Patent Application
20060210520
1. Field of the Invention
The present invention relates to novel Macadamia-lipid based surfactants and derivatives, and emollients, their process of manufacture, their use in the production of surface active derivatives, non-surface active esters, and ester emollients, and skin and hair care preparations containing the surfactants, derivatives and emollients. The surfactants and fatty ester derivatives are useful as emollients, dispersants, emulsifiers and conditioners for hair care and skin care products.
2. Description of the Related Art
Surfactants and derivatives are known for a variety of different applications for cosmetic, pharmaceutical, and medicinal purposes.
Numerous references describe the production and use of surface active derivatives or non-surface active esters, and ester emollients. For example, it is known to use macadamia oil in cosmetic preparations to obtain the benefits of mildness. Surfactants and fatty derivatives useful as emollients, dispersants, emulsifiers and conditioners for hair and skin care products are commonly produced from a wide variety of fatty acids, fatty alcohols and amines, polyamines, dialkyl propylamines, alkanolamines, etc. However, none of these references teach or suggest the specific novel macadamia-based surfactants made from the fatty oil triglyceride obtained from macadamia nuts, or MFTG, of this invention or the use of MFTG to produce surface active derivatives or non-surface active esters, and ester emollients for cosmetics and personal care products.
More specifically, macadamia-based compositions are disclosed in U.S. Pat. No. 5,653,966 to Bertoli et al. discloses a lipid composition for cosmetic products comprising, in part, macadamia oil. The preparation of the lipid composition includes refining the oils.
U.S. Pat. No. 6,464,991 to Walele et al. discloses oat-lipid based derivatives, surfactants and emollients and their use in the production of surface active derivatives, or non-surface active esters, and ester emollients.
U.S. Pat. No. 6,599,936 to Bajor et al. discloses cosmetic skin care methods and compositions containing methyl branched esters. The cosmetic compositions provide control of sebum secretion from sebocytes which cause oily skin, and improved skin feel and skin anti-aging benefits. Example 8 identifies macadamia oil as one ingredient in a cosmetic water-in-oil emulsion.
However, among the foregoing patents, none disclose or suggest the specific novel macadamia lipid based surfactants and derivatives of the invention, a process for preparing same, or the use of such derivatives and surfactants having mildness and emolliency for cosmetics and personal care products.
It is an object of the invention to produce novel Macadamia-based surfactants and derivatives that are made from a naturally renewable source.
It is another object of the present invention to provide surfactants and derivatives that are made from Macadamia fatty triglycerides.
It is another object of the invention to provide novel Macadamia-based surfactants and derivatives for use in hair care, skin care and other personal care products.
It is yet another object of the invention to provide novel Macadamia-based surfactants and derivatives which have a usefulness similar to conventional amides and betaines.
A further object of the invention is to provide novel Macadamia-based surfactants and derivatives for use in skin care products where the skin feel is even better than conventional derivatves.
It is a further object of the invention to provide Macadamia-based surfactants and derivatives having mildness and emolliency for use in skin care and hair care products. A still further object of the invention is to provide novel Macadamia-based surfactants and derivatives having a fatty acid composition profile close to that of the principal constituents of the human skin surface lipids that play a key role in maintaining the normal barrier function of healthy skin.
Yet another object of the invention is to provide novel Macadamia-based surfactants and derivatives having very low to negligible toxicological effects.
Another object of the invention is to provide formulations containing novel Macadamia-based surfactants and derivatives that are very mild and have a very low toxicological profile.
Another object of the invention is to provide low-irritation Macadamia-based surfactants and derivatives for skin care and hair care products.
Another object of the invention is to provide a method of producing mild, emollient, hair care or skin care products using Macadamia-based surfactants and derivatives.
These and other objects are accomplished by providing Macadamia-based surfactants and derivatives that are improved as compared to commercially available surfactants and derivatives, as they are made from a naturally renewable source, namely, Macadamia oil. The surfactants and derivatives are mild; skin and hair care formulations containing the surfactants and derivatives of the invention are mild and emollient, have very low toxicological profiles, and are not irritating to the skin.
The major fatty raw materials used in the process of the invention are fatty triglycerides derived from sources that are naturally renewable, such as coconut oil, soybean oil, sunflower oil, corn oil, and canola oil, castor oil, etc. A preferred source is Macadamia oil extracted from Macadamia nuts.
The surfactants, derivatives, and emollients of the invention are made from fatty oil triglycerides obtained from the extraction of the kernel of Macadamia Nuts.
Macadamia fatty triglycerides (hereinafter referred to as “MFTG”) are essentially comprised of saturated and unsaturated fatty acids. MFTG comprises approximately 80% monounsaturated acids in its triglycerides, of which 21% is Palmitoleic Acid, a naturally occurring skin lipid that is similar to the sebum of human skin. No other known plant oil has a similar composition. The high level of Palmitoleic acid in MFTG enhances its affinity with natural skin lipids and is the key ingredient in anti-aging cream designed to help maturing skin retain its softness, resilience, and youthful appearance. Due to its exceptional composition, it has better moisturizing properties and is very effective in hydrating the lower (dermal) layers of the skin. This type of moisturization will also respond to skin conditions such as eczema, psoriasis and itching of dry skin caused by repeated washing.
