SK4632001A3 - Volumizing hair care compositions containing siloxysilicates - Google Patents

Abstract

This invention relates to an improved formulation hair volumizers which comprise: (a) from 0.01 - 15 percent by weight (based on the total weight of the composition) of a selected liquid MQ resin having an M:Q ratio of 0.5-1.5 and a medium viscosity in the range of 1.0 x 10<3> - 1 x 10<6> centipoise; and (b) from 85 - 99.99 percent by weight (based on the total weight of the composition) of a hair care carrier (also called a vehicle). The compositions of this invention provide hair with increased volume without significant stiffness or stickiness and may be made in the form of a shampoo, conditioner, combination shampoo/conditioner, sprays, liquid rinses, gels or mousses.

Description

Technical field

The present invention relates to improved hair care compositions. In particular, these hair care compositions which can be used as volumizing hair compositions have incorporated selected types of siloxysilicate-based polymers known as MQ silicone resins. This patent application is related to a patent application filed on the same day as this application, which has an IR number of 6232M and belongs to the same company (until now it has not been granted a US number).

BACKGROUND OF THE INVENTION

Research to improve hair care products is ongoing. Due to the existence of different hair types, product types are produced that are designed for individual hair types. One such type of product that is required by customers to create an increased hair volume is hair volumizers. Previous attempts to increase hair volume have involved the use of sprays based on fixatives, gels or foam hardeners designed to enhance the appearance and volume of hair. These products work on the basis of sticking hair into one solid and rigid shape with increased hair volume. The disadvantage of such products is that they cause hair hardness or excessive stickiness and generally do not allow the consumer to reprocess their hair without washing the applied product from its hair and applying it again. The adhesive nature of these volumisers can cause inconvenience in repeated hair styling. Furthermore, such fixation-based products may first cause a volumizing effect, but the continuous use of these products over time may eventually lead to a loss of hair volume.

····················

In addition, the problem is intensifying in people who have fine hair, because this type of hair is particularly sensitive in the prevalence of applied hair care products.

There is a demand for volumising products which are not based on permanent waving or are not spray-based fixatives or gels to form a specific hair shape. Customers want a volumising product that can increase the volume of otherwise straight or thin hair while retaining the ability to rework. Thus, hair volumizers used in this context do not create a constant hair shape, but allow reprocessing and hair re-volumization.

One example of hair styling compositions is disclosed in PCT Patent Application Publication No. WO 95/06057 to Torgerson et al. This reference describes silicone thermoplastic elastomer grafted copolymers and hair and skin care compositions comprising silicone thermoplastic elastomer grafted copolymers. These copolymers are effective in hair spray and foam hardeners. The copolymers described herein are water-soluble or alcohol-soluble or dispersible copolymers based on thermoplastic elastomers having a polymer backbone and two or more hydrophilic polymeric side chains and one or more polysiloxane side chains, wherein the copolymer comprises:

(a) 20 to 89.9% monomer units copolymerizable with (b) and (c);

(b) 10 to 60% of hydrophilic macromonomer units having a polymer moiety and a residue copolymerizable with (a) and (c);

(c) 0.1 to 20% of polysiloxane macromonomer units having a polymer moiety and a residue copolymerizable with (a) and (b).

In U.S. Pat. No. 4,902,499 to Bolich et al. hair care products are provided to provide both improved hair conditioning and hair quality stabilization. &lt; / RTI &gt; The compositions contain from 0.01% to 10% of a silicone-based solid polymer and a volatile carrier. Suitable polymers include reinforced polydimethylsiloxane gum fillers, crosslinked siloxanes, siloxane-based organic substituted gums, siloxane-reinforced resins, and cross-linked siloxane-based polymers.

In European patent application EP 0,240,350 B1, Snyder et al. the use of formulations having hair care properties and stabilizing quality, wherein the formulation comprises (a) a solid silicone-based polymer having a complex viscosity of at least 1 x 10 ⁶ Pa.s (1 x 10 ⁷ poise) selected from the group consisting of siloxane-based organic substituted rubbers, silicone-based elastomers, reinforced polydimethylsiloxane rubbers, siloxane-reinforced resins, and siloxane-based crosslinked polymers; and (b) volatile carriers selected from water, branched or unbranched volatile hydrocarbons having from 1 to 16 carbon atoms and volatile silicones having a boiling point in the range of 99 to 260 ° C, where, when water is the sole carrier, it is present 0.05 to 50 wt. and wherein the use of a silicone-based polymer in processing an aqueous aerosol-based hair care composition is prevented, wherein the silicone-based polymer is in the form of an emulsion containing an anionically stabilized hydroxylated polyorganosiloxane.

Other attempts have included the development of a composition for producing denser hair. PCT Patent Application Publication No. WO 96/38120 to Grossman discloses a denser hair composition and a gelatin-based hair stabilizing composition for topical application to the hair. A formulation comprising an aqueous gelatin solution, a water-soluble film-forming polymer, and an acid neutralizing agent to maintain the pH of the formulation in the range of 6.0 to 9.5 is disclosed. Types of water-soluble film-forming agent for us with this formulation include polyvinylpyrrolidone (PVP), polyvinyl acetate, partially hydrolysable polyvinyl acetate, PVP-vinyl acetate copolymers, polyvinyl alcohol, acrylate-PVP copolymers, and the like, wherein: · · ·· ··· · · · ·· ·· · · · · · ·

The polymers have an average molecular weight in the range of 5,000 to 10,000 daltons.

Siloxane resins are known consisting of triorganosiloxane units and silicon dioxide units, which are commercially available materials, and which are used in the formulation of various products, including adhesives, antifoams, and personal care products, but are not meant to mean that these compounds would be used commercially in hair care products of the type described herein. Such resins are sometimes referred to as &quot; MQ resins because they contain monovalent (M) siloxane units and quaternary (Q) silica units.

In view of the reactivity of the silyl hydride groups, it is sometimes desirable to include these groups in the type of MQ resins. Siloxane resins composed of units of silica and units of the formula HR ¹ R ² SiO 1/2, wherein each substituent R ¹ and R ² may be the same or different and each is selected from the group consisting of hydrogen, monovalent hydrocarbon and monovalent halogenated hydrocarbon, are used very often because silyl hydride functional groups have a high reactivity. Such resins have been used for elastomers based on polyorganosiloxanes. When these resins are used as precursors for other synthetic silicones, it is very often desirable that these resins contain a limited number of silyl groups. US 3,772,247 discloses polyorganosiloxane resins consisting of units of the formula R ³ R ⁴ R ⁵ SiO 1/2, SiO ₂ units and HR ³ SiO and / or HSO 3/2 units, each of R ³ , R ^4, and R ⁵ is independently selected from the group consisting of alkyl, aryl, alkylaryl, alkenyl, cycloalkyl and cycloalkenyl groups. Although such groups have silyl hydride groups, they have a significant and measurable level of divalent or trivalent organosiloxy groups.

In US Patent 4,774,310, Butler discloses MQ resins consisting of units of the formula R ³ R ⁴ R ⁵ SiO _1/2 and SiO ₂ units, wherein the substituents R ³ , R ⁴ and R ⁵ are each independently selected from: A group consisting of alkyl, aryl, alkylaryl, alkenyl, cycloalkyl and cycloalkenyl groups. The MQ resins of this patent are further reacted with disiloxanes using acid catalysis to form MQ-type siloxane resins wherein the M: Q ratio is in the range of 0.4: 1 to 1: 1 and wherein the hydride protective unit fraction of formula H _and R 3 _and SiO ⁿ / 2, where R ⁿ is selected from the same group as defined for the substituents R ^3, R ⁴ and R ^5, is between 0.1 and 30% of the total units present M.

British Patent 2,297,757 to Berthiauma et al. discloses low viscosity siloxysilicates with an established organometallic functional group of the "MQ" type and listed as active ingredients for cosmetic and personal care products. These functional group MQ silicone resins have the general formula

R ¹ R ² II (M ^{1 -} Si - O 1/2) x (M ^{2 -} Si - O 1/2) _y (SiO _4/2 ) _of R ¹ R ² wherein R ¹ and R ² may be either a phenyl group or C 1 -C 12 alkyl and M ¹ and M ² are independently selected from the group consisting of phenyl, phenethyl, polyether, hydrogen, and C 1 -C 23 alkyl (which may include halogen substituted hydrocarbon radicals) and wherein x, y and z are as follows: 0.5 <(x + y) / z <4.0 and either x or y may be 0.

US 5,585,094 Villamarina discloses a method for partially permanent hair quality stabilization wherein an oil-in-water low viscosity emulsion of a blend of two polysiloxane-based polymers (one is dimethylpolysiloxane with a hydroxy group as the end group and the other is methylhydrogenpolysiloxane) is applied at acid pH unreacted state. The crosslinking of the polymers is preferably carried out by heating.

In U.S. Patent 4,963,348, Bolich et al. describes the means

• • · • • · • · • · ···· • · · · • * · • · · • · · · · · · · · · ·· ··

intended to produce a particular hair appearance and preparations comprising an adhesive copolymer with a volatile solvent to obtain and maintain a certain hair appearance.

However, there is a continuing need to provide formulations suitable as hair volumizers which, after use, do not lose hair density or are not too sticky.

It is therefore an object of the present invention to provide volumizing compositions which do not function such that hair becomes sticky when the volume is increased. In particular, an important object of the present invention is to provide hair volumizers which are capable of increasing hair volume without significant adhesion of individual hairs. It is a further object of the present invention to provide a hair volumizer that allows the hair between treatment to be able to be treated and regain volume. It is also an object of the present invention to provide compositions suitable for use as hair volumizers that are significantly effective in increasing hair volume. It is a further object of the present invention to provide compositions suitable for use as hair volumizers that utilize MQ resins and which allow hair to withstand hair pressure. These and other objects of the present invention will be apparent from the following description.

SUMMARY OF THE INVENTION

Compositions of the present invention are hair volumizers which comprise:

(a) 0.01 to 15 wt. % (calculated on the total weight of the formulation) of selected liquid MQ resins having an M: Q ratio of 0.5 to 1.5 and a mean viscosity in the range of 1.0 x 10 ³ to 1 x 10 ⁶ centipoise (cps or cP), e.g. . 0.1 to 10 wt. %, in particular 0.1 to 7.0 wt. % and in particular 0.1 to 4 wt. %; and (b) 85 to 99.99 wt. % (calculated on the total weight of the preparation) of the hair carrier.

The formulations of the present invention provide the hair with the recovery of the hair.

Objemu increased volume without significant hardness or excessive adherence or accumulation of product in the hair, which could contribute to volume loss. The compositions of the present invention can be prepared in the form of shampoos, conditioners, a combination of shampoos and conditioners (so-called 2-in-1 products), sprays, liquid cleansers, gels and foam hardeners.

