CN1231597A - Shampoo compositions - Google Patents

Abstract

A shampoo composition comprising: (a) from about 1% to about 60% by weight of water-soluble surfactant selected from anionic surfactant, nonionic, amphoteric and cationic surfactants and mixtures thereof; (b) from about 0.001% to about 10% by weight of cosmetic agent and/or pharmaceutical active; (c) from about 0.001% to about 10% by weight of diamine dipolyacid component and/or salts thereof; and (d) water. The shampoo compositions of the invention are valuable for the provision of improved hair feel, hair shine and hair volume attributes as well as improved rinsibility and excellent lather volume, cleansing and hair conditioning characteristics.

Description

Shampoo compositions

Technical Field

The present invention relates to cleansing compositions suitable for cleansing hair and/or skin comprising a surfactant system, acosmetic and/or pharmaceutical active, and a diamine dimer acid component.

Background of the invention

The shampoo composition should be capable of cleansing hair and dandruff and be safe to the user. In addition to the requirement for detersive surfactants for cleansing hair, it is also highly desirable that the shampoo contain other additional ingredients such as conditioning agents, styling agents and dandruff control actives.

Parameters important in the formulation of shampoo compositions include characteristics of the application process, such as foam volume, emulsifiability, and rinse feel; and post-use characteristics such as hair shine and hair volume. Therefore, in order to obtain a shampoo having good hair-washing properties and simultaneously providing hair with gloss and excellent volume, it is desired to develop a shampoo which is easy to rinse, has abundant lather and has conditioning properties.

Many proposals have been made to improve the sheeting, foam volume, foam quality, rinse feel, hair sheen and hair volume. For example, conditioning agents such as silicone oils can improve hair feel and appearance; foam boosters such as coconut monoethanolamide can improve foam volume and quality; cationic polymers such as Varisoft (TN) or Luviquat (TN) improve the rinsing feel; the silicone oil can improve the luster of hair; styling agents such as polymeric styling resins can increase hair volume. However, the formulation of shampoos requires a balance of ingredients to be used in order to achieve the desired effect of each ingredient without unduly affecting the properties of the other ingredients, nor without adverse consequences such as excessive deposition on the hair which is difficult to remove due to too high a dosage of certain agents/actives.

Thus, there is a continuing desire for shampoos with improved foam volume and quality and improved hair rinse, and for shampoos with improved hair body and volume. Therefore, it is further desirable to obtain shampoos which foam well, rinse easily, and have improved hair shine and volume characteristics.

It is therefore an object of the present invention to provide shampoos having the above-mentioned characteristics. We have now found that the above effects can be achieved by incorporating a diamine dimer acid component into the shampoo.

Summary of The Invention

Shampoo compositions provided by the present invention comprise:

(a) from about 1% to about 60% by weight of a surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof;

(b) from about 0.001% to about 10% by weight of a cosmetic and/or pharmaceutical active;

(c) from about 0.001% to about 10% by weight of a diamine dimer acid component and salts thereof; and

(d) and (3) water.

Detailed Description

Shampoo compositions as defined herein include any composition capable of cleansing hair and/or skin comprising a detersive surfactant or cleansing component. Shampoo compositions of the invention are particularly useful for cleansing hair and/or skin.

All concentrations and ratios herein are based on the weight of the cleaning composition and surfactant chain length is also based on weight average chain length, unless otherwise specified.

Surfactant system

As an essential feature, the shampoocompositions of the present invention include a surfactant. Surfactants suitable for inclusion in the compositions of the present invention generally have a lipophilic chain length of from about 8 to about 22 carbon atoms and may be selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof. The total amount of surfactant is from about 1% to about 60%, preferably from about 2% to about 30%, more preferably from about 8% to about 25%, and especially preferably from about 10% to about 20% by weight.

Preferably, shampoo compositions of the invention comprise a detersive surfactant, more preferably a water-soluble detersive surfactant, although other surfactants can be used. Particularly preferred surfactants for use herein are selected from anionic, nonionic and amphoteric surfactants. Detergent surfactants as defined herein are any surfactants having a lipophilic chain length of about 8 carbon atoms or greater and which provide cleansing action to the hair and/or skin. Water soluble surfactants as defined herein means that the surfactant is capable of forming a clear isotropic solution when dissolved in water at 0.2% w/w at room temperature (about 20 ℃).

Shampoo compositions of the invention preferably comprise anionic and amphoteric surfactants in combination with one or more nonionic surfactants. The amount of each anionic component, if present, is preferably from about 0.1% to about 20%, more preferably from about 0.1% to about 15%, and especially from about 5% to about 15% by weight of the composition. Also, if present, the amount of each amphoteric or nonionic component is from about 0.1% to about 15% by weight, preferably from about 0.5% to about 10%, and more preferably from about 1% to about 8% by weight.

Anionic surfactants suitable for inclusion in shampoo compositions of the invention include alkyl sulfatesSalts, ethoxylated alkyl sulfates, alkyl ethoxy carboxylates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl isothionates, alkyl succinate carboxylates, alkyl succinate ethoxylates, α -sulfonated fatty acids and their salts and/or esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, alkyl sulfates, acyl sarcosinates, fatty acid/protein condensates and mixtures thereof₁₂-C₂₂Preferably C₁₂-C₁₈More preferably C₁₂-C₁₄。

The shampoo compositions of the present invention comprise a total combined amount of water soluble anionic surfactant from about 0.1% to about 30%, preferably from about 5% to about 20%, more preferably from about 10% to about 20% by weight.

Alkyl sulfate surfactants suitable for inclusion in the compositions of the present invention have the following general formula (i):

R-SO₃-M

wherein R is a straight or branched alkyl or alkenyl group, preferably a straight chain alkyl group, typically having a lipophilic chain length of from about 8 to about 22 carbon atoms, wherein M is selected from the group consisting of alkali metals, ammonium or other suitable monovalent cations or mixtures thereof. Suitable alkyl sulfates for use in the present invention include lauryl sulfate (sold under the trade name Empicol AL 30/t (tn), available from Albright and Wilson Ltd.) and lauryl sulfate.

Such surfactants include short chain alkyl sulfate surfactants, where "short chain" as used herein means having a carbon chain length of about C₁₀Or shorter. Short chain alkyl sulfate surfactants are useful in shampoo compositions to impart good cleansing and rinsing properties to the product and to provide excellent lather characteristics and cationic conditioner removal.

Itwill be appreciated that any particular carbon chain length such as C is said to be a direct function of the synthesis₁₀A proportion of longer and shorter carbon chains may also be included. The numerical values of the above-mentioned species can be controlled by varying the process and the characteristics of the starting materials. Preferred for use herein are short chain alkyl sulfates wherein at least about 50% w/w of the total alkyl sulfate content is C₁₀Or less, it is preferred to use short chain alkyl sulfates having at least about 50% by weight of the total alkyl sulfate content in the alkyl sulfates at about C₈And about C₁₀In particular, it is preferred that at least about 50% by weight of the total alkyl sulfate content of the short chain alkyl sulfates used in the present invention is C₁₀An alkyl sulfate. Although C is₁₀Alkyl sulfates are preferred surfactants for the compositions of the present invention, and mixtures of short chain alkyl sulfates may also be used. Particularly preferred shampoo compositions of the invention contain at least about 80% by weight C₁₀Preferably at least about 90% C₁₀More preferably at least about 95% C₁₀Particularly preferably at least about 97% C₁₀An alkyl sulfate. Suitable short chain alkyl sulfate materials are available under the trade name empicolLC35(TN) from Albright and Wilson Ltd. If present, short chain alkyl sulfate surfaceThe active agent is preferably present in an amount of at least about 0.5%, more preferably at least about 1%, and most preferably at least about 2% by weight of the composition.

Additional anionic surfactants suitable for use in shampoo compositions of the invention are salts of sulfates of the reaction product of 1 mole of a higher aliphatic alcohol and from about 1 to about 12 moles of ethylene oxide with sodium, ammonium and magnesium as preferred counterions. Alkyl ethoxy sulfate surfactants are useful in shampoo compositions to provide a soft hand and good lather volume. Suitable alkyl ethoxy sulfates have the following general formula (II):

RO(C₂H₄O)_xSO₃M

wherein R is a straight or branched alkyl or alkenyl group, preferably a straight chain alkyl group, typically having a lipophilic chain length of from about 8 to about 22 carbon atoms; x is the degree of ethoxylation with an average value in the range of about 2 to about 12; wherein M is selected from alkali metals, ammonium or other suitable monovalent cations or mixtures thereof. The cation M should be chosen so that the salt of the anionic surfactant is soluble in water. Solubility depends on the particular combination of anionic surfactant and cation selected.

The alkyl ethoxy sulfates preferably used in the present invention have an average degree of ethoxylation of from about 2 to about 6 and preferably contain from 2 to 4 moles of ethylene oxide, for example, ammonium lauryl-2 sulfate, ammonium lauryl-3 sulfate and sodium lauryl-3 sulfate. In a preferred embodiment, the anionic surfactant comprises at least about 50%, and especially at least about 75%, by weight of the ethoxylated alkyl sulfate.

In addition to the wide range of ethoxylated alkyl sulfates obtained by conventional sodium catalyzed ethoxylation techniques and subsequent sulfation processes, ethoxylated alkyl Sulfates (NREs) obtained from narrow range ethoxylates are also suitable for use in the water soluble anionic surfactants of the present compositions. Preferred narrow range ethoxylated alkyl sulfates suitable for use in the present invention are selected from the group consisting of alkyl ethoxylates of sulfuric acid containing an average of from about 1 to about 6 moles of ethylene oxide, preferably from about 2 to about 6, more preferably from about 3 to about 4, and especially preferably about 3 moles of ethylene oxide, such as NRE sodium lauryl-3 sulfate. NRE materials suitable for use in the present invention comprise the desired Ethylene Oxide (EO)_n) And higher Ethoxylates (EO)_n+1)、(EO_n+2)、(EO_n+3) Equal and lower Ethoxylates (EO)_n-1)、(EO_n-2)、(EO_n-3) Etc. are distributed. Preferred NRE materials for use in the present invention have a distribution of ethoxylates such that EO is EO_n、EO_n+1And EO_n-1Is greater than the total amount of other ethoxylates (in weight percent). The preferred NRE materials for use in the present invention have the desired ethylene oxide distribution (EO)_n) In the range of EO_n15% to about 45% by weight, EO_n+1About 10% to about 25% by weight Eo_n-1From about 10% to about 25% by weight. More preferred NRE materials contain less than about 9 wt% ethoxylated alkyl sulfates having 7 or more moles of ethylene oxide and less than about 13 wt% non-ethoxylated alkyl sulfates. Suitable lauryl-3 sulfate NRE materials are available under the trademark VITAMINGENAPOL ZRO (TN) narrow range and GENAPOL (TN) narrow range were purchased from Hoechst.

The total amount of the mixture of alkyl sulfate and alkyl ethoxy sulfate anionic surfactants preferably used in the present invention is from about 0.1% to about 30%, preferably from about 5% to about 20%, and particularly preferably from about 10% to about 20% by weight. The individual anionic components are each present in an amount of from about 0.1% to about 20%, preferably from about 0.1% to about 15%, and particularly preferably from about 5% to about 15% by weight of the composition. Particularly preferred for use herein are lauryl sulfate (available under the trade name Empicol AL 30/t (tn) from Albright and wilson Ltd.) and C_12/14AE₃S (available under the trademarks Empicolil AEB/T, AEC/T and AEC 70(TN) from Albright and Wilson Ltd.), in which the ratio of alkyl sulfate to alkyl ethoxy sulfate ranges from about 5: 1 to about 1: 5, preferably from about 3: 1 to about 1: 3, more preferably from about 1: 1 to about 1: 3.