The composition of Macadamia fatty acid triglycerides is as follows:
Surfactants and fatty derivatives useful as emollients, emulsifiers and conditioners for hair and skin care products are commonly produced from a wide variety of fatty acids, fatty alcohols and amines, polyamines, dialkylpolyamines, alkanolamines, etc. Unless otherwise specified herein, the term “derivatives” is a broad term meant to include surfactants, nonsurface active esters, and ester emollients.
The following list of reactants and their respective derivatives such as esters, amides, betaines, quaternaries, etc, is exemplary of the type of reactants and derivatives on which the emollient surfactants and derivatives may be based, and as such, is not to be considered limiting.
Group A (Reactants): Fatty acids or methyl esters of fatty acids or fatty oils sourced from naturally renewable fatty triglycerides of Macadamia nuts.
Group B (Reactants) may be selected from the group consisting of: Alkanolamines such as Monoethanolamine and Diethanolamine; Dialkylaminopropylamines such as Dimethyl Aminopropylamine; Polyamines such as Diethylene triamine, Triethylene tetraamine; primary and secondary amines; and fatty alcohols (linear and/or branched) (C8-C22 alcohols) (ethoxylated or propoxylated).
The preferred reactants used in preparing the surfactants and derivatives of the invention are selected from the group consisting of:
MFTG is used in either exact stoichiometric proportions or in some excess over Reactant B.
In specific embodiment, and by way of illustration, this invention contemplates the production of the following macadamia lipid-based esters, surfactants and derivatives:
It has the following structure:
Where R=Macadamia fatty acids group
Where R=macadamia fatty acids group
The above derivatives have shown usefulness similar to conventional amides and betaines with the additional benefits of being mild to the skin. Additionally, skin feel is even better than when using conventional derivatives.
Some of these surfactants and derivatives are used in skin care and hair care formulations and dermatological preparations. Personal care formulations prepared according to the invention, which contain the surfactants and derivatives added thereto, can be formed, without limitation, into applications such as solutions, emulsions, gels, solids, emulsions, aerosols, powders, creams, granules, or tablets.
Mildness and emolliency of these derivatives is of importance to the improved skin and hair care products including the surfactants and derivatives of the invention. A major aspect of derivatives of this invention is their very low to negligible toxicological effects indicating their mildness to skin care products.
Thus, the advantages of the derivatives of the invention include:
Thus, the novel macadamia oil-based surfactants and derivatives of this invention have unique properties in that they are mild to the skin and have low to negligible toxicological effects. These properties make these derivatives useful as a vehicle or carrier, dispersants, emulsifiers, emollient, solubilizer and conditioners for skin care and hair care formulations such as hair creams, hand cleaners, bath oils, suntan oils, anti-perspirants, perfumes, colognes, cold creams, electric pre-shaves, eye and throat oils, finger nail polish, topical pharmaceutical ointments, lipsticks, stick rouge, skin lotions and creams, skin moisturizers, cleansing creams, and after-bath splash and lotions, as well as other formulations. The foregoing list is only exemplary of the type of compositions in which the macadamia-based surfactants and derivatives of this invention may be used, and, as such, is not to be considered limiting.
The amount of such macadamia oil-based surfactants and derivatives to be used in such compositions is dependent on the type of hair care and skin care compositions, the desired dosage or amount of active ingredient to be delivered, the type and quantity of other ingredients, such as cosmetic ingredients used, the amount and type of functional additives that are utilized, the user's skin and hair type, and the severity and extent of the skin or hair condition, and other parameters that will be apparent to those skilled in the art. Generally, compositions containing the macadamia-based surfactants and derivatives of the invention are topically applied in effective amounts to the affected areas of the skin or to hair. Typically, the amount of surfactants and derivatives used ranges from about 1.0% to about 30.0%, by weight, of the skin care compositions. For example, a facial cream may only have about 5.0%, while a massage oil may have up to about 20% by weight. Still higher amounts may be used in, for example, bath oils, e.g. 50%.
Further, the macadamia-based surfactants and derivatives of this invention possess other unusual physiochemical properties, which can make them suitable for use as emollient carriers in cosmetic formulations, and for use as solvents and emollient carriers in general cleaning compositions, such as in hand, face, and body creams and lotions. Thus, the macadamia-based surfactants and derivatives described herein may serve not only as emollients and carriers, but may also exhibit one or more other functions.
The surfactants and derivatives of the invention have properties such as, being less greasy, less oily, low toxicity, ease of emulsification, acid and alkaline stability, the ability to form gels with suspending agents, water solubility/dispersibility, and the ability to act as solvents for many common skin and hair care ingredients.
The following are non-limiting examples of processes for preparing the surfactant and derivative compositions of the invention (Examples 1 to 15), analytical results for several of said compositions (Examples 16 to 18), as well as uses of the compositions in specific cosmetic or personal care product formulations (Examples 19 to 38). In the Examples, as well as throughout this application, the chemical and scientific symbols have their customary meanings and all percents are weight percents unless otherwise specified.
