CN1241931A

CN1241931A - Shampoo composition comprising silicone emulsion

Info

Publication number: CN1241931A
Application number: CN96180552.8A
Authority: CN
Inventors: 内山浩孝
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1996-11-04
Filing date: 1996-11-04
Publication date: 2000-01-19
Also published as: JPH11500459A; JP3234604B2; EP0938285A1; WO1998019656A1

Abstract

The present invention discloses a shampoo composition comprising a siloxane emulsion comprising a siloxane polymer selected from the group consisting of a polyalkyl siloxane having a molecular weight of at least 20,000, a polyaryl siloxane having a molecular weight of at least 20,000, and amino-substituted siloxane having a molecular weight of at least 5,000, a siloxane resin having a molecular weight of at least 5,000, and mixtures thereof, an anionic surfactant, a compatibilizing surfactant, and a cationic surfactant, wherein the siloxane polymer is dispersed as a particle having an average size of not more than 450 nm; a detersive surfactant; a conditioning agent; and water; wherein the composition is substantially free of siloxane suspending agents.

Description

Shampoo compositions comprising silicone emulsions

Technical Field

The present invention relates to a shampoo composition comprising a silicone emulsion.

Background

Hair becomes soiled by contact with the surrounding environment and by sebum secreted from the hair follicles. Hair soiling can cause a greasy feel to the hair and is also aesthetically undesirable. For this purpose, the hair must be cleaned regularly.

Shampooing cleans the hair by removing excess soil and sebum. However, shampooing has the disadvantage of leaving the hair in a wet, tangled, and generally unmanageable state. After the hair is dry, it is dry, rough, dull or frizzy due to the removal of natural oily substances or other natural hair conditioning and moisturizing substances from the shampooing process. After drying, the hair becomes more static, which can also make it difficult to comb, leading to a condition commonly referred to as "fly-away hair", or undesirable "split ends", especially for long hair.

Extensive research has been conducted to alleviate these post-shampoo problems. The approaches given include post-shampoo hair conditioners such as leave-on products and rinse-off products, as well as hair conditioning shampoos which include both hair cleansing and conditioning functions from a single product. Hair conditioners are usually applied to the hair in a separate step after the washing step. The hair conditioning agent can be rinsed off or left unwashed, depending on the type of product used. However, hair conditioners have the disadvantage of requiring separate and inconvenient handling steps. Conditioning shampoos are popular products because they provide both cleansing and conditioning benefits in one step for the consumer.

In order to provide hair conditioning benefits based on cleansing shampoos, various conditioning actives have been proposed. However, they have not been entirely satisfactory.

One of the problems that exists today is the problem of compatibility between anionic detersive surfactants and most of the conventionally employed cationic conditioning agents. Although efforts have been made to reduce this side effect by using other surfactants, the use of anionic surfactants is highly desirable in part because of their generally superior cleaning performance. On the other hand, some consumers desire mild or non-irritating shampoo compositions, which typically contain other types of surfactants in addition to the anionic surfactant. Thus, there is a need for shampoo compositions that are compatible with a variety of detersive surfactants.

Materials which provide both improved overall conditioning and which can be used to simultaneously maintain cleaning performance by employing anionic detersive surfactants are silicone conditioning agents. However, shampoos containing silicone conditioning agents can impart an unpleasant feel to the hair, for example, after the hair has dried, the hair can have a coated feel, a heavy feel, or a dirty feel. Furthermore, in order to provide excellent dispersibility and storage stability of shampoo compositions containing silicone conditioning agents, it is necessary to employ suspending agents such as acyl derivatives. The use of silicone conditioning agents in combination with suspending agents often results in compositions that are quite viscous and milky in appearance. This is particularly significant for suspending agents such as ethylene glycol stearate.

It is believed that the undesirable feel and instability of the hair caused by silicone conditioning agents is due to the particle size of the silicone conditioning agent. This is more pronounced when the siloxane has a higher molecular weight. Although high molecular weight silicone polymers are known to have very good conditioning efficacy, such as smoothing and combing ease, they may also have larger particle sizes and be thermodynamically unstable. Mechanical shear is known to reduce the particle size of the fluid. High molecular weight siloxane polymers are too viscous to emulsify to the desired particle size. Thus, high molecular weight silicone polymers cannot be formulated at levels that provide the desired conditioning properties without the aid of suspending agents.

Thus, there is a need to provide shampoo compositions comprising high molecular weight silicone polymers which are stable, even without the addition of suspending agents, and which provide overall improved conditioning benefits.

Japanese patent laid-open No. 7-138,136 discloses a hair cleansing composition comprising a surfactant and a water-insoluble highly polymerized silicone emulsion prepared by emulsion polymerization and having an average particle diameter of 0.2 to 50 μm. EP application 674,898-a discloses a conditioning shampoo composition for hair comprising a stable microemulsion of high viscosity silicones having a particle size of less than 0.15 μm, further comprising a deposition polymer and a surfactant. US 5,504,149 discloses a process for preparing high viscosity silicone emulsions wherein water, a cyclic silicone and optionally a mixture of a nonionic surfactant and a cationic surfactant are polymerized using a silanolate or an organosilanealkoxide as an initiator.

Shampoo compositions have been developed comprising silicone emulsions containing high molecular weight silicone polymers made with certain surfactant systems, which are stable, free of silicone suspending agents, and provide overall improved conditioning benefits by being compatible with various conditioning agents.

Summary of The Invention

The present invention relates to shampoo compositions comprising:

(a) a silicone emulsion comprising:

i) from about 0.01 to about 20 weight percent of a silicone polymer,

selected from polyalkylsiloxanes having a molecular weight of at least 20,000, polyalkylsiloxanes having a molecular weight of at least 20,000

A polyarylasiloxane, an amino-substituted siloxane having a molecular weight of at least 5,000, a molecule

A silicone resin in an amount of at least 5,000, and mixtures thereof;

ii) an anionic surfactant;

iii) a compatible surfactant; and

iv) a cationic surfactant;

wherein the silicone polymer is dispersed as particles having an average particle size of no more than about 450 nm;

(b) from about 5 to about 50 wt% of a detersive surfactant;

(c) from about 0.1 to about 20 wt% of a conditioning agent; and

(d) water;

wherein the composition is substantially free of acyl derivative siloxane suspending agents.

Such compositions may satisfy the need for hair conditioning compositions having overall improved conditioning efficacy, and the compositions may be used with a wide range of conditioning agents other than acyl derivative silicone suspending agents.

Detailed Description

All percentages used herein are by weight of the total composition, unless otherwise indicated. All ratios are weight ratios unless otherwise indicated. Unless otherwise indicated, all percentages, ratios, and ingredient levels refer to the actual amount of the ingredient, excluding solvents, fillers, or other ingredients that may be included in commercially available products.

The invention comprises, consists of, or consists essentially of the essential elements, as well as the preferred or other optional ingredients.

All publications, patent applications, and issued patents mentioned herein are incorporated by reference in their entirety.

Silicone emulsions

Shampoo compositions of the invention comprise a silicone emulsion comprising a silicone polymer, an anionic surfactant, a compatible surfactant, and a cationic surfactant. The silicone emulsion is prepared according to an emulsion polymerization process in which an aqueous solution or emulsion of the silicone material is mixed with an anionic surfactant, a compatible surfactant is added, and finally a cationic surfactant is added. The silicone starting material is selected so that the molecular weight of the silicone polymer formed in the resulting silicone emulsion reaches a value and is dispersed as particles having an average particle size of no more than about 450nm, more preferably from about 150 to about 250 nm. Silicone polymers having such particle sizes stabilize silicone emulsions with a wide range of various components.

