WO1994017777A1 - Hair care compositions - Google Patents

Hair care compositions Download PDF

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Publication number
WO1994017777A1
WO1994017777A1 PCT/US1994/001197 US9401197W WO9417777A1 WO 1994017777 A1 WO1994017777 A1 WO 1994017777A1 US 9401197 W US9401197 W US 9401197W WO 9417777 A1 WO9417777 A1 WO 9417777A1
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WO
WIPO (PCT)
Prior art keywords
hair
composition
conditioning
hair conditioning
fatty acid
Prior art date
Application number
PCT/US1994/001197
Other languages
French (fr)
Inventor
Amrit M. Patel
Clarence R. Robbins
Original Assignee
Colgate-Palmolive Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Priority to AU62344/94A priority Critical patent/AU6234494A/en
Publication of WO1994017777A1 publication Critical patent/WO1994017777A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26Aluminium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/12Preparations containing hair conditioners

Definitions

  • the present invention relates to hair care products, more specifically, hair conditioning compositions, methods for manufacturing hair conditioning compositions and methods for conditioning hair. Description of the Prior Art
  • compositions presently in use contain relatively large proportions of nitrogen- and silicone-containing hair conditioning agents which have been recently shown to be detrimental t the environment.
  • nitrogen-containing hair conditioning agents commonly employed are the cationic surface active agents including quaternary ammonium salts such as imidazolinium salts, betaines, etc., as described in U.S. Patent Nos. 5,019,376 and 4,000,077, and cationic polymers such as cationic guar gum, polymer JR, etc., as described in U.S. Patent No. 4,364,837.
  • Exemplary of the silicone-containing hair conditioning agents ar dimethicone and the silicones illustrated in U.S. Patent Nos. 4,818,523, 4,597,962, 4,658,839 and 4,529,586.
  • a hair care composition comprising hair conditioning proportion of an aluminum salt of a fatty acid having to 40 carbon atoms.
  • a further embodiment of the invention relates to a hair care composition containing the above-described aluminum salt and additionally comprising a co-hair conditioning proportion of a water- insoluble oil, lipid or mixture thereof.
  • An additional embodiment of the invention relates to hair care compositions as described above additionally comprising a hair conditioning proportion of a member selected from the group consisting of a cationic hair conditioning agent, a silicone hair conditioning agent a mixtures thereof, the weight ratio of the aluminum salt to the member being in the range of from about 5:1 to about 0.1:1.
  • Another embodiment of the invention relates to a method of manufacturing the hair care compositions described above by forming a aqueous composition having dissolved therein aluminum cations and a salt of the fatty acid, whereby the cations of the fatty acid salt are displaced by the aluminum cations to form, in situ, the aluminum salt of fatty acid.
  • Yet another embodiment of the invention relates to a method fo conditioning hair which comprises applying to the hair a hair conditioni amount of a composition as described above, rinsing the hair after application thereof and drying the same, thereby leaving the hair condi ⁇ tioned due to the conditioning effects of the aluminum salt and the additional hair conditioning agents, where present, in combination.
  • DETAILED DESCRIPTION OF THE INVENTION The present invention is predicated on the discovery that certai aluminum based salt compositions function similarly to commonly employed nitrogen- or silicone-containing hair conditioning agents such as the quaternary ammonium compounds, cationic nitrogen-containing polymers, dimethicone, etc. They have been found to be very substan- tive to hair, to reduce static and to provide sheen and style control.
  • Polyvalent metal salts have been employed in the personal care art primarily for their astringent effects on skin for antiperspirant activity.
  • U.S. Patent No. 3,842,847 discloses the use of inorganic, water-soluble salts of aluminum, hafnium, zirconium and zinc in shampoo and hair treatment compositions to reduce scalp perspiratio thereby resulting in less sebum being transferred to the hair. Hewitt et al also reported anti-static and anti-soiling effects with aqueous rinses of these agents.
  • U.S. Patent No. 3,208,910 (Cassidy) discloses including a water- soluble zirconium carboxylate salt (e.g., acetate) in a hair styling fluid fo imparting body, moisture resistance and sheen to hair.
  • U.S. Patent No. 4,614,200 (Hsuing et al) relates to a method for treating hair to strengthen and improve its physical properties comprising contacting the hair with an aqueous solution including water dispersible polyvalent metal [Al(III), Ce(III), Ce(IV), Fe(III), Zr(IV), Al-Zr coordination complexes] of strong mineral acids.
  • the treatment is appli as a "rinse” and is said to improve the hydrophobicity and body of the hair, to decrease the porosity and increase "set retention" of the hair.
  • T treatment of Hsuing requires the presence of relatively high concentra ⁇ tions of cationic-type conditioner materials to provide a hair-conditioni effect [Example 3].
  • the aluminum based salt systems employed in the compositions and methods of the present invention surprisingly provide a high degre of hair conditioning virtually equivalent to that provided by the cationic type and high molecular weight silicone conditioners known in the art.
  • These aluminum based salt systems may be provided in the aqueous hair care compositions of the invention according to any convenient method.
  • water-soluble or water-dispersible salts e.g., alkali metal, i.e., sodium
  • alkali metal i.e., sodium
  • insoluble aluminum salts of fatty acids are formed in situ or a mixture or complex of the soluble aluminum salt and the fatty acid are formed which, in combination with the co-hair conditioning agent described below, functions as the hair conditioning agent.
  • sodium salts of the fatty acids are prepared by reacting the latter with a solubilized sodium salt (e.g., mono- and di- sodium phosphates) to form the sodium salts of the fatty acids. Further reaction of the fatty acid sodium salts with, e.g., aluminum sulfate, form the fatty acid aluminum salts (or mixture or complex as noted above) in situ.
  • a solubilized sodium salt e.g., mono- and di- sodium phosphates
  • Suitable fatty acids for forming the fatty acid aluminum salts include the higher fatty acids having from about 10 to about 40 carbon atoms, e.g., stearic, Iauric, myristic, palmitic, oleic, arachidic, behenic, lignoceric acids, etc.
  • any suitable water-soluble salts capable of reacting in an aqueous medium with fatty acids to form fatty acid salts which will exchange cations with aluminum when contacted with a soluble aluminum salt may be utilized in the practice of the invention.