Example Nos. 1 through 15 identify surfactants and derivatives produced by the process of the invention. For ease of identification, each ester is identified by both an Example Number and a Reference No., where applicable. This identification system is used in the subsequent Tables.
Although the Examples use only selected compounds and formulations, it should be understood that the examples are illustrative and not limited. Thus, any of the aforementioned Reactants A and B may be substituted according to the teachings of this invention in the following Examples.
(Macadamia Amide—MEA)
182.38 gms. of Macadamia fatty triglycerides (MFTG), also called Macadamia fatty oil (available under the trade name of Oil of Macadamia from Macadamia Oil of Australia, N. South Wales, Australia) were charged to a one liter round bottom 4-neck flask with distillation assembly. To this was added 38.10 gms. of Monoethanolamine (MEA) and 4.52 gms. Sodium Methylate 25% w/w in methanol. Reaction mass was heated under nitrogen to between 105° C. and 120° C. and was kept over a period of 4 hours until the alkalinity was about 20 mg KOH/g. This was a light yellow material that solidified upon cooling. The total mass was collected 225 gms. The distillate of free methanol was approximately 1.25 gms.
(Macadamia Amide MEA and Sodium Methyl Cocoyl Taurate)
The solid amide of Example #1 (Macadamia-Amide-MEA) is blended with an aqueous solution of Sodium Methyl Cocoyl Taurate resulting in a fluid, flowable dispersion paste. Thus, 8 gms. of Macadamia-Amide-MEA of example #1 was mixed at 70° C. with a mixture of 70 gms. of Sodium Methyl Cocoyl Taurate (Tauranol WS conc. from Finetex, Inc. of Elmwood Park, N.J.) and 22 gms. of water. A smooth off-white paste with very good flow was obtained upon cooling with mixing.
(Macadamia-amidopropyl Dimethylamine)
A reaction flask of 500 ml. capacity, with distillation assembly and mixer, was set up under nitrogen. To this was added 213 gms. of Macadamia fatty triglyceride (MFTG) also called Macadamia fatty oil available under the trade name of Oil of Macadamia from Macadamia Oil of Australia, N South Wales, Australia. Heated to 70° C. under nitrogen. To this was added 81 gms. of Dimethylaminopropylamine (DMAPA) and 6.0 gms. Sodium Methylate 25% in methanol. Temperature was brought to 120° C.-125° C. over 45 minutes. Heat input was adjusted to reach 150° C. over the next 30-45 minutes. Reaction was continued at 145° C.-150° C. for 4 hrs with use of vacuum. Reduced pressure ranging from 5 to 22 mm Hg. was used progressively to remove the free DMAPA. The yield upon cooling was 270 gms. The distillate collected was 30 gms. which was almost pure DMAPA. The final product had an alkalinity of 170 mg KOH/g.
(Macadamia-amidopropylbetaine)
To a 500 ml. reaction flask was added 189.93 gms. water and 22.14 gms. Sodium Monochloroacetate (SMCA). All SMCA was dissolved at 25° C. To this was added 37.29 gms. of 1,3 Butylene glycol. A clear liquid was formed. The premelted 47.64 gms. of the product of Example #3 were added to the mixture at 70° C.; the addition was done in three equal portions. These additions were done at 85° C.-86° C. and over a period of approximately one hour. The reaction mass was then held at 85° C. for further two hrs. The alkalinity was found to be 4.95 mg KOH/g and acid value was almost none. A clear colorless liquid with 4.0% sodium chloride and 53.0% of water was obtained. The net yield was 300 gms. as a Betaine.
In a four neck 500 ml. flask equipped with stirrer, condenser, nitrogen inlet and thermometer was added, under nitrogen, 105 gms. of Macadamia amidopropyl dimethyl amine (product of Example #3) and 120 gms. of water and 31.12 gms. butylene glycol. This was mixed and the mixture was brought to 60° C. To this mixture at 60° C. was added 43.80 gms. of Diethyl sulfate. Reaction mixture was kept at between 90° C.-105° C. Any exotherm was controlled by manipulating the heating mantle to maintain temperature below 100° C. Reaction continued for about 3 hrs, when alkalinity was 3.5 mgs KOH/gm. The clear colorless liquid so obtained was completely water soluble and foamed heavily upon dilution with water. The anhydrous yield was 280 gms.
To a 4 neck round bottom flask of 500 ml. capacity equipped with stirrer, condenser, and nitrogen inlet was added 63.18 gms. of Macadamia amide MEA (i.e. Product of Example #1). Heated mildly to 70° C. Added 18.27 gms. of Maleic anhydride. Reaction exothermed to 80° C. Mixture was held at 85° C. for one hour, acidity was found to be 122 mgm. KOH/gm. This was discharged as a clear colorless liquid and the net yield weighed at 81.45 gms.