The following procedure can be used for the preparation of the silicone emulsions according to the invention, which are also conventionally suitable:

(1) admixing a siloxane feedstock selected from the group consisting of cyclic siloxane oligomers such as cyclomethicones known as cyclomethicones, mixed siloxane hydrolysates, silanol-blocked (stopped) oligomers, high molecular weight siloxane polymers, functionalized siloxanes, and mixtures thereof, with a mixture of water and an anionic surfactant;

(2) heating a blend obtained by mixing a silicone material, water and an anionic surfactant to about 75-98 ℃ over a period of about 1-5 hours;

(3) cooling the anionic emulsion polymerized silicone emulsion to a temperature of 0-25 ℃ over a period of about 3-24 hours;

(4) adding a compatible surfactant; and

(5) adding a cationic surfactant.

The overall composition comprises from about 0.01 to 20 weight percent, preferably from about 0.1 to 10 weight percent, of the silicone polymer.

Siloxane polymers

The silicone polymers of the present invention are those which provide excellent conditioning benefits to the hair. These silicone polymers are selected from the group consisting of polyalkylsiloxanes having a molecular weight of at least 20,000, polyarylsiloxanes having a molecular weight of at least 20,000, amino-substituted siloxanes having a molecular weight of at least 5,000, silicone resins having a molecular weight of at least 5,000, and mixtures thereof.

The polyalkylsiloxanes and polyarylsiloxanes useful as the silicone polymers of the present invention include those having the following structural formula (I):wherein R is an alkyl or aryl group and x is an integer of about 200-8,000, such polyalkylsiloxanes having a molecular weight of at least 20,000, preferably at least 100,000, more preferably at least 200,000. "A" represents a group that blocks the end of a siloxane chain. The alkyl or aryl groups substituted on the silicone chain (R) or at the ends of the silicone chain (a) may have any structure so long as the resulting silicone is dispersible, non-irritating, non-toxic, non-harmful, and compatible with the other ingredients of the composition, is chemically stable under normal use and storage conditions, and is capable of being deposited on and conditions the hair when applied to the hair. Is suitable forSuitable A groups include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R groups on the silicon atom may represent the same group or different groups. Preferably both R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, tolyl, and benzyl. Preferred polyalkylsiloxane and polyarylsiloxane polymers are polydimethylsiloxanes, polydiethylsiloxanes and polymethylphenylsiloxanes, and which are blocked with hydroxyl and carboxyl groupsA terminal derivative. Particularly preferred are polydimethylsiloxanes known as dimethicones (dimethicones) and their hydroxy-terminated derivatives known as dimethiconols.

To enhance the shine characteristics of hair, the present invention also employs highly arylated silicones, such as highly phenylated polyethyl silicone, having a refractive index of about 1.46 or greater than 1.46, particularly about 1.52 or greater. When these high refractive index silicones are used, they should be mixed with a spreading agent (spreading agent) as described below, such as a surfactant or a silicone resin, to reduce surface tension and enhance the film forming ability of the material.

Amino-substituted siloxanes suitable for use as the silicone polymer of the present invention include those having the structure of formula (II):

wherein R is CH₃Or OH, x and y are independently integers and depend on the desired molecular weight, wherein y is not 0, a and b are independently integers from 1 to 10, and wherein the average molecular weight is at least 5,000, preferably at least 10,000. This polymer is also known as "aminated polydimethylsiloxane (amodimethicone)".

Suitable amino-substituted siloxanes include those having the following formula (III):

(R¹)_aG_3-a-Si-(-OSiG₂)_n-(-OSiG_b(R¹)_2-b)_m-O-SiG_3-a(R¹)_a (III)

wherein G is selected from hydrogen, phenyl, hydroxy, C₁-C₈Alkyl of (a), preferably methyl; a is 0 or an integer from 1 to 3, preferably equal to 0; b is 0 or 1, preferably 1; the sum of n + m is from 1 to 2,000, preferably from 50 to 150, n may represent a number from 0 to 1,999, preferably from 49 to 149, m may represent an integer from 1 to 2,000, preferably from 1 to 10; r¹Is a monovalent group, satisfies the formula C_qH_2qL, wherein q is an integer from 2 to 8, L may be selected from the following groups:

-N(R²)CH₂-CH₂-N(R²)₂

-N(R²)₂

-N(R²)₃A^-

-N(R²)CH₂-CH₂-NR²H₂A^-wherein R is²Selected from hydrogen, phenyl, benzyl, saturated hydrocarbon radicals, preferably alkyl radicals having 1 to 20 carbon atoms, A^-Is a halide ion.

Particularly preferred amino-substituted siloxanes of the formula (III) are polymers of the formula (IV), which are also referred to as "trimethylsilylaminotimethylsiloxane",

wherein n and m are independently integers of 1 or greater than 1, depending on the desired molecular weight, and a and b are independently integers of 1 to 10, wherein the average molecular weight is at least 5,000, more preferably at least 10,000.

Other useful amino-substituted siloxanes are represented by the following formula (V):

wherein R is³Is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably an alkyl or alkenyl group such as methyl; r⁴Is a hydrocarbon radical, preferably C₁-C₁₈Alkylene or C₁-C₁₈More preferably C₁-C₈An alkyleneoxy group of (a); q^-Is a halide ion, preferably chlorine; r has an average value of 2 to 20, preferably 2 to 8; the average value of s is 20 to 200, preferably 20 to 50.

A silicone resin which is a highly crosslinked polymeric silicone system having a molecular weight of at least 5,000, preferably at least 10,000, may also be used. During the production of silicone resins, trifunctional and tetrafunctional silanes are incorporated into monofunctional or difunctional or monofunctional and difunctional silanes to introduce crosslinking. As is well known in the art, the degree of crosslinking required to form a silicone resin can vary depending on the particular silane units incorporated into the silicone resin. Generally, silicone materials having sufficient trifunctional and tetrafunctional siloxane monomer units (and thus sufficient crosslinking) such that they dry into a rigid or hard film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms indicates the level of crosslinking in a particular silicone material. Silicone materials having a ratio of oxygen atoms to silicon atoms of at least about 1.1 will generally be silicone resins of the present invention. Preferably, the ratio of oxygen atoms to silicon atoms is at least about 1.2: 1.0. Silanes used in the production of silicone resins include monomethyl, dimethyl, trimethyl, monophenyl, diphenyl, methylphenyl, monovinyl and methylvinyl chlorosilanes, and tetrachlorosilane, with methyl substituted silanes being most commonly employed. While not being bound by any theory, it is believed that the silicone resin can increase deposition of other silicones onto the hair and can enhance the shine of the hair due to its high refractive index.

Other useful silicone resins are silicone resin powders, such as the polysilsequioxane designated by the CTFA nomenclature.

