylalcohol), fatty acids, polysaccharides, sorbitan esters, polysorbates (e.g., Polysorbate 20,Polysorbate 40, Polysorbate 60, and Polysorbate 80), diols (e.g., propylene glycol), diolanalogs, triols, triol analogs, cationic polymeric polyols); pH adjusting agent (e.g., citric acid)and a rheology modifier (e.g., PEG-150 pentaerythrityl tetrastearate; hydroxyethylcellulose).Most preferably, the hair care formulation for improving the tensile strength of damaged hairof the present invention, optionally further comprises at least one additional ingredientselected from the group consisting of a mixture of phenoxyethanol andmethylisothiazolinone; tetrasodium ethylene diamine tetraacetic acid; glyceryl stearate;PEG-100 stearate; cetrimonium chloride; cetyl alcohol; stearyl alcohol; citric acid; PEG-150pentaerythrityl tetrastearate and hydroxyethylcellulose.

[0021] Preferably, the hair care formulation for improving the tensile strength of damagedhair of the present invention has a pH of 3 to < 7 (preferably, 3.25 to 6; more preferably, 3.5to 5; most preferably, 3.75 to 4.25). Preferably, the pH of the hair care formulation forimproving the tensile strength of damaged hair of the present invention is adjusted using a pHadjusting agent selected from the group consisting of at least one of citric acid, lactic acid,hydrochloric acid, aminoethyl propanediol, triethanolamine, monoethanolamine, sodiumhydroxide, potassium hydroxide, amino-2-methyl-1-propanol. More preferably, the pHadjusting agent is selected from the group consisting of at least one of citric acid, lactic acid,sodium hydroxide, potassium hydroxide, triethanolamine, amino-2-methyl-1-propanol. Stillmore preferably, the pH adjusting agent includes citric acid. Most preferably, the pHadjusting agent is citric acid.

[0022] Preferably, the method of improving the tensile strength of damaged hair (preferably,damaged mammalian hair; more preferably, damaged human hair; most preferably, damagedhuman scalp hair) of the present invention, comprises: (a) providing a damaged hair, whereinthe damaged hair is selected from the group consisting of chemically damaged hair (e.g., hairdamaged from chemical treatments such as dyeing, bleaching, perming), thermally damagedhair (e.g., hair damaged from exposure to heat such as by ironing, forced drying, styling),mechanically damaged hair (e.g., hair damaged from physical abuse such as friction, pulling,curling) and combinations thereof; (b) selecting a hair care formulation of the presentinvention; and (c) applying the hair care formulation to the damaged hair to provide a treatedhair. More preferably, the method of improving the tensile strength of damaged hair of thepresent invention, comprises: (a) providing a damaged hair, wherein the damaged hair isbleached hair (preferably, bleached Caucasian scalp hair); (b) selecting a hair careformulation of the present invention; and (c) applying the hair care formulation to thedamaged hair to provide a treated hair. Still more preferably, the method of improving thetensile strength of damaged hair of the present invention, comprises: (a) providing adamaged hair, wherein the damaged hair is bleached hair (preferably, bleached Caucasianscalp hair); (b) selecting a hair care formulation of the present invention; and (c) applying thehair care formulation to the damaged hair to provide a treated hair; wherein the methodcomprises improving at least one of the following properties of the treated hair: (I) theYoung's Modulus of the treated hair; wherein the Young's Modulus improvement,YM_Improvement, for the treated hair is at least a 10% (preferably, at least 15%); wherein theYM_Improvement is determined according to the formulaYM_Improvement = [ (YM_T - YM_D) / YM_D ] × 100%wherein YM_Improvement is the % improvement in the Young's Modulus for the treated hair;wherein YM_T is the Young's Modulus for the treated hair and wherein YM_D is the Young'sModulus for the damaged hair before treatment with the hair care formulation; (II) the breakstress of the treated hair; wherein the break stress improvement, BS_Improvement, for the treatedhair is at least 5%; wherein the BS_Improvement is determined according to the formulaBS_Improvement = [ (BS_T - BS_D) / BS_D ] × 100%wherein BS_Improvement is the % improvement in the break stress for the treated hair; whereinBS_T is the break stress for the treated hair and wherein BS_D is the break stress for thedamaged hair before treatment with the hair care formulation; and (III) the fatigue resistanceof the treated hair; wherein the fatigue resistance improvement, FR_Improvement, for the treatedhair is at least 50% (preferably, 60%); wherein the FR_Improvement is determined according to theformulaFR_Improvement = [ (FR_T - FR_D) / FR_D ] × 100%wherein FR_Improvement is the % improvement in the Weibull characteristic lifetime in cycles forthe treated hair (preferably, as measured in the Examples herein); wherein FR_T is the Weibullcharacteristic lifetime in cycles for the treated hair and wherein FR_D is the Weibullcharacteristic lifetime in cycles for the damaged hair before treatment with the hair careformulation. Yet more preferably, the method of improving the tensile strength of damagedhair of the present invention, comprises: (a) providing a damaged hair, wherein the damagedhair is bleached hair (preferably, bleached Caucasian scalp hair); (b) selecting a hair careformulation of the present invention; and (c) applying the hair care formulation to thedamaged hair to provide a treated hair; wherein the method comprises (I) improving theYoung's Modulus of the treated hair; wherein the Young's Modulus improvement,YM_Improvement, for the treated hair is at least a 10% (preferably, at least 15%); and (II)improving the break stress of the treated hair; wherein the break stress improvement,BS_Improvement, for the treated hair is at least 5%. Most preferably, the method of improving thetensile strength of damaged hair of the present invention, comprises: (a) providing adamaged hair, wherein the damaged hair is bleached hair (preferably, bleached Caucasianscalp hair); (b) selecting a hair care formulation of the present invention; and (c) applying thehair care formulation to the damaged hair to provide a treated hair; wherein the methodcomprises (I) improving the Young's Modulus of the treated hair; wherein the Young'sModulus improvement, YM_Improvement, for the treated hair is at least a 10% (preferably, at least15%); (II) improving the break stress of the treated hair; wherein the break stressimprovement, BS_Improvement, for the treated hair is at least 5%; and (III) improving the fatigueresistance for the treated hair; wherein the fatigue resistance improvement, FR_Improvement, forthe treated hair is at least 50% (preferably, 60%).