A 500 ml. round bottom flask equipped with condenser, Nitrogen inlet and stirrer was charged with 195.09 gms. of water and 23.49 gms. of sodium sulfite. The sulfite crystals were completely dissolved. To this was added 81.45 gms. of Macadamia Amide-MEA-Maleate intermediate (product of Example #6). The reaction mixture was held at 85° C. with the controlled addition of the Macadamia amide-MEA-Maleate intermediate. The mixture was gelled initially which fluidized as the reaction continued with the conversion. The yield was 300 gms. net in the flask with pH of 6.5 and showed 35% solids. It was a thick dispersion. A further dilution with additional 40 gms. of water was done. A fluid light yellow dispersion was obtained. This product gave a very good rich foam when dissolved in water and further diluted for washing hands. The skin feel was also very smooth and pleasant without defatting effect.
880.7 gms. of Macadamia fatty triglycerides (MFTG) also called Macadamia oil was charged to a 2 liter round bottom 4-neck flask with distillation assembly under nitrogen. Heated to 82° C. To this was added 109.3 gms. of methanol and 2.0 gms. of Potassium Hydroxide flakes. Reaction mass then mixed at 82° C. for 30 minutes. Allowed to stand for 4 hours and the bottom glycerine layer was removed. The top layer, upon further standing, was a clear liquid methyl ester of Macadamia fatty oil. The residue from the methyl ester layer was approximately 280 gms. The yield as methyl ester was 780 gms. of the top clear liquid. This was further subjected to distillation for removal of methanol, which collection was approximately 40 gms. The finished filtered yield of the methyl ester was 740 gms.
(Isostearyl Macadamiate)
112.80 gms. of Methyl ester of example # 8 was charged to 500 ml. reaction flask with distillation assembly. To this was added, under nitrogen, 127.20 gms. of Isostearyl alcohol and 5.0 gms. of Sodium Methylate 25% in methanol. The mass was reacted at 150° C. for approximately 2 hours and any free methanol or methanol of rection was removed by distillation at reduced pressure of 10 Hg. The methanol distillate collected was approximately 5.0 gms. with some leftover condensate in the condenser. The mass was further refurbished with 3.0 gms. of Sodium Methylate and further reacted at 160° C., with vacuum of 15 mm Hg. The ester was then collected which showed solidification characteristics. The 240 gms. of Isostearyl ester was then washed with 50 gms. of water containing 5.0 gms. Sodium chloride and 1.0 gm. of concentrated Hydrochloric acid adjusted to pH 6. Separation occurred at 75° C. Allowed to stand. Separated bottom layer weighing 60 gms. A second wash was given with 50 gms. water and 5.0 gms. Sodium chloride. Bottom aqueous layer of 60 gms. was drained and the top layer of the ester collected was 225 gms. This wet ester was then dried in the reaction flask at 125° C. at reduced pressure of 25 Hg. The ester was then collected and filtered using diatomaceous earth. A liquid of light yellow color was obtained. The net filtered yield was 225 gms.
(PPG-3 Myristyl Ether Macadamiate)
123 gms. of Methyl ester of example #8 was charged to a 500 ml. reaction flask with distillation assembly. To this was added, under nitrogen, 177 gms. of PPG-3 Myristyl Ether and 5.0 gms. of Sodium Methylate 25% in methanol. The mass was reacted at 150° C. for approximately 2 hours and any free methanol or methanol of reaction was removed by distillation at reduced pressure of 10 Hg. The methanol distillate collected was approximately 5.0 gms. with some leftover condensate in the condenser. The mass was further refurbished with 3.0 gms. of Sodium Methylate and further reacted at 160° C. with vacuum of 15 mm Hg. The ester was then collected which showed solidification characteristics. The 285 gms. of PPG-3 Myristyl Ether ester was then washed with 50 gms. of water containing 5.0 gms. sodium chloride and 1.0 gms. of concentrated Hydrochloric acid adjusted to pH 6. Separation occurred at 75° C. Allowed to stand. Separated bottom layer weighing 60 gms. A second wash was given with 50 gms. water and 5.0 gms. Sodium chloride. Bottom aqueous layer of 60 gms. was drained and the top layer of the ester collected was 225 gms. This wet ester was then dried in the reaction flask at 125° C. at reduced pressure of 25 Hg. The ester was then collected and filtered using diatomaceous earth. A liquid of light yellow color was obtained. The net filtered yield was 225 gms.
(C12-15 Pareth-7 Macadamiate)
112.80 gms. of Methyl ester of example # 8 was charged to 500 ml. reaction flask with distillation assembly. To this was added under nitrogen 141.20 gins. of C12-15 Pareth-7 and 5.0 gms. of Sodium Methylate 25% in methanol. The mass was reacted at 150° C. for approximately 2 hours and any free methanol or methanol of reaction was removed by distillation at reduced pressure of 10 Hg. The methanol distillate collected was approximately 4.0 gms. with some leftover condensate in the condenser. The mass was further refurbished with 3.0 gms. of Sodium Methylate and further reacted at 160° C. with vacuum of 15 Hg. The ester was then collected which showed solidification characteristics. The 250 gms. of crude ester was then washed with 50 gms. of water containing 5.0 gms. sodium chloride and 1.0 gms. of concentrated Hydrochloric acid adjusted to pH 6. Separation occurred at 75° C. Allowed to stand. Separated bottom layer weighing 60 gms. A second wash was given with 50 gms. water and 5.0 gms. Sodium chloride. Bottom aqueous layer of 60 gms. was drained and the top layer of the ester collected was 225 gms. This wet ester was then dried in the reaction flask at 125° C. at reduced pressure of 25 mmHg. The ester was then collected and filtered using diatomaceous earth. A colorless liquid was obtained. The net filtered yield was 220 gms.