Shampoo compositions of the invention may contain an alkyl ethoxy carboxylate surfactant. Alkyl ethoxy carboxylate surfactants are important in providing shampoo compositions with good rinse performance and good lather characteristics.

The alkyl ethoxy carboxylates have the following general formula (III):

R³O(CH₂CH₂O)_kCH₂COO^-M⁺

wherein R is³Is C₁₀-C₁₅Alkyl or alkenyl, preferably C₁₁-C₁₅More preferably C₁₂-C₁₄Alkyl or C₁₂-C₁₃An alkyl group; k is an average ethoxylation number ranging from 2 to about 7, preferably from about 3 to about 6, more preferably from about 3.5 to about 5.5, especially preferably from about 4 to about 5, and most preferably from about 4 to about 4.5; m is a water-soluble cation, preferably alkali metal, alkaline earth metal, ammonium, lower alkanolammonium and monoethanolammonium, diethanolammonium and triethanolammonium, more preferably sodium, potassium and ammonium, most preferably sodium and ammonium and mixtures thereof with magnesium and calcium ions.

A suitable water-soluble anionic alkyl ethoxy carboxylate surfactant for use in the present invention is C₁₂-C₁₄(average EO3-6) Ethoxycarboxylates and C₁₂-C₁₃(average EO3-6) ethoxy carboxylate. Suitable materials include salts of NEODOX 23-4 (TN) available from Shell, Inc. (Houston, Tex., USA). Preferred for use herein are alkyl ethoxy carboxylate surfactants wherein R is³Is C₁₂-C₁₄OrC₁₂-C₁₃Alkyl groups, k, have an average value of from about 3 to about 6, more preferably from about 3.5 to about 5.5, especially from about 4 to about 5, and most preferably from about 4 to about 4.5.

The compositions of the present invention may also include water-soluble nonionic surfactants. Typical nonionic surfactants are selected from ethoxylated alcohols, C₁₂-C₁₄Fatty acid mono-and dialkanolamides, e.g. cocoethanolamide, cocomonoisopropylamide and their ethoxylated derivatives, alkylpolysaccharides, e.g. C₁₀-C₁₈Alkyl polyglycosides and polyhydroxy fatty acid amide surfactants.

The nonionic surfactant is preferably used in combination with other surfactants such as an anionic surfactant and/or an amphoteric surfactant. Nonionic surfactants are generally used in amounts of from about 0.1% to about 15%, preferably from about 0.1% to about 10%, more preferably from about 0.1% to about 8%, most preferably from about 0.5% to about 5%, and especially from about 0.5% to about 2% by weight of the shampoo compositions of the invention.

Ethoxylated alcohol surfactants suitable for use in the present invention include mono-and poly-ethoxylates of mono-, di-and polyhydric alcohols and/or alkylated derivatives thereof. The preferred ethoxylated alcohol surfactants for use in the present invention have the following general formula (IV):

R₁O-(CH₂CH₂O)_x-R₂

wherein R is₁Is C₄-C₃₁Hydrocarbyl, preferably C₆-C₁₉Hydrocarbyl, more preferably C₉-C₁₁Hydrocarbyl, most preferably C₇-C₁₁Hydrocarbyl, including natural or synthetic materials having a straight, branched alkyl, and/or alkenyl configuration; r₂Typicallyhydrogen, C₁-C₈An alkyl or hydroxyalkyl group; x is an average ethoxylation number ranging from 1 to about 20, preferably from about 5 to about 15, more preferably from about 5 to about 12, and most preferably from about 7 to about 10. Other ethoxylates conforming to the above formula are also suitable for use in the present invention, such as ethoxylates formed from one or more of the following alcohols, such as: butanol, isobutanol, hexanol, octanol, decanol, dodecanol, tetradecanol, pentadecanol, octadecanol, eicosanol, docosanol, tetracosanol and triacontanol.

R in a typical alcohol ethoxylate for use in the present invention₂Is hydrogen. C having an average ethoxylation number of about 6 is preferably used in the present invention₉To C₁₁Alcohol (trade name Dobanol 91-6(TN) available from Shell) and C having an average ethoxylation number of about 8₉To C₁₁Alcohol (available under the trade name Dobanol 91-8(TN) from Shell).

Suitable polyhydroxy fatty acid amide surfactants for use in the present invention include materials having the following general formula (V):

in the preferred N-alkyl-, N-alkoxy-or N-aryloxy-, polyhydroxy fatty acid amide surfactants according to formula (V), R₈Is C₅-C₃₁Hydrocarbyl, preferably C₆-C₁₉Hydrocarbyl groups including straight and branched chain alkyl and alkenyl groups or mixtures thereof; r₉Typically hydrogen, C₁-C₈Alkyl or hydroxyalkyl, preferably methyl, or-R¹-O-R²Group, wherein R¹Is C including straight chain, branched chain and cyclic₂-C₈Hydrocarbyl (including aryl), preferably C₂-C₄An alkylene group. R²Is C₁-C₈Straight, branched and cyclic hydrocarbyl including aryl and oxyhydrocarbyl, preferably C₁-C₄Alkyl, in particular methyl or phenyl. Z₂Are polyhydroxyhydrocarbyl moieties containing linear hydrocarbyl chains with at least 2 (if glyceraldehyde) or at least 3 hydroxyl groups (if other reducing sugars) directly attached to the chain, or alkoxylated derivatives (preferably ethoxylated or propoxylated) thereof. Z₂Reducing sugars from the reduction reaction are preferred. Most preferred Z₂Is a glycidyl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, xylose, and glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized, as well as the various sugars described above. These corn syrups may yield Z₂The mixed sugar component of (1). It is to be understood that this by no means excludes other suitable starting materials. Z₂Preferably selected from the following groups: -CH₂-(CHOH)_n-CH₂OH,-CH(CH₂OH)-(CHOH)_n-1-CH₂H,CH₂(CHOH)₂(CHOR)CHOH-CH₂OH, wherein n is an integer from 1 to 5, R' is H or a cyclic mono-or polysaccharide and alkoxylated derivatives thereof. As mentioned above, most preferred is a glycidyl group, wherein n is 4, particularly preferred is-CH₂-(CHOH)₄-CH₂OH。

Most preferred polyhydroxy fatty acid amides have the formula R₈(CO)N(CH₃)CH₂(CHOH)₄CH₂OH, wherein R₈Is C₆-C₁₉Straight chain alkyl or alkenyl. In the compounds of the above formula, R₈-CO-N<For example, cocoamides, stearamides, oleamides, lauramides, myristamides, capramides, palmitamides, tallowamides, and the like.

A preferred process for the preparation of compounds of formula (V) above comprises the substantial absence of lower (C)₁-C₄) The fatty acid triglycerides are reacted with N-substituted polyhydroxyamines in the presence of an alcoholic solvent, but preferably with an alkoxylated alcohol or alkoxylated alkylphenol such as NEODOL, and this reaction utilizes an alkoxide catalyst to yield high yields (90-98%) of the desired product at about 50 ℃ to about 140 ℃. Suitable processes for preparing the desired polyhydroxy fatty acid amide compounds are outlined in US-A-5194639 and US-A-5380891.

It should be recognized that processes for forming polyhydroxy fatty acid amides, along with the polyhydroxy fatty acid amides, also typically produce large amounts of non-volatile by-products such as ester amides and cyclic polyhydroxy fatty acid amides. The amount of these by-products varies depending on the particular reactants and process conditions. The above-mentioned suitable processes are advantageous in that they produce only a very small amount of by-products, including cyclic amide by-products.

Polyhydroxy fatty acid amide surfactants suitable for use in the present invention have the added benefit to shampoo formulators that they can be prepared wholly or predominantly from natural, renewable non-petrochemical sources and are degradable. They are also very low toxic to aquatic organisms.

Other nonionic surfactants suitable for use in the present invention include: long chain tertiary amine oxides of the corresponding general formula:

wherein R is₁An alkyl, alkenyl or monohydroxyalkyl group containing from about 8 to about 18 carbon atoms, an ethylene oxide moiety of from 0 to about 10 and a glyceryl moiety of from 0 to about 1; r₂And R₃Comprises about 1 to about 3And from 0 to about 1 hydroxyl, such as methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl. The arrows in the above formula are conventional representations of semipolar bonds. The long-chain tertiary phosphine oxides correspond to the following general formula:

wherein R comprises an alkyl, alkenyl or monohydroxyalkyl group having from about 8 to about 18 carbon atoms in the chain length, an ethylene oxide moiety of from 0 to about 10 and a glyceryl moiety of from 0 to about 1; r' and R "are independently an alkyl or monohydroxyalkyl group containing from about 1 to about 3 carbon atoms, a long chain dialkyl sulfoxide containing a short chain alkyl or hydroxyalkyl group (typically methyl) of from about 1 to about 3 carbon atoms, and a long hydrophobic chain comprising an alkyl, alkenyl, hydroxyalkyl or ketoalkyl group of from about 8 to about 20 carbon atoms, an ethylene oxide moiety of from 0 to about 10 and a glyceryl moiety of from 0 to about 1.

The compositions useful in the present invention also contain water-soluble amphoteric surfactants in an amount of from about 0.1% to about 15% by weight, preferably from about 0.5% to about 10%, more preferably from about 1% to about 8%, and most preferably from about 1% to about 5% by weight.

Amphoteric surfactants suitable for use in the present invention include zwitterions such as betaines, amidobetaines, and sultaines and:

(a) imidazoline surfactants of formula (VI)

Wherein R is₁Is C₇-C₂₂Alkyl or alkenyl, R₂Is hydrogen or CH₂Z, Z are each CO₂M or CH₂CO₂M, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula (VII):

wherein R is₁、R₂And Z is as defined above. (b) An aminoalkanoate of formula (VIII):

R₁NH(CH₂)_nCO₂M

an iminodialkanoic acid ester of formula (IX):

R₁N[(CH₂)_mCO₂M]₂

and an imido polyalkanoate of formula (X):

wherein n, m, p and q are numbers 1-4, R₁And M is independently selected from the above groupsClustering; and

(c) mixtures thereof.

Suitable amphoteric surfactants of type (a) are sold under the trade names Miranol and Empigen and are also known to include a complex mixture. In general, Miranol is described as having the general formula VI, although CTFA Cosmetic Ingredient Dictionary 3 rd edition indicates an acyclic structure V while another structural isomer is indicated at 4 th edition, where R is₂Are O-linked rather than N-linked. In practice, there may be a complex mixture of cyclic and acyclic, both definitions being given for completeness. But the invention is preferably used in a non-cyclic type.

Typical compounds of suitable amphoteric surfactants of type (a) include compounds of formula VI and/or VII, wherein R is₁Is C₈H₁₇(in particular isooctyl), C₉H₁₉And C₁₁H₂₃An alkyl group. Particularly preferred compounds are those in which R₁Is C₉H₁₉Z is CO₂M,R₂Is H; in the compound R₁Is C₁₁H₂₃Z is CO₂M and R₂Is CH₂CO₂M; in the compound R₁Is C₁₁H₂₃Z is CO₂M,R₂Is H.

In the CTFA nomenclature, suitable materials for use in the present invention include cocoamphocarboxypropionate, especially cocoamphoacetate and cocoamphodiacetate (otherwise known as cocoamphocarboxyglycinate). Specific commercial products include those under the trade names: amphalak 7TX (TN) (sodium carboxymethyltallow polypropylamine), Empigen CDL60(TN) and CDR 60(TN) (Albright&Wilson), Miranol H2MCone (TN), Miranol C2M Con.N.P. (TN), Miranol C2M Con.O.P. (TN), Miranol C2M SF (TN), Miranol CM Special (TN) (Rhone-Poulenc); alkateric 2CIB (TN) (Alkaril Chemicals); amphoerge W-2(TN) (Lonza, Inc.); monateric CDX-38(TN), Monateric CSH-32(TN) (Mona industries); rewoteric AM-2C (TN) (Rewo Chemical group); and Schercotic MS-2(TN) (Scher Chemicals).

