US3424849A - Bath oil composition containing octyl dodecanoate - Google Patents

Bath oil composition containing octyl dodecanoate Download PDF

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US3424849A
US3424849A US471729A US3424849DA US3424849A US 3424849 A US3424849 A US 3424849A US 471729 A US471729 A US 471729A US 3424849D A US3424849D A US 3424849DA US 3424849 A US3424849 A US 3424849A
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oil
esters
alcohols
skin
weight
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Edward J Conklin
Leo F Judge Jr
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Procter and Gamble Co
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    • 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
    • A61K8/37Esters of carboxylic acids
    • 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
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42Amides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations

Definitions

  • the present invention relates to a bath oil of novel composition. More particularly, this invention relates to a bath oil, suitable for cosmetic and therapeutic purposes, which is comprised of particular fatty esters and mineral oil, and which, in its preferred embodiment, contains lower molecular weight alcohols and nonionic surfactants.
  • Improved bat'h oil compositions were later prepared by :mixing with a mineral oil a compound such as isopropyl myristate, or isopropyl pallmitate. Because of the addition of these esters, the resulting surface tension in the oil and ester mixture was less than that of the oil alone. Accordingly, the thickness of the molecular layer on the surface of the water was decreased. Reduction of the thickness of the bath oil layer alleviates the excessively greasy feeling caused by absorption of excess oil on the skin, yet allows deposit of suflicient emollient to keep the skin soft, smooth and fiexibile. This ester also tends to act as an extender or spreading agent. These specific esters, however, failed to satisfactorily solve the problems of the formation of the unsightly oil ring in the bathtub.
  • Another object of the present invention is to provide an improved bath oil composition which has valuable emolliency and therapeutic properties. Another object of this invention is to provide a bath oil composition which retards the formation of the unsightly bathtub ring.
  • Yet a further object of this invention is to provide 'a bath oil composition containing as an essential ingredient, an emmolliency and therapeutic agent which will effectively coat the skin to prevent water loss from the stratum corneum and, at the same time, give the skin a smooth, silky feeling.
  • a novel bath oil composition which is a clear, non-aqueous liquid consisting essentially of from about 20% to about of an ester having moieties containing from about 8 to about 14 carbon atoms, from about 20% to about 80% of a mineral oil, from 0% to about 30% of an alcohol containing from 2 to 10 carbon atoms and from about 0% to about 10% of a synthetic nonionic sunface active agent.
  • esters utilized in the bath oil compositions herein described have moieties containing from about 8 to about 14 carbon atoms. More particularly, the esters of these compositions can conveniently be described as the esters of branched or straight chain saturated aliphatic alcohols having from about 8 to about 14 carbon atoms and preferably from 8 to 12 carbon atoms and branched or straight chain aliphatic fatty acids having from about 8 to about 14 canbon atoms and preferably from 8 to 12 carbon atoms. Although optimumly comprised of esters having from about 8 to about 14 carbon atoms in each moiety, the composition can tolerate up to about 15% of the total ester mixture of alcohols or fatty acids which deviate from the delineated carbon atom limits by not more than 4 carbon atoms.
  • esters are compatible with the other bath oil ingredients. Additionally, valuable therapeutic and emollient effects are attributed to these esters. They render a markedly smoother and silkier feeling to the skin than do the esters of the isopropyl myristate type. They also contribute substantially to alleviating the problem of bathtub ring.
  • esters suitable for use in this invention are Z-ethylhexyl dodecanoate, 2-ethylhexyl octanoate, octyl octanoate, octyl dodecanoate, dodecyl dodecanoate, decyl decanoate, decyl octanoate and octyl 1,1- dimethyldecanoate.
  • esters of this invention can be utilized alone or they can be utilized in admixture with each other in any proportions. In fact, as a preferred embodiment of the present invention, esters derived from natural sources are utilized in this bath oil composition.