  • Exemplary of such salts are mono- and di-alkali metal phosphates (e.g., mono- and di-sodium phosphate), alkali metal oxides or hydroxides, ammonium hydroxide or organic salts with amines such as amino propanol, amino propanediol, triethanolamine, etc.; or almost any source of alkalinity that converts th fatty acids to fatty acid salts.
  • alkali metal oxides or hydroxides e.g., mono- and di-sodium phosphate
  • ammonium hydroxide or organic salts with amines such as amino propanol, amino propanediol, triethanolamine, etc.
  • an alternative is to begin with fatty acid salts.
  • Suitable soluble aluminum salts for reaction with the fatty acid salts to produce the fatty acid aluminum salts in situ include aluminum sulfate, derivatives of aluminum salts of strong acids such as derivatives of aluminum chloride or sulfate, i.e., aluminum chlorhydrate, aluminum chlorhydroxide and other mixed forms of aluminum chloride, sulfate hydroxide, etc.
  • the fatty acid aluminum salts are preferably employed in hair care products and compositions in proportions such that upon applicati of a suitable amount to human hair, a hair conditioning effect is produc in the hair.
  • the fatty acid aluminum salt hair conditioners described herein may be incorporated in hair conditioner, tonic, shampoo, mousse, gel, solid bar hairspray compositions employing the adjuvants commonly employed i the art to formulate such products.
  • the invention will be illustrated below with particular reference to hair conditioner compositions; however, it will be understood that the same basic principles will apply with respect to any hair care product or composition which can accommodate a hair conditioning agent.
  • the hair care products of the invention may contain from about 0.1% to about 10% by weight of the aluminum fatty acid salt It will be understood that, unless otherwise indicated, all percentages expressed herein are by weight based on the total weight of the composition in which the material is incorporated. It is preferred to also include in the hair care product a co-hair conditioning agent comprising at least one lipid or oil. The purpose of t lipid or oil is to deposit on the hair and make the hair softer, smoother and easier to comb.
  • Suitable lipids or oils include long chain alcohols, amides, ester and/or hydrocarbons, e.g., myristyl, cetyl, stearyl behenyl alcohols; stearamide, ethylene glycol distearate; mineral oils and waxes such as microcrystalline and paraffin waxes and petrolatum.
  • the weight ratio of fatty acid aluminum salt to oil or lipid may be in the range of from about 1:1 to about 1:10.
  • an emulsification agent in the aqueous formulation in order to aid in the dispersion of the fatty ac aluminum salt and oil and/or lipid.
  • Any suitable anionic or non-ionic emulsification agent conventionally employed in the art of hair care products may be utilized in the practice of the invention.
  • Illustrative of such emulsification agents are sodium cumene sulfonate, sodium xylene sulfonate, an alkyl sulfate such as sodium dodecyl sulfate, sodium cocoy isethionate, an alkyl ether sulfate such as sodium laureth-2 sulfate, cetearth-20, Neodol (C9-11 Pareth-6) 91-6, Polysorbate-20.
  • fatty acid aluminum salt agents described herein provide hair conditioning effects virtually equivalent to the cationic-typ and silicone hair conditioning agents of the prior art for normal or oily hair, there are limits as to their delivery where higher conditioning effects are required. For example, for treated or damaged or long curly hair, it may be necessary to include a small amount of a cationic-type and/or a silicone hair conditioning agent.
  • the use of the fatty acid aluminum salts greatly reduces the amount of cationic-type or high molecular weight silicone agents required to achieve satisfactory hair conditioning effects, thereb lessening the deleterious effects thereof on the environment.
  • any suitable cationic-type or silicone hair conditioning agent compatible with the remaining ingredients of the composition may be employed.
  • exemplary of the cationic agents are the polymer JRs, the Luviquats such as Luviquat 905, cationic guar gum, distearyl- dimethylammonium chloride, dicetyl dimonium chloride, etc.
  • Suitable silicone hair conditioning agents include dimethicone and amodimethicone. Where a cationic-type or silicone hair conditioning agent is employed in the compositions and methods of the invention, it is only necessary to utilize an amount thereof such that the weight ratio of fatty acid aluminum salt to the cationic-type or silicone agent is from about 20:1 to about 1:1.
  • the hair care products of the invention may have a pH of up to about 5, and preferably from about 2 to about 4.
  • Germaben II 0,50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
  • Germaben II 0.75 0.75 0.75 0.7
  • the subjects were treated according to the following protocol for testing of hair conditioners.
  • Each subject had their whole head shampooed twice with a control product (15% Al SLES-2EO solution).
  • the hair was initially wetted with running tap water (150 ppm hardness) at 105°F.
  • Ten milliliters of control product were measured and applied to the hair for the first application.
  • a cosmetologist worked the product into a lather, rubbing the entire scalp and hair with the fingertips for 60 seconds.
  • Th head was rinsed with running tap water from a spray nozzle for 60 seconds.
  • a second application of the same shampoo (5.0 ml) was then applied to the head, massaged into the hair for 60 seconds and rinsed as before.
  • each subject had their hair parted in the middle of the scalp, ranging from the forehead to the nape of the neck. Seven and one-half milliliters of test product were applied by hand to the subject's hair of a designated side of the head (applicatio hand was immediately rinsed). An equal amount of the second product was immediately applied to the untreated side of the head. Each produc was massaged simultaneously, but separately, into the appropriate side of the head, i.e., left and right, for a total of 15 seconds. The product w left on the hair for 60 seconds. While alternating test areas, each side was then rinsed for a total of 45 seconds, e.g., right 15 seconds, left 15 seconds, right 30 seconds, left 30 seconds.
  • a cosmetologist evaluated each side of the head for wet hair effects. Two sets of combs were used, one for each side of the head. A seven-point intensity scale was used to rate the following wet hair attributes: snags, comb resistance (fine-ended comb), coated feel, degree of oiliness, degree of dryness and squeak.
  • the wet hair was blown dry by using a hand-held blow dryer with the heat setting maintained at high. Each test area was brushed and dried, alternating sides equally, until the hair was completely dry. This was accomplished by using two separate sets of brushes. An assessment of "brushing resistance" was made by the cosmetologist usin the specified seven-point intensity scale.
  • the cosmetologist performed dry hair evaluations using a new set of combs.
  • a seven-point intensity scale was used to rate the following attributes: snags, comb resistance (fine-ended comb), soft feel, coated feel, degree of oiliness, degree of dryness, full and clean.