The silicone resins are conveniently identified according to the shorthand nomenclature system known to those skilled in the art as the "MDTQ" nomenclature. In this system, the siloxane is described in terms of the various monomer units present that make up the siloxane. In short, the symbol M represents a monofunctional unit (CH)₃)₃SiO_0.5(ii) a D represents a difunctional unit (CH)₃)₂SiO; t represents a trifunctional unit (CH)₃)SiO_1.5(ii) a Q represents a tetrafunctional unit SiO₂. The unit symbols with prime notation such as M ', D', T ', Q' represent substituents other than methyl, each of which is specifically defined. Typical substitutable substituents are vinyl, phenyl, amino, hydroxy, and the like. In the MDTQ system, the molar ratios of the various units, either in subscripts to the symbols indicating the total number of each unit in the siloxane (or its average), or in specific indicated ratios in combination with molecular weight, complete the description of the siloxane material. In silicone resins, T, Q, T 'and/or Q' have relatively high molar amounts compared to D, D ', M and/or M', indicating a high degree of crosslinking. However, as previously discussed, the total level of crosslinking can also be expressed by the ratio of oxygen to silicon.

The silicone resins of the present invention are preferably MQ, MT, MTQ, MDT and MDTQ resins. Thus, the preferred siloxane substituent is methyl. MQ resins are particularly preferred, wherein the M: Q ratio is from about 0.5: 1.0 to 1.5: 1.0.

Other references to silicone fluids, silicone gums, and silicone resins are found in Encyclopedia of Polymer Science and Engineering (Encyclopedia of Polymer Science and Engineering), Vol.15, second edition, p.204-308, John Wiley & sons. Inc., 1989, which is incorporated herein by reference.

Anionic surfactants

Anionic surfactants useful in preparing the silicone emulsions of the present invention are those which act as acid catalysts and are compatible with the remaining components when used to polymerize silicone starting materials. Examples of anionic surfactants are alkyl sulfonic acids, aryl sulfonic acids, or alkyl aryl sulfonic acids, wherein the alkyl group can have 1 to 20 carbon atoms and the aryl group can have 6 to 30 carbon atoms. Particularly preferred anionic surfactants are selected from the group consisting of benzenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, and alkylsulfonic acids of 12 to 18 carbon atoms, and mixtures thereof.

Compatible surfactants

Compatible surfactants for use in preparing the silicone emulsions of the present invention are surfactants having the following functions: which can compatibilize anionic emulsion polymerized silicone emulsions with cationic surfactants. While not being bound by any theory, it is believed that if the cationic surfactant is added directly to the anionic mixture obtained after initial emulsion polymerization of the silicone starting material and anionic surfactant, the anionic surfactant contained in the anionic emulsion polymerized silicone emulsion will react with each other by having an ionic charge opposite to that of the cationic surfactant, breaking the emulsion and/or causing undesirable precipitation. Thus, the silicone emulsion resulting from anionic emulsion polymerization must be treated with a compatible surfactant. Useful compatible surfactants are those having an HLB value greater than 9. Particularly useful compatible surfactants are ethoxylated fatty acid esters, such as polyglycerol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene castor oil, polyoxyethylene secondary alkyl ethers, wherein the alkyl group has from 6 to 40 carbon atoms; polyoxyethylene alkyl ethers, wherein the alkyl group has 6 to 40 carbon atoms; polyoxyethylene alkylamines, wherein the alkyl groups have 6 to 40 carbon atoms and can be independently selected; polyoxyethylene alkylamides wherein the alkyl groups have 6 to 40 carbon atoms and can be independently selected; amphoteric betaine surfactant, and polyoxyethylene lanolin. Particularly preferred surfactants of this type are POE (4) lauryl ether, POE (9) lauryl ether, POE (23) lauryl ether, POE (20) stearyl ether and POE (20) sorbitan monopalmitate. Another preferred class of surfactants for compatibilizing anionic emulsions with cationic surfactants is selected from: lauryl dimethyl glycine betaine, coco fatty amidopropyl dimethyl glycine betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolium betaine, N-lauroyl sodium sarcosinate, and lanolin derivatives of quaternary ammonium salts.

Cationic surfactant

After treating the anionic emulsion polymerized silicone emulsion with a compatible surfactant, the emulsion may be treated with a cationic surfactant to obtain the cationic surfactant-containing silicone emulsion of the present invention. Such silicone emulsions are compatible with the various surfactants and conditioning agents of shampoo compositions of the invention, and do not require the use of acyl derivative silicone suspending agents to stabilize the product. The cationic surfactant used to prepare the silicone emulsions of the present invention is any known to those skilled in the art.

Cationic surfactants useful in the present invention are those having the formula:

wherein R is¹、R²、R³And R⁴Independently selected from an aliphatic group having from 1 to about 22 carbon atoms or an aryl, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; x is a salt-forming anion such as halide (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate, and alkylsulfonate. Aliphatic radicals having the exception of carbon and hydrogen atomsIn addition, ether linkages and other groups such as amino groups may be included. The long chain aliphatic group, such as a group of about 12 carbon atoms or more, may be a saturated group or an unsaturated group. Preferably R¹、R²、R³And R⁴Independently selected from C₁-C₂₂An alkyl group. Non-limiting examples of cationic surfactants useful in the present invention include those having the following CTFA designation: quaternium-8, quaternium-24, quaternium-26, quaternium-27, quaternium-30, quaternium-33, quaternium-43, quaternium-52, quaternium-53, quaternium-56, quaternium-60, quaternium-62, quaternium-70, quaternium-72, quaternium-75, quaternium-77, quaternium-78, quaternium-80, quaternium-81, quaternium-82, quaternium-83, quaternium-84, and mixtures thereof.

Another preferred class of cationic surfactants are hydrophilically substituted cationic surfactants wherein at least one of the substituents contains one or more aromatic, ether, ester, amido or amino moieties present as substituents or bonds of the base chain, wherein R is¹-R⁴At least one of the groups comprises one or more hydrophilic moieties selected from alkoxy (preferably C)₁-C₃Alkoxy), polyoxyalkylene (preferably C)₁-C₃Polyoxyalkylene), alkylamido, hydroxyalkyl, alkyl ester, and mixtures thereof. Preferably, the hydrophilically substituted cationic conditioning surfactant comprises from 2 to about 10 nonionic hydrophilic moieties within the above ranges. Preferably the hydrophilically substituted cationic surfactant comprises the following surfactants of formula (II) to formula (VII):

wherein n is 8 to 28, x + y is 2 to about 40, Z¹Is a short-chain alkyl radical, preferably C₁-C₃Alkyl, more preferably methyl, or (CH)₂CH₂O)_zH, wherein X + y + z is at most 60 and X is a salt-forming anion as defined above;

wherein m is 1-5, R⁵、R⁶And R⁷Is independently C₁-C₃₀An alkyl group; the rest is CH₂CH₂OH，R⁸And R⁹One or two of them and R¹⁰Independently is C₁-C₃₀Alkyl radical, the remainder being CH₂CH₂OH, X is a salt-forming anion as defined above;

wherein Z is²Is alkyl, preferably C₁-C₃Alkyl, more preferably methyl; z³Is a short chain hydroxyalkyl group, preferably hydroxymethyl or hydroxyethyl; p and q are independently integers from 2 to 4 (including 2, 4), preferably from 2 to 3, more preferably 2; r¹¹And R¹²Independently a substituted or unsubstituted hydrocarbyl group, preferably C₁₂-C₂₀Alkyl or alkenyl, X is a salt-forming anion as described above;