(Ceteareth-4 Macadamiate)
126.39 gms. of methyl ester of example # 8 was charged to 500 ml. reaction flask with distillation assembly. To this was added, under nitrogen, 173.61 gms. of ceteareth—4 and 5.0 gms. of Sodium Methylate 25% in methanol. The mass was reacted at 150° C. for approximately 2 hours and any free methanol or methanol of reaction was removed by distillation at reduced pressure of 10 mmHg. The methanol distillate collected was approximately 7.0 gms. with some leftover condensate in the condenser. The mass was further refurbished with 3.0 gms. of Sodium Methylate and further reacted at 160° C. with vacuum of 15 Hg. The ester was then collected which showed solidification characteristics. The 290 gms. of crude ester was then washed with 50 gms. of water containing 5.0 gms. sodium chloride and 1.0 gm. of concentrated Hydrochloric acid adjusted to pH 6. Separation occurred at 75° C. Allowed to stand. Separated bottom layer weighing 60 gms. A second wash was given with 50 gms. water and 5.0 gms. Sodium chloride. Bottom aqueous layer of 60 gms. was drained and the top layer of the ester collected was 225 gms. This wet ester was then dried in the reaction flask at 125° C. at reduced pressure of 25 mmHg. The ester was then collected and filtered using diatomaceous earth. A liquid of light yellow color was obtained. The net filtered yield was 225 gms.
(Macadamia Amide-MIPA)
234.09 gms. of Macadamia fatty triglycerides (MFTG) also called Macadamia fatty oil (available under the trade name of Oil of Macadamia from Macadamia Oil of Australia, N South Wales Australia) were charged to a one liter round bottom flask with distillation assembly. To this was added 60.09 gms. Monoisopropanol amine (MIPA) and 5.82 gms. sodium Methylate 25% w/w in methanol. Reaction mass was heated under nitrogen to between 105° C. and 120° C. and was kept over a period of 4 hrs until the alkalinity was about 35 mg KOH/g. This was a light yellow material that solidified upon cooling. The total mass was collected 225 gms. The distillate of free methanol was approximately 4.5 gms.
To a 4 neck round bottom flask of 500 ml. capacity equipped with stirrer, condenser, and nitrogen inlet was added 63.18 gms. of Macadamia amide MEA (i.e., product of Example #13). Heated mildly to 70° C. Added 18.27 gms. of Maleic anhydride. Reaction exothermed to 80° C. Mixture was held at 85° C. for one hour. Acidity was found to be 124 mgm. KOH/gm. This was discharged as a light amber liquid and the net yield weighed at 80 gms.
A 500 ml. round bottom flask equipped with condenser, Nitrogen inlet and stirrer was charged with 195.09 gms. of water and 23.49 gms. of sodium sulfite. The sulfite crystals were completely dissolved. To this was added 81.45 gms. of Macadamia Amide-MIPA-Maleate intermediate (product of Example #14 ). The reaction mixture was held at 85° C. with the controlled addition of the Macadamia amide-MEA-Maleate intermediate. The mixture was gelled initially which fluidized as the reaction continued with the conversion. The yield was 300 gms. net in the flask with pH of 6.5 and showed 35% solids. It was a thick dispersion. A further dilution with additional 40 gms. of water was done. A fluid light yellow dispersion was obtained. This product gave a very good, rich foam when dissolved in water and further diluted for washing hands. The skin feel was also very smooth and pleasant without defatting effects.
The Macadamia-based esters, surfactants and derivatives have the following featured properties:
Ease of emulsification.
Good refractive index.
Emolliency with good after-feel.
Lack of greasiness/pleasant skin feel.
Lack of oiliness while imparting good lubrication.
Low cloud point and pour point.
High spreading coefficient.
Alcohol solubility.
Additive for Antiperspirant formulations.
Low toxicity.
Hydrolytic stability.
Solvent for many skin and hair additives including sunscreens.
The Macadamia based esters, surfactants and derivatives are advantageous in that they are non-oily, tasteless, inert, essentially nontoxic and non-sensitizing, and stable. The Macadamia-based esters, surfactants and derivatives are useful as emollients, solubilizers, moisturizers, plasticizers, sunscreen vehicles/solvents, de-oilers/degreasers, and emulsifiers/co-emulsifiers. The foregoing list is only exemplary of the type of composition in which Macadamia esters may be used and, as such, is not to be considered limiting.
The amount of Ester used in an aqueous surfactant composition depends on the type and quantity of other ingredient used, and the amount and type of functional additives that are utilized. Typically the amount of Macadamia ester used ranges from about 0.5% to about 50% by weight of the aqueous surfactant composition, and preferably, from about 0.5% to about 10% by weight of Macadamia esters are used.