  • the cosmetologist used a thermostatically controlled curling iron to make a single curl within each test area for an equal amount of time. An assessment of curl tightness (i.e., shape, bounce and hold) was then performed by the cosmetologist. Afterwards, the hair was styled and an assessment made on styling ease.
  • non-quat/non-silicone formulae performed equally for squeak, coated feel and degree of oiliness.
  • the non-quat/non-silicone product treated hair was judged to feel more oily when dry than the current, thus feeling more conditioned. It provided a tighter curl than the current conditioner, although the current was judged to provide easier snag removal and less comb resistance on dry hair.
  • the non-quat/non-silicone product was found to be equivalent to the quat formula for static flyaway control.
  • Formulation VI contains no cationic-type or silicone hair conditioners, yet still provides good conditioning (ease of wet and dry combing), static control, sheen and style control. This conditioner woul be particularly suited for oily or normal hair.
  • Formulation V is basically the same as Formulation VI except that, to increase ease of wet and dry combing, hydroxyethyl cellulose is replaced with Polymer JR-30M in the same proportion. This formulation would be suitable for normal or treated hair.
  • Formulation VII is identical to Formulation V except that it contains, in addition to Polymer JR-30M, an additional 1% dimethicone t further increase ease of wet and dry combing which makes it ideal for treated or damaged long curly. hair.
  • Formulation VIII has a higher level of stearic acid and aluminum sulfate than Formulation VI which gives better static control, but does not increase conditioning (ease of wet and dry combing).
  • Formulation IX delivers higher conditioning than Formulation VII. As the level of dimethicone increases, conditioning is enhanced.
  • Formulation X delivers higher conditioning than Formulation VI. As the level of Polymer JR-30M increases, conditioning is enhanced.
  • Formulation XI yields the highest degree of conditioning. It has the highest level of Polymer JR-30M, as well as dimethicone.
  • the comb In evaluating conditioning effects, the comb must pass through the tress in a root-to-tip direction due to the frictional effects created by the cuticle scales which are arranged like shingles on a roof. Therefore, to properly form a tress, one must first determine the orientation of the hair. It is extremely important that the hair is bound at the root end.
  • a 3.5 gram swatch is separated from a 50 gram bundle of hair and bound tightly at the root end with an electrical clamp.
  • An alternative method is to bind the end of the swatch with string and then fold it over itself to form a loop. This loop is then boun by a small elastic band. If desired, an opened paper clip can be passed through the loop to serve as a hook to hang the tresses waiting to be combed from a horizontal rod.
  • the assembled tresses are then washed with 1 cc of a 1.5% active solution of an anionic surfactant, usually sodium lauryl ether-2 sulfate, to remove any dirt or oil and then rinsed with water. This is followed by a second wash and rinse cycle. The tresses are then combed to remove any loose hairs that were not properly crimped.
  • an anionic surfactant usually sodium lauryl ether-2 sulfate
  • Pre-washed untreated tresses are combed by two expert judges before treatment to ensure they all comb with the same relative ease. Tresses differing substantially from the. arithmetic mean are removed from the test. The tresses are then re-weighed. Tresses not weighing within 0.25 grams of each other are removed from the test. These extra steps eliminate tress differences as a potential source of error in the combing data.
  • the pre-washed and pre-combed tresses are now ready for treatment with the test product. The tresses are first rinsed under running tap water at 105°F and then a syringe is used to apply 1 cc of test product which is worked into the tress with the fingers for 1 minute.
  • the treated tress is rinsed for 30 seconds under running tap water.
  • a second application of test product (1 cc for 1 minute) is followed by a final rinse with 105°F running tap water for 1 minute.
  • Tresses are not used for more than one test because they become damaged from repeated combings.
  • the tresses should be identifiable to the researcher, but not to the judge evaluating the combing. This eliminates any unintentional bias due to treatment.
  • Each tress should be combed with its own designated comb to prevent the potential of any cross-over of conditioning effects from one tress to the next.
  • the evaluator first removes it from the supporting rod. The tress is held firmly by the clamp with one hand while the comb is held by the fingers of the other hand. The tress is spread open slightly and then placed against the large teeth of the comb. The large teeth are used first to detangle the hair. The thumb of the comb hand is used as a guide to keep the tress in place. Then the fine teeth of the comb are moved along the tress to perform the final evaluation. The resistance to movement is gauged by the amount of force necessary to move the comb from the root-to-tip end.
  • Treated tresses may be combed dry first to determine the conditioning effects provided by each product. Tresses should then be wetted by dipping gently into a glass of water or preferably by spraying with an aqueous aerosol mist. Once wet, the tresses should be combed again. The differences between product treatments will become more pronounced as the force required to move the comb through the hair is increased by the extra effort required to detangle the hair. The best conditioners work to reduce the combing force by reducing both interfiber friction and detangling the hair. Generally, 6 to 9 tresses are combed as described above and placed in order of combing ease on a comparative basis using 3 or sometimes 2 tresses per treatment.
  • the trained panelist is then asked to rate the ease of combing on a scale of 1 to 10 where 1 is difficult and 10 is very easy.
  • the data is analyzed statistically using both rank analysis (Friedman Non-parametric test) and ANOVA.
  • rank analysis is the most sensitive for detecting differences between the tresses.

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Abstract

A hair care composition comprising a hair conditioning proportion of an aluminum salt of a fatty acid having 10 to 40 carbon atoms or a mixture or complex of a water-soluble aluminum salt and a water-soluble or water-dispersible salt of a fatty acid having 10 to 40 carbon atoms. The composition may additionally comprise a co-hair conditioning proportion of a water-insoluble oil, lipid or mixture thereof and/or a hair conditioning proportion of a member selected from the group consisting of a cationic hair conditioning agent, a silicone hair conditioning agent and mixtures thereof, wherein the weight ratio of the aluminum salt to the member is in the range of from about 5:1 to about 0.1:1. Methods of manufacturing hair care compositions and applying the same to the hair are also disclosed.