[0023] Some embodiments of the present invention will now be described in detail in thefollowing Examples.Type Description SourceSyngas a gas mixture of CO and H₂ prep. well knownLigand 1 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl]-2,2-diyl]bis(oxy)]dibenzo[d,f][1,3,2]dioxaphosphepin The Dow Chemical CompanySynthesis S1: Synthesis of MPr-aldD₇MPr-ald

[0024] A propyl-aldehyde terminated material (MPr-aldD₇MPr-ald) having the structureCH₃ CH₃ CH₃O=C-G-Si-O-(Si-O)₇-Si-G-C=O| | | HH CH₃ CH₃ CH₃wherein each G is independently a -CH₂CH₂- group or a -CHCH₃- group; was preparedaccording to the following procedure. In a nitrogen filled glovebox, hydroformylationcatalyst (Acetylacetonato) dicarbonylrhodium (I) (Rh(acac)(CO)₂) (9.3 mg, 0.0359 mmol),Ligand 1 (58.1 mg, 0.069 mmol) and heptane (10.0 g, 99.8 mmol) were added into a 30 mLglass vial with a magnetic stir bar. The mixture was stirred on a stir plate until ahomogeneous solution formed. This solution was transferred to an air-tight syringe with ametal valve and subsequently removed from the glove box. In a ventilated fume hood, 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17-octadecamethylnonasiloxane-1,17-diyl)divinyl(MViD₇MVi) from Dow Silicones Corporation (700 g, 1.027 mol) was loaded to a 2LAutoclave-reactor. The reactor was sealed and loaded into the holder. The reactor waspressurized with nitrogen up to 100 psi via the dip-tube and was carefully relieved through avalve connected to the headspace for three times. The reactor was then pressure tested bypressurizing to 300 psi with nitrogen. After the pressure was released, the catalyst solutionwas added to the reactor via the sample loading port. The reactor was pressurized withsyngas to 100 psi and then released for three times prior to being pressurized 80 psi via thedip-tube. Reaction temperature was set to 70°C. Agitation rate was set to 800 RPM. Theintermediate cylinder containing syngas and the reactor were connected when the desiredtemperature was reached. The pressure was set to 100 psi. The reaction progress wasmonitored by a data logger which measured the pressure in the intermediate cylinder as itsupplied syngas to the reactor via a pressure reducing regulator. The resulting productcontained MPr-aldD₇MPr-ald.Synthesis S2: Synthesis of MPr-aldD₂₅MPr-ald