It is known that a large number of commercially available amphoteric surfactants of the above type are in a charge-neutral form withWith surfactants, e.g. hydroxide counterions or anionic sulfate or sulfonate, especially sulfated C₈-C₁₈Alcohol, C₈-C₁₈Ethoxylated alcohols or C₈-C₁₈Those of the acylglyceride type are manufactured and sold in a mixture. However, in view of the softness and stability of the product, preferred are such compositions: which is substantially free of (non-ethoxylated) sulfated alcohol surfactant. It is also noteworthy that the concentration and weight ratio of amphoteric surfactant in the present invention are based on the surfactant in its uncomplexed form, and any anionic surfactant counter ion is considered to be a part of the total anionic surfactant component content.

Typical materials of preferred amphoteric surfactants of type (b) include N-alkyl polytrimethylene polycarboxymethylamines, sold under the names Amphalak X07(TN) and Amphalak 7CX (TN), by BerolNobel, and also salts, in particular triethanolammonium salt and N-lauryl- β -aminopropionate and N-lauryl-imino-dipropionate, sold under the trade name Deriphat (TN) by Henkel and under the trade name Miritaine (TN) by Rhone-Poulenc.

Betaine surfactants suitable for use in the present invention include those of the formula R₅R₆R₇N⁺(CH₂)_nCO₂An alkyl betaine of M and an amido betaine of formula (XI):

wherein R is₅Is C₁₁-C₂₂Alkyl or alkenyl, R₆And R₇Are respectively C₁-C₃Alkyl radical, R₈Is hydrogen or methyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium, and n and M are each a number from 1 to 4. Preferred betaines include cocoamidopropyl dimethyl carboxymethyl betaine and lauryl amidopropyl dimethyl carboxymethyl betaine.

Is suitable for being included in the hairThe water-soluble surfactant in the composition comprises alkylamido surfactants of the formula:

wherein R is₁Is C₇To C₂₂Alkyl or alkenyl, R₂And R₃Are respectively C₁To C₃Alkyl radical, R₄Is hydrogen or methyl, M is H, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium, and M and n are numbers from 1 to 4. Preferred for use in the present invention is cocamidopropyl hydroxysturaine.

Water-soluble amine oxide surfactants suitable for inclusion in the compositions of the present invention include alkyl amine oxides R₅R₆R₇NO and an amidoamine oxide of the formula:

wherein R is₅Is C₁₁To C₂₂Alkyl or alkenyl, R₆And R₇Are respectively C₁To C₃Alkyl radical, R₈Is hydrogen or methyl, M is H, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium, and M and n are numbers from 1 to 4. Preferred amine oxides include cocamidopropyl amine oxide, lauryl dimethyl amine oxide, and myristyl dimethyl amine oxide.

Cationic surfactants suitable for use in the present invention include quaternary ammonium surfactants selected from the group consisting of mono C₈To C₁₆Preferably C₁₀To C₁₄N-alkyl or alkenyl ammonium surfactants in which the remaining N position is substituted by methylhydroxyethyl or hydroxypropyl. Typical cationic surfactants useful in the present invention include: dihydrogenated tallow amido ethyl hydroxyethylammonium N-methosulfate, available from Witco under the trade designation Varisoft CB110 (TN). It will be appreciated that cationic quaternary ammonium surfactants may act as conditioning cosmetic agents in the compositions of the present invention.

Cosmetic and/or pharmaceutical active

As another important feature, the shampoo compositions of the present invention comprise a cosmetic and/or pharmaceutical active, preferably in an amount of from about 0.001% to about 10%, more preferably from about 0.01% to about 5%, most preferably from about 0.1% to about 3%, and particularly preferably from about 0.1% to about 1% by weight.

Cosmetic agents suitable for use in the present invention are any agents capable of improving the appearance and/or feel of hair and/or skin. The cosmetic agents preferably used in the present invention improve the feel and/or appearance of hair and/or skin by depositing on the hair and/or skin. Cosmetic agents suitable for use in the present invention include conditioning agents such as polyquaternium10, polyquaternium 16, hydroxypropyl guar gum, and hydroxypropyl ammonium trichloride; setting agents, for example, polyvinylpyrrolidone vinyl acetate, vinyl acetate/crotonic acid, vinyl acetate/vinylbutylbenzoate crotonic acid, octylacrylamide acrylate/butylaminoethyl methacrylate, polyquaternium 11, polyvinylpyrrolidone dimethylethyl methacrylate, vinyl carprolactam/polyvinylpyrrolidone/dimethylaminoethyl methacrylate, polyquaternium 4, sodium polystyrene sulfonate, vinyl acrylate/crotonate/vinyl neodecanoate copolymer; and hair moisturizers such as methyl gluceth-10, D-panthenol, PEG-6 capric/caprylic glycerides, glycerin, wheat protein hydrolysate, tocopherol acetate.

Conditioning agent

The conditioning agent as described above is an essential ingredient for improving the appearance and/or feel of hair and/or skin. The conditioning agents preferably used in the present invention should be deposited on the hair and/or skin in order to provide conditioning characteristics during and after use of the shampoo compositions of the present invention.

Conditioning agents suitable for use in the present invention are selected from the group consisting of silicone materials, fatty alcohols, polymeric resins, polyol carboxylates, cationic polymers, insoluble oils and oil derived materials and mixtures thereof.

By definition, diamine dimer acid should not be included in the conditioning agents of the present compositions because, while the incorporation of diamine dimer acid improves the appearance and/or feel of hair and/or skin, these effects are due, at least in part, to a mechanism other than deposition on hair and/or skin, including limiting the deposition of undesirable materials on hair and/or skin.

Siloxane feedstock

Suitable silicone conditioning agents for use herein are non-volatile and insoluble in the shampoo composition and are incorporated in the shampoo composition as an emulsion, i.e., a discrete discontinuous phase of dispersed insoluble droplets. These droplets are suspended with a suspending agent, and a number of suitable non-repulsive examples will be described below. The dispersed silicone conditioning agent component comprises a silicone fluid hair conditioning agent such as a silicone fluid and may also comprise other ingredients such as a silicone resin for the purpose of enhancing the deposition efficiency of the silicone fluid or for example enhancing the shine of the hair, particularly with silicone conditioning agents having a high refractive index (e.g. greater than about 1.46) (e.g. highly phenylated silicones).

The silicone conditioning agent phase may contain a volatile silicone component. Generally, if volatile silicones are used, non-volatile silicone starting ingredients such as silicone gums and resins will often be used in commercially available forms as solvent borne carriers.

The viscosity of the silicone conditioning component used in the present invention is preferably from about 20 to about 2,000,000 centistokes, more preferably from about 1,000 to about 1,800,000, more preferably from about 50,000 to about 1,500,000, most preferably from about 100,000 to about 1,500,000, measured at 25℃ using a glass capillary viscometer as described in Dow coming corporation Test Method CTM0004,7 months 20, 1970.

Generally, the silicone conditioning component is used in the shampoo compositions of the present invention in an amount of from about 0.05% to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.1% to about 5%, and most preferably from about 0.1% to about 3% by weight of the composition. The minimum amount used in a particular composition should be effective to provide conditioning performance. The maximum amount used is not limited theoretically, but is not actually used. Although large amounts are effective, it is generally unnecessary and expensive to use amounts in excess of about 8%.

One silicone fluid that may be used in the present invention is a silicone oil. The term "silicone oil" means having a viscosity of less than 1,000 at 25 ℃Flowable silicone materials of 000 centistokes. Generally, the viscosity of the fluid is between about 5 and 1,000,000 centistokes at 25℃, preferably between about 10 and about 100,000. Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers and mixtures thereof. Other insoluble, nonvolatile silicone fluids having hair conditioning properties may also be used. Particularly more preferred silicone oils include polyalkyl or polyaryl siloxanes having the following general formula (XII):

wherein R is an aliphatic, preferably alkyl or alkenyl, or aryl group, R may be substituted or unsubstituted, and x is an integer from 1 to about 8000. Suitable unsubstituted R groups include alkoxy, aryloxy, alkaryl, aralkyl, aralkenyl, alkylamino, and ether-substituted, hydroxy-substituted, and halogen-substituted aliphatic and aryl groups. Suitable R also includes cationic amines and quaternary ammonium groups.

The aliphatic or aryl groups substituted on the silicone chain may contain any structure so long as the final silicone remains fluid at room temperature, is hydrophobic, neither radiation nor toxic, is not harmful to the hair and/or skin, is compatible with the other composition components, is chemically stable under normal use and storage conditions, is insoluble in the composition, is capable of being deposited on the hair and/or skin, and has a hair and/orskin conditioning effect. The two R groups on the silicon atom of each monomeric siloxane unit may be the same or different groups. Preferably, the two groups are the same.

Preferably the alkyl and alkenyl substituents are C₁-C₅Alkyl and alkenyl, more preferably C₁-C₄Most preferably C₁-C₂. Other alkyl, alkenyl or alkynyl-containing groups may be straight or branched chain aliphatic moieties (e.g., alkoxy, alkaryl, and alkylamino), preferably having from 1 to 5 carbon atoms, more preferably from 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms, and most preferably from 1 to 2 carbon atoms. As noted above, the R substituent may also contain an amino functionality, such as an alkylamino groupIt may be a primary, secondary or tertiary amine or a quaternary ammonium. They include mono-, di-and tri-alkylamino and alkoxyamino groups, wherein the chain length of the aliphatic moiety is preferably as described above. The R substituents may also be substituted with other groups, e.g. halogen (e.g. chloride, fluoro)Hydrides and bromides), halogenated aliphatic or aryl groups, and hydroxyl groups (e.g., hydroxyl-substituted aliphatic groups). Suitable halogenated R groups include, for example, trihalogenated (preferably fluoro) alkyl groups such as-R¹-C(F)₃Wherein R is¹Is C₁-C₃An alkyl group. Typical polysiloxanes include polymethyl 3,3,3 trifluoropropyl siloxane.

Non-volatile polyalkylsiloxane fluids that may be used include, for example, polydimethylsiloxane. These silicones can be obtained, for example, from General Electric company, Viscasil R and SF 96 series, Dow Corning 200 series from Dow Corning. Also suitable for use in the present invention are Dow Corning DC 1664(TN)60,000cstk polydimethylsiloxane having a particle size of 300nm, which is preferably used in combination with a deposition aid.Polydimethylsiloxanes known as dimethicone oils are known. Other suitable R groups include methyl, methoxy, ethoxy, propoxy, and aryloxy.

Methoxy, ethoxy, propoxy, and aryloxy. The three R groups at the siloxane terminus can also be the same or different groups. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. Preferred siloxanes are polydimethylsiloxane, polydiethylsiloxane and polymethylphenylsiloxane. Polydimethylsiloxane is particularly preferred.

Polyalkylaryl siloxane fluids may be used, also including, for example, polymethylphenylsiloxane. These siloxanes are available as SF1075 methylphenyl Fluid from General Electric company or 556 CosmeticGrade Fluid from Dow Corning.

Polyether siloxane copolymers that may be used include, for example, polypropylene oxide modified polydimethylsiloxanes (e.g., Dow Corning DC-1248), although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The amount of ethylene oxide and polypropylene oxide must beSufficiently small to prevent dissolution in water and combinations thereof. Alkylamino substituted siloxanes which may be used in the present invention include compounds of the formula:

wherein x and y are integers depending on the molecular weight, and the average molecular weight is between about 5000 and 10000. This polymer is also known as aminodimethicone (amodimethicone).