Description

"HAIR CARE COMPOSITIONS"
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to hair care products, more specifically, hair conditioning compositions, methods for manufacturing hair conditioning compositions and methods for conditioning hair. Description of the Prior Art
Many hair conditioning compositions presently in use contain relatively large proportions of nitrogen- and silicone-containing hair conditioning agents which have been recently shown to be detrimental t the environment. Among the nitrogen-containing hair conditioning agents commonly employed are the cationic surface active agents including quaternary ammonium salts such as imidazolinium salts, betaines, etc., as described in U.S. Patent Nos. 5,019,376 and 4,000,077, and cationic polymers such as cationic guar gum, polymer JR, etc., as described in U.S. Patent No. 4,364,837. Exemplary of the silicone-containing hair conditioning agents ar dimethicone and the silicones illustrated in U.S. Patent Nos. 4,818,523, 4,597,962, 4,658,839 and 4,529,586.
It is an object of the present invention to provide effective hair conditioning compositions having little or no nitrogen- or silicone- containing hair conditioning agents incorporated therein.
It is a further object of the present invention to provide a method for the manufacture of effective hair conditioning compositions.
It is an additional object of the present invention to provide a method of conditioning hair which requires the application of little or n nitrogen- or silicone-containing hair conditioning agents.
SUMMARY OF THE INVENTION These and other objects are realized by the present invention, one embodiment of which relates to a hair care composition comprising hair conditioning proportion of an aluminum salt of a fatty acid having to 40 carbon atoms.
A further embodiment of the invention relates to a hair care composition containing the above-described aluminum salt and additionally comprising a co-hair conditioning proportion of a water- insoluble oil, lipid or mixture thereof. An additional embodiment of the invention relates to hair care compositions as described above additionally comprising a hair conditioning proportion of a member selected from the group consisting of a cationic hair conditioning agent, a silicone hair conditioning agent a mixtures thereof, the weight ratio of the aluminum salt to the member being in the range of from about 5:1 to about 0.1:1.
Another embodiment of the invention relates to a method of manufacturing the hair care compositions described above by forming a aqueous composition having dissolved therein aluminum cations and a salt of the fatty acid, whereby the cations of the fatty acid salt are displaced by the aluminum cations to form, in situ, the aluminum salt of fatty acid.
Yet another embodiment of the invention relates to a method fo conditioning hair which comprises applying to the hair a hair conditioni amount of a composition as described above, rinsing the hair after application thereof and drying the same, thereby leaving the hair condi¬ tioned due to the conditioning effects of the aluminum salt and the additional hair conditioning agents, where present, in combination. DETAILED DESCRIPTION OF THE INVENTION The present invention is predicated on the discovery that certai aluminum based salt compositions function similarly to commonly employed nitrogen- or silicone-containing hair conditioning agents such as the quaternary ammonium compounds, cationic nitrogen-containing polymers, dimethicone, etc. They have been found to be very substan- tive to hair, to reduce static and to provide sheen and style control.
Polyvalent metal salts have been employed in the personal care art primarily for their astringent effects on skin for antiperspirant activity.
U.S. Patent No. 3,842,847 (Hewitt et al) discloses the use of inorganic, water-soluble salts of aluminum, hafnium, zirconium and zinc in shampoo and hair treatment compositions to reduce scalp perspiratio thereby resulting in less sebum being transferred to the hair. Hewitt et al also reported anti-static and anti-soiling effects with aqueous rinses of these agents. U.S. Patent No. 3,208,910 (Cassidy) discloses including a water- soluble zirconium carboxylate salt (e.g., acetate) in a hair styling fluid fo imparting body, moisture resistance and sheen to hair.
U.S. Patent No. 4,614,200 (Hsuing et al) relates to a method for treating hair to strengthen and improve its physical properties comprising contacting the hair with an aqueous solution including water dispersible polyvalent metal [Al(III), Ce(III), Ce(IV), Fe(III), Zr(IV), Al-Zr coordination complexes] of strong mineral acids. The treatment is appli as a "rinse" and is said to improve the hydrophobicity and body of the hair, to decrease the porosity and increase "set retention" of the hair. T treatment of Hsuing requires the presence of relatively high concentra¬ tions of cationic-type conditioner materials to provide a hair-conditioni effect [Example 3].
The aluminum based salt systems employed in the compositions and methods of the present invention surprisingly provide a high degre of hair conditioning virtually equivalent to that provided by the cationic type and high molecular weight silicone conditioners known in the art.
These aluminum based salt systems may be provided in the aqueous hair care compositions of the invention according to any convenient method.
It is preferred, however, to form the aluminum salt based component in situ during preparation of the hair care product. Briefly, water-soluble or water-dispersible salts (e.g., alkali metal, i.e., sodium) o the fatty acids are formed or solubilized in an appropriate aqueous medium. While it is in no way intended to limit the invention by the soundness or accuracy of any theories set forth herein to explain the nature of the invention, it is postulated that when an inorganic aluminu salt (e.g., aluminum sulfate) is added thereto, the sodium ions of the fatt acid salts are displaced by aluminum ions to form water-insoluble aluminum salts of mono-, di- and tri-fatty acids in a water-dispersed condition.
At present, it is unclear whether insoluble aluminum salts of fatty acids are formed in situ or a mixture or complex of the soluble aluminum salt and the fatty acid are formed which, in combination with the co-hair conditioning agent described below, functions as the hair conditioning agent.
More particularly, sodium salts of the fatty acids are prepared by reacting the latter with a solubilized sodium salt (e.g., mono- and di- sodium phosphates) to form the sodium salts of the fatty acids. Further reaction of the fatty acid sodium salts with, e.g., aluminum sulfate, form the fatty acid aluminum salts (or mixture or complex as noted above) in situ.
Suitable fatty acids for forming the fatty acid aluminum salts include the higher fatty acids having from about 10 to about 40 carbon atoms, e.g., stearic, Iauric, myristic, palmitic, oleic, arachidic, behenic, lignoceric acids, etc.
It will be understood by those skilled in the art that, in those instances where the fatty acid aluminum salts appear to be formed in situ, any suitable water-soluble salts capable of reacting in an aqueous medium with fatty acids to form fatty acid salts which will exchange cations with aluminum when contacted with a soluble aluminum salt ma be utilized in the practice of the invention. Exemplary of such salts are mono- and di-alkali metal phosphates (e.g., mono- and di-sodium phosphate), alkali metal oxides or hydroxides, ammonium hydroxide or organic salts with amines such as amino propanol, amino propanediol, triethanolamine, etc.; or almost any source of alkalinity that converts th fatty acids to fatty acid salts. Of course, as will be understood by those skilled in the art, an alternative is to begin with fatty acid salts. Suitable soluble aluminum salts for reaction with the fatty acid salts to produce the fatty acid aluminum salts in situ include aluminum sulfate, derivatives of aluminum salts of strong acids such as derivatives of aluminum chloride or sulfate, i.e., aluminum chlorhydrate, aluminum chlorhydroxide and other mixed forms of aluminum chloride, sulfate hydroxide, etc.