[0025] A propyl-aldehyde terminated material (MPr-aldD₂₅MPr-ald) having the structureCH₃ CH₃ CH₃O=C-G-Si-O-(Si-O)₂₅-Si-G-C=O| | | HH CH₃ CH₃ CH₃wherein each G is independently a -CH₂CH₂- group or a -CHCH₃- group; was preparedaccording to the following procedure. In a nitrogen filled glovebox, hydroformylationcatalyst (Acetylacetonato) dicarbonylrhodium (I) (Rh(acac)(CO)₂) (0.0252 g), Ligand 1 (1.63g) and toluene (50 g) were added into a 125 mL glass vial with a magnetic stir bar. Themixture was stirred at room temperature on a stir plate until a homogeneous solution wasformed. The solution was transferred to an air-tight syringe with a metal valve andsubsequently removed from the glove box. In a ventilated fume hood,bis-dimethylvinylsiloxy-terminated polydimethylsiloxane with an average of 25dimethylsiloxy (D) units per molecule (MViD₂₅MVi) from Dow Silicones Corporation (1000g) was loaded to a 2 liter Autoclave-reactor. The reactor was sealed and pressurized withnitrogen up to 100 psig (689 kPa) via the dip-tube and was carefully relieved through a valveconnected to the headspace. The pressure / vent cycle with nitrogen was repeated threetimes. Pressure testing was subsequently performed by pressurizing the reactor with nitrogento up to 300 psig (2086 kPa). After the pressure was released, the catalyst solution was addedto the reactor via the sample loading port. The reactor was pressurized with syngas to 100psig (689 kPa) and then vented for three times prior to being pressurized to 20 psig (138 kPa)below the desired pressure via the diptube. Reaction temperature was set to 80°C. Heaterand agitation were turned on. The cylinder containing the syngas for the reaction and thereactor were connected when the desired temperature was reached. A mass flow totalizerwas used to monitor the reaction progress.Synthesis S3: Synthesis of MPr-aldMPr-ald

[0026] A propyl-aldehyde terminated material (MPr-aldMPr-ald) having the structureCH₃ CH₃O=C-G-Si-O-Si-G-C=O| | HH CH₃ CH₃wherein each G is independently a -CH₂CH₂- group or a -CHCH₃- group; was preparedaccording to the following procedure. In a nitrogen filled glovebox, hydroformylationcatalyst (Acetylacetonato) dicarbonylrhodium (I) (Rh(acac)(CO)₂) (18.1 mg, 0.0699 mmol),Ligand 1 (88.0 mg, 0.105 mmol) and toluene (5.0 g, 0.054 mmol) were added into a 30 mLglass vial with a magnetic stir bar. The mixture was stirred on a stir plate until ahomogeneous solution formed. This solution was transferred to an air-tight syringe with ametal valve and subsequently removed from the glove box. In a ventilated fume hood, 1,3-divinyltetramethyldisiloxane (44.8 g, 240 mmol) and the toluene (40.0 g, 488 mmol) wereloaded to a 300-mL Parr-reactor. The reactor was sealed and loaded into the holder. Thereactor was pressurized with nitrogen up to 100 psi via the diptube and was carefully relievedthrough a valve connected to the headspace for three times. The reactor was then pressuretested by pressurizing to 300 psi with nitrogen. After the pressure was released, the catalystsolution was added to the reactor via the sample loading port. The reactor was pressurizedwith syngas to 100 psi and then released for three times prior to being pressurized 80 psi viathe dip-tube. Reaction temperature was set to 90°C. Agitation rate was set to 500 RPM.The intermediate cylinder containing syngas and the reactor were connected when the desiredtemperature was reached. The pressure was set to 100 psi. The reaction progress wasmonitored by a data logger which measured the pressure in the 300 ml intermediate cylinderas it supplied syngas to the reactor via a pressure reducing regulator.Synthesis S4: Synthesis of MDPr-aldM

[0027] A propyl-aldehyde terminated material (MDPr-aldM) having the structureCH₃CH₃Si-O-CH₃H₃C-Si-O-Si-G-C=O| | HCH₃ H₃Cwherein each G is independently a -CH₂CH₂- group or a -CHCH₃- group; was preparedaccording to the following procedure. In a nitrogen filled glovebox, hydroformylationcatalyst (Acetylacetonato) dicarbonylrhodium (I) (Rh(acac)(CO)₂) (6.7 mg, 0.026 mmol),Ligand 1 (30.2 mg, 0.0360 mmol) and toluene (5.0 g, 0.054 mmol) were added into a 30 mLglass vial with a magnetic stir bar. The mixture was stirred on a stir plate until ahomogeneous solution formed. This solution was transferred to an air-tight syringe with ametal valve and subsequently removed from the glove box. In a ventilated fume hood,vinylmethylbis(trimethylsiloxy)silane (20.2 g, 81.2 mmol) and the toluene (57.7 g, 627mmol) were loaded to a 300-mL Parr-reactor. The reactor was sealed and loaded into theholder. The reactor was pressurized with nitrogen up to 100 psi via the dip-tube and wascarefully relieved through a valve connected to the headspace for three times. The reactorwas then pressure tested by pressurizing to 300 psi with nitrogen. After the pressure wasreleased, the catalyst solution was added to the reactor via the sample loading port. Thereactor was pressurized with syngas to 100 psi and then released for three times prior to beingpressurized 80 psi via the dip-tube. Reaction temperature was set to 90°C. Agitation ratewas set to 500 RPM. The intermediate cylinder containing syngas and the reactor wereconnected when the desired temperature was reached. The pressure was set to 100 psi. Thereaction progress was monitored by a data logger which measured the pressure in the 300 mlintermediate cylinder as it supplied syngas to the reactor via a pressure reducing regulator.Synthesis S5: Synthesis of MacidD₇Macid