DETAILED DESCRIPTION OF THE INVENTION

The compositions of the present invention are prepared with one or more selected liquid MQ resins having an M: Q ratio of 0.5 to 1.5 (also referred to as (x + y) / z ratio for formula IA or x '/ z' ratio). if the segments x and y are the same as in formula IB) and the viscosity is in the range of 1.0 x 10 ³ to 1 x 10 ⁶ centipoise (cps or cP) or 1.0 to 1 x 10 ³ Pa.s; in particular 1.5 x 10 ³ to 1 x 10 ⁶ cps, and in particular 1000 to 100000 cps, even more preferably 1000 to 50 000 cps, and even more preferably 1000 to 20000 cps, e.g. 2000 to 14000 cps, with a sub-example of 3000 to 12000 cps. Although higher viscosity MQ resins (e.g., 50,000 to 10,000 cps) may be used, it is more preferred to use lower viscosity MQ resins.

MQ resins suitable for use in the present invention may be represented by the general formula IA

R ⁴ R ⁵

II (IA) (M ¹ —Si — O _1/2 ) _x (M2-Si-O _1/2 ) _y (SiO _4/2 ) _z

Αθ R ⁷ wherein R ^4, R ^5, R ⁶ and R ⁷ are each independently selected from the group consisting of phenyl and branched or unbranched hydrocarbon chain of 1 to 12 carbon atoms, in particular branched or unbranched alkyl of 1 to 12 carbon atoms more preferably branched or unbranched alkyl having 1 to 5 carbon atoms, and in particular methyl;

M ¹ and M ² are each independently selected from the group consisting of (a) a hydrogen atom, (b) phenyl, and a hydrogen atom; 9 · 9 (c) phenethyl, (d) a polyether of the formula II CH ₂ - (CH _{2) n} - [0-CH (R ¹⁰⁾ CH _{2] u} - _{(0-CH2 -CH2)} -OR ^{11 (II)} wherein the index n is 1 to 20 and the - (CH ₂ ) - chain may optionally contain one or two unsaturated bonds; u and v are indices selected independently from 0 to 20, with the condition that u + v>1; R ¹⁰ is selected from alkyl of 1 to 20 carbon atoms; and R ¹¹ is selected from the group consisting of H, -CH 3, and -C (O) CH 3; and (e) a branched or unbranched hydrocarbon chain of 1 to 24 carbon atoms optionally substituted with a hydrocarbon radical of 1 to 3 carbon atoms which is substituted with halogen, with a specific meaning for R ² , which is alkyl of 1 to 24 carbon atoms, in particular methyl; and wherein (x + y) / z is a number in the range of 0.5 to 1.5, preferably equal to 1; and the values of the substituents R ⁴ , R ⁵ , R ⁶ , R ⁷ and x, y, z, M ¹ and M ² are selected such that the MQ resin is a fluid having a viscosity of 1.0 x 10 ³ to 1 x 10 ⁶ centipoise , e.g. 1.5 x 10 ³ to 1 x 10 ⁶ centipoise.

A particular type of MQ resin of formula IA wherein x and y are not the same may be represented by formula IB

R ¹ (R 2 SiO _{1/2) x.} (SiO, _{/ 2) of the.} ^(s)

R ³ wherein R ¹ and R ³ are each independently selected from the same group as defined for R ⁴ , R ⁵ , R ^6, and R ⁷ in formula IA; R ² is selected from the same group as defined for M ¹ and M ² ; and x '/ z' is a number in the range of 0.5 to 1.5.

The partial MQ resin used in the present invention is a liquid polymer based on trimethylsiloxysilicate, especially with an M: Q ratio of 1 (e.g., a resin obtained from General Electric Company, Waterford,

New York as "MQ-A). As described in more detail below, it has been found that low viscosity liquid MQ resins with a M: Q 2 ratio do not provide a significant volume and do not exhibit a significant adhesive property on the hair; solid MQ resins with an M: Q 2 ratio do not provide a significant volume and do not exhibit a significant adhesive property on the hair; and solid MQ resins with a M: Q ratio of 0.7 to 1.0 provide volume but do not exhibit hair adhesive properties.

The carrier in which the MQ resin is present is a member selected from the group consisting of spray, hair formulations applied after washing hair, shampoos, conditioners and 2-in-1 shampoos to stabilize hair quality. These products may in particular be formed with a volatile carrier (which is a carrier having a measurable water vapor pressure), e.g. volatile silicones, C 2 -C 3 alcohols, isopropyl myristate, water and mixtures thereof, with the proviso that if water is only a single carrier, at least one surfactant is also used. One class of preferred carriers are volatile silicones having a boiling point between 99 ° C and 260 ° C. The silicones may be either linear or cyclic polydimethylsiloxanes, wherein the cyclic polydimethylsiloxanes contain 3 to 7 silicon atoms, most preferably 5 silicon atoms. These volatile silicones can be used alone or in combination with other volatile carriers. The partial volatile silicone is cyclomethicone (especially D5 cyclomethicone).

When water is the only carrier, a surfactant is also present in an amount of 0.1 to 50 wt. % of the total preparation.

Shampoos can be used as carriers to which MQ resin has been added. Suitable shampoos include both conventional shampoos and hair quality stabilizing shampoos. Individual shampoos include those prepared with a surfactant, a stabilizer, and a selected MQ resin. Other optional ingredients, e.g. thickeners, preservatives, fragrances, opacifiers, foam modifiers, etc., may be included in such formulations as set forth in the next section of the invention.

• · · • · · • · • · · · · • ·· » • · • · · • · • · · · · · · · · · ·· ·

Suitable surfactants include:

(a) the surfactant anionics disclosed in LJS patents 4,902,499 and US 4,963,348 by Bolich et al., both of which are incorporated herein by reference, e.g.

(i) alkyl sulphates and alkyl ether sulphates of the general formula R ²⁰ OSO ₃ M and R ²⁰ O (C 2 H 4 O) SO ₃ M, where R ²⁰ is alkyl or alkenyl having 10 to 20 carbon atoms, index w being a number ranging from 1 to 10 and M is a designation for a water-soluble cation, e.g. ammonium, sodium, potassium and triethanolamine;

(ii) fatty acid reaction products (e.g., derived from coconut oil) esterified with isethionic acid and neutralized with sodium hydroxide;

(iii) succinamates (e.g., disodium N-octadecylsulphosuccinates, tetrasodium N- (1,2-dicarboxyethyl) -N-octadecylsuccinamates, sodium sulfosuccinate diamyl ester, sodium sulfosuccinate dihexyl ester and sodium sulfosuccinate dioctyl ester having a (iv) sodium olonate; 12 to 24 carbon atoms;

(b) the amphoteric materials disclosed in U.S. Patent 4,902,499 to Bolich et al., incorporated herein by reference, e.g.

(i) aliphatic derivatives of secondary and tertiary amines, in which the aliphatic radical may have a branched or unbranched chain, wherein one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains an anionic water-soluble group (e.g. carboxy, sulfonate, sulfate, phosphate or phosphonate). Examples of such compounds include sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate, N-alkyltaurines, N- (higher alkyl) aspartic acids (e.g., the products sold under the name "MIRANOL described in US Patent 2,528,378);

(ii) zwitterionic surfactants, e.g. derivatives such as aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic radicals may have branched or unbranched 11

• · · • • · • · • · ···· • · · · · · • · • · • · • · · · · • · ·· · · · • ·

a straight chain wherein one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains an anionic water-soluble group (e.g., carboxy, sulfonate, sulfate, phosphate or phosphonate);

(iii) betaines, e.g. higher alkylbetaine, e.g. cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethyl-α-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl-bis- (2-hydroxyethyl) carboxymethylbetaine, stearyl-bis- (2-hydroxypropyl) carboxymethylbetaine, carboxymethylbetaine, carboxymethylbetaine, α-carboxyethyl betaine and cocamidopropyl betaine;

(c) nonionic surfactants, including those selected from the group described in U.S. Patent 4,741,855 to Grot et al., incorporated herein by reference, including:

(i) polyethylene oxide condensates of alkylphenols, wherein the alkyl portion of the alkylphenol has 6 to 12 carbon atoms and may be branched or unbranched, and the ethylene oxide portion is present in an amount of 10 to 60 moles of ethylene oxide per mole of alkylphenol;

(ii) the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine, which differ depending on the desired hydrophobic / hydrophilic balance (e.g. compounds containing 40 to 80% by weight polyoxyethylene and having a molecular weight of 5,000 to 11,000) with a hydrophobic base composed of the reaction product of ethylenediamine and an excess of propylene oxide, wherein the base has a molecular weight of 2500 to 3000);

(iii) the condensation products of a C8-C18 branched or unbranched chain of aliphatic alcohols with ethylene oxide (e.g., a coconut alcohol-ethylene oxide condensate having 10 to 30 moles of ethylene oxide per mole of coconut alcohol where the coconut fraction has 10 to 14 carbon atoms);

(iv) long chain tertiary amine oxides of general formula 12

• • · • · · • · • · ···· • · · · · · • · • · • · • · · · · • · · · · · ·

ca (R ³⁰ ) (R ³¹ ) (R ³² ) N -> O where R ³⁰ is C 8 -C 18 alkyl, alkenyl or monohydroxyalkyl having 0 to 10 ethylene residues and 0 to 1 glyceryl residue; and the substituents R ³¹ and R ³² may be the same or different and each is independently selected from the group consisting of alkyl of 1 to 3 carbon atoms of 0 to 1 hydroxy. The arrow in the structure is a standard representation of hemipolar binding. Examples of suitable long chain tertiary amine oxides include cocamidopropylamine oxide and lauramine oxide;

(v) long chain tertiary phosphine oxides of the formula R ²⁰ R ²¹ R ²² P → O, wherein R ²⁰ contains an alkyl of 8 to 18 carbon atoms, an alkenyl or monohydroxyalkyl radical, 0 to 10 ethylene oxide residues and 0 to 1 glyceryl residue ; and R ²¹ and R ²² are each independently selected from C 1 -C 3 alkyl or monohydroxyalkyl (the arrow in the structure is a standard representation of a hemipolar bond); and (vi) long chain dialkyl sulfoxides containing one short alkyl or hydroxyalkyl chain having 1 to 3 carbon atoms (especially methyl) and one long hydrophobic chain having an alkyl group of 8 to 20 carbon atoms, an alkenyl, hydroxyalkyl or ketoalkyl group with 0 to 10 ethylene oxide residues and 0 to 1 glyceryl residue.