wherein R is¹³Is a hydrocarbon radical, preferably C₁-C₃Alkyl, more preferably methyl; z⁴And Z⁵Independently a short chain hydrocarbyl group, preferably C₂-C₄Alkyl or alkenyl, more preferably ethyl; a is from 2 to about 40, preferably from about 7 to about 30, and X is a salt-forming anion as described above;wherein R is¹⁴And R¹⁵Independently is C₁-C₃Alkyl, preferably methyl; z⁶Is C₁₂-C₂₂A hydrocarbyl, alkylcarboxyl or alkylamido group; a is a protein, preferably collagen, keratin, milk protein, silk protein (silk), soy protein, wheat protein or hydrolysed forms thereof; x is a salt-forming anion as described above;

wherein b is 2 or 3, R¹⁶And R¹⁷Independently is C₁-C₃A hydrocarbyl group, preferably methyl; x is a salt-forming anion as described above. Non-limiting examples of hydrophilically substituted cationic surfactants useful in the present invention include those having the following CTFA designation: quaternium-16, quaternium-61, quaternium-71, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzed keratin, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed silk protein, quaternium-79 hydrolyzed soy proteinWhite, quaternium-79 hydrolyses wheat proteins. Particularly preferred compounds comprise the following commercially available materials: VARIQUAT K1215 and 638 (available from Witco Chemical); MACKPRO KLP, MACKPRO WLW, MACKPRO MLP, MACKPRO NSP, MACKPRONLW, MACKPRO WWP, MACKPRO NLP, MACKPRO SLP (available from Mclntyre); ETHOQUAD 18/25, ETHOQUAD O/12PG, ETHOQUADC/25, ETHOQUAD S/25, and ETHODUOQUAD (available from Akzo); DEHYQUATSP (available from Henkel) and ATLAS G265 (available from ICI Americas).

Salts of primary, secondary and tertiary fatty amines are also suitable as cationic surfactants. The alkyl group of such amines preferably has from about 12 to about 22 carbon atoms, and it may be a substituted or unsubstituted group. Such amines useful in the present invention include stearamidopropyl dimethylamine, diethylaminoethyl stearamide, dimethyl stearylamine, dimethyl soyamine (soyamine), soyamine, myristylamine, tridecylamine, ethyl stearylamine, N-tallow propane diamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine, dihydroxyethyl stearylamine, and eicosyl docosanamine. Suitable amine salts include halides, acetates, phosphates, nitrates, citrates, lactates and alkyl sulfates. Such salts include stearylamine hydrochloride, soya amine chloride, stearylamine formate, N-tallowylpropane diamine dichloride, and stearamidopropyl dimethylamine citrate. Cationic amine surfactants useful in the present invention are disclosed in U.S. Pat. No. 4,275,055 (issued to Nachtigal et al, 6/23 1981), which is incorporated herein by reference.

The cationic surfactants useful in the present invention may also include a plurality of quaternary ammonium moieties or amino moieties, or mixtures thereof.

Detersive surfactant

The composition of the present invention comprises a detersive surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. The purpose of the detersive surfactant is to provide the composition with cleaning properties. The term "detersive surfactant" is used herein to distinguish these surfactants from those primarily used for emulsification, i.e., those that provide emulsification efficacy and have low cleaning performance. In any event, however, it should be recognized that many surfactants have both emulsifying and detersive properties. Emulsifying surfactants are not intended to be excluded from the present invention. The detersive surfactant may be the same as or different from the surfactant contained in the silicone emulsion described above.

The composition may generally comprise from about 5 to about 50 wt% of detersive surfactant, preferably from about 8 to 30 wt%, more preferably from about 10 to 25 wt%, based on the weight of the composition.

Anionic surfactants

Anionic surfactants suitable for use in the present invention are alkyl and alkyl ether sulfates. These have the respective general formula ROSO₃M and RO (C)₂H₄O)_xSO₃M, wherein R is an alkyl or alkenyl group having from about 8 to about 30 carbon atoms, x is an integer from 1 to about 10, M is hydrogen or a cation such as ammonium, alkanolammonium such as triethanolamine, monovalent metal ions such as sodium and potassium, polyvalent metal cations such as magnesium and calcium. Preferably, M is selected so that the anionic surfactant component is water soluble. The anionic surfactant should be selected such that its krafft temperature is about 15 ℃ or less, preferably about 10 ℃ or less, more preferably about 0 ℃ or less. It is also preferred that the anionic surfactant is soluble in the composition.

The krafft temperature refers to the temperature at which the solubility of the ionic surfactant becomes measured by the lattice energy and heat of hydration, corresponding to a temperature at which the solubility of the surfactant in water increases discontinuously and steeply with increasing temperature. Each type of surfactant has a krafft temperature that is characteristic of it. Generally, the krafft temperature of ionic surfactants is well known in the art. See, for example, the following references (which are incorporated herein by reference): myers, Drew, "Surfactant Science and Technology" (surface Science and Technology), pp.82-85, VCH Publishers (New York, New York, USA) (ISBN 0-89573-.

Of the above alkyl and alkyl ether sulfates, it is preferred that R in the alkyl and alkyl ether sulfates have from about 12 to about 18 carbon atoms. Alkyl ether sulfates are generally prepared as condensation products of ethylene oxide and monohydric alcohols having from 8 to 24 carbon atoms. The alcohol may be derived from fats, such as coconut oil, palm kernel oil, tallow, etc., or may be a synthetic alcohol. Lauryl and straight chain alcohols derived from coconut and palm oil are preferred. This alcohol is reacted with about 1 to 10, preferably about 3, molar proportions of ethylene oxide to form a mixture having, for example, an average of 3 moles of ethylene oxide per 1 mole of alcohol in the molecule, and this mixture is sulfated and neutralized.

Specific examples of alkyl ether sulfates suitable for use in the present invention include: sodium and ammonium salts of cocoalkyltriglycol ether sulfates; sodium and ammonium salts of tallow alkyl triethylene glycol ether sulphate, sodium and ammonium salts of tallow alkyl hexaoxyethylene sulphate. Particularly preferred alkyl ether sulfates are mixtures of individual compounds wherein the compounds in the mixture have an average alkyl chain length of from about 12 to 16 carbon atoms and an average degree of ethoxylation of from about 1 to 4 moles of ethylene oxide. This mixture also contains 0 to about 20 wt% of C_12-13A compound; about 60 to about 100 wt% C_14-15-16Compound, 0 to about 20 wt% of C_17-18-19A compound; about 3 to about 30 weight percent of a compound having a degree of ethoxylation of 0; about 45 to about 90 weight percent of a compound having a degree of ethoxylation of from 1 to 4; about 10 to 25 weight percent of a compound having a degree of ethoxylation of from about 4 to 8; from about 0.1 to about 15 weight percent of a compound having a degree of ethoxylation greater than about 8.

Other suitable anionic surfactants are water-soluble salts of organic, sulfuric acid reaction products of the general formula [ R¹-SO₃-M]Wherein R is¹Is a straight or branched chain, saturated aliphatic hydrocarbon group having from about 8 to about 24 carbon atoms, preferably from about 10 to about 18 carbon atoms; m is a cation as described previously. Examples of such detersive surfactants are the salts of the products obtained by reacting hydrocarbons of the methane series, including iso-, neo-, and n-paraffins, having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms, with organic sulfuric acids of sulfonating agents, such as sulfur trioxide, sulfuric acid, according to well-known sulfonation processes, including bleaching and hydrolysis processes. Preferably sulfonatedC₁₀-C₁₈Alkali metal and ammonium salts of n-paraffins.