[0028] A carboxy functional organosiloxane compound (MacidD₇Macid) having the structureCH₃ CH₃ CH₃O=C-G-Si-O-(Si-O)₇-Si-G-C=O| | | OHHO CH₃ CH₃ CH₃wherein each G is independently a -CH₂CH₂- group or a -CHCH₃- group; was preparedaccording to the following procedure. MPr-aldD₇MPr-ald prepared according to Synthesis S1(195.3 g) was loaded to a 250 mL European style flask equipped with a PTFE coatedmagnetic stir bar. Air was sparged subsurface with a needle at 100 cc / min and the mixturewas stirred with the magnetic stirrer at maximum speed. The reaction was stopped after 64hrs yielding a clear slightly yellow product liquid. The clear slightly yellow product liquid(194.6 g) was collected and analyzed by ¹H NMR spectroscopy which indicated the reactionreached 96.6% aldehyde conversion with 89.7% acid and 4.0% formyl ester.Synthesis S6: Synthesis of MacidD₂₅Macid

[0029] A carboxy functional organosiloxane compound (MacidD₂₅Macid) having thestructureCH₃ CH₃ CH₃O=C-G-Si-O-(Si-O)₂₅-Si-G-C=O| | | OHHO CH₃ CH₃ CH₃wherein each G is independently a -CH₂CH₂- group or a -CHCH₃- group; was preparedaccording to the following procedure. MPr-aldD₂₅MPr-ald (572 g, 0.272 mol) preparedaccording to Synthesis S2 was loaded to a 500 mL European style flask equipped with aPTFE coated magnetic stir bar. Air was sparged subsurface with a needle at 200 cc / min andthe mixture was stirred with the magnetic stirrer at maximum speed. The reaction wasstopped after 72 hrs yielding a clear slightly colored product liquid. The clear, slightlycolored product liquid (550.7 g) was collected and analyzed by ¹H NMR spectroscopy whichindicated the reaction reached 98.4% aldehyde conversion with 91.2% acid and 7.2% formylester.Synthesis S7: Synthesis of MacidMacid

[0030] A carboxy functional organosiloxane compound (MacidMacid) having the structureCH₃ CH₃O=C-G-Si-O-Si-G-C=O| | OHHO CH₃ CH₃wherein each G is independently a -CH₂CH₂- group or a -CHCH₃- group; was preparedaccording to the following procedure. A 4-necked flask tube was charged with a magneticstirrer and 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dipropanal (Mpr-aldMpr-ald) (99 g, 0.40mol). Air was bubbled, subsurface at 100 cc / min. A stir plate was used and set at 1,050 rpm;the 4-neck flask was positioned 4 cm above the stirrer. The reaction was monitored after 93hr, 114 hr, 142 hr, 304 hr and 768 hr. The reaction was stopped after 768 hr. The clearslightly yellow product liquid (100 g) was collected and analyzed by ¹H NMR spectroscopywhich indicated the reaction reached 97.3% aldehyde conversion with 90.4% acid and 3.3%formyl ester.Synthesis S8: Synthesis of MDacidM

[0031] A carboxy functional organosiloxane compound (MDacidM) having the structureCH₃CH₃Si-O-CH₃H₃C-Si-O-Si-G-C=O| | OHCH₃ H₃Cwherein each G is independently a -CH₂CH₂- group or a -CHCH₃- group; was preparedaccording to the following procedure. A 250 mL glass jar was charged with a PTFE-coatedmagnetic stirrer and 3,3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propanal (MDPr-aldM) (100g, 0.34 mol). Air was bubbled, subsurface at 100 cc / min. A stir plate was used and set at 900rpm. The reaction was monitored by ¹H NMR spectroscopy after 120 hr under theseconditions, the reaction was stopped to afford a clear slightly yellow product liquid (100 g).This material was collected and analyzed by ¹H NMR spectroscopy which indicated thereaction reached 99.7% aldehyde conversion with 90.5% acid and 3.0% formyl ester.Comparative Examples C1-C13 and Example F1: Formulations