The stabilizers include one or more members selected from the group consisting of the following members selected so that the final amount of stabilizer added is in the range of 0.1 to 7.0%:

(a) long-chain aliphatic alcohols having more than 14 carbon atoms, e.g. 20 to 40 carbon atoms, and mixtures of such long chain aliphatic alcohols (e.g., an alcohol having a carbon number greater than 14 and an PETROLITE ethene homopolymer C-7138 from Petrolite Corporation, St. Louis, Missouri);

(b) acrylate / steareth-20 methacrylate copolymers (e.g., ACULYN® 22 from Rohm & Haas, Philadelphia, Pennsylvania); and 99 99 acrylate-based copolymers (eg, ACULYN® 33 acrylic copolymer; ACUSOL® 445, 810 and 830; ACRYSOL® ASE 75 from Rohm &Haas); and C 10 -C30 acrylate / alkyl acrylate crosslinked polymer (PEMULEN ™ polymer-based emulsifiers from BF Goodrich Company, Brecksville, Ohio, especially products designated TR-1 and TR-2). For the ACULYN® 33 acrylate copolymer product having a pH in the range of 2.1 to 3.5, the step of neutralizing with sodium phosphate (e.g., sodium phosphate medium), sodium hydroxide, or a cosmetically acceptable organic amine is performed. to raise the pH to about 6.5;

(c) agents disclosed in U.S. Patent No. 5,015,415, incorporated herein by reference, and in particular N, N-disubstituted phthalamic acids and their ammonium salts selected from the group represented by Formula III

Wherein R ²⁴ and R ²⁵ may be the same or different and each is selected from the group consisting of a branched or unbranched chain of C 10 -C 40 alkyl groups and a branched or unbranched chain of C 10 -C 40 arylalkyl groups (e.g. the substituents R ²⁴ and R ²⁵ are the same and each is selected from the group consisting of stearyl and hydrogenated tallow (e.g., STEPAN® SAB-2 and STEPAN® TAB-2 from Stepan Company, Northfield, Illinois).

The stabilizing agents should have a certain class of quality and purity that is acceptable for cosmetic use, or they should be cleaned as necessary to make them cosmetically acceptable. Further information on these agents can be found in U.S. Patent 5,015,415 to Goz et al. and in our copending U.S. application Ser. 08 / 933.521.

• 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

Shampoo carriers, which can be used as binders for the selected MQ resins described, can be prepared as solutions, suspensions or emulsions containing soft, aqueous, lather, and hair quality stabilizing detergent-based formulations containing (by weight% of the total weight of the formulation):

(a) 4.00 to 60.00% of a cleaning surfactant selected from the group consisting of at least one anionic detergent selected from the group consisting of C 8 -C 18 alkyl sulfates, C 8 -C 18 alkylethenoxy ether sulfates containing 1 to 5 ethenoxy groups per molecule, C10-C18 acyl isethionates, C10-C20 alkylsulfonates, C10-C20 alkylene sulfonates, and mixtures thereof; and optionally at least one of:

(i) 0.10 to 5.00% of an anionic hydrotropic C 1 -C 3 alkylbenzene sulfonate or C 5 -C 6 alkylsulfate;

(ii) 0.10 to 15.00% of an amphoteric surfactant selected from the group consisting of C8-C18 alkyl betaines, C8-C18 alkylsulfobetaines, C8-C18 alkyl amidoalkylbetaines with 2 to 3 carbon atoms in the betaine moiety, C 8 -C 18 alkylamidoalkylsulfobetaines in the amide moiety and 2 to 3 carbon atoms in the sulfobetaine moiety, C 8 -C 18 alkyl amphoacetates, C 8 -C 18 alkyl amphopropionates, cocamidopropyl betaine and mixtures thereof; and (iii) 0.1 to 4.0% nonionic surfactant, in particular a member selected from the group consisting of C 8 -C 22 monoethanolamides and mixtures thereof, and C 8 -C 22 diethanolamides and mixtures thereof, in particular cocamonoethanolamide and cocadiethanolamide;

with the proviso that the total amount of the purifying surfactant does not exceed 60 wt. % of the total amount of the composition, preferably in the range of 6 to 30%;

(b) 0.10 to 7.0% (particularly 0.10 to 5.00%) stabilizing 15

• · · • · · • · • · ···· • · · · · · • · · • · • · ·· · · · · · · ·· 9

an agent selected from the group described above, in particular polyacrylic acid, polyacrylic acid derivatives, acrylate-based copolymer, acrylate-based copolymer, and polymeric emulsifiers, e.g. C10-C30 alkyl acrylate / crosslinked polymers with specialty products, including ACULYN® 33, TAB-2, SAB-2 and PEMULEN ™, ACULYN®® 22, acrylate / steareth- 20 methacrylate and ACULYN® (e.g. 50/50);

(c) optionally quaternized cellulose-based polymers (in particular at least one quaternized cellulose-based polymer, e.g. Polykvaternium-10);

(d) equilibrium water or aqueous environment.

Where appropriate, additional ingredients may be added to hair quality shampoos, as in (e):

(e) 0.01 to 10.0% of water-insoluble hair quality stabilizing agents selected from the group consisting of:

(i) 0.10-6.00% water-insoluble silicones selected from the group consisting of dimeticones and silicones, e.g. silicones disclosed in U.S. Patent 4,741,855, incorporated herein by reference, including polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyestersiloxane based copolymers, and mixtures thereof in an amount of 0.1 to 10.00%, preferably 0.5 to 5.0%, e.g. polydimethylsiloxanes having a viscosity at 25 ° C of 5 to 600,000 centistokes (e.g., 60000 centistokes) available from General Electric Company as Vicasil series and from Dow Corning Corporation as Dow Corning 200 series, polymethylphenylsiloxanes having a viscosity at 25 ° C of 15 to 30000 centistokes (e.g., SF 1075 Methylphenyl Fluid from General Electric Company and Dow Corning 556 Grade Fluid from Dow Corning Corporation), polypropylene modified polydimethylsiloxane as well as ethylene oxide or mixtures of ethylene oxide and propylene oxide modified materials;

• · • ·· • · · · • • • • ···· • · · · · · • · • • • • • • • • • • • · · · · • · ·· · · · · ·

(ii) mixtures of at least one of (d) (i) with 0.1 to 3.00% of a cationic polymer, e.g. a polyquaternary compound selected from the group consisting of a quaternized cellulose-based polymer (in particular at least one quaternized cellulose-based polymer, e.g. Polykvaternium-10);

(iii) non-cellulose quaternary compounds (e.g. Polykvaternium-7); and (iv) a mixture of at least one of (d) (i) 0.01 to 3.00% of a cationic polymer, e.g. a polyquaternary compound selected from the group consisting of a mixture comprising at least one quaternized cellulose-based polymer with a non-cellulosic quaternary polymer to be treated.

The use of certain silicones may make it necessary to use suspending or hair-quality stabilizing agents as described in this application and in the patent literature.

Another sub-type of shampoo can be prepared by combining 0.1-15% MQ resin, 4-60% surfactant, e.g. synthetic surfactant, 0.5 to 7.0% stabilizer (calculated at 100% active level), and the remainder being water. Examples of suitable surfactants include ammonium lauryl sulfate, ammonium laureth sulfate, trietylamínlaurylsulfát, t rietylamínlauretsulfát, triethanolamine, trietanolamínlauretsulfát, monoethanolamine, monoetanolamínlauretsulfát, dietanolamínlaurylsulfát, dietanolamínlauretsulfát, monoglyceride, sodium laurate, sodium lauryl sulfate, sodium laureth sulfate, lauryl sulfate, potassium laureth phosphate, lauryl-N-methylglycine, cocoyl-N-methyl glycine, cocoyl sulfate, ammonium lauroyl sulfate, monoethanolamine cocoyl sulfate, sodium lauroyl sulfate, monoethanolamine cocoyl potassium lauroyl potassium trietanolamínlauroylsulfát, trietanolamínlauroylsulfát, monoetanolamínkokoylsulfát, monoetanolamínlauroylsulfát, tridecylbenzene sulfate and sodium dodecylbenzenesulfonate, and further those described in U.S. Patent 4,902,499 to Bolich and company. in columns 4 to 6, incorporated herein by reference.

Another sub-example of a suitable means of administration. The formulations of the present invention are conditioners. Individual formulations are those prepared with lipid materials, cationic surfactants and water. Such formulations can be found in U.S. Patent 5,120,531, incorporated herein by reference.

Compositions of lipid materials useful in the present invention are water-insoluble compounds having both hydrophobic and hydrophilic residues. Examples of suitable lipid materials are naturally occurring or synthetic acids, acid derivatives, alcohols, esters, ethers, ketones, alcohol ethoxylates and amides having a carbon chain of 12 to 22 carbon atoms, preferably of 12 to 18 carbon atoms and of 16 to 22 carbon atoms . Specific examples include esters, e.g. cetyl palmitate and glyceryl monostearate; alcohols, e.g. cetyl alcohol and stearyl alcohol. The individual lipid materials are (a) stearyl alcohol as the sole lipid material, and (b) a mixture of 55 to 65% cetyl alcohol and the remainder stearyl alcohol. These lipid materials include naturally occurring or synthetic aliphatic alcohols, aliphatic alcohol ethoxylates and aliphatic esters.

Cationic surfactants useful in forming such conditioners include those described in U.S. Patent No. 5,120,531, herein incorporated by reference, and others. Particular examples include amino-containing cationic surfactants or quaternary ammonium hydrophilic residues which are positively charged when dissolved in aqueous preparations, e.g. having the general formula (R ¹⁰ ) (R ¹¹ ) (R ¹² ) (R ¹³ ) N ⁺ - X, wherein R ¹⁰ is hydrogen, C 1 -C 22 aliphatic or aromatic, aryl or alkylaryl C 12 -C 22; R ¹¹ is an aliphatic group having 1 to 22 carbon atoms; R ¹² and R ¹³ are each independently selected from the group consisting of C 1 -C 3 alkyl; and X is an anion selected from the group consisting of halogen, acetate, phosphate, nitrate, and alkyl sulfate radicals. Aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether bonds as well as other groups, e.g. amide. Examples of quaternary ammonium salts include cetyltrimethylammonium chloride ("cetrimonium chloride"), lauryltrimethyl chloride 18. Lamonium ("laurtrimonium chloride"), tricetylmethylammonium chloride ("tricetylmonium chloride, stearyldimethylbenzylammonium chloride"("stearalkoniumchloride") and di (partially hydrogenated tallow)) distearyldimonium chloride, etc .;

The individual groups of hair quality stabilizing agents are selected from the group consisting of quaternary ammonium compounds, in particular dicetyldimonium chloride, distearyldimonium chloride, and other cationic materials disclosed for cationic surfactants.