Macadamia-based esters, surfactants and derivatives possess unusual physico-chemical properties. In particular, they possess higher spreading coefficient that can make them beneficial and unique components of sophisticated delivery system such as in hand, face, and body creams and lotions.
Macadamia-based esters, surfactants and derivatives may be used in skin care compositions. The amount used in skin care compositions is dependent on the type of skin care composition, the type and quantity of cosmetic ingredients used and the amount and type of functional additives. Typically, the amount ranges from about 0.5% to about 80% by weight of the skin care composition. For example, a facial cream may only have about 0.5% whereas a massage oil may have up to about 80% by weight. Still higher amounts may be used in, for example, bath oils, e.g., 95%.
Further, the Macadamia-based esters described herein act as solvents and/or vehicles for solid organic, ultraviolet (uv) absorbers. Such esters also function as plasticizers for polymers contained in skin care compositions, and act as auxiliary suspending agents capable of assisting in the suspension of ingredients in skin care compositions and also may function as a dye leveling agents and dye carriers. Thus, the Macadamia based esters, when used in skin care compositions, serves not only as emollients and carriers, but also exhibits one or more other functions.
It is understood that the embodiments described herein are merely exemplary and that a person skilled in the art may make many variations and modifications without departing from the spirit and scope of the invention. All such modifications and variations are intended to be included within the scope of the invention described herein.
An analysis of the esters was conducted as to appearance, color, surface tension, spreading coefficient, freezing point, percentage of water, refractive index, and specific gravity. The results are presented in Table I below.
Where the esters are:
A = Isostearyl Macadamiate
B = PPG-3 Myristyl ether Macadamiate
C = C12-15 Pareth-7 Macadamiate
D = Ceteareth-4 Macadamiate
E = Finsolv TN
The two most commonly used solid organic crystalline sunscreens are Benzophenone-3 (2 hydroxy 4-methoxy benzophenone) and Parsol 1789 (Butyl—methoxy dibenzoyl methane). These two sunscreens are difficult to dissolve and keep in solution for use in sunscreen formulations for optimal SPF (Sun Protection Factor). Higher solvency for a sunscreen active is desirable as it allows higher concentrations of the sunscreen active ingredient in a formulation. This advantageously raises the SPF ratings for the formulations. The liquid organic sunscreens that are commonly used are octylsalicylate (os) and octyl-methoxycinnamate (omc). Macadamia esters exhibit superiority over commonly used and marketed cosmetic emollients/materials.
The high solvency exhibited by the macadamia based esters of the invention for the solid crystalline organic sunscreens is an advantageous effect in formulating sunscreen products for the skincare markets. Thus, besides being cosmetic emollients, these esters are excellent solvents for the above-mentioned organic sunscreens. A further aspect of these esters, beside being solubilizers for sunscreens, is to render anti-washoff effect. This effect is very attractive in formulating long lasting sunscreen products allowing the sunscreen to remain on the skin for a longer period of time.
The solubility characteristics of macadamia based esters are tabulated in Table III below. They are soluble in most commonly used solvents, emollients and vehicles employed in cosmetic product formulations.
Where the Macadamia based surface active esters are:
A = Isostearyl Macadamiate
B = PPG-3 Myristyl ether Macadamiate
C = C12-15 Pareth-7 ether Macadamiate
D = Ceteareth-4 ether Macadamiate
Key:
−− indicates insoluble
+ indicates soluble
An evaluation of the use of Macadamia-based esters in bar soaps was conducted as described below. The results show improvements in the properties of bar soaps upon inclusion of the Macadamiate ester. Soap bars containing Syndet base 96-143-1 and combo bar (25% syndet base 96-143-1 and 75% Bradford soap base 80/20) have the following features during processing of the soap bars and after washing with said bars:
Results of Standard Bar without Macadamia-based Additives/Esters of the Invention:
To the above soap bar containing 100% syndet base 96-143-1 and combo bar (25% syndet base 96-143-1 and 75% Bradford soap base 80/20) was added 1% Macadamia-based esters. The typical processing was followed, i.e, syndet base 96-143-1 or combo bar (25% syndet base 96-143-1 and 75% Bradford Tallow/coco soap base 80/20) was added to the amalgamator with esters, fragrance was incorporated, and the bar colored and refined as usual. The resulting bar was found to have the following additional beneficial properties in addition to those properties described above for the control bar:
Results of Soap Bars Comprising Macadamia-Based Esters of the Invention
Transparent Combo Bar
Two transparent combo bars were prepared as follows:
Procedure:
Clarity and emolliency are better in Combo Bar A with Surfine AZI-A and Finsolv TN. Clarity is excellent in formulation B with Isostearyl Macadamiate, with good emolliency and feel. Clarity was tested against light.