Cationic silicone fluids which may be used in the compositions of the present invention include compounds of the formula:

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

wherein G is selected from hydrogen, phenyl, OH, C₁-C₈Alkyl, preferably methyl; a represents 0 or an integer from 1 to 3, preferably equal to 0; b represents 0 or 1, preferably equal to 1; the total number of n + m is from 1 to 2000, preferably from 50 to 150, n represents a number from 0 to 1999, preferably from 49 to 149, m represents an integer from 1 to 2000, preferably from 1 to 10; r₁Is C₉H₂₉A monovalent residue of L, wherein q is an integer from 2 to 8, L is selected from the group consisting of:

-N(R₂)CH₂-CH₂-N(R₂)₂

-N(R₂)₂

-N(R₂)₃A^-

-N(R₂)CH₂-CH₂-N+R₂H₂A^-

wherein R is₂Selected from hydrogen, phenyl, benzyl, saturated hydrocarbon radicals, preferably alkyl radicals containing from 1 to 20 carbon atoms, A^-Represents a halide ion.

Particularly preferred cationic silicones corresponding to the above formula are the polymers known as "trimethylsilylaminomethylpolysiloxanes", the formula being as follows:others for this purposeThe silicone cationic polymer of the inventive composition has the formula:

wherein R is₃Represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, more preferably an alkyl group or an alkenyl group such as a methyl group; r₄Represents a hydrocarbon group, preferably C₁To C₁₈Alkalkenylene radical or C₁To C₁₈Preferably C₁To C₈Alkylene oxide group; q is a halide ion, preferably a chloride ion; r represents an average statistical value from 2 to 20, preferably 2 to 8; s represents an average statistical value from 20 to 200, preferably from 20 to 50. These compounds are described in more detail in US-A-4185017. A particularly preferred polymer of this type is sold under the trade name "UCARSILICONE ALE 56" (TN) by UNION CARBIDE.

Another silicone fluid that is particularly useful in silicone conditioning agents is an insoluble silicone gum. The term "silicone gum" as used herein refers to a polysiloxane starting material having a viscosity of greater than or equal to 1000000 centistokes at 25 ℃. Silicone gums are described by Petrarch, others include US-A-4152416, Spitzer et al, published 3/1/1979, and Noll, Walter, Chemistry and Technology of Silicones, New York; academic Press 1968. Further described Silicone gums are the General Electric Silicone Rubber Product Data sheetssetsse 30, SE33, SE54 and SE 76. Generally, the mass molecular weight of the "silicone gum" is greater than about 200000, and is generally between about 200000 and about 1000000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly (dimethylsiloxane) (diphenylsiloxane) (methylvinylsiloxane) copolymer, and mixtures thereof.

Preferred silicone hair and/or skin conditioning agents include mixtures of dimethicone gums having a viscosity of greater than about 1000000 centistokes and dimethicone oils having a viscosity of from about 10 to about 100000 centistokes, wherein the ratio of gum to fluid is from about 30: 70 to about 70: 30, preferably from about 40:60 to about 60: 40.

Another non-volatile, insoluble silicone fluid conditioning agent is a high refractive index silicone having a refractive index of at least about 1.46, preferably at least about 1.48, more preferably at least about 1.52, and most preferably at least about 1.55. Although not required to be limiting, the refractive index of the polysiloxane fluid is generally less than about 1.70, and generally less than about 1.60. Silicone "fluids" include oils and gums.

Suitable high refractive index polysiloxane fluids for purposes of the present invention include those represented by the general formula (XII) above, as well as cyclic polysiloxanes such as represented by the formula:

wherein R is as defined above and n is a number from about 3 to about 7, preferably 3 to 5. The high refractive index polysiloxane fluid contains a sufficient amount of aryl-containing R substituents to increase the refractive index to the value desired above. In addition, R and n must be chosen so that the material is non-volatile as described above.

Aryl-containing substituents include alicyclic and heterocyclic five and six atom number aromatic rings, as well as substituents containing fused five or six atom number rings. The aromatic ring itself may be substituted or unsubstituted. Substituents include aliphatic substituents, as well as alkoxy substituents, acyl substituents, ketones, halogens (e.g., Cl and Br), amines, and the like. Typical aryl-containing groups include substituted and unsubstituted aromatic hydrocarbons, e.g. phenyl, and phenyl derivatives, e.g. containing C₁-C₅Alkyl-or alkenyl-substituted phenyl, e.g. allylphenyl, methylphenyl and ethylphenyl, vinylphenyl, e.g. styryl, and phenylalkyne (e.g. phenyl C)₂-C₄An alkyne). Heterocyclic aryl groups include substituents derived from furan, imidazole, pyrrole, pyridine, and the like. Fused aromatic ring substituents include, for example, naphthalene, coumarin, and purine.

Generally, the high refractive index polysiloxane fluids have a value of at least about 15%, preferably at least about 20%, more preferably at least about 25%, more preferably at least about 35%, and most preferably at least about 50% aryl-containing substituents. Although the present invention is not intended to be limiting, the value of the aryl substituent is less than about 90%, generally more preferably less than about 85%, and preferably between about 55% and about 80%.

These polysiloxane fluids are also characterized by relatively high surface tensions due to the aryl substituents. Generally, the surface tension of the polysiloxane fluid is at least about 24 dynes/cm²And typically at least about 27 dynes/cm². For this purpose, the surface tension was determined by a deNouy ring tensiometer according to the Dow corning corporation Test Method CTM0461 (11/23 1971). The change in surface tension can be determined according to the experimental method described above or according to ASTM method D1331.

Preferably, the high refractive index polysiloxane fluid contains a phenyl or a mixed substituent of a phenyl derived substituent (preferably phenyl) and an alkyl substituent, preferably C₁-C₄Alkyl (most preferably methyl), hydroxy, C₁-C₄Alkylamino (especially-R)¹NHR²NH₂Wherein R is¹And R²Are respectively C₁-C₃Alkyl, alkenyl and/or alkoxy). High refractive index polysiloxanes are commercially available from Dow Corning corporation (Midland, Michigan, USA) Huls American (Piscataway, New Jersey, USA) and General Electric Silicones (Waterford, New York, USA).

It is preferred to utilize a high refractive index silicone solution with a spreading agent, such as a silicone resin or surfactant, in order to reduce the surface tension sufficiently to enhance spreading and thereby increase the shine of the hair (which is then dried) after treatment with the composition. Generally, the amount of spreading agent is sufficient to reduce the surface tension of the high refractive index polysiloxane fluid by at least about 5%, preferably by at least about 10%, more preferably by at least about 15%, more preferably by at least about 20%, and most preferably by at least about 25%. Reducing the surface tension of the silicone fluid/spreading agent mixture improves the shine of the hair.

In addition, the spreading agent preferably reduces the surface tension by at least about 2 dynes/cm²Preferably at least about 3 dynes/cm²More preferably at least about 4 dynes/cm²Most preferably toAbout 5 dynes/cm less²。

The surface tension of the polysiloxane fluid and spreading agent mixture is preferably 30 dynes/cm based on the proportions present in the final product²Or less, more preferably about 28 dynes/cm²Or less, most preferably about 25 dynes/cm²Or smaller. Generally, the surface tension will range from about 15 to about 30, more preferably from about 18 to about 28, and most preferably from about 20 to about 25 dynes/cm²In the meantime.

The weight ratio of highly aromatic polysiloxane fluid to spreading agent is generally between about 1000: 1 to about 1: 1, preferably between about 100: 1 to about 2: 1, more preferably between about 50: 1 to about 2: 1, and most preferably between about 25: 1 to about 2: 1. When fluorinated surfactants are used, in particular high polysiloxanes, the proportion of spreading agent is effective due to the action of those surfactants. Thus, ratios greater than 1000: 1 may be used.

References which describe suitable silicone fluids include US-A-2826551, Geen; US-A-3964500, Drakoff, published 1979, 6.22; US-A-4364837, Pader and GB-A-849433 Woolston and "silicon compounds" published by Petrarch Systems inc.1984 (which provides A large, although not complete, list of suitable polysiloxane fluids).

An optional ingredient included in the silicone hair and/or skin conditioning agents is a silicone resin. Polysiloxane resins are highly crosslinked polymeric siloxane systems. Crosslinking is produced by incorporating trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during the preparation of the polysiloxane resin. As is well known in the art, the degree of crosslinking required to produce a silicone resin varies with the particular silane units incorporated into the silicone resin. Generally, the silicone materials have a sufficient amount of trifunctional and tetrafunctional siloxane monomer units (and thus a sufficient amount of crosslinking) so that they dry into a rigid or hard film known as a silicone resin. The ratio of oxygen atoms to silicon atoms represents the amount of crosslinking in a particular polysiloxane material. Silicone materials having at least about 1.1 oxygen atoms per silicon atom are generally referred to herein as silicone resins. Preferably, the ratio of oxygen atoms to silicon atoms is at least about 1.2: 1.0. Silanes used in the preparation of silicone resins include monomethyl, dimethyl, trimethyl, monophenyl, diphenyl, methylphenyl, monovinyl, methylvinyl-chlorosilane, and tetrachlorosilane, with methyl-substituted silanes being most commonly used. Preferred resins are GESS4230 and SS4267 supplied by General Electric. Commercially available silicone resins are usually supplied in dissolved form as low viscosity volatile or nonvolatile silicone fluids. It will be apparent to those skilled in the art that the silicone resins useful in the present invention are provided and incorporated into the compositions of the present invention in dissolved form as described above. Background material on polysiloxanes includes a discussion of polysiloxane fluids, gums and resins, and methods of preparing polysiloxanes, see encyclopedia of Polymer Science and Engineering, Vol.15, second edition, p.204-308, John Wiley&Sons, Inc., 1989.

Silicone materials and silicone resins are conveniently identified according to the shorthand nomenclature system, which is well known to those skilled in the art as the "MDTQ" nomenclature. Under this system, the polysiloxane is described in terms of various siloxane monomer units in its constituent. Briefly, the symbol M represents a monofunctional unit (CH)₃)₃SiO₅(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 first unit symbols such as M ', D', T 'and Q' represent substituents other than methyl, and must be specifically defined in each case. Typical switchable substituents include, for example, vinyl, phenyl, amine, hydroxyl, and the like. The molar ratios of the various units, whether subscripts to the symbols indicating the total number of each unit (or average number thereof) in the silicone or specific ratios in combination with molecular weight, are described for the silicone materials under the MDTQ system. Greater moles of T, Q, T ' and/or Q ', D, D ', M andand/or M' represents a higher degree of crosslinking. However, as noted above, the overall level of crosslinking is also expressed in terms of the ratio of oxygen to silicon.

The silicone resins used in the present invention are preferably MQ, MT, MTQ, MDT and MDTQ resins. Thus, the preferred polysiloxane substituent is methyl. Particularly preferred are MQ resins, wherein M: Q is from about 0.5: 1.0 to about 1.5: 1.0, the average molecular weight of the resin being from about 1000 to about 10000.

When used, the weight ratio of non-volatile silicone fluid having a refractive index of less than 1.46 to silicone resin component is preferably from about 4: 1 to about 400: 1, preferably from about 9: 1 to about 200: 1, more preferably from about 19: 1 to about 100: 1, especially when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as described above. Since the silicone resin component is part of the same phase in the silicone fluid composition, i.e., the conditioning active, the total amount of fluid and resin should be included in the amount determined for the conditioning agent of the composition.