The fatty acid aluminum salts are preferably employed in hair care products and compositions in proportions such that upon applicati of a suitable amount to human hair, a hair conditioning effect is produc in the hair. It will be understood by those skilled in the art that the fatty acid aluminum salt hair conditioners described herein may be incorporated in hair conditioner, tonic, shampoo, mousse, gel, solid bar hairspray compositions employing the adjuvants commonly employed i the art to formulate such products. The invention will be illustrated below with particular reference to hair conditioner compositions; however, it will be understood that the same basic principles will apply with respect to any hair care product or composition which can accommodate a hair conditioning agent.
Generally, the hair care products of the invention may contain from about 0.1% to about 10% by weight of the aluminum fatty acid salt It will be understood that, unless otherwise indicated, all percentages expressed herein are by weight based on the total weight of the composition in which the material is incorporated. It is preferred to also include in the hair care product a co-hair conditioning agent comprising at least one lipid or oil. The purpose of t lipid or oil is to deposit on the hair and make the hair softer, smoother and easier to comb. Suitable lipids or oils include long chain alcohols, amides, ester and/or hydrocarbons, e.g., myristyl, cetyl, stearyl behenyl alcohols; stearamide, ethylene glycol distearate; mineral oils and waxes such as microcrystalline and paraffin waxes and petrolatum.
The weight ratio of fatty acid aluminum salt to oil or lipid may be in the range of from about 1:1 to about 1:10.
Depending, of course, upon the type of hair care product contemplated, it is also preferred to employ an emulsification agent in the aqueous formulation in order to aid in the dispersion of the fatty ac aluminum salt and oil and/or lipid. Any suitable anionic or non-ionic emulsification agent conventionally employed in the art of hair care products may be utilized in the practice of the invention. Illustrative of such emulsification agents are sodium cumene sulfonate, sodium xylene sulfonate, an alkyl sulfate such as sodium dodecyl sulfate, sodium cocoy isethionate, an alkyl ether sulfate such as sodium laureth-2 sulfate, cetearth-20, Neodol (C9-11 Pareth-6) 91-6, Polysorbate-20.
Although the fatty acid aluminum salt agents described herein provide hair conditioning effects virtually equivalent to the cationic-typ and silicone hair conditioning agents of the prior art for normal or oily hair, there are limits as to their delivery where higher conditioning effects are required. For example, for treated or damaged or long curly hair, it may be necessary to include a small amount of a cationic-type and/or a silicone hair conditioning agent.
In any event, the use of the fatty acid aluminum salts greatly reduces the amount of cationic-type or high molecular weight silicone agents required to achieve satisfactory hair conditioning effects, thereb lessening the deleterious effects thereof on the environment.
Any suitable cationic-type or silicone hair conditioning agent compatible with the remaining ingredients of the composition may be employed. Exemplary of the cationic agents are the polymer JRs, the Luviquats such as Luviquat 905, cationic guar gum, distearyl- dimethylammonium chloride, dicetyl dimonium chloride, etc.
Suitable silicone hair conditioning agents include dimethicone and amodimethicone. Where a cationic-type or silicone hair conditioning agent is employed in the compositions and methods of the invention, it is only necessary to utilize an amount thereof such that the weight ratio of fatty acid aluminum salt to the cationic-type or silicone agent is from about 20:1 to about 1:1.
The hair care products of the invention may have a pH of up to about 5, and preferably from about 2 to about 4.
The following examples illustrate, but do not limit, the inventio Unless otherwise indicated, all parts are by weight and all temperatures are in βC. -
% FORMULATIONS
Ingredients
Part A I II III IV V
Deionized Water QS QS 03 s as
Sodium Phosphate Monobasic 0.50 0.50 0.50 0.50 0.50
Sodium Phosphate Dibasic 0.25 0.25 0.25 0.25 0.25
Polymer JR-30M 0.30 — — — —
Luviquat 905 — — — 0.20
Hydroxyethyl Cellulose — 0.30 0.25 0.30 —
Propylene Glycol 1.00 1.00 1.00 1.00 1.00
Sodium Cumene Sulfonate 2.00 2.00 2.00 2.00 2.00
Part P
Cetyl Alcohol 3.50 3.50 3.00 3.50 3.50
Mineral Oil D-50 *** 2.50 2.50 3.00 2.50 2.50
Emulgade 1000-NI * 2.00 3.00 3.00 3.00 2.00
Stearic Acid 1.50 1.50 1.50 1.50 1.50
Part C
Aluminum Sulfate ** 0.65 0.60 0.65 0.65 0.65
Deionized Water
Part D 3.00 3.00 3.00 3.00 3.00
Dimethicone 60,000 cps
Part E — — — 0.50 —
Perfume 0.50 0.50 0.50 0.50 0.50
Germaben II 0,50 0.50 0.50 0.50 0.50
TOTAL: 100.00 100.00 100.00 100.00 100.0C
* Cetearyl Alcohol and Cetearth-20 ** AI2SO4 • 14H20 *** Draketex D-50 (Pemreco Co.) The ingredients of Part A were mixed together at 87°C and Part B was added thereto. The mixture was stirred for ten minutes and Part C was added at 87°C. The mixture was stirred for an additional ten minutes at 87°C and allowed to cool while stirring to 70°C. At 70°C, dimethicone was added to Formulation IV. The mixtures were then cooled to 40°C and the fragrance and preservative were added.