Hand and Body Lotion with Sunscreen
Five formulations of hand and body lotion with sunscreen were prepared as follows:
Procedure:
1. Disperse Carbomer in water.
2. Heat to 70° C., add sorbitol and EDTA.
3. Add all phase II ingredients together and heat to 70° C.
4. Add phase II ingredients to phase I ingredients with good mixing.
5. Add triethanolamine, and continue mixing until 45° C.
6. Add Glydant, continue mixing to room temperature, discharge and label.
Results: Formulations A through F so prepared were tested for skin feel, emolliency, slip, stickiness, and moisturizing effect on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. Results are as follows:
Waterproof Sunscreen Lotion
Procedure:
Formulations A through F so prepared were tested for skin feel, emolliency, slip stickiness, water rinseoff resistance and moisturizing effect on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. Results were as follows:
High SPF Sunscreen Lotion (Cold Process)
Procedure:
1. Combine ingredients of Phase I and mix well.
2. Dissolve Hydroxyethylcellulose into vortex of the agitating water phase.
3. Allow the cellulose to fully hydrate prior to adding sodium chloride. Add Natrlfine TP-T. Mix until uniform.
4. Add ingredients of Phase II slowly into ingredients of Phase I with slow agitation.
5. Mix until homogeneous.
Formulations A through F so prepared were tested for skin feel, emolliency, slip, water rinseoff resistance and moisturizing effect on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. Results were as follows:
High SPF Sunscreen Lotion
Procedure:
Formulations A through F so prepared were tested for skin feel, emolliency, slip, water rinseoff resistance and moisturizing effect on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. Results were as follows:
Sunblock Cream
Procedure:
1. Heat water to 80° C.
2. Add magnesium aluminium silicate slowly with stirring, mix until smooth.
3. Add remaining ingredients of Phase I and mix until smooth while maintaining temperature.
4. Heat ingredients of Phase II to 75° C., and add to ingredients of Phase I.
5. Mix until cool to 45° C. and discharge.
Formulations A through F so prepared were tested for skin feel, emolliency, slip, stickiness, moisturizing effect and water rinseoff resistance on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. Results were as follows:
Non-Whitening Antiperspirant Stick
Procedure:
Formulations A through F so prepared were tested for emolliency, skin feel, slip and stick structure on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. Results are as follows:
Deodorant Stick
Procedure:
1. Charge all ingredients into a suitable vessel.
2. Heat to 80° C., with mixing, allowing all ingredients to dissolve.
3. Cool to 60° C. and cast into stick moulds.
Formulations A through F so prepared were tested for skin feel, slip, stick structure, emolliency and tackiness on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. Results were as follows:
Emollient Cleansing Lotion
Procedure:
1. Disperse Carbomer into water.
2. Add balance of Phase I ingredients and heat to 75° C.
3. Mix Phase II ingredients together and heat to 75° C.
4. Add Phase II ingredients to Phase I ingredients, with mixing.
5. Combine Phase III ingredients, then add to the above and begin cooling.
6. At 40° C., add Phase IV ingredients and continue cooling to 30° C.
Formulations A through F so prepared were tested for slip, skin feel, and emolliency on a scale of 1 to 5, with 1 represent the best and 5 representing poor. Results are as follows:
Hand and Body Lotion
Procedure:
1. Disperse carbomer in water.
2. Heat to 70° C.
3. Add sorbitol 70% and tetrasodium EDTA.
4. Weigh all Phase II ingredients together and heat to 70° C.
5. Add ingredients of Phase II to ingredients of Phase I with mixing.
6. Add triethanolamine, continue mixing until 45° C.
7. Add preservative.
Formulations A through F so prepared were tested for skin feel, slip and emolliency on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. Results were as follows:
Foaming Characteristics of Macadamia oil-based Surfactants
Test comprises 0.1 gram macadamia oil-based surfactant in 100 ml. water in a 500 ml. graduated cylinder with stopper. Give 10 strokes on the cylinder by hand. The results were measured in terms of foam height, initially and after 5 minutes, the nature of the foam, and the durability of the foam.
Conditioning Shampoo
This is a comparison of Macadamia Betaine (Example # 4) to Cocoamidopropylbetaine (CAPB), a commercially available betaine from McIntyre Group, University Park, Ill. Table IV below sets forth the ingredients and the test results follow.
Procedure:
1. Charge water and heat to 70° C.
2. Add other ingredients in the order listed above.
3. Bring temperature to 75° C.
4. Mix well until uniform.
5. Cool to 45° C.
6. Add fragrance and preservative.
7. Add Sodium Chloride.
8. Mix gently, cooling to 35° C.
The properties of formulations A and B are as follows:
Both Formulations A and B are clear, viscous gels, but Formulation B is more viscous. Formulations A and B so prepared were tested for skin feel, emolliency, and slip on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. The results were as follows:
Formulation B, the product of invention, gave superior skin feel, emolliency, and slip.
Shower Gel
This is a comparison of Macadamia Betaine (Example # 4) to Cocoamidopropylbetaine (CAPB), a commercially available betaine from McIntyre Group. Table V below sets forth the ingredients and the test results follow.
Procedure:
The properties of the two formulations A and B are as follows:
Both Formulations A and B are clear, viscous gels, but Formulation B is more viscous. Formulations A and B so prepared were tested for skin feel, emolliency, and slip on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. The results were as follows:
Formulation B, the product of invention, gave superior skin feel, emolliency, and slip.