Fatty alcohols

Fatty alcohols suitable for use as hair/skin conditioning agents in the present invention have the general formula R-OH, wherein R is a straight or branched chain hydrocarbyl group, preferably a straight chain containing from about 8 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms. It is to be understood that any particular carbon chain length is defined, such as C₁₆Are averages and thus may contain specific ratios of longer and shorter carbon chains as a direct function of their synthesis. Suitable fatty alcohols for use in the present invention include cetyl alcohol (trade name CO-1695(TN), available from Procter and Gamble Ltd. and Laurex16(TN) available from Albright and Wilson Ltd.); and stearyl alcohol (commercially available under the trade designation CO1895(TN) from Procter and Gamble ltd. and Laurex18(TN) from Albright and wilson ltd.).

Water-soluble resin

Additional conditioning agents suitable for use in the present invention are water soluble resins having a molecular weight in the range of about 8000 to about 2000000. Water-soluble, as used herein, means that the material is sufficiently soluble in water at a concentration of about 0.1% by weight therein at about 25 c to form a substantially clear solution to the naked eye. The water-soluble resins useful as conditioning agents in the present invention are nonionic polyethylene glycol polymers having the general formula:

H(OCH₂CH₂)_nOH

wherein n is the average value of ethoxylation and ranges from about 1000 to about 25000, preferably from about 10000 to about 20000. Nonionic resins suitable for use in the present invention include narrow molecular weight distribution PEG14M (available from Amerchol under the tradename PolyoxWSRN3000(TN)) and broad molecular weight PEG2M (available from Amerchol under the tradename PolyoxWSRN10 (TN)).

Esters of polyhydroxy carboxylic acids

Suitable for use herein as conditioning agents are liquid polyhydroxy carboxylic acid esters. These polyhydroxy esters are derived from a polyhydroxy compound and one or more carboxylic acids. In other words, these esters contain a portion of the polyol and a portion or portions from the carboxylic acid. These carboxylic acid esters are also referred to as liquid polyhydroxy fatty acid esters, since carboxylic acids and fatty acids are often used interchangeably by those skilled in the art. As used in accordance with the present invention, the term liquid refers to a fluid that is visually flowable (to the naked eye) at ambient conditions (about 1 atmosphere at about 25 ℃).

Liquid polyhydroxy polyesters suitable for use in the present invention include polyols, particularly sugars, sugar alcohols or sugar ethers, which are esterified with at least two fatty acid groups. However, the polyol starting material preferably has at least about 4 esterifiable hydroxyl groups. Examples of preferred polyols are sugars, including mono-and disaccharides, sugar alcohols or sugar ethers. Examples of monosaccharides containing 4 hydroxyl groups are xylose and arabinose and sugar alcohols from xylose, which have 5 hydroxyl groups, i.e. xylitol. The monosaccharide erythrose is also suitable for use in the present invention because it contains three hydroxyl groups, as well as sugar alcohols derived from erythrose, i.e., erythritol containing 4 hydroxyl groups. Suitable monosaccharides having 5 hydroxyl groups are galactose, fructose and sorbose. Sugar alcohols derived from sucrose and hydrolysates of glucose and sorbose containing 6 hydroxyl groups, such as sorbitol, are also suitable. Examples of disaccharide polyols that can be used include maltose, lactose and sucrose, all of which contain 8 hydroxyl groups. In addition, sugar ethers are also suitable for use in the present invention, such as sorbitan.

The polyol used in the liquid polyhydroxy ester preferably has from about 4 to about 12 hydroxyl groups, more preferably from about 4 to about 11 hydroxyl groups, and most preferably from about 4 to about 8 hydroxyl groups. Preferred polyols suitable for use in the preparation of the polyesters of the present invention are selected from erythritol, xylitol, sorbitol, glucose and sucrose. Particularly preferred is sucrose.

Preferred polyhydroxy starting materials having at least 4 hydroxyl groups must be esterified on at least two hydroxyl groups with fatty acids containing from about 8 to about 22 carbon atoms, preferably from about 8 to about 14 carbon atoms. Examples of such fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, arachidonic acid, behenic acid, and erucic acid. The fatty acid is derived from natural or synthetic fatty acid; they may be saturated or unsaturated and include positional and geometric isomers. However, in order to provide a liquid polyester suitable for use in the present invention, at least about half of the fatty acids incorporated into the polyester molecule must be unsaturated fatty acids, saturated short chain fatty acids, or mixtures thereof.

Liquid polyhydroxy fatty acid polyesters suitable for use as conditioning agents in the present invention must contain at least two fatty acid ester groups. It is not necessary that all of the hydroxyl groups of the polyol be esterified with fatty acids, but it is preferred that the polyester contain no more than two unesterified hydroxyl groups. Most preferably, substantially all of the hydroxyl groups of the polyol are esterified with the fatty acid, i.e., the polyol portion is substantially fully esterified. The fatty acids esterified with the polyol molecules may be the same or mixed, but as noted above, a substantial amount of unsaturated acid ester groups and/or saturated short chain acid ester groups must be present to provide fluidity.

To illustrate the above, sucrose di-fatty acid ester may be suitable, but is not preferred because it has more than two unesterified hydroxyl groups. Sucrose hexafatty acid ester is preferred because it has no more than two unesterified hydroxyl groups. Most preferred compounds have all of the hydroxyl groups esterified with fatty acids, including liquid sucrose octa-substituted fatty acid esters.

The following are non-limiting examples of specific liquid polyhydroxy fatty acid polyesters containing at least two fatty acid ester groups suitable for use in the present invention: glucose dioleate, glucose diester of soybean oil or cottonseed oil fatty acid (unsaturated), mannose diester of mixed soybean oil or cottonseed oil fatty acid, galactose diester of oleic acid, arabinose diester of linoleic acid, xylose dilinoleate, sorbitol dioleate, sucrose dioleate, glucose trioleate, glucose triester of soybean oil or cottonseed oil fatty acid (unsaturated), mannose triester of mixed soybean oil or cottonseed oil fatty acid, galactose triester of oleic acid, arabinose triester of linoleic acid, xylose trioleate, sorbitol trioleate, sucrose trioleate, glucose tetraoleate, glucose tetraester of soybean oil or cottonseed oil fatty acid (unsaturated), mannose tetraester of mixed soybean oil or cottonseed oil fatty acid, galactose tetraester of oleic acid, arabinose tetraester of linoleic acid, glucose tetraester of mixed soybean oil or cottonseed oil fatty acid, glucose tetraester of fatty acid (unsaturated), glucose tetraester of oleic acid, glucose tetraester of linoleic acid, glucose tetraester of mixed soybean oil or cottonseed oil fatty acid, Xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, sorbitol hexaester of unsaturated soybean oil or cottonseed oil fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate and mixtures thereof.

Preferred liquid polyol polyesters of the present invention have a complete melting point of less than about 30 c, preferably less than about 27.5 c, and more preferably less than about 25 c. The complete melting point of the present invention is measured by Differential Scanning Calorimetry (DSC). The term "complete melting point" refers to a melting point measured by a known technique of Differential Scanning Calorimetry (DSC). The complete melting point is the temperature at which the baseline, i.e., the hotline, intersects the trailing edge tangent of the endothermic peak. In the present invention, when measuring the complete melting point, the scanning temperature generally used is 5 deg.C/min. Techniques for measuring the complete melting point are described more fully in US-A-5306514 (Letton et al, 26/4 of 1994).

Typical liquid polyhydroxycarboxylic acid esters suitable for use in the present invention are poly sucrose soyate or poly sucrose cottonseed oil fatty acid esters, available from Procter and Gamble.

The polyhydroxy fatty acid polyesters suitable for use in the present invention can be prepared by a variety of methods known to those skilled in the art. These methods include: transesterification of a polyol or a glycerin fatty acid ester having a methyl group or an ethyl group with various catalysts; acylation of the polyhydroxy compound with fatty acid chloride; acylation of the polyol with a fatty acid anhydride; acylation of the polyol with a fatty acid; see US-A-3463699(Rizzi, 15.6.1976); US-A-4517360 and 4518772(Volpenhein 1985). The liquid polyhydroxycarboxylic acid conditioning agents suitable for use in the present invention are biodegradable.

Cationic polymers

Cationic cellulose-derived polymeric materials suitable for use as conditioning agents in the present invention include materials having the general formula:

A-O(-R-N+R₁R₂-R₃-M)

wherein a is a cellulose anhydroglucose residue; r is alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene and mixtures thereof; r₁、R₂And R₃Respectively, alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms,total number of carbon atoms per cationic moiety (i.e., R)₁、R₂And R₃Total number of carbon atoms) of about 20 or less; m is an anionic counterion as described above.

Suitable cationic cellulosic polymers for use in the present invention have a molecular weight of from about 400000 to about 1500000, preferably from about 500000 to about 1500000, most preferably from about 800000 to about 1200000, a charge density of from about 0.6 to about 3meq./gr., preferably from about 0.7 to about 2.0meq./gr., most preferably from about 0.9 to about 1.5 meq./gr.. Cationic cellulose is availablefrom the polymer jr and LR series of amerchol corp. (Edison, NJ, USA) as a salt of hydroxyethyl cellulose reacted with trimethylammonium substituted epoxide, known in the industry (CTFA) as Polyquaternium 10.

The water-soluble cation of the present invention may be dissolved in the shampoo composition, or may be dissolved in a complex coacervate phase formed by the cationic polymer and the anionic surfactant in the shampoo composition. Complex coacervates of cationic polymers may also be formed with other optional anionic components of the shampoo composition.

Insoluble oil

The compositions of the present invention may also comprise as conditioning agent an insoluble perfume or cosmetic oil or wax or mixtures thereof, in an amount of up to about 10%, preferably about 3% by weight. By insoluble oil or wax as used herein is meant that they are insoluble in the product matrix at 25 ℃.

Suitable insoluble cosmetic oils and waxes for use as conditioning agents in the present invention include: c₈-C₃₀C of fatty acid₁-C₂₄Esters such as isopropyl myristate, myristyl myristate and cetyl ricinoleate, C of benzoic acid, beeswax, saturated and unsaturated fatty alcohols such as behenyl alcohol₈-C₃₀Esters, hydrocarbons such as mineral oil, petrolatum squalane and squalene, polybutene, fatty sorbitan esters (see US-A-3988255, Seiden, 26.10.1976), lanolin and oil-like lanolin derivatives, animal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, rice bran oil, linseed oil, jojobA oil, apricot kernel oil, walnut oil, palm nut oil, pistachio nut oil, sesame seed oil, rapeseed oil, cade oil, corn oil, peach kernel oil, poppy seed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, glucose seed oil and sunflower seed oil, and C of dimer acids and trimer acids₁-C₂₄Esters such as diisopropyl dimer acid ester, diisostearyl maleate ester, diisostearyl dimer acid ester, and triisostearyl trimer acid ester, and mixtures thereof.

Oil-derived materials

The compositions of the present invention may contain oil-derived compoundsMixtures of physical or oil derived conditioning agents. Suitable oil-derived conditioning agents for use in the present invention include water-soluble plant and animal-derived softeningAgents such as triglycerides with inserted polyethylene glycol chains, ethoxylated mono-and diglycerides, polyethoxylated lanolin and ethoxylated tallow derivatives. A preferred class of oil derived conditioning agents used has the general formula:

wherein n is from about 5 to about 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and wherein R comprises an aliphatic residue having an average of from about 5 to about 20 carbon atoms, preferably from about 7 to about 18 carbon atoms.

Such suitable ethoxylated oils and fats include the following polyethylene glycol derivatives: glyceryl cocoate (glyceryl cocoate), glyceryl caproate, glyceryl caprylate, glyceryl tallate, glyceryl palmitate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, and glyceryl fatty esters derived from triglycerides such as palm oil, almond oil, and corn oil, preferably glyceryl tallate and glyceryl cocoate.