% FORMULATIONS
Normal Oily Treated
Hair Hair Hair
Ingredients X. -ML VII
Part A
Deionized Water αs as as
Sodium Phosphate Monobasic 0.50 0.50 0.50
Sodium Phosphate Dibasic 0.25 0.25 0.25
Polymer JR-30M 0.30 — 0.30
Hydroxyethyl Cellulose — 0.30 —
Propylene Glycol 1.00 1.00 1.00
Sodium Cumene Sulfonate 2.00 2.00 2.00
Part B
Cetyl Alcohol 3.50 3.50 3.50
Heavy White Mineral Oil 2.50 2.50 2.50
(Britol-50)
Cetearyl Alcohol/Cetearth-20 2.00 3.00 2.00
Stearic Acid 1.50 1.50 1.50
Part C
Aluminum Sulfate 0.65 0.65 0.65
Deionized Water 3.00 3.00 3.00
Figure imgf000009_0001
Dimethicone 60,000 cps — — 1.00
Part E
Perfume (Consierra LCV) 0.35 0.35 0.35
Germaben II 0.75 0.75 0.75
TOTAL: 100.00 100.00 100.00 The above ingredients were admixed as described in Example 1. Example 3
% FORMULATIONS
Ingredients VIII IX X XI
Part A
Deionized Water as as as as
Sodium Phosphate Monobasic 0.80 0.50 0.50 0.5
Sodium Phosphate Dibasic 0.40 0.25 0.25 0.2
Polymer JR-30M — — 0.50 0.5
Hydroxyethyl Cellulose — 0.30 — —
Propylene Glycol 1.00 1.00 1.00 1.0
Sodium Cumene Sulfonate 2.00 2.00 2.00 2.
Part B
Cetyl Alcohol 3.50 3.50 3.50 3.5
Heavy White Mineral Oil 2.50 2.50 2.50 2.5
(Britol-50)
Cetearyl Alcohol/Cetearth-20 2.00 3.00 2.00 2.0
Stearic Acid 2.50 1.50 1.50 1.5
Part C
Aluminum Sulfate 1.05 0.65 0.65 0.6
Deionized Water 3.00 3.00 3.00 3.
Part P
Dimethicone 60,000 cps — 2.00 — 2.0
Part E
Perfume 0.35 0.35 0.35 0.3
Germaben II 0.75 0.75 0.75 0.7
TOTAL 100.00 100.00 100.00 100.
The above ingredients were admixed as described in Example 1.
The above formulations were subjected to salon testing as follows:
To profile attributes and effectiveness of the non-nitrogen quaternary system against a current product based on the presence of quaternary nitrogen components, a quaternary nitrogen component containing hair conditioner presently sold in Australia and several othe countries was selected as the control for this test. It is based on the qua cetyl trimethyl ammonium chloride and is termed "current" in this test. This current formula was tested against the non-quat/non-silicone Formula VI of Example 2. Two other products were included in this study, but are not described in the results below. The test was a double blind study conducted in the Sensory Hair Salon in Piscataway, New Jersey. A balanced complete block design was utilized testing the products against each other in a half-head test. The product presentation order was randomized and evaluations balanced to ensure they were used equally on both sides of the head. Forty-eight female subjects were recruited for this study, each satisfying the following criteria:
• minimum age 18 years
• hair not washed within 48 hours of testing • hair not chemically treated within 7 days
• hair approximately 5 inches in length.
The subjects were treated according to the following protocol for testing of hair conditioners.
Each subject had their whole head shampooed twice with a control product (15% Al SLES-2EO solution). The hair was initially wetted with running tap water (150 ppm hardness) at 105°F. Ten milliliters of control product were measured and applied to the hair for the first application. A cosmetologist worked the product into a lather, rubbing the entire scalp and hair with the fingertips for 60 seconds. Th head was rinsed with running tap water from a spray nozzle for 60 seconds. A second application of the same shampoo (5.0 ml) was then applied to the head, massaged into the hair for 60 seconds and rinsed as before.
To establish two testing areas, each subject had their hair parted in the middle of the scalp, ranging from the forehead to the nape of the neck. Seven and one-half milliliters of test product were applied by hand to the subject's hair of a designated side of the head (applicatio hand was immediately rinsed). An equal amount of the second product was immediately applied to the untreated side of the head. Each produc was massaged simultaneously, but separately, into the appropriate side of the head, i.e., left and right, for a total of 15 seconds. The product w left on the hair for 60 seconds. While alternating test areas, each side was then rinsed for a total of 45 seconds, e.g., right 15 seconds, left 15 seconds, right 30 seconds, left 30 seconds. Upon completion of the conditioning procedure and while th hair was still wet, a cosmetologist evaluated each side of the head for wet hair effects. Two sets of combs were used, one for each side of the head. A seven-point intensity scale was used to rate the following wet hair attributes: snags, comb resistance (fine-ended comb), coated feel, degree of oiliness, degree of dryness and squeak.
The wet hair was blown dry by using a hand-held blow dryer with the heat setting maintained at high. Each test area was brushed and dried, alternating sides equally, until the hair was completely dry. This was accomplished by using two separate sets of brushes. An assessment of "brushing resistance" was made by the cosmetologist usin the specified seven-point intensity scale.
Subsequently, the cosmetologist performed dry hair evaluations using a new set of combs. A seven-point intensity scale was used to rate the following attributes: snags, comb resistance (fine-ended comb), soft feel, coated feel, degree of oiliness, degree of dryness, full and clean. Finally, the cosmetologist used a thermostatically controlled curling iron to make a single curl within each test area for an equal amount of time. An assessment of curl tightness (i.e., shape, bounce and hold) was then performed by the cosmetologist. Afterwards, the hair was styled and an assessment made on styling ease.
The linearity of responses was assumed, but not tested. The normality assumption was tested for monadic data obtained from each o the two test formulations.
An appropriate transformation was applied to normalize data which showed a statistically significant (p < .05) departure from normality. The normally distributed monadic data was analyzed using a paired t-test for related measures. If the data resisted normalization after transformation for the monadic data, each effect induced by the test products was assessed individually. A test based on frequency distribution or on rank was used.
On wet hair, current and the non-quat/non-silicone formulae performed equally for squeak, coated feel and degree of oiliness. The non-quat/non-silicone product treated hair was judged to feel more oily when dry than the current, thus feeling more conditioned. It provided a tighter curl than the current conditioner, although the current was judged to provide easier snag removal and less comb resistance on dry hair. Importantly, the non-quat/non-silicone product was found to be equivalent to the quat formula for static flyaway control.