[0032] A hair conditioner formulation was prepared in each of Comparative ExamplesCF1-CF13 and Example F1 having the formulation noted in TABLE 1.TABLE 1Formulation ExamplesIngredient C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 1Rheology modifier¹ -- -- -- 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4Emulsion stabilizer² -- -- -- 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Emulsifier³ -- -- -- 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Chelating agent⁴ -- -- -- 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2Preservative⁵ -- -- -- 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5MViMVi ⁶ -- -- -- -- -- -- -- -- 4.0 -- -- -- -- --MViD₇MVi ⁷ -- -- -- -- -- -- -- -- -- -- 4.0 -- -- --MDViM ⁸ -- -- -- -- -- -- -- -- -- 4.0 -- -- -- --PDMS 5 cSt ⁹ -- -- -- -- -- -- -- -- -- -- -- 4.0 -- --Commercial¹⁰ -- 100 96 -- -- -- -- -- -- -- -- -- -- --Tocopherol¹¹ -- -- -- -- -- -- -- -- -- -- -- -- 0.4E-2 0.4E-2Synthesis S5 -- -- 4 -- 4.0 -- -- -- -- -- -- -- -- 4Synthesis S6 -- -- -- -- -- -- -- 4.0 -- -- -- -- -- --Synthesis S7 -- -- -- -- -- 4.0 -- -- -- -- -- -- -- --Synthesis S8 -- -- -- -- -- -- 4.0 -- -- -- -- -- -- --DI water q.s. 100Citric acid q.s. pH 4¹ CELLOSIZE™ hydroxyethyl cellulose PCG-10 Europe from The Dow Chemical Company² Crodacol CS50 cetearyl alcohol from Croda Inc.³ Arlacel 165 glyceryl stearate (and) PEG-100 stearate from Croda Inc.⁴ VERSENE™ 220 crystal tetrasodium EDTA from The Dow Chemical Company⁵ Neolone PE phenoxyethanol (and) methylisothiazolinone from Lanxess⁶ 1,3-divinyltetramethyldisiloxane from The Dow Chemical Company⁷ Bis-dimethylvinylsiloxy-terminated polydimethylsiloxane (DP=7) from The Dow Chemical Company⁸ Vinylmethylbis(trimethylsiloxy)silane from The Dow Chemical Company⁹ XIAMETER™ PMX-200 silicone fluid 5 cSt from The Dow Chemical Company¹⁰ Olaplex® No. 3 hair protector from Olaplex¹¹ (±)-a-tocopherol from Sigma Aldrich T3251Hair tensile strengthening performance

[0033] Studies to evaluate the improvement in the tensile strength of damaged hair treatedwith the leave on conditioner formulations of Comparative Examples C1-C12 andExample 1 were performed as follows. Caucasian, 8 hour bleached hair from InternationalHair Importers was used for the testing. Each tress weighed 2 grams. The hair tresses werefirst rinsed with water for 30 seconds. Then a 9% w / w aqueous solution of sodium laurylsulfate (0.2 g / g of hair) was massaged into the hair tresses for 30 seconds. Then the hairtresses were rinsed with water for 60 seconds. Excess water was removed from the tresses bypassing each tress between the index and middle fingers of the hand. The tresses were thentreated with a leave on conditioner formulation of Comparative Examples C1-C12 andExample 1 at 0.15 g formulation / g of hair by massaging the formulation into the wet / damphair for 1 minute. The tresses were then hung and left to dry overnight at room temperature.