Other suitable anionic surfactants are reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, where, for example, the fatty acids are derived from coconut oil or palm oil; sodium or potassium salts of fatty acid amides of methyl taurate, wherein the fatty acids are derived, for example, from coconut oil. Other similar anionic surfactants are described in the following patent documents: US2,486,921; US2,486,922; US2,396,278, which are incorporated herein by reference.

Other anionic surfactants suitable for use in the present invention are succinates, such as disodium N-octadecyl sulfosuccinate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N- (1, 2-dicarboxyethyl) -N-octadecyl sulfosuccinate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl ester of sodium sulfosuccinic acid.

Other anionic surfactants suitable for use in the present invention are surfactants derived from amino acids. Non-limiting examples of such surfactants include N-acyl-L-glutamate, N-acyl-N-methyl alanine salt, N-acyl sarcosinate salt.

Other useful surfactants are those derived from taurine (also known as 2-aminoethanesulfonic acid). An example of such an acid is N-acyl-N-methyltaurate.

The term "olefin sulfonate" as used herein refers to compounds produced by sulfonating α -olefin by uncomplexed sulfur trioxide and then neutralizing the acid reaction mixture under conditions such that the sulfone formed in the reaction is hydrolyzed to form the corresponding hydroxy-alkanesulfonate.

The α -olefin used to form the olefin sulfonate is a mono-olefin having from about 12 to about 24 carbon atoms, preferably from about 14 to about 16 carbon atoms, preferably a straight-chain olefin.

Specific examples of α -olefin sulfonate mixtures of the type described above are described in U.S. Pat. No. 3,332,880 (issued to Pfleumer and Kessler on 7/25 of 1967) which is incorporated herein by reference.

Another class of anionic surfactants suitable for use in the present invention are the β -alkoxyalkanesulfonates, these surfactants having the general formula

Wherein R is¹Is a straight chain alkyl group having about 6 to 20 carbon atoms, R²Is a lower alkyl group having about 1 to 3 carbon atoms, preferably 1 carbon atom, and M is as previously described. Many other anionic surfactants suitable for use in the present invention are described in the following documents, all of which are incorporated herein by reference: McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by m.c. publishing co, and US 3,929,678. Preferred anionic surfactants for use in the present invention include: ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, sodium laureth,Sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl ammonium sulfate, lauroyl ammonium sulfate, cocoyl sodium sulfate, lauroyl sodium sulfate, cocoyl ammonium sulfatePotassium sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium N-lauroyl-L-glutamate, triethanolamine, N-lauroyl-L-glutamate, sodium N-lauroyl-N-methyltaurate, sodium N-lauroyl-N-methylaminopropionate, and mixtures thereof.

Amphoteric surfactants and zwitterionic surfactants

The shampoo composition may comprise an amphoteric surfactant and/or a zwitterionic surfactant.

Amphoteric surfactants useful in shampoo compositions of the invention include derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be a straight or branched chain and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and the other contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Zwitterionic surfactants useful in shampoo compositions of the invention include aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals are straight or branched chain radicals and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and the other contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. These compounds have the general formula:

wherein R is²Containing an alkyl, alkenyl or hydroxyalkyl group having from about 8 to 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; y is selected from nitrogen, phosphorus and sulfur atoms; r³Is an alkyl or monohydroxyalkyl group containing from 1 to about 3 carbon atoms; when Y is a sulfur atom, X is 1, and when Y is a nitrogen or phosphorus atom, X is 2; r⁴Is an alkylene or hydroxyalkylene of from 1 to about 4 carbon atoms, and Z is a group selected from carboxylate, sulfonate, sulfate, phosphonate, and phosphate.

Examples of amphoteric and zwitterionic surfactants also include sulfobetaines (sultaines) and amidosulfobetaines. Of sulfobetaines, including amidosulfobetainesExamples are: coco dimethyl propyl sulfobetaine, stearyl dimethyl propyl sulfobetaine, lauryl bis- (2-hydroxyethyl) propyl sulfobetaine, etc.; and amidosulfobetaines, such as cocoamidodimethylpropyl sulfobetaine, stearyl amidodimethylpropyl sulfobetaine, lauryl amidobis- (2-hydroxyethyl) propyl sulfobetaine, and the like. Preferred are amidohydroxysultaines such asC₁₂-C₁₈Alkylamidopropyl hydroxysultaines, especially C₁₂-C₁₄Alkyl amidopropyl hydroxysultaines, such as lauryl amidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other sulfobetaines are described in US 3,950,417, which is incorporated herein by reference.

Other suitable amphoteric surfactants are those of the formula R-NH (CH)₂)_nAmino alkanoate salts of COOM, formula R-N [ (CH)₂)_mCOOM]₂And mixtures thereof; wherein n and m are numbers from 1 to 4, R is C₈-C₂₂Alkyl or alkenyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.

Examples of suitable aminoalkanoates include N-alkylaminopropionate and N-alkyliminodipropionate, specific examples of which include N-lauryl- β -aminopropionic acid or a salt thereof and N-lauryl- β -iminodipropionic acid or a salt thereof, and mixtures thereof.

Other suitable amphoteric surfactants include those represented by the formula:

wherein R is¹Is C₈-C₂₂Alkyl or alkenyl, preferably C₁₂-C₁₆；R²And R³Independently selected from hydrogen, CH₂CO₂M、CH₂CH₂OH、CH₂CH₂OCH₂CH₂COOM or (CH)₂CH₂O)_mH, wherein m is an integer from 1 to about 25, R⁴Is hydrogen, CH₂CH₂OH or CH₂CH₂OCH₂CH₂COOM, Z isCO₂M or CH₂CO₂M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as an alkali metal (e.g., lithium, sodium, potassium), an alkaline earth metal (beryllium, magnesium, calcium, strontium, barium) or ammonium. This type of surfactant is sometimes also classified as an imidazoline type amphoteric surfactant, however, it should be recognized that they are not necessarily derived directly or indirectly from imidazoline intermediates. Suitable such materials are commercially available under the trade name MIRANOL, to be understood as complex mixtures comprising such materials, for R²In the case of hydrogen, these may be present in protonated and unprotonated forms, depending on their pH. All such variations and species are intended to be encompassed by the above formula.

Examples of surfactants of the above formula are mono-and dicarboxylic acid salts. Specific examples thereof include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate), and cocoamphoacetate.

Commercially available amphoteric surfactants include those sold under the trade names: MIRANOL 2M conc.n.p., MIRANOL C2M conc.o.p, MIRANOL C2M SF, MIRANOL CM SPECIAL (MIRANOL, Inc.); ALKATERIC 2CIB (Alkaril Chemicals); AMPHOTERGE W-2(Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32(Mona industries); REWOTERIC AM-2C (Rewo chemical group); SCHERCOTERIC MS-2(Scher Chemicals).