Such suitable oil derived conditioning agents are from the crovol (TN) series of crovol ep40(PEG20 evening primrose glyceride evolving primrose), crovol ep70(PEG60 evening primrose glyceride evolving primrose), crovol a-40(PEG20 almond glyceride), crovol a-70(PEG60 almond glyceride), crovol m-40(PEG20 corn glyceride),crovol m-70(PEG60 corn glyceride), crovol-40 (PEG12 palm kernel glyceride), crovol pk-70(PEG45 palm kernel glyceride), and their solan (TN) feedstocks such as SolanE, E50 and X polyethoxylated lanolin and Aqualose L-20 (PEG 63637) from stroklanolin (PEG 24W and Aqualose 2) (PEG 15). Further suitable surfactants are the Varonic LI (TN) series of surfactants available from Sherex chemical Co. (Dublin, Ohio, USA), and the Rewoderm (TN) series of compounds from Rewo. Examples include Varonic LI48 (polyethylene glycol (n =80) glyceryl tallowate, also known as PEG80 glyceryl tallowate), Varonic LI 2(PEG28 glyceryl tallowate), Varonic LI 420(PEG200 glyceryl tallowate), Varonic LI 63 and 67(PEG30 and PEG80 glyceryl cocoate), Rewoderm LI 5-20(PEG-200 palmitate), Rewoderm LI S-80(PEG-200 palmitate and PEG-7 glyceryl cocoate), Rewoderm LIS-75(PEG-200 palmitate and PEG-7 glyceryl cocoate), and mixtures thereof. Other oil-derived emollients that are suitable for use are PEG derivatives of corn, avocado and babassu oils and Softigen767(TN) (PEG (6) capric/caprylic glycerides).

Conditioners also suitable for use in the present invention are derived from complex vegetable fats extracted from the fruit of the shea butter (Butyrospermum Karkii Kotschy) and their derivatives. This vegetable fat, known as shea butter, is widely used in various ways in medium to non, such as making soap and as a skin cream, which is sold by Sederma (78610 Le per En levels, france). Particularly suitable are ethoxylated derivatives of shea butter, Lipex (tn) chemicals from karlsham Chemical Co. (Columbos, Ohio, USA), such as Lipex 102E-75 and Lipex 102E-3 (ethoxylated mono-and diglycerides of shea butter), and crovol (tn) series substances from Croda Inc. (new york, USA) such as crovol sb-70 (ethoxylated mono-and diglycerides of shea butter). Briefly, ethoxylated derivatives of mango, cocoa and eastern gymnospermaceae plant butters may be used as conditioners in the compositions of the present invention. Although these materials are classified as ethoxylated nonionic materials, it is understood that non-ethoxylated vegetable oils or fats may be present in specific proportions.

Other suitable oil derived hair and/or skin conditioning agents include ethoxylated derivatives of the following oils: almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, apricot kernel oil, walnut oil, palm nut oil, pistacia species oil, sesame seed oil, rapeseed oil, juniper oil, corn oil, peach kernel oil, poppy seed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grape seed oil, and sunflower seed oil.

Oil derived hair and/or skin conditioning agents most preferably used in the present invention include Lipex102-3(TN) (ethoxylated derivative of PEG-3 shea butter) and Softigen767(TN) (PEG-6 capric/caprylic glycerides).

Setting agent

Shampoo compositions of the invention may contain one or more styling agents as additional cosmetic agents. Styling agents suitable for use in the present invention are a class of materials that help the user retain a particular shape of the hair after using the shampoo.

The hair styling agents suitable for use in the present invention are selected from a variety of resins and gums. Styling agents preferred for use in the present invention include shampoo-compatible polymers, which are typically homopolymers or copolymers of hydrophobic monomers. In addition, the hydrophilic polymer used as a styling agent in the present invention may be a copolymer of a hydrophilic monomer and a hydrophobic monomer or a mixture thereof. Examples of composite polymer systems are described in US-A-3222329, US-A-3577517, US-A-4272511 and US-A-4196190. Examples of block polymer systems are described in U.S. Pat. No. 3, 3907984, U.S. Pat. No. 3, 4030512 and UA-A-4283384.

Pharmaceutically active substances

To provide additional benefits to the hair and/or skin, pharmaceutical actives useful in the compositions of the present invention include anti-lice actives, antibiotics, anti-inflammatory actives, and anti-dandruff actives. The pharmaceutical actives described herein include pharmaceutical and pharmaceutical actives.

Particulate anti-dandruff actives

The shampoo compositions may contain as a pharmaceutically active substance one or more particulate anti-dandruff agents. For controlling dandruff on the scalp, an anti-dandruff active is used in a safe dose and is effective. For example, particulate anti-dandruff agents include sulfur, selenium sulfide and pyrithione salts. Preferred are heavy metal salts of 1-hydroxy-2-pyridinethione and selenium disulfide. The particulate anti-dandruff agent is in crystalline form and is insoluble in the composition. Generally, particulate anti-dandruff agents are used in amounts of from about 0.1% to about 5%, preferably from about 0.3% to about 5%, by weight of the composition. The particular amount used is not critical as long as an effective amount to control dandruff is used when the composition is used in a conventional manner for skin or hair cleansing.

Selenium sulphide is a major commodity. Generally, selenium sulfide is considered to be a compound of one mole of selenium and two moles of sulfur. However, it may also be in the form of a cyclic structure Se_xS_yWherein x + y = 8. US-A-2694668(Baldwin et al, published 16.11.1954), US-A-3152046(Kapral, published 10.6.1984), US-A-4089945(Brinkman, published 16.5.1978), US-A-4885107(Wetzel, published 12.12.1989) disclose selenium disulfide as an active ingredient in anti-dandruff shampoo compositions.

The selenium sulfide (selenium disulfide) preferably averages less than about 15 μ, more preferably less than about 10 μ. These measurements are determined using a forward laser light scattering device (e.g., a Malvern3600 instrument). Selenium sulfide, if used, is typically present in shampoo compositions of the invention in an amount of from about 0.1% to about 5.0%, preferably from about 0.3% to about 2.5%, more preferably from about 0.5% to about 1.5% by weight of the composition.

Preferred pyrithione anti-dandruff agents are water insoluble salts of 1-hydroxy-2-pyridinethione. Preferred salts are formed from heavy metals, such as zinc, tin, cadmium, magnesium, aluminum and zirconium. The most preferred metal is zinc. The most preferred active is the zinc salt of 1-hydroxy-2-pyrithione, often referred to as Zinc Pyrithione (ZPT). Other cations such as sodium are also suitable. Such anti-dandruff agents are known in the art. 1-hydroxy-2-pyridinethione salts for use in anti-dandruff shampoos are disclosed in US-A-2809971(Bemstein, published 10/15/1957); US-A-3236733(Karsten et al, 1966, 2 month 22); US-A-3753196(Parran, published 1973, 8/21); US-A-3761418(Parran, published 1973, 25.9); US-A-4345080(Bolich, published 1982, 8.17); US-A-4323683(Bolich et al, published 1982, 6.4.9); US-A-4379753(Bolich, published 1983, 12.4 months); US-A-4470982(Winkler, published 1984, 9/11). Particularly preferred are 1-hydroxy-2-pyridinethione salts in platelet form, wherein the particles have an average size of up to about 20 microns, preferably up to about 8 microns, more preferably up to about 5 microns.

The pyrithione salts are generally used in amounts of from about 0.1% to about 3%, preferably from about 0.3% to about 2%, by weight of the shampoo composition.

Other particulate anti-dandruff actives include sulfur. Generally, sulfur is used as an anti-dandruff agent in an amount of from about 1% to about 5%, more preferably from about 2% toabout 5%, by weight of the composition.

Diamine dimer acid component

As another important feature, the compositions of the present invention include a diamine dimer acid component and/or salts thereof. The dimer acids described herein are diacids, triacids and tetraacids and their salts, preferably diacids. Diamine dimer acids and/or salts thereof can improve hair volume, shine, foam volume and ease of rinsing.

Diamine dimer acids suitable for use herein include any diamine dimer acid that improves foam volume and/or hair shine and/or ease of rinsing in a shampoo composition.

Diamine dimer acids suitable for use in the present invention may be synthesized, for example, by reacting a diamine with an anhydride. The diamine starting material for the preparation of diamine dimer acid comprises a diamine having the general formula:

R₁R₂N-(CH₂)_n-NR₃R₄

wherein R is₁、R₂、R₃And R₄Selected from hydrogen and C₁To C₄Alkyl or alkenyl, preferably wherein R₁And R₃Is hydrogen, more preferably R₁、R₂、R₃And R₄Is hydrogen; n is an integer from 1 to 8, preferably from 2 to 4, in particular 2. Preferred diamines for use in the present invention include 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, with 1, 2-ethylenediamine being particularly preferred. As noted above, any anhydride capable of reacting with a diamine to form a diamine dimer acid may be used in the present invention. A typical anhydride suitable for use in the present invention is maleic anhydride.

Diamine dimer acids suitable for use in the present invention may also be synthesized, for example, by reacting A diacid with A dihalogen-substituted hydrocarbyl group under basic conditions (e.g., sodium hydroxide solution at A pH of about 11.2) as disclosed in WO-A-95/12570, WO-A-96/01803, WO-A-96/01802, and US-A-5466867. Suitable diacid starting materials for use in the present invention include amino acids (or salts thereof) such as L-aspartic acid. The dihalo-substituted hydrocarbyl groups suitable for use in the present invention have the general formula:

X-(CH₂)_n-Y

wherein X and Y are halogen, e.g. Br, Cl, preferably both X and Y are Br or Cl; n is a number from 2 to about 8, preferably from 2 to 6, more preferably from 2 to 4. Typical dihalogen substituted hydrocarbyl groups suitable for use in the present invention include ethylene dibromide and ethylene dichloride.

The dimer acid of the diamine dimer acids preferably used in the present invention is a diacid, preferably a diacid having a hydrocarbyl chain length of from about 3 to about 10 carbon atoms, more preferably from about 4 to about 6 carbon atoms, and most preferably about 4 carbon atoms. Typical diamine dimer acids from diacids suitable for use in the present invention include ethylene diamino disuccinic acid (EDDS), ethylene diamine diaminetetraglutaric acid (EDDG) and 2-hydroxypropanediamine disuccinic acid (HPDDS), which is disclosed in U.S. patent application 08/026884.

Most preferred for use in the present invention is ethylenediamine disuccinic acid (EDDS). Preferred EDDS compounds for use in the present invention are in the free acid form and in the sodium or magnesium salt form thereof. Typical examples of preferred sodium salts of EDDS include Na₂EDDS and Na₃EDDS。

Most preferably, a sodium complex is included in shampoo compositions of the invention. These complexes may be added to the composition in the form described above, or may be added during the process of preparing the composition by means of an inert sodium salt such as NaCl or Na₂SO₄With an EDDS compound added as an acid or as a salt or complex. When EDDS compounds are added with inert sodium salts during the preparation, the molar ratio of sodium to EDDS is preferably greater than 1: 1, preferably greater than 3: 1, in order to ensure the formation of the desired sodium complex.

The structure of the EDDS acid form is shown below:

EDDS can be synthesized, for example, from readily available and inexpensive raw materials such as maleic anhydride and ethylenediamine, as shown below:

a more detailed description of the process for the synthesis of EDDS from commercially available starting materials is found in US-A-3158635(Kezerian and Ramsay, 11.24.1964).

The synthesis of EDDS from maleic anhydride and ethylenediamine results in a mixture of three optical isomers, [ R, R], [ S, S]and [ S, R], due to two asymmetric carbon atoms. The biodegradation of EDDS is optical isomer specific and the [ S, S]isomer is degraded most rapidly and completely.

[ S, S]of EDDS]Isomers can be synthesized from L-aspartic acid and 1, 2-dibromoethane as follows:

more details of the reaction of L-aspartic Acid with 1, 2-dibromoethane to form the [ S, S]isomer of EDDS are found in Stereospermic Ligands and theory Complexes of ethylene-disuccinic Acid, Inorganic Chemistry, Vol.7 (1968), et al, pages 2405-2412, by neutral and Rose.