Formulation VI contains no cationic-type or silicone hair conditioners, yet still provides good conditioning (ease of wet and dry combing), static control, sheen and style control. This conditioner woul be particularly suited for oily or normal hair. Formulation V is basically the same as Formulation VI except that, to increase ease of wet and dry combing, hydroxyethyl cellulose is replaced with Polymer JR-30M in the same proportion. This formulation would be suitable for normal or treated hair. Formulation VII is identical to Formulation V except that it contains, in addition to Polymer JR-30M, an additional 1% dimethicone t further increase ease of wet and dry combing which makes it ideal for treated or damaged long curly. hair.
Formulation VIII has a higher level of stearic acid and aluminum sulfate than Formulation VI which gives better static control, but does not increase conditioning (ease of wet and dry combing).
Formulation IX delivers higher conditioning than Formulation VII. As the level of dimethicone increases, conditioning is enhanced.
Formulation X delivers higher conditioning than Formulation VI. As the level of Polymer JR-30M increases, conditioning is enhanced.
Formulation XI yields the highest degree of conditioning. It has the highest level of Polymer JR-30M, as well as dimethicone.
An ease of combing test was conducted employing the above- described formulations using 10-inch European virgin brown hair tresses.
In evaluating conditioning effects, the comb must pass through the tress in a root-to-tip direction due to the frictional effects created by the cuticle scales which are arranged like shingles on a roof. Therefore, to properly form a tress, one must first determine the orientation of the hair. It is extremely important that the hair is bound at the root end.
In order to confirm the orientation of the hair, hold an end of the tress with one hand. Clasp the tress between the thumb and forefinger of the other hand and move it along the entire length of the tress. Repeat the procedure holding the other end of the tress and, moving in the opposite direction, determine the direction of least resis¬ tance. This is the root-to-tip direction. This procedure is more easily performed if the tress or thumb and forefinger are first wetted.
After establishing the orientation of the hair, a 3.5 gram swatch is separated from a 50 gram bundle of hair and bound tightly at the root end with an electrical clamp.
An alternative method is to bind the end of the swatch with string and then fold it over itself to form a loop. This loop is then boun by a small elastic band. If desired, an opened paper clip can be passed through the loop to serve as a hook to hang the tresses waiting to be combed from a horizontal rod.
The assembled tresses are then washed with 1 cc of a 1.5% active solution of an anionic surfactant, usually sodium lauryl ether-2 sulfate, to remove any dirt or oil and then rinsed with water. This is followed by a second wash and rinse cycle. The tresses are then combed to remove any loose hairs that were not properly crimped.
Pre-washed untreated tresses are combed by two expert judges before treatment to ensure they all comb with the same relative ease. Tresses differing substantially from the. arithmetic mean are removed from the test. The tresses are then re-weighed. Tresses not weighing within 0.25 grams of each other are removed from the test. These extra steps eliminate tress differences as a potential source of error in the combing data. The pre-washed and pre-combed tresses are now ready for treatment with the test product. The tresses are first rinsed under running tap water at 105°F and then a syringe is used to apply 1 cc of test product which is worked into the tress with the fingers for 1 minute. The treated tress is rinsed for 30 seconds under running tap water. A second application of test product (1 cc for 1 minute) is followed by a final rinse with 105°F running tap water for 1 minute. Tresses are not used for more than one test because they become damaged from repeated combings.
In a blind product test, the tresses should be identifiable to the researcher, but not to the judge evaluating the combing. This eliminates any unintentional bias due to treatment.
Each tress should be combed with its own designated comb to prevent the potential of any cross-over of conditioning effects from one tress to the next. When combing a tress, the evaluator first removes it from the supporting rod. The tress is held firmly by the clamp with one hand while the comb is held by the fingers of the other hand. The tress is spread open slightly and then placed against the large teeth of the comb. The large teeth are used first to detangle the hair. The thumb of the comb hand is used as a guide to keep the tress in place. Then the fine teeth of the comb are moved along the tress to perform the final evaluation. The resistance to movement is gauged by the amount of force necessary to move the comb from the root-to-tip end. Treated tresses may be combed dry first to determine the conditioning effects provided by each product. Tresses should then be wetted by dipping gently into a glass of water or preferably by spraying with an aqueous aerosol mist. Once wet, the tresses should be combed again. The differences between product treatments will become more pronounced as the force required to move the comb through the hair is increased by the extra effort required to detangle the hair. The best conditioners work to reduce the combing force by reducing both interfiber friction and detangling the hair. Generally, 6 to 9 tresses are combed as described above and placed in order of combing ease on a comparative basis using 3 or sometimes 2 tresses per treatment. The trained panelist is then asked to rate the ease of combing on a scale of 1 to 10 where 1 is difficult and 10 is very easy. The data is analyzed statistically using both rank analysis (Friedman Non-parametric test) and ANOVA. Generally, the rank analysis is the most sensitive for detecting differences between the tresses.
The results are set forth below:
Ease of Combing Test
(Scale 1-10 / 10=Best) Average of 12 Readings FORMULATIONS V V V VII VII VIII IX X XI
Wet Combing 8.50 7.10 9.20 7.15 9.70 9.50 10.00
Dry Combing 9.00 8.00 9.50 8.10 9.90 9.90 10.00

Claims

"HAIR CARE COMPOSITIONS"WE CLAIM:
1. A hair care composition comprising a hair conditioning proportion of (1) an aluminum salt of a fatty acid having 10 to 40 carbon atoms or (2) a mixture or complex of a water-soluble aluminum salt and a water-soluble or water-dispersible salt of a fatty acid having 10 to 40 carbon atoms.
2. The composition of claim 1 additionally comprising a co- hair conditioning proportion of a water-insoluble oil, lipid or mixture thereof.
3. The composition of claim 1 or 2 additionally comprising an aqueous medium and a proportion of emulsifying agent to form an emulsion of said hair conditioner.
4. The composition of claim 1 additionally comprising a hair conditioning proportion of a member selected from the group consisting of a cationic hair conditioning agent, a silicone hair conditioning agent and mixtures thereof, the weight ratio of said aluminum salt to said member being in the range of from about 5:1 to about 0.1:1.
5. The composition of claim 1 in the form of a tonic, shampoo, conditioner, mousse, gel, solid bar or hairspray.
6. The composition of claim 1 wherein said fatty acid is stearic acid.
7. The composition of claim 2 wherein said lipid or oil is a long chain alcohol, amide, ester, hydrocarbon or mixture thereof.