  • One of these preferred ester ingredients can be prepared by the alcoholysis of a mixture of light cut coconut methyl esters with a mixture of light out coconut alcohols.
  • light cut coconut in this context, refers to a coconut fraction containing the following approximate distribution of carbon chain lengths: 4% C 60% C 35% C and 1% C
  • Another preferred ester component characterized in column 2 of Table I, and referred to hereinafter as essentially octyl dodecanoate can be prepared in the same manner by utilizing a mixture of middle cut coconut methyl esters, i.e., a fraction containing the following approximate distribution of carbon chain lengths: 1% C 68% C 24% C and 7% C and a mixture of light out coconut alcohols as identified above.
  • liquid esters of the present invention such as octyl octanoate, octyl dodecanoate, and Z-ethylhexyl dodecanoate, are clear, mobile liquids with high boiling points and high flash points. They are very soluble in common organic solvents but insoluble in water. Dodecyl dodecanoate is a solid and is hard and wax-like with a more limited solubility in organic and inorganic solvents. Additionally, all of the esters of this invention are nearly odorless and colorless, which in conjunction with their low potential for irritation and oily consistency make them excellent bath oil adjuvants.
  • the esters of this invention can advantageously be prepared by the process known as alcoholysis. During this reaction, the alcohol moiety of an ester of an organic acid is replaced by that of another alcohol. Such methyl esters as those of octanoic, decanoic or dodecan'oic acids can, accordingly, be permitted to react with alcohols containing from about 8 to about 14 carbon atoms to obtain the esters of this invention.
  • Catalysts suitable for use in this reaction are strong bases such as the aluminum alkoxide of the free alcohol, sodium methoxide or acids such as sulfuric or hydrochloric acid. Other methods suitable for preparation of these esters are described in Kelley, Organic Chemistry, 2nd ed. (1957), at pp. 167 169. It is not intended that the esters of this novel composition be limited to any particular source or method of preparation; the only restriction on these esters is embodied in the description of the moieties.
  • these esters should comprise from about 20% to about 80% by weight of the total bath oil composition. In the preferred embodiment of this invention, however, the esters should be used at a level of from about 40% to about 75% by weight of the total composition. If these limitations are not met, optimum therapeutic, emollient and cosmetic effects are not attained. In addition, the problem of bathtub rings is accentuated.
  • Oils suitable for conjoint use with the hereinbefore disclosed esters may be selected from a large class of materials.
  • the preferred oil is mineral oil, as it appears to be absorbed in greater quantities on the skin and gives longer lasting comfort and smoothness.
  • Mineral oil is a colorless, transparent, oily liquid that is obtained from crude petroleum by refining. Essentially all of the unsaturated and aromatic hydrocanbons and other impurities are removed, and the resulting oil product is clear and water-white or nearly water-white.
  • the United States Pharmacopoeia defines two types of white mineral oil, or liquid petrolatum. One type, which has a kinematic viscosity of not more than 37 centistokes at 37.8 C. (100 F.), is termed light; the other, with a kinematic viscosity of not less than 38.1 centistokes, is termed heavy.
  • a white mineral oil that has a Saybolt viscosity of not more than 172 at 100 F. is referred to as light white mineral oil, while one that has a Saybolt viscosity of not less than 177 is termed heavy white mineral oil. While either of these mineral oils or mixtures thereof may advantageously be utilized in this composition, as an especially preferred embodiment herein, light white mineral oil is utilized herein.
  • oils can be substituted for the mineral oil.
  • examples of other oils which can be used beneficially in the composition of this invention are vegetable oils such as sesame oil, cottonseed oil or corn oil.
  • Other acceptable vegetable oils are sweet almond oil, olive oil, wheat germ oil, rice bran oil and peanut oil.
  • Animal oils that may be utilized in this bath oil composition are lanolin, neats foot oil, bone oil, sperm oil, cod liver oil, and the like.