Examples of conditioners to which a selected MQ resin may be added include those prepared from 0.1-10.0% lipid material, 0.5-5.0% cationic surfactant and water.

After-washing hair care compositions can be prepared by combining said MQ resin (or mixture thereof) with water (preferably distilled or deionized water) or a water / alcohol mixture, e.g. in a ratio of 20: 1 to 1: 2 as part of the carrier. Also included is 0.1 to 1.0% surfactant. The carrier is present in an amount of 75 to 99.5 wt. %, preferably 85 to 99 wt. %, more preferably 90 to 99 wt. % of the total preparation.

Sprays can be prepared by mixing 0.01-10% MQ resin (or mixtures thereof) with one or more volatile substances, e.g. water, alcohol, ethanol, cyclomethicone, as described above, with 0.1 to 10% of at least one surfactant if water is present in a significant amount, and optionally with one or more of the admixtures described.

Further sub-examples of carriers suitable for applying the volumizing compositions of the present invention (which may be in the form of shampoos, hair quality stabilizers, hair quality stabilizers, sprays and the like) are known to the skilled artisan, see e.g. U.S. Patent 3,577,517 to Kobot et al .; US 3,907,984 Calvert et al .; US 4,012,501 Farber; US 4,223,009 Chakrabarti et al .; US 4,283,384 Jacquet et al .; all herein incorporated by reference.

In addition to the described basic formulations for shampoos and conditioners, one or more of the following ingredients may be required, including a mixture of each of the ingredients:

(A) an agent designed for viscosity-regulating shampoos, eg. polyvinyl alcohol, ethyl alcohol, acrylic acid polymers, cellulose ethers, long chain diethanolamide (e.g., PEG 3 lauramide), ethylene oxide and propylene oxide block polymers, sodium chloride, sodium sulfate, water-soluble polymers (e.g. guar polysaccharide), in particular thickened hydroxypropylcellulose, guar hydroPEG 120 methylglucosodioleate, pentaevents, e.g. xypropyltrimonium chloride, rytrityltetrastearate and xanthan gum;

(a1) an agent intended for viscosity-regulating conditioners, e.g. polyvinyl alcohol, ethyl alcohol, cellulose ethers, polyacrylamides, water-soluble polymers (e.g. hydroxyethylcellulose, guar polysaccharide and starch), in particular thickeners, e.g. hydroxyethylcellulose and guar hydroxypropyltrimonium chloride;

(b) fragrances (perfumes), e.g. cosmetically acceptable fragrances used in hair care products;

(c) preservatives, e.g. an antimicrobial agent, in particular a combination of methylchloromethylisothiazolinone and methylisothiazolinone (sold under the trademark KATHON® CG by Rohm & Haas, Philadelphia, Pennsylvania), but also benzyl alcohol, ethylparaben, propylparaben and imidazolidinylurea, DMDM hydantoin, 2-nitro-2-nitro-1-nitro-2-nitro-2-nitro , 3-diol ("Bronopol") and combinations thereof. Particular examples may include a potentiator, e.g. ethylenediaminetetraacetic acid or its sodium salt (e.g. Bronopol and EDTA, e.g. 0.04% Bronopol and 0.1% EDTA; formalin, DMDM hydantoin and EDTA, e.g. 0.1% formalin, 0.45% DMDM hydantoin and 0 2% EDTA);

(d) coloring or dyeing agents, peroxisers (eg ethylene glycol distearate, sodium octyl sulphate, titanium dioxide or mica) and opacifiers (eg glycol distearate, aliphatic ethoxylates,

• · · • · · • · • · ···· • · · · · · • · · • · · · · · · · · · · · ·· ·

latex opacifiers, stearamide monoethanolamine stearate (MEA), sodium cetyl stearate and lanolin derivatives) suitable for use in hair care products;

(e) a pH adjusting agent, e.g. citric acid, sodium carbonate, etc .;

(f) complexing agents, e.g. ethylenediaminetetraacetic acid, and their sodium salts.

These additives may be included in appropriate amounts by individual decision in the range of about 0.1 to 60 wt. %, preferably about 0.5 to 40 wt. % of the total weight of the preparation.

It will be appreciated by those skilled in the art that the formulations prepared according to the present invention may have a permanent volumizing effect over a period of time so that the use of the products prepared according to the present invention can be alternated with other types of commercial shampoos to achieve and maintain the desired level of volumizing effect. Although the increase in hair volume will vary from person to person, generally the volume increases in the range of 10 to 40%, as measured by the manikin test described in the next section of this invention, measuring the volume change while using the compositions of the present invention. In general, the effect on thin, fine hair will be more pronounced than on thick, long, rough hair.

It should be noted that the compositions of the present invention provide volumizing effects without significant fixation (sticky) character or chemical adhesion between the hair strands, whereby the hair can be reprocessed by a second combing or re-inhalation. Such a procedure could not be effective with the hair being glued, as this could lead to breakage of the joints formed between the hair by fixation and the consequent loss of the fixative styling effect. The loss of fixation in the compositions of the present invention can be determined by the test described in the next section of the invention, in which the stability of the curl over time is measured.

• · ······················································· ·· ··· ··

Examples of formulations that can be prepared according to the present invention include:

Shampoos

Composition A - 0.1 to 7.5%, in particular 0.1 to 5%, more preferably 0.25 to 2.5%, of selected liquid MQ resins (e) and the remainder being shampoo binder. For hair quality stabilizing shampoos, 0.1 to 3.0%, and in particular 0.1 to 2.0%, of a hair quality stabilizing agent may also be included.

Composition B - 10-18% of a surfactant, in particular an anionic surfactant selected from the group consisting of ammonium lauryl sulfate, ammonium lauretsulfate, ammonium lauryl ether sulfate, sodium laurethether sulfate, ammonium lauryl ether sulfate, ammonium laurethether sulfate, and mixtures thereof; 0.25 to 2.5% of the selected MQ resin; 0.10 to 5.00% hair quality stabilizer; 1 to 3% admixture which acts as a foam modifier and / or viscosity modifier (e.g., at least one member selected from the group consisting of cocamidodiethanolamine, cocamidomonoethanolamine and comaidopropylbetaine); and the remainder is water or other suitable medium, which may contain an effective amount of a preservative as well as a fragrance and coloring agent.

Composition C - 10-20% of a mixed surfactant system comprising at least one anionic and at least one amphoteric surfactant in a ratio of 60:40 to 4/60 (examples of suitable anionic surfactants are described in composition B and examples of suitable amphoteric surfactants are cocamidopropylbetaine and cocamidopropylamine oxide) ;

0.25 to 2.5% of the selected MQ resin; with 0.10 to 5.00% hair quality stabilizer; and the remainder is water or other suitable medium, which may contain an effective amount of a preservative as well as a fragrance and coloring agent.

Conditioners

0.1 to 7.5%, in particular 0.1 to 5%, more preferably 0.2 to 2.5% of the selected MQ resins (e) and the remainder as carrier of the formulation.

• · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·· ··· ··

Composition D - 1 to 4% lipid material (e.g. stearyl alcohol and mixtures of stearyl alcohol and cetyl alcohol); 1 to 3% of a quaternized compound (e.g., at least one of dicetylmonium chloride, distearyldimonium chloride and cetyltrimonium chloride; and the remainder being water or other suitable medium which may contain an effective amount of a preservative as well as a fragrance and coloring agent.

Volumizing sprays

0.01 to 7.5%, in particular 0.03 to 5.0%, more preferably 0.05 to 2.0% of selected volatile carrier MQ resins, e.g. ethanol.

Volumizing hair formulations after washing

0.1 to 7.5%, in particular 0.1 to 5.0%, more preferably 0.2 to 2.5% of selected MQ resins with a carrier, e.g. water, with an appropriate amount of surfactant / stabilizer (e.g., ceteth-20 and cetrimonium chloride) to maintain emulsion stability (the amount of stabilizer depends on the amount of MQ resin used).

Hair sprays with fixation allowance

0.01 to 7.5%, in particular 0.05 to 2.0% of selected liquid MQ resins (e); 0.1 to 20%, in particular 0.5 to 15% of a volatile carrier; 72.5 to 99.89%, in particular 83 to 99.45% of a fixing binder (which may contain a volatile carrier, e.g. ethanol);

wherein each of the ingredients may be a single ingredient or a combination of ingredients.

In general, the formulations of the present invention can be prepared by standard techniques. If MQ resin is used, it can be added in several ways. For shampoo formulations, the MQ resin can be added alone, either alone or together with cyclomethicone or dimethicone, as described in the following examples. Alternatively, the MQ resin may be added to the heated oil phase prior to emulsion formation.

The formulations of the present invention make it easier to maintain the appearance and structure of the hair. Use of such formulations

• · · ···· · · • · • • • • · « • • • · · · • e · · · · · · · · · · ·· ·

apparently affects hair conditioning and does not appear to be affected by the presence of hair quality stabilizers. Tests have also shown that the increase in volume is not reduced by re-use, as is the case with fixatives that accumulate in the hair.

A further feature of the present invention is that the materials of the invention have the ability to be prepared and used in hair wash compositions. Thus, fixative-based volumizers are commonly prepared as leave-in products, which is not the case with the present invention, in which they can be prepared as either leave-in or wash products.

The formulations of the present invention may also be used in combination with fixatives without loss of volumizing effect. Tests have shown that the described MQ resins do not interfere with the action of the fixatives.

It will be understood that the formulations of the invention, although sometimes described as "consisting of," containing, etc., also include formulations which may, where appropriate and intended, contain not only the particular component (s) mentioned, but also various combinations of relevant ingredients for a given formulation.

DETAILED DESCRIPTION OF THE INVENTION

The following examples are given by way of illustration and are not intended to limit the scope of the invention in any way. Unless otherwise indicated, in the examples as well as elsewhere in the text, the percentages are by weight. %, based on 100% active level for all impurities, and all chemical and technical terms have their general and customary meanings unless otherwise specified. All temperatures are in degrees Celsius. These conventions are also used throughout the rest of the invention.

Examples 1 to 4

Hair Quality Stabilizing Formulations • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Hair quality stabilizing formulations were prepared using the types and amounts of materials listed in Table I. In a suitable container, hydroxyethylcellulose was dispersed in distilled water at room temperature. Then, the C 9 -C 11 alcohol ethoxylate (EO 6: 1, "C 9 -C 11 Pareth-6") was added with stirring and the resulting solution was heated to 75 ° C. Ceteth-20, steareth-20, stearyl alcohol, isostearamidopropyldimethylamine and dicetyldimonium chloride were combined in a suitable vessel and heated to 75 ° C with stirring. With both solutions at 75 ° C, the aqueous phase was then added to the oily phase with stirring. The resulting emulsion was stirred at 75 ° C for 10 minutes and then cooled to 60 ° C. Liquid trimethylsiloxysilicate was dissolved in cyclomethicone and added to the emulsion at 62 ° C. The emulsion was then cooled to 38 ° C at which fragrance and preservative were added. The final formulation was continuously cooled to room temperature. The MQ resin used was trimethylsiloxysilicate ("MQ-A") obtained from General Electric Company.