8. The composition of claim 3 wherein said emulsifying agent is anionic or non-ionic.
9. The composition of claim 3 wherein said emulsion has a pH up to about 5.
10. The composition of claim 4 wherein said cationic hair conditioning agent is a cationic polymer.
11. The composition of claim 10 wherein said cationic polymer is Polymer JR.
12. The composition of claim 4 wherein said silicone hair conditioning agent is dimethicone.
13. A hair care composition comprising an aqueous emulsion of (a) a hair conditioning proportion of an aluminum salt of a fatty acid having 10 to 40 carbon atoms; (b) a co-hair conditioning proportion of a water-insoluble oil, lipid or mixtures thereof, the weight ratio of said aluminum salt to said co-hair conditioner being from about 1:1 to about 1:10; and (c) an emulsifying agent.
14. The composition of claim 13 additionally comprising a hair conditioning proportion of a member selected from the group consisting of a cationic hair conditioning agent, a silicone hair conditioning agent and mixtures thereof, the weight ratio of said aluminum salt to said member being in the range of from about 5:1 to about 0.1:1.
15. The composition of claim 13 wherein said fatty acid is stearic acid.
16. The composition of claim 13 wherein said lipid or oil is long chain alcohol, amide, ester, hydrocarbon or mixture thereof.
17. The composition of claim 13 wherein said emulsifying agent is anionic or non-ionic.
18. The composition of claim 13 wherein said emulsion has a pH up to about 5.
19. The composition of claim 14 wherein said cationic hair conditioning agent is a cationic polymer.
20. The composition of claim 19 wherein said cationic polymer is Polymer JR.
21. The composition of claim 14 wherein said silicone hair conditioning agent is dimethicone.
22. The composition of claim 13 additionally comprising adjuvants.
23. The composition of claim 13 in the form of a tonic, shampoo, conditioner, mousse, gel, solid bar or hairspray.
24. A hair care composition comprising an aqueous emulsion of (a) from about 0.1% to about 10% by weight of a hair conditioning aluminum salt of a fatty acid having 10 to 40 carbon atoms (b) from about 3% to about 15% by weight of a hair conditioning water- insoluble oil, lipid or mixture thereof, the weight ratio of said aluminum salt to said oil, lipid or mixture thereof being from about 1:1 to about 1:10; (c) an amount of an emulsifying agent to form said aqueous emul¬ sion of (a) and (b); and (d) from about 95% to about 70% by weight of water.
25. The composition of claim 24 additionally comprising from about 0.1% to about 3% by weight of a member selected from the group consisting of a cationic hair conditioning agent, a silicone hair conditioning agent and mixtures thereof.
26. The composition of claim 24 wherein said fatty acid is stearic acid.
27. The composition of claim 24 wherein said lipid or oil is a long chain alcohol, amide, ester, hydrocarbon or mixture thereof.
28. The composition of claim 24 wherein said emulsifying agent is present in an amount from about 0.5% to about 10% by weight and is anionic or non-ionic.
29. The composition of claim 24 wherein said emulsion has a pH up to about 5.
30. The composition of claim 25 wherein said cationic hair conditioning agent is a cationic polymer.
31. The composition of claim 25 wherein said cationic polymer is Polymer JR or a Luviquat.
32. The composition of claim 25 wherein said silicone hair conditioning agent is dimethicone.
33. The composition of claim 24 in the form of a tonic, shampoo, conditioner, mousse, gel, solid bar or hairspray.
34. The composition of claim 24 additionally comprising up to about 90% by weight of adjuvants.
35. A method for conditioning hair which comprises applying to the hair on one's head a hair conditioning amount of the composition of claim 1, rinsing the hair after said application and drying the same, thereby leaving the hair conditioned due to the conditioning effects of the aluminum salt.
36. A method for conditioning hair which com- prises applying to the hair on one's head a hair conditioning amount of the composition of claim 2, rinsing the hair after said application and drying the same, thereby leaving the hair conditioned due to the conditioning effects of the aluminum salt and said co-hair conditioner, in combination.
37. A method for conditioning hair which comprises applying to the hair on one's head a hair conditioning amount of the composition of claim 4, rinsing the hair after said application and drying the same, thereby leaving the hair conditioned due to the conditioning effects of the aluminum salt and said member, in combination.
38. A method for conditioning hair which comprises applying to the hair on one's head a hair conditioning amount of the composition of claim 14, rinsing the hair after said application and drying the same, thereby leaving the hair conditioned due to the conditioning effects of the aluminum salt, said co-hair conditioner and said member, in combination.
39. A method of manufacturing the composition of claim 1 comprising forming an aqueous composition having dissolved therein aluminum cations and a salt of the fatty acid whereby (1) the cations of said fatty acid salt are displaced by said aluminum cations to form, in situ, said aluminum salt of a fatty acid or (2) a mixture or complex of said aluminum cations and said fatty acid salt is formed.
PCT/US1994/001197 1993-02-10 1994-02-09 Hair care compositions WO1994017777A1 (en)

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GB2283754A (en) * 1993-11-11 1995-05-17 Procter & Gamble Liquid personal cleansing composition
WO1996002229A2 (en) * 1994-07-19 1996-02-01 Unilever Plc Soap composition
WO2012156177A1 (en) * 2011-05-13 2012-11-22 Unilever Plc Hair treatment compositions
WO2011154315A3 (en) * 2010-06-10 2012-12-27 Unilever Plc Hair care composition
US20190070083A1 (en) * 2017-09-05 2019-03-07 Henkel Ag & Co. Kgaa Hair treatment agent with a polyvalent metal cation i
DE102018127296A1 (en) * 2018-10-31 2020-04-30 Henkel Ag & Co. Kgaa Bis (triethoxysilylpropyl) amine in combination with polyvalent metal cations

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GB2283754A (en) * 1993-11-11 1995-05-17 Procter & Gamble Liquid personal cleansing composition
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WO1996002229A2 (en) * 1994-07-19 1996-02-01 Unilever Plc Soap composition
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WO2012156177A1 (en) * 2011-05-13 2012-11-22 Unilever Plc Hair treatment compositions
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DE102018127296A1 (en) * 2018-10-31 2020-04-30 Henkel Ag & Co. Kgaa Bis (triethoxysilylpropyl) amine in combination with polyvalent metal cations

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