Clear and Mild Skin Cleansing Gel
This is a comparison of Macadamia Betaine vs CAPB when used in combination with Example # 2. Table VI below sets forth the ingredients and test results follow.
Procedure:
The properties of Formulations 1-4 of Example #33 are as follows:
Formulations 1-4 so prepared were tested for skin feel, emolliency, and slip on a scale of 1 to 5, with 1 representing the best and 5 representing poor result. The results were as follows:
Gentle Facial Cleaner
This is a comparison of Macadamia betaine (Example #4) to Disodium Cocoamphodiacetate, a commercially available amphoteric betaine from McIntyre Group
Procedure:
1. Charge water (1) and heat to 70 C
2. Add other ingredients (2) through (6) in the order listed above.
3. Bring temperature to 75° C.
4. Mix well until uniform.
5. Cool to 45° C.
6. Add ingredients (7) through (9) in the order set forth above.
7. Mix gently, cooling to 35° C.
The properties of the two formulations A and B of Example #34 are as follows:
Both Formulations A and B are clear, viscous gels, but Formulation B is more viscous. Formulations A and B so prepared were tested for skin feel, emolliency, and slip on a scale of 1 to 5, with 1 representing the best and 5 representing poor results. The results were as follows:
Formulation B, the product of invention, gave superior skin feel, emolliency, and slip.
Shower and Bath Gel
This is a comparison of Macadamia-based betaine and Macadamia-based ester emollient to commercial cocobetaine and commercial ester emollients. Table VIII below sets forth the ingredients and test results follow.
Procedure:
The properties of the formulations 1-4 of Example # 35 are as follows:
2 in 1 Clear Conditioning Shampoo
This is a comparison of Macadamiaamide MEA, Diethyl sulfate quatemium of Macadamia with commercially available substantive quaternary ammonium compounds. Table IX below sets forth the ingredients and test results follow.
Procedure:
The properties of the formulations A-D of Example #36 as follows:
Formulations A and B gave superior skin feel, emolliency, and slip.
Comparative Substantivity Properties
Sustantivity is defined as the ability of the quaternary (or Cationic) substance to be attracted to an anionic surface such as hair and wool. Substantivity is taken as a conditioning efficacy parameter for hair care products. In the industry, the Rubine Dye Uptake Test is typically performed to screen for the property of substantivity. A contol fabric swatch of wool is treated in water without any treatment with a quaternary compound. The test articles, i.e., fabric swatches, are applied with a certain level of activity to the same weight fabric swatches as the control swatch. The treated fabric swatches are rinsed and then further treated in a solution of anionic acid dye such as Rubin Red Dye. The treatment with dye solution allows the fabric to attract the strong anionic dye solution with the help of a quaternary compound that has been applied to the swatch. The depth of color is stronger or weaker depending upon the substantivity (higher or lower) of the quaternary. The deeper the color, the greater the substantivity of the quaternary.
The Rubine Dye Uptake Test was performed using the following materials:
The control swatch is treated in water without quaternary compound. Separate swatches for each quaternary substance are treated for 5 minutes with mild stirring in separate beakers. The swatches are then individually (separately) rinsed with water.
The control swatch and treated swatches are further treated (each one in a separate beaker) with dye solution for 5 minutes and rinsed in tap water at 40 C. The swatches are allowed to air dry. The depth of the dye uptake is compared. The higher the color depth, the higher the substantivity of the quaternary.
The results of the test are set forth in Table X below, where a substantivity rating of 1 is the best, and a rating of 10 is poor.
As can be seen in Table X, DES quaternary of Macadamia (Example # 5) shows superior substantivity in this group of quaternaries tested. This is indicative of high substantivity for its use as a conditioning agent for hair care products. Hair is similar to wool fibers. Accordingly, wool is used as a sample textile material, serving a dual purpose in testing quaternaries.
Comparative Conditioning Properties
Conditioning efficacy is judged by evaluating wet and dry comb characteristics and flyaway features of the hair tresses treated with the conditioners. A comparative study was done using the quaternary of this invention (Product of Example #5) as compared to other commercially marketed products.
A prototype formulation of Conditioner Base was made as shown below:
Procedure:
Mix hydroxyethylcellulose (i.e., Natrosol 250HHRCS) in water. Dissolve completely at 50° C. Add propylene glycol and PEG 75 Lanolin. Mix for 30 minutes, clear system after adding three ingredients in water. Add Conditioners shown in the Table XI. Rinse hair tresses in tap water for 1 second. Transfer rinsed hair tresses into combined portion of phases A & B. Mix for 5 minutes. Remove tresses and rinse with tap water running on it for 15 seconds. Hang each wet sample by clamping one end of the tresses. Perform a wet and dry comb test. The attached table gives the results of comparative conditioning properties, with a rating of 1 being the best, and a rating of 10 being poor.
As can be seen in Table XI Macadamia Quat (the product of invention Example #5) shows superior conditioning properties in this group of quaternaries tested. This is indicative of its benefits for use as a conditioning agent for hair care products.