·····································

Table I

material Pr. 1 weight. % Pr. 2 weight. % Pr. 3 weight. % Pr. 4 weight. % Distilled water 93.85 93, 85 93.85 93.85 hydroxyethyl 0.50 1.00 1.0 1.0 C9-C11 Pareth-6 0.20 0.20 0.20 0.20 Ceteth-20 0.50 0.50 0.50 0, 50 Steareth-20 0.50 0.50 0.50 0.50 stearyl 2.00 2.00 2.00 2.00 Izostearamidopropyl- dimethylamine 0.80 0.80 0.80 0.80 dicetyldimonium 1.50 1.50 1.50 1.50 Liquid trimethylsiloxy- silicate 2.50 2.50 0.75 1.50 Cyclometicon (D5) 2.50 2.50 2.50 2.50 Fragrance 0.75 0.75 0.75 0.75 Metylchlórmetyl- isothiazolinone and Methylisothiazolinone 0.07 0.07 0.07 0.07

• · • ·· • · • · • • • • • · · · • · · · • • • · • • • · • • • • • • • · · · · • » · · · • · • ·

Example 5

Formulation stabilizing hair quality

A sample (300 g) of the hair quality stabilizing formulation was prepared with the following materials: 0.50% hydroxyethylcellulose; 93.35% distilled water; 2.75% cetearyl alcohol; 0.50% stearamidopropyldimethylamine; 0.15% polyglyceryl-3-diisostearate; 0.25% citric acid; 0.20% methyldibromoglutaronitrile and phenoxyethanol (MERGUARD® 1200 from Calgon Corporation, Pittsburgh, Pennsylvania); 0.15% glyceryl monostearate; 1.50% distearyldimonium chloride; 0.25% of the MQ resin described in Examples 1-4; 0.4% fragrance. Hydroxyethylcellulose and distilled water were combined in a suitable vessel with stirring. The solution was heated to 80 ° C. Cetearyl alcohol, distearyldimonium chloride, stearamidopropyldimethylamine, glyceryl monostearate and polyglyceryl 3-diisostearate were combined in a separate vessel and heated to 80 ° C with stirring. When both mixtures reached a temperature of 80 ° C, the aqueous phase was added to the oil phase with stirring. The resulting emulsion was cooled to 60 ° C and silicone MQ resin was added with stirring. When the temperature reached 38 ° C, fragrance and preservative were added. The final formulation was then cooled to room temperature.

Examples 6 and 7

Shampoo formulations

Shampoo formulations were prepared using the types and amounts of materials listed in Table II. In a suitable vessel, 10 wt. % distilled water, sodium EDTA (four), sodium monohydrophosphate, ammonium lauryl sulfate, sodium deceth-3-sulfate, sodium cumenesulfonate, and cocamidopropyl betaine. The resulting solution was heated to 90 ° C with stirring. The remaining 10 wt. % distilled water and Polykvaternium-10. The contents of this small vessel were then added to the solution at near boiling point. In a suitable container:

• · · • ft · • · • · • · · · • · · · • · • · · • · • · · · · · · · · · • · ·

isosteareth-20, a C 20 -C 40 alcohol and distearyldimonium chloride. After dissolution, the mixture was added to the aqueous solution with stirring at 90 ° C. The resulting emulsion was then cooled to 60 ° C. Liquid trimethylsiloxysilicate (the same MQ resin as in Examples 1-4) was dissolved in cyclomethicone and added to the emulsion at 60 ° C with stirring. The resulting mixture was cooled to 38 ° C at which fragrance and preservative were added. The final formulation was cooled to room temperature. It should be noted that the same procedure was used in Example 7, but did not use sodium deceth-3-sulfate, isosteareth-20, distearyldimonium chloride or cyclomethicone.

• • · • • · • · • · • · · · • · · · · · • · · • · • · • · · • · · · · ·· ·

Table II

material Pr. 6 weight. % Pr. 7 weight. % Distilled water q. with. q. with. EDTA (four) sodium 0.10 0.10 Sodium hydrogen phosphate 0.20 0.20 Ammonium lauryl sulfate 3.36 8.26 Sodium deceth-3-sulfate 4.50 0 Sodium cumenesulfonate 2.80 0.66 cocamidopropyl 9.00 9.00 Polyquaternium-10 0.90 0.55 Isosteareth-20 0.80 0.00 C20-C40 alcohols 4.00 2.00 distearyidimonium 1.00 0, 00 Liquid trimethylsiloxysilicate 2.50 1.00 Cyclometicon (D5) 2.50 0, 00 Fragrance 1.20 0.75 methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07

q. with. - as appropriate

Examples 8 and 9

Shampoo formulations

Shampoo formulations were prepared using the types and amounts of materials listed in Table III. In a suitable container, 90 wt. % distilled water and sodium phosphate and stirred for 10 minutes. Ammonium lauryl sulfate was added to the flask and stirred for 5 minutes. The resulting solution was heated to a temperature of 29

• · · • • · • · • · ···· • · · · · · • · · • · • · · · · · · · · · • · ·

lot 50 ’C. The remainder of the distilled water and Polykvaternium-10 were pre-mixed for 1-2 minutes and added to the vessel with stirring for a further 15 minutes. Cocadiethanolamide ("cocamid DEA"), guar polysaccharide and distearyldimonium chloride were combined in a separate vessel and heated to 50 ° C with occasional stirring. When both vessels reached a temperature of 50 ° C, they were combined while stirring. Silicone MQ resin (same resin as in Examples 1-4) and dimeticone (if included in the formulation) were separately added to the flask and mixed for 15 minutes. The vessel was then allowed to cool. The acrylate-based copolymer ("ACULYN ® 33") and the fragrance were premixed and added to the emulsion. When the temperature of the mixture reached 38 ° C, a preservative was added. The final formulation was cooled to room temperature.

Table III

material Pr. 8 weight. % Pr. 9 weight. % Distilled water q. with. q. with. Ammonium lauryl sulfate 16.80 16.80 Sodium dihydrogen phosphate 0, 30 0.30 Polyquaternium-10 0.25 0.25 cocodiethanolamide 2.00 2.00 Guar polysaccharide 0.22 0.22 distearyidimonium 0.25 0.25 dimethicone 0.00 1.00 MQ resin 2.50 2.50 Acrylate-based copolymer 1.65 1, 65 Fragrance 0.75 0.75 methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0, 07

q. with. - as needed

• • · • ·· ···· • · · • · ··· · · · · ·· • · · • · · · · ·· ··· ·· ··

Examples 10 and 11

Shampoo formulations

In a suitable container, 90 wt. % distilled water and sodium phosphate. Ammonium lauryl sulfate was added to the flask. The resulting solution was heated to 90 ° C. The remainder of the distilled water and Polykvaternium-10 were pre-mixed for 1-2 minutes and added to the vessel with stirring for a further 15 minutes. Cocadiethanolamide, C20-C40 alcohols and distearyldimonium chloride were dissolved in a separate vessel and added to the solution with stirring. The resulting emulsion was allowed to cool. Silicone MQ resin (the same resin as in Examples 1-4) and dimeticone (if included in the formulation) were separately added to the solution with stirring at 60 ° C. When the emulsion temperature reached 38 ° C, fragrance and preservative were added. The final formulation was cooled to room temperature.

• • · • • · • · t » ···· • · · · · · • · · • e • · • · · · · · · · ·· ·

Table IV

material Pr. 10 weight. % Pr. 11 weight. % Distilled water q. with. q. with. Ammonium lauryl sulfate 16.80 16.80 Sodium phosphate 0.30 0.30 Polyquaternium-10 0.25 0.25 cocodiethanolamide 2.00 2.00 C20-C40 alcohols 2.00 2.00 distearyidimonium 0.25 0.25 dimethicone 0.00 1.00 MQ resin 2.50 2.50 Fragrance 0.75 0.75 Methylchloromethylisothiazolinone and methylisothiazolinone 0, 07 0, 07

q. with. - as needed

Examples 12 and 13

Shampoo formulations

In a suitable vessel, 90 wt. % distilled water and sodium dihydrogen phosphate. Ammonium lauryl sulfate was added to the flask. The resulting solution was heated to 60 ° C. The remainder (10 wt%) of distilled water and Polykvaternium-10 were combined in a small vessel. The contents of the small vessel were then added to the solution at near boiling point for a further 15 minutes with stirring. Cocadiethanolamide, guar polysaccharide and distearyldimonium chloride were dissolved and combined in a separate vessel and added to the solution with stirring. After dissolution, the mixture was stirred at 60 ° C with stirring

• · • ·· • f • · • · • · ···· • · · · ·· · • · · • · · · · • · · · · ·· ··

was added to an aqueous solution. Silicone MQ resin (the same resin as in Examples 1-4) and dimeticone (if included in the formulation) were separately added to the emulsion while stirring at 60 ° C. Phthalic acid distearylamide (TAB-2) was dissolved in a separate vessel and added to the mixture after cooling to 55 ° C. When the temperature of the mixture reached 38 ° C, fragrance and preservative were added. The final formulation was then cooled to room temperature.

Table V

material Pr. 12 weight. % Pr. 13 weight. % Distilled water q. with. q. with. Ammonium lauryl sulfate 16.80 16.80 Sodium phosphate 0.30 0.30 Polyquaternium-10 0.25 0.25 cocodiethanolamide 2.00 2.00 Guar polysaccharide 0.22 0.22 distearyidimonium 0.25 0.25 dimethicone 0.00 1.00 MQ resin 1.00 1.00 Fragrance 0.75 0.75 methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07 Phthalic acid distearylamide 2.00 2.00

q. with. - as needed

Examples 14 and 15

Shampoo formulations

90% by weight were combined in a suitable vessel with stirring.

• · · • ·· ···· • · · • · ··· · · • · · • · • · · · · ·· ··· ·· ·

distilled water; and a crosslinked polymer of 10 to 30 carbon atoms acrylates and alkyl acrylates ("PEMULEN ™ TR-1"). Ammonium lauryl sulfate and then sodium phosphate were added to the vessel with stirring. The remainder (10 wt%) of distilled water and Polykvaternium-10 were combined in a small vessel. The contents of the small vessel were then added to the solution under stirring for a further 15 minutes. Cocadiethanolamide, guar polysaccharide, fragrance and distearyldimonium chloride were combined in a separate vessel and added slowly to the solution with vigorous stirring. Silicone MQ resin (the same resin as in Examples 1-4) and dimeticone (if included in the formulation) were separately added to the emulsion while stirring at 60 ° C. The final formulation was obtained after addition of the preservative. (Note: heating was the same as in the method of Examples 12 and 13). The final formulation was then cooled to room temperature.