[0034] The treated and dried hair tresses were then cut at the mid-section, laying down thefibers on a dark background. A single representative cut fiber was then selected for eachtress and secured one of its ends at the side of the sample holder. Two brass crimps werethen passed across the fiber. The brass crimps were then positioned on the grooves of thesample holder and pressed in place. The crimped fiber was then placed on a numberedplastic plate. This process was then repeated for 30 to 40 separate fibers for each tress. Onceall the fibers were prepared, they were soaked in deionized water at pH 6 in a plastic bowl.The fibers were allowed to rest in the deionized water in the plastic bowl for 1 hr. The plasticbowl was then moved to a climate controlled room at 50% relative humidity and 22°C,where the test machines were located. The diameter of each of the fibers was measured usinga FDAS-770 Fibre Dimensional Analysis System from Diastron to obtain 3 measures of eachfiber's diameter at 3 different positions along the fiber. The fibers were then moved to aDiastron MTT-175 Miniature Tensile Tester from Diastron coupled with a UV-1000controller to perform the tensile strength analysis of the fibers. The average Young'sModulus and Break Stress measured for the hair fibers from each tress are reported in TABLE2.TABLE 2Ex. Additive Young's Modulus (MPa) Break Stress (MPa)C1 Untreated hair 2,290 154C2 Commercial¹ 2,260 152C3 Commercial¹ + Synthesis S5 2,540 162C4 No additive 2,150 145C5 Synthesis S5 2,360 150C6 Synthesis S7 2,440 157C7 Synthesis S8 2,210 153C8 Synthesis S6 2,350 154C9 MViMVi ² 2,280 158C10 MDViM ³ 2,230 158C11 MViD₇MVi ⁴ 2,080 150C12 PDMS 5 cSt⁵ 2,090 1511 Synthesis S5 + tocopherol⁶ 2,670 163¹ Olaplex® No. 3 hair protector from Olaplex² 1,3-divinyltetramethyldisiloxane from The Dow Chemical Company³ Vinylmethylbis(trimethylsiloxy)silane from The Dow Chemical Company⁴ Bis-dimethylvinylsiloxy-terminated polydimethylsiloxane (DP=7) from The Dow Chemical Company⁵ XIAMETER™ PMX-200 silicone fluid 5 cSt from The Dow Chemical Company⁶ (±)-a-tocopherol from Sigma Aldrich T3251Hair fatigue resistance performance

[0035] Studies to evaluate the improvement in the fatigue resistance of damaged hair treatedwith the leave on conditioner formulations of Comparative Examples C1-C3, C4-C13 andExample 1 were performed as follows. Caucasian, 8 hour bleached hair from InternationalHair Importers was used for the testing. Each tress weighed 2 grams. The hair tresses werefirst rinsed with water for 30 seconds. Then a 9% w / w aqueous solution of sodium laurylsulfate (0.2 g / g of hair) was massaged into the hair tresses for 30 seconds. Then the hairtresses were rinsed with water for 60 seconds. Excess water was removed from the tresses bypassing each tress between the index and middle fingers of the hand. The tresses were thentreated with a leave on conditioner formulation of Comparative Examples C1-C3, C4-C13and Example 1 at 0.15 g formulation / g of hair by massaging the formulation into thewet / damp hair for 1 minute. The tresses were then hung and left to dry overnight at roomtemperature.

[0036] The treated and dried hair tresses were then cut at the mid-section, laying down thefibers on a dark background. A single representative cut fiber was then selected for eachtress and secured one of its ends at the side of the sample holder. Two brass crimps werethen passed across the fiber. The brass crimps were then positioned on the grooves of thesample holder and pressed in place. The crimped fiber was then placed on a numberedplastic plate. This process was then repeated for 40 to 50 separate fibers for each tress. Thediameter of each of the fibers was measured using a FDAS-770 Fibre Dimensional AnalysisSystem from Diastron to obtain 3 measures of each fiber's diameter at 3 different positionsalong the fiber. The fibers were then moved to a Diastron Cyc 801 / 802 fatigue tester fromDiastron coupled with a UV-1000 controller to perform the fatigue analysis of the fibers. Theinstrument then applied a cycling force, which was repeated until failure (hair breakage). Thebroken fiber was then removed from the tester and returned to the cassette so that the nextfiber could be loaded and tested. The number of cycles to breakage for each fiber wasrecorded. The experimental conditions for the fatigue testing were fixed for all theexperiments with a constant Strain (5%), strain rate 40 mm / s, cycle limit=300,000, at roomtemperature and 55% relative humidity. The data was exported to Microsoft Excel to utilizeMatlab (Mathworks) to analyze the results to determine the fatigue resistance for the hairfibers from each tress according to a cumulative form of the Weibull function shown in thefollowing equationF(x) = 1 - e^-(x / α)^βwherein F(x) is the probability of the fiber breaking in x cycles, α is the characteristic lifetimeat which 63.5% of the fibers have broken and β is a shape factor determined by fitting theresults curve. The results are reported in TABLE 3.TABLE 3Fatigue ResistanceEx. Additive Characteristic Lifetime (Cycles) FRImprovement (%)C1 Untreated hair 4,217 0C2 Commercial¹ 3,332 -21.0C4 No additive 4,000 -5.2C5 Synthesis S5 4,984 18.2C6 Synthesis S7 5,221 23.8C7 Synthesis S8 5,061 20.0C8 Synthesis S6 7,730 83.3C9 MViMVi ² 4,137 -1.9C10 MDViM ³ 4,006 -5.0C11 MViD₇MVi ⁴ 4,284 1.6C12 PDMS 5 cSt⁵ 4,414 4.7C13 Tocopherol⁶ 4,557 8.11 Syn S5 + tocopherol⁶ 7,132 69.1¹ Olaplex® No. 3 hair protector from Olaplex² 1,3-divinyltetramethyldisiloxane from The Dow Chemical Company (TDCC)³ Vinylmethylbis(trimethylsiloxy)silane from TDCC⁴ Bis-dimethylvinylsiloxy-terminated polydimethylsiloxane (DP=7) from TDCC⁵ XIAMETER™ PMX-200 silicone fluid 5 cSt from TDCC⁶ (±)-a-tocopherol from Sigma Aldrich T3251Comparative Example C14 and Example F2-4: Formulations