  • oils may be used either alone or in conjunction -with each other. They may be mixed in any suitable ratio and may be specifically formulated for particular uses.
  • the oil component should be used at a level of from about 20% to about by weight of the total composition.
  • the oil component is added in amounts of from about 25% to about 60% by weight of the total composition.
  • the product has little greasy feeling and is optimumly suited for retarding moisture loss from the skin.
  • a nonionic surface active agent is present in this composition.
  • the nonionic surfactants which are broadly suitable for use in this invention may be defined as those surfactants which do not ionize in water solution.
  • Pluronic a well known class of nonionic surfactants is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1100 to 2500.
  • the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where polyoxyethylene content is about 5 0% of the total weight of the condensation product.
  • nonionic surfactants include:
  • the polyethylene oxide condensates of alkylphenols, e.g., the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkylphenol.
  • the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, n-octene, or n-nonene, for example.
  • Fatty acid esters of polyoxyethylene sorbitan containing from about to about 40 oxyethylene units per molecule and containing fatty acid groups having from about 8 to about 18 carbon atoms.
  • the arrow in the formula is a conventional representation of a semipolar bond.
  • amine oxides suitable for use in this invention include dimethyldodecylamine oxide, diethyloctylamine oxide, dimethyldecylamine oxide, diethyltetradecyla-mine oxide, dimethylhexadecylamine oxide, di- (hydroxymethyl)dodecylamine oxide, di(hydroxymethyl) tetradecylamine oxide, di(hydroxyethyl)octy1amine oxide, di(hydroxyethyl)decylamine oxide.
  • acyl moieties are normally derived from naturally occurring glycerides (e.g., coconut oil, palm oil, soybean oil, and tallow), but can be derived synthetically (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer- Tropsch process).
  • nonionic surface active agents act both as an emulsifier and as a dispersant. They assist in retarding the formation of the objectionable bathtub ring and assist in dispersing the ester and oil mixture over the surface of the water.
  • the ethoxylated nonionics described in 1) through (4) above are utilized in the composition of this invention.
  • these ethoxylated nonionics are mild when contacted with the skin. They allow the maximum amounts of the emollient to be adsorbed on the surface of the skin.
  • these preferred ethoxylated nonionic surface active agents are the following: The condensation product of one mole of dodecylphenol with about 20 moles of ethylene oxide, the condensation prodduct of one mole of nonylphenol with about 9.5 moles of ethylene oxide, the condensation product of one mole of hexylphenol with about 10 moles of ethylene oxide.
  • the amides described in 6) above are utilized in the composition of this invention. These particular amides can be utilized alone or in combination with the alcohols and hereinbefore described nonionics of this composition. These amides actually emulsify the oil and ester mixture in the bath water. A stable, cloudy, white emulsion is formed in the bath water and no floating emollient layer can be discerned. With an emulsion of this type, only a controlled amount of the oil and ester mixture is deposited on the skin. This is particularly advantageous for people with greasy or oily skin who desire to take advantage of the softening effect of a bath oil yet do not wish to have more than a controlled amount of oil and ester deposited on their skin. An emulsion of this type is also particularly valuable in reducing and, for all practical purposes, eliminating the bathtub ring as the emulsified oil and ester flow out of the tub with the water.
  • these amides are the following: N,N diethanoldodecanamide, N,N diethanoltetradecan amide, N,N dicthanolhexadecanamide, N,N diethanoldecanamide, N,N diethanoloctanamide, N ethanoldodecanamide, N ethanoltetradecanamide, N ethanoloctanamide, N ethanolnonanamide, octanamide and decanamide.
  • nonionic surface active agents should comprise from about 0% to about 10% of the composition of this invention.
  • the capability of the nonionic to effectively insure adequate dispersion and emulsification of the oil and ester drops off substantially when used at levels below about 2% by weight of the total composition. Above the 10% level the surface active agent does not contribute materially, in proportion to its weight, to the effectiveness of the bath oil composition. Maximum effectiveness of the nonionic surface active agent is attained at about 4% to 8% by weight of the total composition.