• • · • • · • · • · ···· • · · · · · • · • · · · • · · · · · · · · · • · · ·

Table VI

material Pr. 14 weight. % Pr. 15 weight. % Distilled water q. with. q. with. Ammonium lauryl sulfate 55,00 55, 00 Sodium phosphate 0.30 0.30 Polyquaternium-10 0.20 0.20 cocodiethanolamide 2.00 2.00 Guar polysaccharide 0.15 0.15 distearyidimonium 0.25 0.25 dimethicone 0.00 0.75 Silicone MQ resin 2.25 2.25 Fragrance 0.75 0.75 methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07 Crosslinked polymer based acrylates and C10-C30 alkyl- acrylates 0, 30 0, 30

q. with. - as needed

Example 16

Spray formulation

A spray formulation can be prepared with the following ingredients: 0.17% dimethicone copolyol; 0.2% cyclomethicone (pentamer); 0.001% octylsalicylate; 0.001% benzophenone-3; 0.001% hydrolyzed animal keratin; 0.35% fragrance; 1.0% MQ resin (same type as used in Examples 1-4) and the amount of ethanol as needed (e.g., 95%). SD alcohol and trimethylsiloxysilicate were combined in a suitable vessel. Dimeticonkopolyol, cyclo35

• • · ···· ·· · · · • • · • · ·· • • • ··· • · · · · · · · • · · · · ·· ··

Meticon, octylsalicylate, benzophenone-3, hydrolyzed keratin and fragrance were added to the solution and the resulting mixture was placed in a spray bottle.

Evaluation of functionality

Functional evaluations were performed in terms of volume enhancement, adhesive properties, and aesthetics.

The following examples describe these evaluations.

Control conditioner for test performed on mannequins

Example A

A control sample was prepared using the following ingredients:

Part 1 - 4.50% cetyl alcohol; 2.50% stearyl alcohol; 2.40% glyceryl monostearate; 1.00% cyclomethicone; 0.50% of a mixture of polysorbate 80, cetyl acetate and acetylated lanolin alcohol (SOLULAN® 98 from Amerchol Corporation, Danbury, Connecticut); 1.50% mineral oil, 2.50% white petrolatum; 0.50% propylene glycol;

Part 2 - amount of deionized water as appropriate; 4.00% dodecyltrimonium chloride in aqueous isopropanol (ARQUAD® 12-50 from Akzo, Chicago, Illinois);

Part 3 - 0.50% Diazolidinylurea; 0.75% fragrance.

All materials in Part 1 were combined with stirring and heated to 80 ° C. All materials in Part 2 were combined in a separate vessel with stirring and heated to 80 ° C. When both parts reached a temperature of 80 ° C, the mixture of part 1 was added to the mixture of part 2 with stirring at 80 ° C for 10 minutes and then cooled to 40 ° C. When the combined mixture reached a temperature of 40 ° C, the additive from part 3 was added and mixed until the whole mixture was homogeneous. The resulting mixture was then cooled to room temperature.

• • · ···· · · • · • • • • · • · • • • · · · • • • • • • • • • · · · · · · · · · • · · ·

Volumetric test performed on a manikin

It has been found necessary to have a reliable hair volume test that correlates more accurately with real conditions on human hair. To accomplish this requirement, a volume test performed on mannequins has been developed.

Hair volume is related to the volume of the overall hair strand composition on the head, not the volume of the individual strands. Depending on the partial hair treatment and the length of the hair, the individual hair strand on the head is connected to several other hair strands and serves as a support. For example, in fine hair, the hair strands are less able to bear the weight of their own as well as the weight of other hair strands. As a result, the hair on the head is collapsed and thus has a smaller volume. In view of the relationship between hair volume and hair structure as a whole, any hair volume test to be predictive of volume on real hair must use a pattern of hair strand composition to maintain the same structure as on the actual head. The most common methods do not smooth the problem depending on the conditions mentioned, since a large number of them rely on the measurement of the volume of the individual hair strands, the composition of the exposed hair strands or the curls. Since all the hair strands in the curl are attached together at one end rather than individually attached in many places, the individual hair forms a mutual support, thereby creating volume. Therefore, a good prediction cannot be obtained by measuring the volume of curls.

British Patent 2,297,757 describes a modified procedure by Robbins and Crawford, in which the measurement of cadre provides analytical data. Since the possibility of the hair strands in the curl to give the impression of an increased hair volume is scarce, the results of this method, which would correlate with customer experience on real hair, could be unexpected.

When working on a laboratory scale with the formulations of the present invention, volume measurements were performed on mannequins that had real human hair attached in many places

• · · • · · • • • • ···· • · · · · · • • • • • · • • • • • • • · · · · · · · · · · · · ·

all over his head. As a result, this method of fastening hair allows to mimic the same types of spatial arrangement of hair that are produced in real human subjects. Tests carried out in the salon on one half of the human subject's head and extended tests conducted by women at home confirmed that the volume test on mannequins is very predictive of the actual volume changes occurring with customers.

The volume test on mannequins uses the traditional saloon methodology, which involves adjusting one half of the head as well as image analysis techniques to determine the amount of volume change. In this test, prior to application, volume measurements of a portion of the hair on each side of the head were made to remove any deviation caused by the uneven distribution of the hair between the two halves. The treatment was carried out and then dried. All formulations of the invention were tested against the light conditioning formulation. It was necessary to use a hair quality stabilizing formulation as a control to eliminate any increased volume that could occur in the friction damage that occurs during the treatment of the manikin's head. Ragging or roughening of the hair surface is a widely accepted method of increasing hair volume. For decades, hair fraying has been used to create a significantly larger hair volume. The fact that the control conditioner does not affect the hair volume negatively has been demonstrated by the following results. All volume changes measured at the control adjustments were positive, indicating that the post-treatment volume was never less than before the treatment. (Note: Pre-application volumes were after hair cleaning).

To demonstrate that the control conditioner (Example A) did not reduce volume, a series of experiments were performed to confirm the use of the light conditioning formulation as a control. For hair quality stabilizing formulations, the formulation prepared according to the method of Example 1 without MQ resin was tested against a light hair stabilizing formulation formulation prepared according to Example A. No significant difference in results was observed (-4.8% difference, p-value 0.27) ). For shampoo studies38

• · • ·· • · · · • • • • ···· • · · · • e • · • • • • • • • • • • • · · · · · · · · · · · · ·

the same procedure was used for me; the formulation prepared according to the method of Example A was tested against the formulation prepared according to the method of Example 8, but without the MQ resin. No significant difference was observed between the volumes of the two formulations determined (difference 3%, p-value 0.73) confirming that the control conditioner did not cause hair volume reduction.

The dummy heads used in the volume experiments were "Sarahs" purchased from Pivot Point International, Chicago, Illinois. Before carrying out the experiment, the heads of the manikins were cleaned with a detergent solution containing 20% SLES-2EO, 5% cocamidopropyl betaine and 0.8% sodium cumene sulphonate. To minimize fraying, the detergent was applied to the hair by spraying. The heads were then washed under running water at a temperature of 38 ° C (100 ° F) until the wash water was clean. The heads of the manikins were washed twice, once with 5 ml of detergent solution and then again with 2.5 ml of solution. After washing, the hair of the manikins was combed with a brush and trimmed to be straight. The hair was allowed to dry overnight. The hairs of the manikins shall be combed (as far as possible) after washing so that the actual volume measured is influenced by the hair as little as possible. In the experiments, adjustments were made on both halves separately. Each half was then first wetted with 100 ° F (38 ° C) water before being treated with 3 ml of either the control or bulk formulation. One half of the manikin head, which was treated with a bulking formulation, was changed with each additional test. After treatment, the test formulations were applied to the hair, allowed to act for 30 seconds, the hair was washed with water at 38 ° C (100 ° F) until the wash water was clean and at least 60 seconds had elapsed. In experiments in which a bulk formulation was applied and washed more than once, applications were performed on one half sequentially rather than alternating the individual applications on both halves of the head. For conditioners containing MQ resins (Examples 1 to 5), application was performed followed by volume measurement. For shampoos containing MQ resins (Examples 7-15), three shampoo washes were performed prior to volume measurement. The product of Example 6 was only performed

• · · ···· · · · · • • • • • · · • • • · · · • • • • • • • · · · · · · · · · · · · · · ·

one wash. Actual changes on the heads of the mannequins were measured using a Zeiss Kontron image analyzer coupled to a Sony XC-77CE miniature CCD camera model with a 60mm Nikon AF Micro-Nikkor lens. The dummy image was captured with a video camera, digitized, and each half was measured using a program created specifically for this purpose. Actual volume changes were determined after cleansing the measured heads of the dummies, adjusting the head, and repeating the measurements. Percent changes in volume for each half were calculated using the following formula:

Vgtrany ⁼ 100 X [Vgtranes (θθ) ^- Vgtranes (before)] / Vgtranes (before) where Vgtranes is the actual volume measured for each half of the head, while before and after indicates values measured before and after adjustment.

The percentage change in volume for each treatment is then represented by the formula

AV - pravaEdit “AVk _{0n control}

To determine volume changes for each treatment, measurements were performed on at least five model heads per experiment. Data for the control and treated sides of the heads was determined using a paired t-test. Results may also include p-values, which is acceptable in terms of statistical practice; A p-value greater than 0.05 represents the statistical significance of the data at a 95% confidence level.

Volume measurement data were obtained for the formulations described in Examples 1 to 15 and are shown in Table VII. Data represent the average of at least five determinations.

A a aa aaa aa aaa a a a a a a aa a

Table VII

Example % vol magnification p-value 1 24.4 0,039 2 21, 9 0,032 3 - - 4 20, 7 0,008 5 26.1 0,014 6 37.3 0,058 7 21.8 0,025 8 20.0 0,044 9 20.7 0,003 10 16, 7 0,045 11 - - 12 20.1 0,017 13 - - 14 29.2 0,007 15 21.1 0,020

Almost all of the volume increases shown in Table VII are statistically significant (p <0.05). The volume increase values of 16.6 to 37.3% indicate that the formulations of the present invention are very effective in producing a noticeable hair volume increase.