[0037] A hair conditioner formulation was prepared in each of Comparative Example C14and Examples F2-F4 having the formulation noted in TABLE 4.TABLE 4Formulation ExamplesIngredient C14 2 3 4Rheology modifier¹ 0.5 0.5 0.5 0.5Cetyl alcohol 2.1 2.1 2.1 2.1Stearyl alcohol 0.9 0.9 0.9 0.9Conditioning surfactant² 3.3 3.3 3.3 3.3Preservative³ 0.5 0.5 0.5 0.5Tocopherol⁴ -- 0.1E⁻² 0.2E⁻² 0.4E⁻²Synthesis S5 -- 1 2 4DI water q.s. 100Citric acid q.s. pH 4¹ CELLOSIZE™ hydroxyethyl cellulose PCG-10 Europe from The Dow ChemicalCompany² Ammonyx CETAC-30 cetrimonium chloride (30%) from Stepan³ Neolone PE phenoxyethanol (and) methylisothiazolinone from Lanxess⁴ (±)-a-tocopherol from Sigma Aldrich T3251Hair tensile strengthening performance

[0038] Studies to evaluate the improvement in the tensile strength of damaged hair treatedwith the leave on conditioner formulations of Comparative Example C14 and Examples2-4 were performed as follows. Caucasian, 8 hour bleached hair from International HairImporters was used for the testing. Each tress weighed 2 grams. The hair tresses were firstrinsed with water for 30 seconds. Then a 9% w / w aqueous solution of sodium lauryl sulfate(0.2 g / g of hair) was massaged into the hair tresses for 30 seconds. Then the hair tresses wererinsed with water for 60 seconds. Excess water was removed from the tresses by passingeach tress between the index and middle fingers of the hand. The tresses were then treatedwith a leave on conditioner formulation of Comparative Example C14 and Examples 2-4 at0.15 g formulation / g of hair by massaging the formulation into the wet / damp hair for 1minute. The tresses were then hung and left to dry overnight at room temperature.

[0039] The treated and dried hair tresses were then cut at the mid-section, laying down thefibers on a dark background. A single representative cut fiber was then selected for eachtress and secured one of its ends at the side of the sample holder. Two brass crimps werethen passed across the fiber. The brass crimps were then positioned on the grooves of thesample holder and pressed in place. The crimped fiber was then placed on a numberedplastic plate. This process was then repeated for 30 to 40 separate fibers for each tress. Onceall of the fibers were prepared, they were soaked in deionized water at pH 6 in a plastic bowl.The fibers were allowed to rest in the deionized water in the plastic bowl for 1 hr. The plasticbowl was then moved to a climate controlled room at 50% relative humidity and 22 °C,where the test machines were located. The diameter of each of the fibers was measured usinga FDAS-770 Fibre Dimensional Analysis System from Diastron to obtain 3 measures of eachfiber's diameter at 3 different positions along the fiber. The fibers were then moved to aDiastron MTT-175 Miniature Tensile Tester from Diastron coupled with a UV-1000controller to perform the tensile strength analysis of the fibers. The average Young'sModulus and Break Stress measured for the hair fibers from each tress are reported in TABLE5.TABLE 5Ex. Additive Conc. Young's Modulus (MPa) Break Stress (MPa)C14 No additive -- 1,060 1452 Syn. S5 + tocopherol 1 wt% 1,780 1563 Syn. S5 + tocopherol 2 wt% 930 1334 Syn. S5 + tocopherol 4 wt% 1,330 145

Claims

We claim:

1. A hair care formulation, comprising:(a) a dermatologically acceptable vehicle; and(b) a tensile strength improving additive; wherein the tensile strength improvingadditive comprises:(bl) a (±)-a-tocopherol; and(b2) a carboxy functional organosiloxane compound of formula IR²R²R²Ο-R¹-Si-O-Si-O-Si-R¹-OH| | |HOR²R²R²xwherein x is 0 to 25; wherein each R¹ is independently selected from analkylene radical containing 1 to 10 carbon atoms; wherein each R² is independentlyselected from the group consisting of an alkyl group of 1 to 18 carbon atoms, an arylgroup of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, and ahydrocarbonoxy-functional group of 1 to 18 carbon atoms.