  • lower molecular weight alcohols are added to this composition.
  • the addition of these alcohols performs several functions.
  • these alcohols act as a coupling agent which pulls the surface active agent into the mixture of oil and ester. In this manner, a homogeneous system is formed.
  • These alcohols also help disperse the oil and ester mixture, thus again causing a decrease in the thickness of the oil and ester layer on the water and again decreasing the greasy feeling of the skin and the formation of objectionable bathtub ring.
  • Physical properties of the composition of this invention such as viscosity, cloud point and freezing point, can also be advantageously adjusted through the use of these alcohols.
  • these alcohols can be used as a solvent for the higher molecular weight esters of this invention.
  • Lower molecular weight aryl alcohols have the additional advantage of being perfume fixatives.
  • Alcohols suitable for use in this invention include straight or branched chain saturated aliphatic alcohols having from about 2 to about 6 carbon atoms and aryl and alicylic alcohols having from about 5 to about 10 carbon atoms. Also suitable for use herein are the polyhydric alcohols having from about 2 to about 6 carbon atoms. Alcohols containing from about 2 to about 6 carbon atoms are preferred for use in this invention. Specific examples of suitable alcohols are ethanol, propanol, butanol, hexanol, benzyl alcohol, cyclohexanol, 1,2- ethanediol, 1,2-propanediol. Ethanol is the preferred alcohol of this invention.
  • These alcohols can be added to this composition in amounts from 0% to about 30% by weight of the total composition.
  • the practical minimum to obtain all of the above-stated advantages is about 2%.
  • the preferred range for the addition of these alcohols is from 5% to 15% by weight of the total composition.
  • Colors and perfumes well known in the art may be added in measured amounts to suit individual tastes and add aesthetic appeal. Silicone compounds can also be added to create a smoother feeling and prevent foaming of the bath oil. If foaming is desired, sOap or other anionic surface active agents can be added for this purpose. Deodorants and antibacterial agents can be incorporated into the bath oil as a further improvement.
  • the ingredients were added in the order listed below. Between each addition, the product was stir-red to insure uniformity of the final bath oil. Since a major factor in consumer acceptance of this type of product is odor, and in view of the high dilution of the product in usage, relatively high levels of perfume are used in these formulations.
  • Essentially octyl dodecanoate 50 Light white mineral oil (graded by United States Pharmacopoeia) 35 Condensation product of nonyl phenol with 9.5 moles of ethylene oxide Isopropyl alcohol 7 Perfume and color 3
  • the octyl dodecanoate component was prepared by the alcoholysis of a mixture of middle cut coconut methyl ethers with a mixture of light out coconut alcohols.
  • the middl cut coconut fraction contained the following distribution of carbon chain lengths 1% C10, 68% C1 24% C14 and 7% C10.
  • the light out fraction contained 4% Cu, 60% Ca, 35% C and 1% C12.
  • EXAMPLE II The following bath oil compositions were prepared. In all the formulations listed below, the product was a clear, homogenous, liquid mixture which, when applied in the normal bathtub manner to the skin, left it feeling smooth, soft and silky. The formation of the bathtub ring was substantially retarded during use of several formulations by using the dispersants and emulsifiers as hereinbefore described.
  • the esters, octyl octanoate, octyl dodecanoate, dodecyl octanoate and dodecyl dodecanoate were prepared from coconut fractions.
  • the octyl octanoate ester is the reaction product of light cut coconut methyl esters and light out coconut alcohols.
  • the octyl dodecanoate ester is the reaction product of middle cut coconut methyl esters and light out coconut alcohols while the dodecyl octanoate ester is the reaction product of light cut coconut methyl esters and middle cut coconut alcohols.
  • Middle cut coocnut methyl esters and middle cut coconut alcohols were utilized in preparing the dodecyl dodecanoate.