Evidence that the observed volume increase is due to MQ resin MQ-A and not to the carrier is supported by the results of an experiment in which the hair quality stabilizing formulation of Example 1 was compared in a volume test performed on mannequins with the same formulation but without MQ resin. Compared to the conditioner without MQ resin-treated side, 41 was observed

• · · ···· · · · · • • • • • • · • • • · · · • • • · · · · · · · · · · · · ·

yielded a 25% volume increase on the side treated with the MQ resin formulation, confirming that the change in volume was due to the resin and not to the carrier.

Tests on human subjects

Another assay of the volumizing efficacy of the formulations of the invention was performed on human subjects. In separate tests, female subjects were provided with either a volumizing conditioner according to the method of Example 1 or a volumizing shampoo according to the method of Example 9. Subjects were given expert guidance on how to use the test product followed by an experiment of 5 days for conditioner and 10 days for in the case of shampoo.

Subjects noted their assessment of the efficacy of the volume-enhancing effect of the test products compared to their normal hair volume. A scale of 1 to 5 was used for evaluation, with 1 indicating a significantly smaller volume and 5 indicating a significantly increased volume. The collected data were analyzed using the Wilcoxon Signed Rank Test described in Practical Nonparametric Statistics, 2 ^nd Ed., WJ Conover, John. Wiley & Sons, New York 1980. The results showed that a significant increase in hair volume was obtained after using both conditioner and shampoo at a 95% confidence level.

Curl stability test against time

Three long curls of clean European hair (3.5 g each) were prepared for each experiment. Before editing the locks on each measured its length when fully combed (L _o). The long curls were moistened with water, completely leveled, and then the water was removed by pressure. Then the long curls were suspended from the root portion and rotated with a standard 2.22 cm [7/8 inch (2.54 cm)] plastic curling iron, secured with a plastic pin, and dried for a minimum of 16 hours. After drying, the plastic chips were carefully removed, the curl was treated with a 2.5% solution of the tested MQ resin dissolved in toluene. This solvent was used because it forms a solution with the tested MQ resins. Test solutions were sprayed on long curls using a Seaquist P22 / 290 pump capable of delivering 0.25 g of solution at

»· • ·· • · · · ···· • · · · · · • • • • · · • • • • • • • • • • · · · · · · · · · · • · · ·

single use. To ensure uniform application, the solution was sprayed at a distance of 15 cm [6 inches (6 x 2.54 cm)]. Each curl was sprayed four times from the front and four times from the back to obtain a total of 2 g of solution. The freshly sprayed long curl was dried for 1 hour. It was then kept in a humidity chamber at 21 ° C and 80% relative humidity. Length measurements were taken after 0, 0.25, 0.5, 1, 2, 3, 4 and 24 hours. The percent stability of the curves versus time at each reading was calculated according to the following formula:

% stability = [L _o - L (t)] / [Lu - L (0)] where L _o is the hair length after complete combing, L (t) is the hair length at time t and L (0) is the hair length at time 0. Data are given in Table VIII as a percentage. All MQ resins used were obtained from General Electric Company.

····························

999 99

Table VIII

MQ resin 15 min 1 hour 4 hours 24 hours 50% solution of solid trimethylsiloxysilicate in cyclomethicone (MQ-B) ^{a, d} 43.3 * 39.8 * 35.0 * 34.1 * Trimethylsiloxysilicate (MQ-A) ^a 2.2 -6.1 -5.5 -5.1 Tetradecyldimethylsiloxysilicate (MQ-D) ^a ' ^b 2.4 2.5 3.6 4.1 Octadecyldimethylsiloxysilicate (MQ-E) ^{a, b} 24.3 3.0 3.4 4.5 C16-C18 alkyldimethylsiloxysilicate (MQ-G) ^a ' ^b ' ^e 11.6 8.3 4.3 4.2 C20-C24 alkyldimethylsiloxysilicate (MQ-F) ^{a, c, e} 9.7 2.1 2.0 3.1 Poly (oxyethylene) dimethylsiloxy silicate (MQ-H) ^{a, c, e} 15, 9 * 16.3 * 9.7 7.8

^and obtained from General Electric Company ^b each M unit of the polymer is substituted with a long chain alkyl group ^c each M unit of the polymer is substituted with a poly (oxyethylene) group ^{d a} commercial product from General Electric Company ^e described in US Patent 5,684,112

Toluene was the baseline control value for all time curl stability tests performed. Statistically significant values are marked with an asterisk.

Of the MQ resins listed in Table VIII, only &quot; MQ-B has significant cadmium stability over time over the entire 24 hours of the experiment, which means that this resin has a strong adhesive character. The fixation mechanism could therefore contribute to the increase in the volume reported for this resin in Table IX.

• · • ·· • · • · ···· • en · · • · • · 99 • • • • • 9 • • • 9 • · · · · · · · · 9 · · ·

MQ-A liquid MQ resins, on the other hand, did not exhibit significant cadmium stability over time and therefore did not have a significant adhesive character. Notwithstanding this drawback, they provide, as can be seen from the examples in the table

VII, liquid MQ resin significant volume.

Overview of examples

As an overview of the examples, Table IX shows the volume measurements performed with the MQ resins described in Table VIII, wherein each of the MQ resins was prepared either as the shampoo formulation of Example 8 only or the conditioner formulation of Example 1, or both. The amount of MQ resin for these formulations was 2.5% active material.

The data in the column labeled &quot; coating amount &quot; in Table IX shows the relative coating value and was obtained from woolen samples (7 x 11 cm) that were moistened at 38 ° C with running water, treated for 1 minute with 1 ml of test product ( either shampoo containing test MQ resin or conditioner containing test MQ resin) were then washed for 1 minute at 38 ° C with running tap water. The deposited MQ resin layer was then measured by ESCA (chemical analysis by electron spectroscopy). The technique is used to qualitatively and quantitatively determine the elemental composition of solid surfaces. The solid surface on which the products were tested was wool, which is chemically and morphologically similar to human hair and often used as a substitute for human hair because it is easy to work with. As already known to the expert, the ESCA technique uses a photoelectric effect to obtain data on the chemical composition of a solid surface. The sample surface is irradiated with X-ray photons that interact with atoms on the surface of the material. If the photons have sufficient energy, the electrons are emitted from their orbital surface atoms. The kinetic energies of these emitted photoelectrons are then measured with an electron spectrometer. The relationship that describes this process is: · e · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ··· ··

BE = x-ray energy - KE where KE and BE are the measured kinetic energy and the calculated binding energy of the emitted photoelectron. The ionization potential is characteristic of the individual elements and the electron sublayer from which the electron is emitted and serves to identify various elements on solid surfaces. The characteristic peak of the MQ resin was first determined using pure material. The peak areas present in the test sample were used to determine the relative concentrations of the elements in the surface sample. The deposited MQ resin is characterized by a peak of different shape Si, which makes it possible to distinguish MQ resins from other silicones, e.g. dimethicone. The percentage of Si present can be determined from the peak value. Three wool samples were prepared for each test sample. Of the three wool samples, two were first analyzed. If large differences were found between the two wool samples, a third wool sample was also measured for verification. This process was performed using the examples in Table IX. The values in the column for the sample amount were calculated by dividing the values obtained from the measurement of the amount of deposited layer of the individual MQ resins by the value from the measurement of trimethylsiloxysilicate resin (MQ-A). That is, these values are the relative amount of deposited layer of different resins over MQ-A resins.

• • · • • • · • · · ···· • · · · ·· · • • • • • • • • • · • • • · · • · · · • • · • • • · · • • · • • ·

ω well ω about CJ) ABOUT CJ) ABOUT WHAT • -3 < rt cn H ABOUT H ABOUT H · 3 * H IS) H · X- H rt) 3 about WITH 3 well 3 ' 3> 3 ¹ σ> H ABOUT I— ¹ rt I— ¹ rt Ω 3 lO 3 3 0 · < 0 1 0 1 ABOUT OJ 0 3 · < 3 cAP 1 3 WHAT x x n x ABOUT X CL X OJ X " rt) > (D < 0 I— ⁴ * < IS) Id · < Ω. 3 · rt 3 rt cn x ω WHAT cn CJ) Ω WHAT rt) 0 * < ABOUT > < H H H H > < 3 Ω 3 I— ¹ N 3 · 3 * CD 3 ¹ OJ I— ¹ OJ 3 * I— ¹ I— ¹ (D WHAT rt WHAT H ft H t— ¹ H 3 ¹ H CL 3 3 · rt 3 0 3 x- XT x * X * XT X * 3 X * CL 3 3 · X " · h- OJ ' 3 · 0) ' OJ ' OJ ' 3 OJ ' 3 Ω 0 0 rt * rt) ' ft 3 · rt I— ¹ rt rt) rt 3 0 X rt x 3 CL CL rt CD 3 > < C < H · 3 · < FROM-*. rt CD CJ) 3 CJ) with D with 3 with 3 with H with 3 rt) ' 3 · ABOUT H lO rt) lO rt) lO 1 lO 3 ¹ 3 · 3 3 ¹ 1 3 1 rt I rt 1 1 1 with 3 ABOUT 3 x rt) about Ηζ n σ lO XT x- rt 3 ¹ 3 · * - · 1 OJ ' OJ ' 'C 1 1 00 rt rt 3 · 1 C H H < i-3 < i-3 i-3 3 Ω 3 H H rt) fl> OJ ' C D) ' C rt) rt) ABOUT C (D ABOUT XT xr 3 3 xr X N 3 · x- 3 C C OJ ' OJ ' C I— ¹ Ό OJ ' C 3 rt ft rt about C rt 0J ql ' OJ ' OJ ' 3 WHAT OJ ' *-WITH * - * (D rt < < rt (D 0 about 3 3 CJ) CJ) Ω < ' XT X 0 ABOUT 1 ABOUT 1 1 C K) ro ro IS) IS) 3 * about 3> WITH well > 0 • · •  · • · • · • • · 3 CD 1 → 3 * I- ¹ 3> 3> 3 * lO 3 ω cn i-3 • -3 cn H Ω 3 45th rt < »u about C C about C well IS) cn OJ 3 about 3 3 3 ABOUT about WHAT Ω < ' Ω ^ C ' about about X * Ω * 3 well about 1 ABOUT well about N 3 1 3 ¹ X ω < x CJ) < cn < M < + X CJ) < + Ä M < < IS) ABOUT OJ about OJ about 01 0) IS) ABOUT OJ IS) 0 OJ N > 3 3 3 3 3 3 3 h- ⁴ 3 3 here 3 3 3 WHAT -J CL T3 CL Ό CL Ό Ό CL Ό CL Ό rt) 3 · 3 ABOUT' 3 · ABOUT' H 0 ' ABOUT' ►u 3 ABOUT' ►fc. 3 ABOUT' 3 rt) <AP 0 3 Ω 3 Ω 3 3 Ω 3 Ω 3 OJ CL 3 H · H Op 3 · Op 3 XT ABOUT + ABOUT + ABOUT + 1 ABOUT + ABOUT + ABOUT > < □ 45th 3 <Ti 3 EN) IS) 3 WHAT 3 IS) σ rt) ' 0 ' rt) ' CD ' 3 * rt) ' about LJ. 3 WHAT 3 3 H ⁴ 00 3 3 rt) 3 * cAP 3 cAP 1 + o \ P bp C WHAT 00 * - * 1 CD cAP about ABOUT ABOUT about ABOUT about about ABOUT ABOUT ABOUT ABOUT ABOUT OJ Ό w σ 1 IS) WHAT cn WHAT WHAT σ cn about about about about LJ. 3 * IS) ω about -J j IS) σ about OJ (D ABOUT σ IS) <40 4 ^ 3 N CL C 3 3 ** - * rt) ABOUT 3 rt OJ ABOUT IS) M IS) about 3 * t- ⁴ about about t “ ⁴ 3 * < 3 3 with > 3 rt) OJ 3 <J1 I— ¹ WHAT σ> -J cn -J 00 WHAT LJ. 3 ABOUT about Cn IS) about what 1- -about about about rt rt) N < <! WHAT WHAT rt) rt 1 C about