2. The hair care formulation of claim 1, wherein the hair care formulationcomprises less than 0.01 wt%, based on weight of the hair care formulation, of a cationicpolymer.

3. The hair care formulation of claim 1, wherein the hair care formulationcomprises less than 0.05 wt%, based on weight of the hair care formulation, of a polymerselected from the group consisting of an anionic polymer, a nonionic polymer and mixturesthereof.

4. The hair care formulation of claim 1, wherein the hair care formulationcomprises less than 0.05 wt%, based on weight of the hair care formulation, of an oxazolinefunctionalized polymer; wherein the oxazoline functionalized polymer is a molecule havingrepeating units and at least one oxazoline group.

5. The hair care formulation of claim 1, wherein the hair care formulationcomprises less than 0.005 wt%, based on weight of the hair care formulation, of apolycarbodiimide compound; wherein the polycarbodiimide compound has at least twocarbodiimide groups per molecule and wherein the carbodiimide groups are linear triatomicmoieties depicted by the formula -(N=C=N)-.

6. A method for improving the tensile strength of damaged hair comprising:(a) providing a damaged hair, wherein the damaged hair is selected from the groupconsisting of chemically damaged hair, thermally damaged hair, mechanically damaged hairand combinations thereof;(b) selecting a hair care formulation, comprising:(A) a dermatologically acceptable vehicle; and(B) a tensile strength improving additive; wherein the tensile strengthimproving additive comprises:(B1) a (±)-a-tocopherol; and(B2) a carboxy functional organosiloxane compound of formula IR²R²R²Ο-R¹-Si-O-Si-O-Si-R¹-OH| | |HOR²R²R²xwherein x is 0 to 25; wherein each R¹ is independently selected from analkylene radical containing 1 to 10 carbon atoms; wherein each R² isindependently selected from the group consisting of an alkyl group of 1 to 18carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to18 carbon atoms, and a hydrocarbonoxy-functional group of 1 to 18 carbonatoms; and(c) applying the hair care formulation to the damaged hair to provide a treated hair.

7. The method of claim 6, wherein the damaged hair is bleached hair.

8. The method of claim 7, wherein the method comprises improving the Young'sModulus of the treated hair; wherein the Young's Modulus improvement, YM_Improvement, forthe treated hair is at least a 10%; wherein the YM_Improvement is determined according to theformulaYM_Improvement = [ (YM_T - YM_D) / YM_D ] × 100%wherein YM_Improvement is the % improvement in the Young's Modulus for the treated hair;wherein YM_T is the Young's Modulus for the treated hair and wherein YM_D is the Young'sModulus for the damaged hair before treatment with the hair care formulation.

9. The method of claim 8, wherein the method comprises improving the breakstress of the treated hair; wherein the break stress improvement, BS_Improvement, for the treatedhair is at least 5%; wherein the BS_Improvement is determined according to the formulaBS_Improvement = [ (BS_T - BS_D) / BS_D ] × 100%wherein BS_Improvement is the % improvement in the break stress for the treated hair; whereinBS_T is the break stress for the treated hair and wherein BS_D is the break stress for thedamaged hair before treatment with the hair care formulation.

10. The method of claim 6, with any one or more of the following provisos:(i) with the proviso that the hair care formulation comprises less than 0.01 wt%,based on weight of the hair care formulation, of a cationic polymer;(ii) with the proviso that the hair care formulation comprises less than 0.05 wt%,based on weight of the hair care formulation, of a polymer selected from the group consistingof an anionic polymer, a nonionic polymer and mixtures thereof;(iii) with the proviso that the hair care formulation comprises less than 0.05 wt%,based on weight of the hair care formulation, of an oxazoline functionalized polymer;wherein the oxazoline functionalized polymer is a molecule having repeating units and atleast one oxazoline group; and(iv) with the proviso that the hair care formulation comprises less than 0.005 wt%,based on weight of the hair care formulation, of a polycarbodiimide compound; wherein thepolycarbodiimide compound has at least two carbodiimide groups per molecule and whereinthe carbodiimide groups are linear triatomic moieties depicted by the formula -(N=C=N)-.

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