  • the terms light and middle have been hereinbefore defined.
  • Formulation 1 Parts by weight Octyl dodecanoate 50
  • Light white mineral oil graded by United States 1,2-propanediol 11 8
  • Formulation 5 Parts by weight Octyl dodecanoate 43
  • Light white mineral oil U.S.P. Grade 47
  • Ethanol 5 Formulation 6:
  • Octyl dodecanoate 46 Light white mineral oil (U.S.P. Grade) 35 The condensation product of nonyl phenol with 9.5 moles of ethylene oxide 7 Ethanol 6 N,N-diethanoldodecanamide 6 Formulation 10:
  • Octyl dodecanoate 50 Light white mineral oil (U.S.P. Grade) 41 N-ethanoloctanamide 4 Ethanol 5 Formulation 13:
  • Octyl octanoate 50 Light white mineral oil (U.S.P. Grade) 40 N,N-diethanoldodecanamide 5 Butanol 5 Formulation 15:
  • Octyl dodecanoate 46 Light white mineral oil (U.S.P. Grade) 35 The condensation product of nonyl phenol with 9.5 moles of ethylene oxide 7 Ethanol 6 N-ethanoldodecanamide 6 Formulation 16:
  • Dodecyl octanoate 46 Light white mineral oil (U.S.P. Grade) 36
  • other of the esters in the range hereinbefore delineated may be substituted for the ones mentioned either in a single compound form or at the blends derived from such natural sources as coconut oil. Substitution of higher molecular weight esters results in oilier products, while substitution of lower molecular weight esters results in less oily products. Use of esters beyond the essentially C -C ester results in a very thick product which also tends to increase the problem of the bathtub ring. Below the essentially C -C ester, the product loses therapeutic and emollient value.
  • any of the hereinbefore described oils, nonionic surface active agents or alcohols may be substituted in the examples in accordance with this invention.
  • Perfumes and color are added to suit individual taste, but they atfect this invention only by adding aesthetic appeal.
  • a clear, non-aqueous liquid composition containing 60% by Weight of octyl dodecanoate, 30% by Weight of light white mineral oil and 10% by weight of benzyl alcohol.
  • a clear, non-aqueous liquid composition containing 50% by weight of octyl dodecanoate, 37% by weight of light white mineral oil, 6% by weight of the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide and 7% by Weight of ethanol.
  • a clear, non-aqueous liquid composition containing 46% by weight of octyl dodecanoate, 35% by Weight of light white mineral oil, 7% by weight of the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide, 6% by weight of ethanol, and 6% by Weight of N,N-diethan0lododecanamide.

Description

United States Patent Office 3,424,849 Patented Jan. 28, 1969 3,424,849 BATH OIL COMPOSITION CONTAINING OCTYL DODECANOATE Edward J. Conklin, Forest Park, and Leo F. Judge, Jr.,
Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed July 13, 1965, Ser. No. 471,729 US. Cl. 424--365 3 Claims Int. Cl. A61k 7/00; A61l 23/00 The present invention relates to a bath oil of novel composition. More particularly, this invention relates to a bath oil, suitable for cosmetic and therapeutic purposes, which is comprised of particular fatty esters and mineral oil, and which, in its preferred embodiment, contains lower molecular weight alcohols and nonionic surfactants.
The beneficial effect of oil on the skin is Well known. Dermatologists have long extolled the merits of oil in protecting and reconditioning skin, especially dry skin.
In this connection, dry, pruritic, scaly and pediatric dermatoses all appear to be caused, at least to some degree, by lack of water in the outer skin layer, the stratum corneum. Skin lipids play a significant role in keeping the skin soft and flexible by preventing Water loss from the stratum corneum. The cells of this outer layer are highly hydrophilic and will swell considerably when immersed in water or when water is supplied by internal means through the sweat glands. However, when the humidity is low, water present in the skin may be lost at a higher rate than it can be replaced internally. This water loss, in turn, tends to cause skin dryness and related problems. The purpose of the bath oil is to augment the skin lipids by forming a protective film on the skin. The bath oil thus assists in keeping moisture in the stratum corneum and, accordingly, tends to keep the skin soft, silky and smooth without the danger of chappiug.