Suitable betaine surfactants, i.e., zwitterionic surfactants, for use in the shampoo compositions of the present invention are those represented by the formula:wherein R is¹Selected from COOM and CH (OH) CH₂SO₃M，R²Is lower alkyl or hydroxyalkyl; r³Is lower alkyl or hydroxyalkyl; r⁴Selected from hydrogen and lower alkyl; r⁵Is a higher alkyl or alkenyl group; y is lower alkyl, preferably methyl; m is an integer from 2 to 7, preferably from 2 to 3; n is an integer of 1 or 0; m is hydrogen or a cation as previously described, such as an alkali metal, alkaline earth metal or ammonium. The term "lower alkyl" or "hydroxyalkyl" refers to straight chains having from 1 to about 3 carbon atomsSaturated aliphatic and substituted hydrocarbon groups of a chain or branched chain, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like. The term "higher alkyl or alkenyl" refers to straight or branched chain saturated (i.e., "higher alkyl") and unsaturated (i.e., "higher alkenyl") aliphatic hydrocarbon groups having from about 8 to about 20 carbon atoms, for example, lauryl, cetyl, stearyl, oleyl, and the like. It will be understood that the term "higher alkyl or alkenyl" includes mixtures of groups which may contain one or more intermediate chains, such as ether or polyether chains, or non-functional substituents, such as hydroxyl or halogen, wherein the free radicals retain hydrophobic character.

Examples of the surfactant betaine of the above formula (when n is 0) used in the present invention include alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl- α -carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis- (2-hydroxyethyl) carboxymethyl betaine, stearyl bis- (2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl γ -carboxypropyl betaine, lauryl-bis- (2-hydroxypropyl) - α -carboxyethyl betaine, and the like.

Specific examples of amido betaines and amido sulfobetaines for use in shampoo compositions of the invention include amido carboxybetaines, such as cocoamidodimethylcarboxymethylbetaine, laurylamidedimethylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine, laurylamidobis- (2-hydroxyethyl) carboxymethylbetaine, cocoamido-bis- (2-hydroxyethyl) -carboxymethylbetaine, and the like. Representative of amidosulfobetaines are cocoamidodimethylsulfopropyl betaine, stearylamidogimethylsulfopropyl betaine, laurylamido-bis- (2-hydroxyethyl) -sulfopropyl betaine, and the like.

Nonionic surfactant

Shampoo compositions of the invention may comprise a nonionic surfactant. The nonionic surfactant is selected from those compounds produced by the condensation of alkylene oxide-based compounds, which are hydrophilic, with hydrophobic organic compounds, which may be aliphatic or alkyl aromatic.

Examples of preferred nonionic surfactants for use in shampoo compositions of the invention are:

(1) polyethylene oxide condensates of alkyl phenols, such as the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms and in either a straight or branched chain configuration, with ethylene oxide present in amounts of from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol;

(2) substances obtained by condensation of ethylene oxide with the product formed by the reaction of propylene oxide and ethylenediamine;

(3) condensation products of aliphatic alcohols having from about 8 to about 18 carbon atoms and in a linear or branched configuration with ethylene oxide, such as the cocol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of cocol, the cocol portion having from about 10 to about 14 carbon atoms;

(4) the term [ formula ] ]Wherein R is¹Containing alkyl, alkenyl or monohydroxyalkyl groups having from about 8 to about 18 carbon atoms and having from 0 to about 10 ethylene oxide moieties, from 0 to about 1 glyceryl moiety, R²And R³Containing from about 1 to about 3 carbon atoms, and from 0 to about 1 hydroxyl group, such as methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl;

(5) the term [ formula ] ]Wherein R comprises an alkyl, alkenyl or monohydroxyalkyl group having a chain length of from about 8 to about 18 carbon atoms and having from 0 to about 10 ethylene oxide moieties, from 0 to about 1 glyceryl moiety, and R' are alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms;

(6) long chain dialkyl sulfoxides containing one short chain alkyl or hydroxyalkyl group (typically methyl) of 1 to about 3 carbon atoms and one long chain hydrophobic chain comprising an alkyl, alkenyl, hydroxyalkyl or ketoalkyl group of about 8 to about 20 carbon atoms, 0 to about 10 ethylene oxide moieties, 0 to about 1 glyceryl moiety;

(7) alkyl Polysaccharide (APS) surfactants (e.g., alkyl polyglucosides), examples of which are described in US4,565,647, which is incorporated herein by reference; this document discloses APS surfactants having a hydrophobic group of from about 6 to about 30 carbon atoms and a polysaccharide group (e.g., a polyglucoside) as the hydrophilic group; optionally, a polyalkylene oxide group is present to link the hydrophobic and hydrophilic moieties; also, the alkyl group (i.e., hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, unsubstituted or substituted (e.g., with a hydroxyl group or a ring); preferred materials are alkyl polyglucosides, which are commercially available from Henkel, ICI Americas, and Seppic; and

(8) such as RO (CH)₂CH₂)_nThose polyoxyethylene alkyl ethers of H and OCH of the formula R (O)₂CH(OH)CH₂(OCH₂CH₂)_nThose polyethylene glycol (PEG) glycerol fatty acid esters of OH wherein n is from 1 to about 200, preferably from about 20 to about 100, and R is an alkyl group having from about 8 to about 22 carbon atoms.

Conditioning agent

Conditioning agents well known in the art may also be included in the present invention. Suitable conditioning agents include cationic surfactants such as those described above for preparing silicone emulsions, water-soluble cationic polymers, fatty compounds, nonvolatile dispersed silicones, hydrocarbons, proteins and mixtures thereof. Conditioning shampoo compositions of the invention comprise from about 0.01 to about 20 wt% of these conditioning agents.

Water-soluble cationic polymers

Water soluble cationic polymers are useful in the present invention. By "water soluble" is meant that the polymer is sufficiently soluble in water to form a substantially clear solution when viewed with the naked eye as a 0.1% strength solution in water (i.e., distilled or equivalent) at 25 ℃. Preferably the polymer should be sufficiently soluble to form a substantially clear solution at a concentration of 0.5%, more preferably at a concentration of 1.0% by weight.

The water-soluble cationic polymers of the present invention generally have a weight average molecular weight of at least about 5,000, preferably at least about 10,000, and less than about 10,000,000. Preferably, the molecular weight is from about 100,000 to about 2,000,000. Cationic polymers typically have cationic nitrogen-containing moieties, such as quaternary ammonium or cationic amino moieties, and mixtures thereof.

The cationic charge density is preferably at least about 0.1meq/g, more preferably at least about 0.2 meq/g, preferably less than about 3.0meq/g, more preferably less than about 2.75 meq/g.

The cationic charge density of the cationic polymer can be measured according to the Kjeldahl method, which is well known to those skilled in the art. It will be appreciated by those skilled in the art that the charge density of the amino-containing polymer will vary depending on the pH and the isoelectric point of the amino groups. The charge density should be within the above range at the intended pH of use.

Any anionic counterion can be used in the water-soluble cationic polymer, provided that the water solubility criteria is met. Suitable counterions include halides (e.g. chloride, bromide, iodide or fluoride, preferably chloride, bromide or iodide), sulfate and methylsulfate. Other ions may also be used, as the above listed ions are non-exclusive.

The cationic nitrogen-containing moiety is typically present as a substituent on a portion of the total monomer units of the cationic hair conditioning polymer. Thus, water-soluble cationic polymers include copolymers, terpolymers, etc. of quaternary ammonium or cationic amine substituted monomer units and other non-cationic units referred to herein as spacer monomer units. Such polymers are well known in the art, and a variety of polymers are described in the following references: international Cosmetic Ingredient Dictionary, 5 th edition, 1993, incorporated herein by reference.