EDDS can also be prepared fermentatively with the strain Actinomycetes (MG417-CF17), preferably inhibited with phospholipase C&D, as described in inst. micro. chem. tokyo,141, japan.

A preferred form of EDDS suitable for inclusion in the present invention is an aqueous solution of EDDS [ S, S]isomers neutralized with sodium hydroxide, wherein about 30% of the EDDS is the free acid, wherein the EDDS complex is present as the trisodium salt, and forms at least about 95% of the total aminocarboxylate. The amine carboxylate is available from PalmerResearch Laboratories, a division of Association Octel.

The total amount of diamine dimer acid present in the compositions of the present invention is from about 0.001% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.5% to about 3%, and especially preferably from about 1% to about 3% by weight. In the most preferred embodiment, the amount of diamine dimer acid component is at least about 0.5%, preferably at least about 1% by weight.

We have found that compositions comprising a specific amount and ratio of surfactant system and diamine dimer acid in combination with a cosmetic and/or pharmaceutical active can further improve post-shampoo properties such as rinsability, shine and volume. Such compositions provide particularly good rinse-off, hair shine and volume characteristics in specific compositions, i.e., wherein the ratio of total surfactant to diamine dimer acid is from about 40: 1 to about 5: 1, preferably from about 30: 1 to about 10: 1.

According to another aspect of the present invention there is provided a shampoo composition comprising:

(a) from about 1% to about 60% by weight of a water soluble surfactant selected from the group consisting of anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof;

(b) from about 0.001% to about 10% by weight of a cosmetic and/or pharmaceutical active;

(c) from about 0.001% to about 10% by weight of a diamine dimer acid component and/or salt thereof; and

(d) and (3) water.

Wherein the ratio of (a) to (c) is from about 40: 1 to about 5: 1.

Suspending agent

The compositions of the present invention include a crystal suspending agent. Other suspending agents useful as suspension conditioners (or other materials) and thickening compositions may also optionally be used. The purpose of the crystalline suspending agent is to aid in suspending an emulsion of the dispersed phase fluid conditioning agent or other particulate material or insoluble fluid in the shampoo composition and to impart pearlescence to the product.

An effective amount of a crystalline suspending agent is used to suspend the conditioner or particulate anti-dandruff agent (if present). Generally, the suspension should be stable for at least one month at ambient temperature. Preferably, the shelf life is longer, e.g., at least three months, preferably 6 months, and most preferably at least about 24 months. Typically, the compositions of the present invention comprise from about 0.5% to about 10% by weight of a crystal suspending agent or mixtures thereof. The crystalline suspending agent is preferably present in shampoo compositions of the invention in an amount of from about 0.5% to about 5%, more preferably from about 1% to about 4%, and most preferably from about 1% to about 3% by weight.

Preferred crystalline suspending agents are acyl derivatives and amine oxides, especially acyl derivatives, especially those which are soluble in the mixed solution and then crystallise on cooling. These materials contain long chains (e.g., C)₈-C₂₂Preferably C₁₄-C₂₂More preferably C₁₆-C₂₂) Aliphatic groups, i.e. long chain acyl derivatives and long chain amine oxides and mixtures thereof. Including glycol long chain esters, alkanolamides of long chain fatty acids, long chain esters of long chain fatty acids, glyceryl long chain esters, long chain esters of long chain alkanolamides, long chain alkyl dimethyl amine oxides, and mixtures thereof.

Examples of crystalline suspending agents are described in US-A-4741855 (Grote and Russell, published 3.3.3.1988). Suitable suspending agents for use in the present invention include ethylene glycol esters of fatty acids, preferably having from about 14 to about 22 carbon atoms, more preferably 16 to 22 carbon atoms. Ethylene glycol stearates, mono-and distearates are more preferred, but distearates containing less than about 7% mono stearate are particularly preferred. Other suspending agents include alkanolamides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably from about 16 to 18 carbon atoms. Preferred alkanolamides are stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide, and stearic monoethanolamide stearate polyethylene glycol fatty esters having from about 16 to about 22 carbon atoms up to 7 ethyleneoxy units, preferably ethylene glycol stearate, both monostearate and distearate, but it is particularly preferred that the distearate contain less than about 7% of monostearate, alkanolamides of fatty acids having from about 16 to about 22 carbon atoms, preferably from about 16 to 18 carbon atoms, such as stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide, and stearic monoethanolamide. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanolamides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate). In addition to the preferred materials described above, there are also useful as suspending agents ethylene glycol esters of long chain carboxylic acids, long chain amine oxides and alkanolamides of long chain carboxylic acids.

Suspending agents also include long chain amine oxides, e.g. alkyl (C)₁₆-C₂₂) Dimethyl amine oxides, such as stearyl dimethyl amine oxide. If the composition contains amine oxides or long-chain acyl derivatives as surfactants, the suspending action can also be provided by these amine oxides or acyl derivatives without the need for additional suspending agents, provided that at least some of them are present in crystalline form.

Other long chain acyl derivatives that may be used include N, N-dihydrocarbyl (C)₁₂-C₂₂Preferably C₁₆-C₁₈) Aminobenzoic acids and their soluble salts (e.g. Na and K salts), especially N, N-di (C)₁₆-C₁₈And hydrogenated tallow) amidobenzoic acid, which are commercially available from Stepan corporation (Northfield, Illinois, USA).

Other suitable suspending agents include fatty alcohols or fatty acid materials having from about 12 to about 22 carbon atoms. Suitable fatty acid or fatty alcohol thickeners include Laurex NC (TN) (C12/14 fatty alcohol) from Albright and Wilson and Prifac7908(TN) (palm kernel fatty acid) from Unichema. Also suitable for use in the present invention are fatty acid esters of glucosides, such as PEG120 methyl glucoside dioleate (trade name glucimate DOE 120(TN), available from Amercol).

Crystalline suspending agents are incorporated into shampoos by dissolving the suspending agent in a solution containing water and surfactant at a temperature above the melting point of the suspending agent. The suspending agent is then recrystallized, typically by cooling the solution to a temperature sufficient to cause crystallization.

Optional suspending agents thickeners and viscosity modifiers, and the like, when used, are generally present in an amount of from about 0.01% to about 10%, most preferably from about 0.02% to about 5.0% by weight of the total composition. In general, the content of optional suspending agents and other viscosity modifiers should preferably be as low as possible to achieve the effect imparted by the substance added.

Optional suspending agents that may be used include polymeric thickeners such as carboxyvinyl polymers. Preferred carboxyvinyl polymers include acrylic acid/ethyl acrylate copolymers and carboxyvinyl polymers sold under the trade name Carbopol resin by b.f. goodrich company, for example, acrylic acid copolymers crosslinked with polyallyl sucrose (described in US-A-2798053, Brown, published 1957, month 7, 2). These copolymers are available from b.f. goodrich company, for example, carbopol (tn)934,940,941 and 956. These resins consist essentially of colloidal water-soluble polyalkenyl polyether cross-linked acrylic acid polymer cross-linked with 0.75% to 2.00% of a cross-linking agent such as polyallyl sucrose or polyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934 is a water-soluble acrylic polymer crosslinked about 1% of a sucrose polyalkyl ether having an average of about 5.8 allyl groups per sucrose molecule. Also suitable for use in the present invention are hydrophobically modified cross-linked acrylic polymers having amphiphilic character commercially available under the tradenames Carbopol 1382, Carbopol 1342 and Pemulen TR-1(CFTA definition: acrylate/alkyl 10-30 acrylate cross-linked polymers). Also suitable for use herein are polyalkenyl polyether crosslinked acrylic polymers and hydrophobically modified crosslinked acrylic polymers.

Carboxyvinyl polymers are copolymers of a monomer mixture comprising monomeric ethylenically unsaturated carboxylic acids and from about 0.01% to about 10% by weight based on the total weight of the monomers of a polyether polyol having at least 4 carbon atoms bonded to at least 3 hydroxyl groups and having at least more than 1 alkenyl group attached to each polyether molecule. Other mono-olefinic monomer species may even be present in the monomer mixture in a major amount, if desired. Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable when exposed to air.

Preferred polyols for preparing the carboxyvinyl polymer include polyols selected from the group consisting of: oligosaccharides, and their reduced derivatives in which the carbonyl group is converted to an alcohol group, and pentaerythritol; more preferred are oligosaccharides, most preferred is sucrose. Preferably, the hydroxyl groups of the polyol are modified with allyl ether groups, having at least two allyl ether groups per polyol molecule. When the polyol is sucrose, it is preferred to have at least about 5 allyl ether groups per sucrose molecule. Preferably, the polyether of the polyol comprises from about 0.01% to about 4% of the total monomers, more preferably from about 0.02% to about 2.5%.

Preferred monomeric ethylenically unsaturated carboxylic acids useful in the preparation of the carboxyvinyl polymers used in the present invention include monomeric, polymerizable, monoethylenically unsaturated lower aliphatic carboxylic acids of α - β, more preferably monoalkenylacrylic acids which are monomers of the following structure (XIII):

wherein R is a substituent selected from the group consisting of hydrogen and lower alkyl; most preferred is acrylic acid.

Preferred carboxyvinyl polymers for use in the formulations of the present invention are those having a molecular weight of at least about 750000, more preferably having a molecular weight of at least about 1250000, and most preferably having a molecular weight of at least about 3000000.

Other materials may also be used as selective suspending agents, including materials that impart a gelatinous viscosity to the composition, for example, water soluble or colloidally water soluble polymers such as cellulose ethers (e.g., hydroxyethyl cellulose), guar gum, polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl guar gum, starch and starch derivatives and other thickeners, viscosity modifiers, gelling agents, and the like. Mixtures of these materials may also be used.

Another suspending agent that may be used is xanthan gum. Shampoo compositions using xanthan gum as A suspending agent for silicone hair conditioning components are described in US-A-4788006(Bolich and Williams, 11.29.1988). Xanthan gum is a commercially available biosynthetic gum. It is a heteropolysaccharide with a molecular weight greater than 1 million. It is believed to contain D-glucose, D-mannose and D-glucuronic acid in a molar ratio of 2.8: 2.0. The polysaccharide was partially acetylated with 4.7% acetyl groups. Data and Their details are given in Whistler, Roy L.Editor Industrial guidelines-Polysaccharides and Their Derivatives New York: Academic Press, 1973. Kelco, a Division of Merck&co, inc. When used as a suspending agent for silicone hair conditioning components, the xanthan gum is typically present in the formulation of a flowable liquid in an amount of from about 0.02% to about 3%, preferably from about 0.03% to about 1.2% by weight of the composition of the present invention.

Optional ingredients

Various other optional ingredients are described herein. Typical components are described below.

Thickening agent

Shampoo compositions of the invention may additionally comprise one or more thickening agents in a total amount of from about 0.1% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.5% to about 3% by weight.

Nonionic water-soluble cellulose ethers may be used in the compositions of the present invention as thickeners, and widely used commercially available nonionic cellulose ethers include methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and ethyl hydroxyethyl cellulose. Particularly preferably used as thickeners are hydrophobically modified hydroxyethylcellulose raw materials. Commercially available for use in the present invention is NATROSOL PLUS Grade 330 CS (TN), which is a hydrophobically modified hydroxyethyl cellulose available from Aqualon Company, Wilmington, Delaware. The raw material has 0.4 to 0.8 wt% of C₁₆An alkyl substituent. The hydroxyethyl molar substitution of the feed is 3.0 to 3.7. Before modificationThe average molecular weight of the water-soluble cellulose is about 300,000. Another material is sold under the trade name NATROSOLPLUS CS Grade D-67(TN) by Aqualon Company, Wilmington, Delaware. The raw material contains 0.50-0.95 wt% of C₁₆And (4) substitution. The hydroxyethyl molar substitution of the feed is from 2.3 to 3.7. The average molecular weight of the water-soluble cellulose before modification was about 700,000.