In the first attempts to use a bath oil, oil was simply poured into the water and an oil film was formed on the surface of the water. As the bather stepped into and out of the bath water, his skin was coated with the oil floating on the water. This method of application left the skin with an excessively greasy feeling and was found to leave a visible coating of oil on the skin, some of which rubbed off on garments. The oil coating was also visible as a bathtub ring. Therapeutically, this method did accomplish the results of coating the skin to retard evaporation of moisture, but the problems it raised prevented wide consumer acceptance.
Improved bat'h oil compositions were later prepared by :mixing with a mineral oil a compound such as isopropyl myristate, or isopropyl pallmitate. Because of the addition of these esters, the resulting surface tension in the oil and ester mixture was less than that of the oil alone. Accordingly, the thickness of the molecular layer on the surface of the water was decreased. Reduction of the thickness of the bath oil layer alleviates the excessively greasy feeling caused by absorption of excess oil on the skin, yet allows deposit of suflicient emollient to keep the skin soft, smooth and fiexibile. This ester also tends to act as an extender or spreading agent. These specific esters, however, failed to satisfactorily solve the problems of the formation of the unsightly oil ring in the bathtub.
It has now been discovered that an improved bath oil composition can be prepared which not only renders the skin as soft and pliable as previous products but which also aids in eliminating the troublesome problem of bathtub rings.
Accordingly, it is a primary object of the present invention to provide an improved bath oil composition which has valuable emolliency and therapeutic properties. Another object of this invention is to provide a bath oil composition which retards the formation of the unsightly bathtub ring.
Yet a further object of this invention is to provide 'a bath oil composition containing as an essential ingredient, an emmolliency and therapeutic agent which will effectively coat the skin to prevent water loss from the stratum corneum and, at the same time, give the skin a smooth, silky feeling.
Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
It has now been discovered that the foregoing objects of the present invention are attained with a novel bath oil composition which is a clear, non-aqueous liquid consisting essentially of from about 20% to about of an ester having moieties containing from about 8 to about 14 carbon atoms, from about 20% to about 80% of a mineral oil, from 0% to about 30% of an alcohol containing from 2 to 10 carbon atoms and from about 0% to about 10% of a synthetic nonionic sunface active agent.
The esters utilized in the bath oil compositions herein described have moieties containing from about 8 to about 14 carbon atoms. More particularly, the esters of these compositions can conveniently be described as the esters of branched or straight chain saturated aliphatic alcohols having from about 8 to about 14 carbon atoms and preferably from 8 to 12 carbon atoms and branched or straight chain aliphatic fatty acids having from about 8 to about 14 canbon atoms and preferably from 8 to 12 carbon atoms. Although optimumly comprised of esters having from about 8 to about 14 carbon atoms in each moiety, the composition can tolerate up to about 15% of the total ester mixture of alcohols or fatty acids which deviate from the delineated carbon atom limits by not more than 4 carbon atoms.
It was surprising to discover that bath oil compositions containing these fatty esters fulfilled the objectives of this invention. Heretofore, it had been thought that only those esters which were of the isopropyl myristate and isopropyl palmitate variety could be used in combination with other bath oil ingredients. That is, it was heretofore considered essential to employ esters which structurally had a long acyl moiety and a very short alkyl chain. It was also suspected that esters having a more symmetrical configuration would not possess the property of being compatible with the essential bath oils.
It has been unexpectedly found, however, that these esters are compatible with the other bath oil ingredients. Additionally, valuable therapeutic and emollient effects are attributed to these esters. They render a markedly smoother and silkier feeling to the skin than do the esters of the isopropyl myristate type. They also contribute substantially to alleviating the problem of bathtub ring.