Examples of suitable water-soluble cationic polymers include copolymers of vinyl monomers having cationic amine or quaternary ammonium functionality with water-soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates, vinyl caprolactone and vinyl pyrrolidone. Alkyl and dialkyl substituted monomers are preferredHaving a structure of C₁-C₇Alkyl radical, more preferably C₁-C₃An alkyl group. Other suitable spacer monomers include vinyl esters, vinyl alcohol (prepared by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol.

The cationic amine can be a primary, secondary, or tertiary amine, depending on the particular material and pH of the composition. In general, it is preferred to employ secondary and tertiary amines, especially tertiary amines.

Amine-substituted vinyl monomers can be polymerized in the amine form and then optionally converted to ammonium by quaternization. The amines can also be similarly quaternized after the formation of the polymer. For example, the tertiary amine functionality may be quaternized by reaction with a salt of the formula R 'X, wherein R' is a short chain alkyl group, preferably C₁-C₇Alkyl, more preferably C₁-C₃Alkyl, X is an anion which forms a water soluble salt with the quaternary ammonium.

Suitable cationic amino and quaternary ammonium monomers include: vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and quaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl portion of these monomers is preferably lower alkyl, such as C₁-C₃Alkyl, more preferably C₁And C₂An alkyl group. Suitable amine-substituted vinyl monomers suitable for use in the present invention include dialkylaminoalkyl acrylates, methacrylates, dialkylaminoalkyl acrylamides, and dialkylaminoalkyl methacrylamides, wherein the alkyl group is preferably C₁-C₇Hydrocarbyl, more preferably C₁-C₃An alkyl group.

The water-soluble cationic polymers of the present invention may comprise a mixture of monomer units derived from amine and/or quaternary ammonium substituted monomers and/or compatible spacer monomers.

Examples of suitable cationic polymers include: copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salts (e.g., chloride salts) (also known in the industry as polyquaternium-16 by "CTFA", e.g., from BASF corporation) are commercially available under the LUVIQUAT (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (also known in the industry as "CTFA" as polyquaternium-11), such as that commercially available from Gaf corporation (Wayne, NJ, U.S. A.) under the trade name GAFQUAT (e.g., GAFQUAT 755N); cationic diallyl quaternary ammonium-containing polymers, including, for example: homopolymers of dimethyldiallylammonium chloride and copolymers of acrylamide and dimethyldiallylammonium chloride, known in the industry as polyquaternium-6 and polyquaternium-7, respectively, by "CTFA"; and inorganic acid salts of amino-alkyl esters of homo-and copolymers of unsaturated carboxylic acids having 3 to 5 carbon atoms as described in U.S. Pat. No. 4,009,256, also incorporated herein by reference.

Other cationic polymers that may be used include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives. Suitable cationic polysaccharide polymers include those having repeating units of the formula:

wherein A is an anhydroglucose residue, such as a starch or cellulose anhydroglucose residue; r is an alkyleneoxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or a combination thereof; r¹、R²And R³Independently of each other, alkyl, aryl, alkaryl, aralkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, the total number of carbon atoms per cationic moiety (i.e., R)¹、R²And R³Total number of carbon atoms in) is preferably about 20 or less; x is an anionic counterion as previously described, such as halide, sulfate, nitrate, and the like.

Preferred cationic cellulose polymers are those obtainable from Amerchol Corp. (Edison, NJ, USA) as polymers of the Polymer JR, LR and SR series, as salts of hydroxyethyl cellulose reacted with an epoxide substituted with trimethylammonium, also known in the industry as polyquatemium-10 by "CTFA". Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl fiber reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry as polyquaternium-24 by "CTFA", commercially available from Amerchol Corp. (Edison, NJ, USA) under the trade designation Polymer LM-200.

Other water soluble cationic polymers that may be used include cationic guar derivatives such as hydroxypropyl trimonium chloride guar (commercially available from Celanese Corporation as its Jaguar R series). Other materials include quaternary nitrogen-containing cellulose ethers (as described in U.S. Pat. No. 3,962,418, which is incorporated herein by reference in its entirety) and etherified cellulose and starch (as described in U.S. Pat. No. 3,958,581, which is incorporated herein by reference).

The present invention preferably employs those water soluble cationic polymers selected from the group consisting of polyquaternium-7, polyquaternium-10, polyquaternium-11, and mixtures thereof.

Fatty compounds

Fatty compounds including fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof are preferred conditioning agents. It will be appreciated that the compounds disclosed in this section of the specification may in some cases be classified in a number of ways, for example, certain fatty alcohol derivatives may also be classified as fatty acid derivatives. It should also be recognized that certain such compounds may have the properties of a nonionic surfactant and thus are also classified as nonionic surfactants. However, a given classification is not intended to be a limitation on a particular compound, but is merely for convenience of classification and nomenclature. Non-limiting examples of fatty alcohols, fatty acids, fatty alcohol derivatives and fatty acid derivatives are described in the following references: international Cosmetic Ingredient Dictionary, 5 th edition, 1993, and CTFA Cosmetic Ingredient handbook, 2 nd edition, 1992, both of which are incorporated herein by reference.

The fatty alcohols useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty alcohols may be straight or branched chain alcohols, and may be saturated or unsaturated. Non-limiting examples of fatty alcohols include: decanol, undecanol, dodecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, isocetyl alcohol, behenyl alcohol, linalool, oleyl alcohol, cholesterol, cis-4-tert-butylcyclohexanol, myricyl alcohol, and mixtures thereof. Particularly preferred fatty alcohols are selected from the group consisting of cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol and mixtures thereof.

The fatty acids useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty acids may be straight or branched chain acids, and may be saturated or unsaturated. Dibasic acids, tribasic acids, and other polybasic acids meeting the carbon number requirements of the present invention may also be included. Salts of these fatty acids are also encompassed by the present invention. Non-limiting examples of fatty acids include: lauric acid, palmitic acid, stearic acid, behenic acid, arachidonic acid, oleic acid, isostearic acid, sebacic acid, and mixtures thereof. Particularly preferred fatty acids are selected from palmitic acid, stearic acid and mixtures thereof.

Fatty alcohol derivatives defined herein include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols, and mixtures thereof. Non-limiting examples of fatty alcohol derivatives include: materials such as methyl stearyl ether; 2-ethylhexyl lauryl ether; stearyl acetate; cetyl propionate; cetyl polyoxyethylene ether (ceteth) series compounds, e.g.ceteth-1 to ceteth-45, which are glycol ethers of cetyl alcohol, wherein the numbers indicate the number of ethylene glycol moieties present; octadecyl polyoxyethylene ether (steareth) series compounds, such as steareth-1 to steareth-100, which are glycol ethers of stearyl alcohol, wherein the numbers indicate the number of glycol moieties; ceteareth-1 to ceteareth-100, which are glycol ethers of cetyl/stearyl alcohol, i.e. glycol ethers predominantly containing mixtures of fatty alcohols of cetyl and stearyl alcohols, where the numbers areRepresents the number of ethylene glycol moieties present; c of the previously described ceteth, steareth, ceteareth compounds₁-C₃₀An alkyl ether; polyoxyethylene ethers of branched alcohols such as octyl lauryl alcohol, lauryl pentadecyl alcohol, hexyldecyl alcohol, and isostearyl alcohol; polyoxyethylene ethers of behenyl alcohol; PPG ethers such as PPG-9-steareth-3, PPG-11 stearyl ether, PPG-8-ceteth-1 and PPG-10 cetyl ether; and mixtures of all of the above. Preferably, steareth-2, steareth-4, ceteth-2 and mixtures thereof are used.