Table IX

·· ···· · · · · ··· · · · · · · ·

In Table IX, the resin labeled "MQ-A provides a better volume without significant adhesive character" (Table VIII). In contrast to this embodiment, it was observed that none of the MQ resins having an M: Q ratio of 2 gave a significant volume; these resins were of little or no adhesive character (Table VIII) and provided no volume irrespective of the fact that they were applied in amounts (relative values) comparable to or greater than the preferred trimethylsiloxysilicate resins (MQ-A), which were also found to be they have no significant adhesive character. MQ-B resins provided a significant volume, but unlike MQ-A resins, they were characterized by an adhesive nature. Due to their adhesive nature, MQ-B resins can be expected to have the same drawbacks as conventional fixative polymers.

Examples 16 and 17

The products of Examples 16 and 17 were prepared from 16.8% ammonium lauryl sulfate; 0.30% sodium dihydrogen phosphate; 0.25% Polykaternia-10; 2.00% cocodiethanolamide 0.22% guar polysaccharide; 0.25% distearyldimonium chloride; 0.50% phthalic acid distearylamide; 1.76% sodium cumenesulfonate; 0.75% fragrance; 0.07% preservative (KATHON® CG) next to the amounts of admixtures listed in Table X. Distilled water was used in the necessary amount to prepare 100% (q. P.). MQ-A is the same as MQ-A described in the previous examples.

Table X

admixture Example 16 Example 17 MQ Resin (MQ-A) 0.75 0.60 dimethicone 1.00 2.00 ACULYN® 22 0.90 0.90 ACULYN® 33 0.84 0.84 Distilled water q. with. q. with.

90% of distilled water and fos48 were combined in a suitable vessel.

Sodium formate, stirred for 10 minutes and heated to 50 ° C. ACULYN® 22 acrylates, ACULYN® 33 acrylate copolymer and ammonium lauryl sulfate were added to the flask, the pH was raised to 7.0 with 50% sodium hydroxide, and the mixture was stirred for 10 minutes. Sodium cumene sulphate was then added and stirred until dissolved. The pH was then lowered to 6.0-6.5 with 50% citric acid. The remainder of the distilled water and Polykvaternium-10 were premixed for 1-2 minutes and added to the vessel. Cocadiethanolamide, guar polysaccharide and distearyldimonium chloride were mixed in a separate vessel and heated to 50 ° C with stirring, then added to the main vessel with stirring. Phthalic acid distearylamide was separately dissolved at 45-50 ° C, then added to the vessel with stirring. Silicone MQ resin was added to the flask and stirred for 15 minutes, then dimeticone was added and stirred for 15 minutes. The vessel was then allowed to cool. When the temperature of the mixture dropped to 40 ° C, a fragrance was added. When the temperature of the mixture reached 38 ° C, a preservative was added. The final formulation was then cooled to room temperature.

Claims (25)

What is claimed is: 1. A hair care composition comprising an effective amount of an MQ resin of Formula IA R ⁴ R ⁵ II (M ^{1 -} Si - 01/2) x (M ^{2 -} Si - 01/2) _y (SiO _4/2 ) _of R 6 R ⁷ (IA) wherein M ¹ and M ² are each independently selected from the group consisting of (a) hydrogen, (b) phenyl, (c) phenethyl, (d) a polyether of the formula II CH ₂ - (CH ₂₎ n [0-CH (R ¹⁰⁾ CH _{2] u} - (0- CH ₂ —CH ₂ ) —OR ¹¹ (II) wherein the index n is a number from 1 to 20 and the - (CH 2) - chain may optionally contain one or two unsaturated bonds; u and v are indices selected independently from 0 to 20, with the condition that u + v>1; R ¹⁰ is selected from alkyl of 1 to 20 carbon atoms; and R ¹¹ is selected from the group consisting of H, -CH 3, and -C (O) CH 3; and (e) a branched or unbranched hydrocarbon chain of 1 to 24 carbon atoms optionally substituted with a hydrocarbon radical of 1 to 3 carbon atoms which is substituted with halogen; and wherein (x + y) / z is a number in the range of 0.5 to 1.5; and the meanings of the substituents R ⁴ , R ⁵ , R ⁶ , R ⁷ and x, y, z, M ¹ and M ² are selected such that the MQ resin is a fluid having a viscosity of 1.0 x 10 ³ to 1 x 10 ⁶ centipoise . ················································ Composition according to claim 1, characterized in that it is a water-based shampoo. Composition according to claim 1, characterized in that it is a water-based conditioner. The composition of claim 1, wherein the composition is a spray. Composition according to claim 1, characterized in that it is a hair care product after washing. The composition of claim 1, comprising (a) 0.01 to 15 wt. %, based on the total weight of the composition, of the MQ resin of Formula IA; and (b) 85 to 99.99 wt. %, calculated on the total weight of the composition, of a carrier for the hair care composition selected from the group consisting of shampoos, spray conditioners, and hair wash compositions. The composition of claim 1, wherein the viscosity of the MQ resin is in the range of 1.5 x 10 ³ to 1 x 10 ⁶ centipoise. The composition of claim 1, wherein the viscosity of the MQ resin is in the range of 1000 to 100000 centipoise. The composition of claim 1, wherein the viscosity of the MQ resin is in the range of 1000 to 50,000 centipoise. • · • · · • 1 • · ···· • · · · • e • · • · • • • • • • • • • • · • · · · · · · · · · · · The composition of claim 1, wherein the MQ resin has the general formula IB R ¹ , (IB) (R ² -Si-O _1/2 ) _x '(SiO _4/2 ) _of R 3 wherein R ² is selected from the same group as defined for M ¹ ; R ¹ and R ³ are each independently selected from the same group as defined for R ⁴ ; and x '/ z' is a number in the range of 0.5 to 1.5. The composition of claim 1, wherein M ¹ and M ² are each independently selected from the group consisting of branched or unbranched alkyl of 1 to 23 carbon atoms. Composition according to claim 11, characterized in that M ¹ , M ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each methyl. The composition of claim 10, wherein R ² is selected from the group consisting of branched or unbranched alkyl of 1 to 23 carbon atoms. The composition of claim 13, wherein R ¹ , R ² and R ³ are each methyl. The composition of claim 1, wherein (x + y) / z = 1. The composition of claim 10, wherein x '/ z' = First ·············································· 17th t ý composition m that x '/ z' = according to claim = 1. 14, characterized by 18th composition according to claim 1, characterized by 1 t ý m that extra contains fixation means. • 19th composition according to claim 2, characterized by by containing 0.1 to 7.5% MQ resin. The composition of claim 19, comprising 0.1 to 5.0% MQ resin. The composition of claim 19, comprising 0.1 to 3.0% MQ resin. 22. The composition of claim 19, comprising 0.2 to 2.5% MQ resin. 23. A composition according to claim 18 comprising 0.1 to 2.0% of a hair quality stabilizer. 24. The composition of claim 2 comprising from about 4.00% to about 60.00% of a surfactant selected from the group consisting of an anionic detergent selected from the group consisting of C8-C18 alkyl sulfates, C8-C18 alkylethenoxy ether sulfates. containing 1 to 5 ethenoxy groups per molecule, C10-C18 acyl isethionates, C10-C20 alkylsulfonates, C10-C20 alkylene sulfonates, and mixtures thereof; and optionally at least one of: (i) 0.10 to 5.00% of an anionic hydrotropic alkylbenzene sulphonate of 1 to 3 carbon atoms or an alkyl sulphate of 5 to 6; Carbon atoms; (ii) 0.10 to 15.00% of an amphoteric surfactant selected from the group consisting of C 8 -C 18 alkyl betaines, C 8 -C 18 alkylsulfobetaines, C 8 -C 18 alkyl amido alkyl betaines and 2 to 3 carbon atoms in the betaine moiety, C 8 -C 18 alkylamidoalkylsulfobetaines in the amide moiety with 2 to 3 carbon atoms in the sulfobetaine moiety, C 8 -C 18 alkyl amphoacetates, C 8 -C 18 alkyl amphopropionates, cocamidopropyl betaine and mixtures thereof; and (iii) 0.1 to 4.0% nonionic surfactant; with the proviso that the total amount of the purifying surfactant does not exceed 60 wt. % of the total amount of the composition. 25. The composition of claim 1, further comprising 0.10 grade. 2, characterized by up to 5.00% stabilizer pros 26. The composition of claim 3, further comprising lipid materials and at least one cationic surfactant. The composition of claim 26, wherein the at least one cationic surfactant is selected from the group consisting of cationic surfactants containing an amino group or quaternary ammonium hydrophilic moieties. The composition of claim 27, wherein the at least one cationic surfactant is selected from the group consisting of compounds of formula (R ¹⁰ ) (R ¹¹ ) (R ¹² ) (R ¹³ ) N ⁺ -X, wherein the substituent R ¹⁰ is a hydrogen atom, an aliphatic group having 1 to 22 carbon atoms or an aromatic, aryl or alkylaryl group having 12 to 22 carbon atoms; sub ······ · · · · · · · · · · · · · · · · · · · · · · The substituent R ¹¹ is an aliphatic group with 1 to 22 carbon atoms; R ¹² and R ¹³ are each independently selected from the group consisting of C 1 -C 3 alkyl; and X is an anion selected from the group consisting of halogen, acetate, phosphate, nitrate, and alkyl sulfate radicals.