The compositions of the present invention may also be based on urethane-based polyethylene glycol copolymer thickeners such as urethanesC₁-C₂₀Alkyl PEG copolymers (available under the trade name Acrosyl 44(TN) from Rohm and Haas). The urethane-based copolymer thickener can provide excellent thickening performance, improve foam characteristics and maintain a desired rinse feel.

The compositions of the present invention may also include nonionic or anionic polymeric thickening components, especially water-soluble polymeric materials, having a molecular weight greater than about 20000. By "water soluble polymer" is meant that the material forms a substantially clear solution at a concentration of 1% in water at 25 ℃, and that the material increases the viscosity of the water. Examples of water-soluble polymers to be used which can be used as additional thickening powders according to the invention are: hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone K-120, dextrins, such as Dextran purified grade 2P, available from D&O Chemicals, carboxymethyl cellulose, plant extracts, such as gum arabic, ghatti gum, and tragacanth gum, seaweed extracts, such as sodium alginate, propylene glycol alginate, and sodium carrageenan (sodium carrageenan). Preferred additional thickeners for the compositions of the present invention are natural polysaccharide materials. Examples of such materials are guar gum, locust bean gum and xanthan gum. Also preferred for use herein are hydroxyethyl celluloses having a molecular weight of about 700000.

The viscosity of the finished composition (Brookfield DV II + (or DV II), 1rpm, Cone CP41 or CP52,3 minutes, 26.7 ℃, neat) is preferably at least about 500CPs, more preferably from about 1000 to about 50000CPs, especially from about 2000 to about 30000CPs, and even more especially from about 2000 to about 8000 CPs.

Additional optional ingredients include, for example, preservatives such as sodium benzoate, DMDM hydantoin, benzyl alcohol, methyl paraben, propyl paraben, and imidazolidinyl urea; cationic conditioning agents including cationic conditioning surfactants and cationic conditioning polymers; quaternary polymeric foam boosters, such as Polyquaternium10, are preferably present in an amount of from about 0.01% to about 0.2% by weight of the composition; a fatty alcohol; block polymers of ethylene oxide and propylene oxide, such as pluronic f88(TN) available from BASF Wyandotte; sodium chloride, sodium sulfate; ammonium xylylenesulfonate; propylene glycol; polyvinyl alcohol; ethanol; PH adjusters such as sodium dihydrogen phosphate, disodium phosphate, citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, and the like; chelating agents, such as EDTA and the like in an amount of less than about 0.5% by weight of the composition; electrolytes such as magnesium sulfate; a fragrance; and a dye. These optional ingredients are generally used in amounts of about 0.01% to about 10% of the composition. The above-mentioned optional components are not absolute, and additional optional components may be used.

Water (W)

The compositions of the present invention comprise from about 20% to about 98.998% by weight water, preferably from about 50% to about 85%, more preferably from about 60% to about 85% by weight water.

The pH of the compositions of the present invention is critical and should be in the range of from 2 to about 10, preferably from about 4 to about 10, more preferably from about 6 to about 9, and most preferably from about 6.5 to about 8.5.

The present invention does not include detergent compositions for laundry operations, i.e., does not include conventional laundry detergent additives such as enzymes, brighteners, dye transfer inhibitors, and the like.

The invention is illustrated by the following non-limiting examples. In these examples, all concentrations are based on 100% active, and the abbreviations are defined as follows:

anion 1C₁₀Sodium alkyl sulfate (Empicolil LC35(TN) from Albright and

Wilson(A&W))

the anion 2 lauryl-3 ammonium sulfate (Empicoli EAC/TP (TN)) from A&W

The anion 3 ammonium lauryl sulfate (Empicoli AL30(TN) from A&W)

Narrow range anionic 4 sodium lauryl-3 sulfate (Genapol ZRO narrow range (TN) from

Hoecsht)

The zwitterion 1 Cocoamidopropyl hydroxy sultaine (Miritaine CBS (TN)) is obtained from

Rhone-Poulenc)

Zwitterionic 2-cocoamidopropyl dimethylcarboxymethylbetaine (as Tegobetane)

F (TN) from TH Goldschmidt)

Nonionic ethoxylated fatty alcohol (available as Dobanol 91-8(TN) from Shell)

EDDS ss ethylenediamine disuccinic acid (from palm Research Laboratories)

Conditioning agent 1 Dimethicone 40:60 (CF 1233 from GE Silicones)

Conditioning agent 2 cetyl alcohol (Laurex 16(TN) from A&W)

Conditioning agent 3 stearyl alcohol (Laurex 18(TN) from A&W)

Conditioning agent 4 hydroxyethyl cellulose containing epichlorohydrin and trimethylamine (Polymer LR-

400(TN)/Amerchol)

Conditioning 5 nonionic PEG14M resin (Polyox WSRN3000(TN) available from

Amerchol)

In addition to the above materials, the compositions of the present invention may additionally include thickening agents such as sodium chloride, and suspending agents such as ethyleneglycol distearate EGDS (Radi 72666(TN) available from Faci), as well as perfumes, dyes and other trace materials.

Examples I to XII

The following are cleansing compositions in the form of shampoos, which are non-limiting representatives of the invention:

IIIIIIVVVIIVIIVIIVIIVIIXIXII anion 1555-6-10-3 anion 2-10-1015-15 anion 3-5510-anion 45-5-6-12123 zwitterion 1-25-53-zwitterion 25-5-4655-36 nonionic 23-6-538 EDDS 2.00.81.21.71.55.03.02.50.754.00.251.5 conditioner 10.5-0.70.8-0.30.51.50.40.30.50.7 conditioner 20.10.50.10.150.3-0.4-0.1 conditioner 30.5-0.5-0.40.30.10.30.20.4- -

8 conditioner 4-0.5-0.10.5- - -0.2-conditioner 5-0.2-0.1- - -0.3- - -

5 thickening agent 0.5-0.2-0.5-0.40.1

5EGDS 1.51.00.12.02.50.51.01.0-1.51.02.0 water to 100

Shampoo compositions of the invention are prepared in a premix tank, a portion of the anionic surfactant (except ammonium lauryl sulfate, if present) and other surfactants (at least about 50% by weight of the total surfactant mixture) and a portion of the water are mixed and heated to about 72 ℃. Once the temperature reached about 72 ℃, fatty alcohol, tetrasodium EDTA, citric acid, ethylene glycol distearate, and sodium benzoate were added for further mixing. If present, the conditioning polymer may be added at this point. After mixing for at least about 30 minutes, the mixture is cold worked and the conditioning polymer can be added at this point. After mixing for at least about 30 minutes, the mixture is cooled to about 32 ℃ (e.g., by a heat exchanger). The following were then added to the cooled mixture: diamine dimer acid, remaining surfactant (including any ammonium lauryl sulfate), dimethicone blend (if present), sodium chloride, perfume, other conditioning agents and water, and trace materials.

Shampoo compositions of the invention provide improved hair feel, shine and volume and improved rinsing, lather volume, cleansing and conditioning properties.

Claims (17)

1. A shampoo composition comprising:

(a) from about 1% to about 60% by weight of a surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof;

(b) from about 0.001% to about 10% by weight of a cosmetic and/or pharmaceutical active;

(c) from about 0.001% to about 10% by weight of a diamine dimer acid component and salts thereof; and

(d) and (3) water.

2. The composition of claim 1 wherein the polyacid of the diamine dimer acid is a diacid.

3. A composition according to claims 1 and 2 wherein the diamine dimer acid component is selected from the group consisting of ethylene diamino disuccinic acid (EDDS), ethylene diamine diaminetetraglutaric acid (EDDG), 2-hydroxypropanediamine disuccinic acid (HPDDS) and mixtures thereof.

4. A composition according to any one of claims 1 to 3 wherein the diamine dimer acid component is ethylene diamino disuccinic acid (EDDS).

5. A composition according to any one of claims 1 to 4 wherein the diamine dimer acid component is present as an aqueous solution which is a [ S, S]isomer of EDDS neutralized with sodium hydroxide, wherein about 30% of the EDDS remains in the free acid form, and wherein the EDDS complex is present as the trisodium salt.

6. A composition according to any of claims 1 to 5 wherein the amount of diamine dimer acid component is from about 0.1% to about 5%, preferably from about 0.5% to about 3%, more preferably from about 1% to about 3% by weight.

7. A composition according to any one of claims 1 to 6 wherein the amount of diamine dimer acid component is at least about 0.5%, preferably at least about 1% by weight.

8. A composition according to any one of claims 1 to 7 wherein the ratio of the total amount of surfactant to the total amount of diamine dimer acid ranges from about 40: 1 to about 5: 1, preferably from about 30: 1 to about 10: 1.

9. A composition according to any one of claims 1 to 8, wherein the total amount of surfactant is from about 2% to about 30%, preferably from about 8% to about 25%, more preferably from about 10% to about 20% by weight.

10. A composition according to any of claims 1 to 9 wherein the anionic surfactant is selected from the group consisting of alkyl sulfates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, alkyl ethoxy carboxylates, N-acyl glutamates, acyl isethionates, alkyl succinate sulfonates, alkyl succinate ethoxy sulfonates, α -sulfonated fatty acids and their salts and/or esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, acyl sarcosinates, fatty acid/protein condensates and mixtures thereof.

11. A composition according to any of claims 1 to 10 wherein the anionic surfactant is selected from the group consisting of alkyl sulfates, ethoxylated alkyl sulfates, alkyl ethoxy carboxylates and mixtures thereof.

12. A composition according to any one of claims 1 to 11, which additionally comprisesComprising from about 0.1% to about 15% by weight of a nonionic surfactant selected from ethoxylated alcohols, C₁₂-C₁₄Fatty acid monoethanolamides and diethanolamides, e.g. cocoethanolamide, cocomonoisopropylamide and ethoxylated derivatives thereof, polysaccharide surfactants, e.g. C₁₀-C₁₈Alkyl polysaccharides and polyhydroxy fatty acid amide surfactants.

13. The composition according to any one of claims 1 to 12, additionally comprising an amphoteric surfactant selected from:

(a) imidazoline derivatives of formula (IV)

Wherein R is₁Is C₇-C₂₂Alkyl or alkenyl, R₂Is hydrogen or CH₂Z, Z are each CO₂Or CH₂CO₂M, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or an ammonium derivative of formula (V):wherein R is₁、R₂And Z is as defined above. (b) An aminoalkanoate of formula (VI): r₁NH(CH₂)_nCO₂M an iminodialkanoic acid ester of the formula (VII): r₁N[(CH₂)_mCO₂M]₂And an imido polyalkanoate of formula (VIII):

wherein n, m, p and q are numbers 1-4, R₁And M is independently selected from the above groups; and

(c) mixtures thereof.

14. A composition according to any one of claims 1 to 13 comprising an additional amphoteric surfactant selected from the group consisting of alkyl betaines, amido betaines, alkyl sultaines and mixtures thereof.

15. A composition according to any one of claims 1 to 14 wherein the level of cosmetic and/or pharmaceutical active is from about 0.001% to about 5%, preferably from about 0.1% to about 2%, more preferably from about 0.1% to about 1% by weight.

16. A composition according to any one of claims 1 to 15 wherein the cosmetic agent is a hair and/or skin conditioning agent selected from silicone materials, fatty alcohols, polymeric resins, polyol carboxylates, cationic polymers, insoluble oils and oil derived materials and mixtures thereof.

17. A composition according to claim 16 wherein the hair and/or skin conditioning agent is selected from the group consisting of silicone materials, fatty alcohols and mixtures thereof.