Fatty acid derivatives as defined in the present invention include fatty acid esters of fatty alcohols as defined in the preceding paragraph and fatty acid esters of fatty alcohol derivatives as defined in the preceding paragraph when these fatty alcohol derivatives have esterifiable hydroxyl groups, fatty acid esters of alcohols other than fatty alcohols and the fatty alcohol derivatives described in the preceding paragraph, hydroxyl-substituted fatty acids and mixtures thereof. Non-limiting examples of fatty acid derivatives include: ricinoleic acid, glyceryl monostearate, 12-hydroxystearic acid, ethyl stearate, cetyl palmitate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethylene glycol monostearate, polyoxyethylene distearate, propylene glycol monostearate, propylene glycol distearate, trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate, dimethyl sebacate, PEG-15 cocoate, PPG-15 stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, PEG-8 laurate, PPG-2 isostearate, PPG-9 laurate and mixtures thereof. Preferred are glyceryl monostearate, 12-hydroxystearic acid and mixtures thereof.

Hydrocarbons

Hydrocarbons are used as conditioning agents in the present invention. Useful hydrocarbons include straight chain hydrocarbons, cyclic hydrocarbons and branched chain hydrocarbons, which may be saturated or unsaturated hydrocarbons. The hydrocarbon preferably has from about 12 to about 40 carbon atoms, preferably from about 12 to about 30 carbon atoms, and more preferably from about 12 to 22 carbon atoms. The invention also includes hydrocarbon polymers of alkenyl monomers, such as C₂-C₆Of alkenyl monomersA hydrocarbon polymer. These polymers may be linear or branched. Linear polymers generally have a relatively short chain length and have the total number of carbon atoms previously described for this segment. The branched polymer may have a substantially higher chain length. The number average molecular weight of such materials can vary widely, but is generally up to about 500, preferably from about 200 to about 400, more preferably from about 300 to about 350. Book (I)Various grades of mineral oil may also be employed in the invention. Mineral oil is a liquid mixture of hydrocarbons obtained from petroleum. Specific examples of suitable hydrocarbon materials include: paraffin oil, mineral oil, dodecane, isododecane, hexadecane, isohexadecane, eicosene, isoeicosene, tridecane, tetradecane, polybutene, polyisobutene, and mixtures thereof. Isododecane, isohexadecane, and isoeicosene are commercially available from Presperse, South Plainfield, NJ as Permethyl 99A, Permethyl 101A and Permethyl 1082. Copolymers of isobutylene and n-butene are also commercially available as Indopol H-100 from Amoco Chemicals. The hydrocarbon conditioning agents preferably employed in the present invention are selected from the group consisting of mineral oil, isododecane, isohexadecane, polybutene, polyisobutene, and mixtures thereof.

Suspending agent

Shampoo compositions of the invention are substantially free of acyl derivative silicone suspending agents. By "substantially free of" is meant that the suspending agent is not present in an amount sufficient to provide any suspending effect on the silicone polymer. It will be appreciated that small amounts of the same suspending agent may be included to provide a pearlescent effect to the composition. In the present invention, the presence of small amounts of suspending agents which provide only a pearlescent effect is not intended to be excluded, however, they do not provide a suspending effect to the silicone polymer. Generally, at levels below about 1.5%, no suspending effect on the silicone polymer can be seen.

Suspending agents of the present invention include those that exist in crystalline form. These suspending agents are described in US4,741,855, which is incorporated herein by reference. These preferred suspending agents include: ethylene glycol esters of fatty acids having from about 16 to about 22 carbon atoms, such as ethylene glycol stearate, including monostearate and distearate, are preferred.

Optional Components

Various additional ingredients may also be formulated into the compositions of the present invention. These ingredients include: other conditioning agents such as hydrolyzed collagen, hydrolyzed keratin, proteins, plant extracts, and nutrients; a hair retention polymer; other surfactants such as anionic surfactants; thickeners such as xanthan gum, guar gum, hydroxyethyl cellulose, methyl cellulose, starch and starch derivatives; viscosity modifiers such as methanolamides of long chain fatty acids such as coconut monoethanolamide; preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolinyl urea; solvents such as polyvinyl alcohol, ethanol, and low molecular weight volatile and non-volatile silicone fluids; pH adjusting agents such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts such as potassium acetate and sodium chloride; colorants such as any of FD & C or D & C dyes; hair oxidizing (bleaching) agents such as hydrogen peroxide, perborates and persulfates; hair reducing agents, such as thioglycolates; a fragrance; chelating agents, such as sodium edetate; and polymeric plasticizers such as glycerin, diisobutyl adipate, butyl stearate, and propylene glycol; ultraviolet and infrared sunscreens and absorbers such as octyl salicylate. The compositions generally contain from about 0.01 to about 10.0 wt%, preferably from about 0.05 to about 5.0 wt%, of each optional ingredient.

Examples

The following examples further illustrate embodiments within the scope of the present invention. These examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention, since various changes and modifications can be made without departing from the spirit and substance of the present invention. Unless otherwise indicated, each ingredient is distinguished by chemical or CTFA designation.

Examples I to V

The components shown below were prepared according to conventional methods well known in the art. A suitable method is as follows: polyquaternium-10, polyethylene glycol (when present), mineral oil and detersive surfactant are dispersed in water to form a homogeneous mixture. To this mixture, the ingredients other than the silicone emulsion and the fragrance were added and stirred. The mixture obtained is cooled by passing through a heat exchanger and the silicone emulsion and fragrance are added. The obtained composition was poured into a bottle to prepare a shampoo composition.

Content of each component (%)

EXAMPLE No. I II III IV V polyoxyethylene lauryl ether-3-ammonium sulfate 15.012.012.012.012.0 ammonium lauryl sulfate 5.04.04.04.04.0 Silicone emulsion^*16.06.06.06.06.0 Polyquaternium-100.51.01.01.01.0 mineral oil 0.51.01.01.01.0 cetyl 0.70.70.70.70.7 stearyl alcohol 0.30.30.30.30.3 behenyl trimethyl ammonium chloride 0000.50.5 cocamidopropyl betaine 0000.50 sodium lauroyl sarcosinate 00000.5 polyethylene glycol 000.50.50.5 Cocoathanolamide 0.90.90.70.70.7 ethylene glycol distearate 1.51.51.500 fragrance 0.50.50.5050.5 preservative 0.20.20.20.20.2

Enough amount of water and enough amount of water

Aggregate 100100100100100

^*1Silicone emulsion: an emulsion having the following components:

33% Dimethylsiloxanol

5.4% Cyclopolydimethylsiloxane

0.8% sodium dodecylbenzenesulfonate

1.6% POE (18) nonylphenyl ether

0.8% cetyl trimethyl ammonium chloride

0.45% preservative

57.95% water

Dimethiconol was included at an average molecular weight of about 280,000, an average particle size of about 160nm, and was present at a level of 2% throughout the composition.

Claims

1. A shampoo composition comprising:

(a) a silicone emulsion comprising:

i) from about 0.01 to 20 weight percent of a silicone polymer, based on the weight of the entire composition

Selected from polyalkylsiloxanes having a molecular weight of at least 20,000, having a molecular weight of at least 20,000