Examples of specific esters suitable for use in this invention are Z-ethylhexyl dodecanoate, 2-ethylhexyl octanoate, octyl octanoate, octyl dodecanoate, dodecyl dodecanoate, decyl decanoate, decyl octanoate and octyl 1,1- dimethyldecanoate.
The esters of this invention can be utilized alone or they can be utilized in admixture with each other in any proportions. In fact, as a preferred embodiment of the present invention, esters derived from natural sources are utilized in this bath oil composition.
One of these preferred ester ingredients, characterized in column 1 of Table I, can be prepared by the alcoholysis of a mixture of light cut coconut methyl esters with a mixture of light out coconut alcohols. It is to be understood that light cut coconut, in this context, refers to a coconut fraction containing the following approximate distribution of carbon chain lengths: 4% C 60% C 35% C and 1% C Another preferred ester component characterized in column 2 of Table I, and referred to hereinafter as essentially octyl dodecanoate, can be prepared in the same manner by utilizing a mixture of middle cut coconut methyl esters, i.e., a fraction containing the following approximate distribution of carbon chain lengths: 1% C 68% C 24% C and 7% C and a mixture of light out coconut alcohols as identified above.
An analysis of these coconut cut esters follows.
The liquid esters of the present invention, such as octyl octanoate, octyl dodecanoate, and Z-ethylhexyl dodecanoate, are clear, mobile liquids with high boiling points and high flash points. They are very soluble in common organic solvents but insoluble in water. Dodecyl dodecanoate is a solid and is hard and wax-like with a more limited solubility in organic and inorganic solvents. Additionally, all of the esters of this invention are nearly odorless and colorless, which in conjunction with their low potential for irritation and oily consistency make them excellent bath oil adjuvants.
The esters of this invention can advantageously be prepared by the process known as alcoholysis. During this reaction, the alcohol moiety of an ester of an organic acid is replaced by that of another alcohol. Such methyl esters as those of octanoic, decanoic or dodecan'oic acids can, accordingly, be permitted to react with alcohols containing from about 8 to about 14 carbon atoms to obtain the esters of this invention. Catalysts suitable for use in this reaction are strong bases such as the aluminum alkoxide of the free alcohol, sodium methoxide or acids such as sulfuric or hydrochloric acid. Other methods suitable for preparation of these esters are described in Kelley, Organic Chemistry, 2nd ed. (1957), at pp. 167 169. It is not intended that the esters of this novel composition be limited to any particular source or method of preparation; the only restriction on these esters is embodied in the description of the moieties.
According to the present invention, these esters should comprise from about 20% to about 80% by weight of the total bath oil composition. In the preferred embodiment of this invention, however, the esters should be used at a level of from about 40% to about 75% by weight of the total composition. If these limitations are not met, optimum therapeutic, emollient and cosmetic effects are not attained. In addition, the problem of bathtub rings is accentuated.
Oils suitable for conjoint use with the hereinbefore disclosed esters may be selected from a large class of materials. The preferred oil is mineral oil, as it appears to be absorbed in greater quantities on the skin and gives longer lasting comfort and smoothness.
Mineral oil is a colorless, transparent, oily liquid that is obtained from crude petroleum by refining. Essentially all of the unsaturated and aromatic hydrocanbons and other impurities are removed, and the resulting oil product is clear and water-white or nearly water-white. The United States Pharmacopoeia defines two types of white mineral oil, or liquid petrolatum. One type, which has a kinematic viscosity of not more than 37 centistokes at 37.8 C. (100 F.), is termed light; the other, with a kinematic viscosity of not less than 38.1 centistokes, is termed heavy. Since viscosity is usually expressed in Saybolt seconds, this distinction between grades should be understood as follows: A white mineral oil that has a Saybolt viscosity of not more than 172 at 100 F. is referred to as light white mineral oil, while one that has a Saybolt viscosity of not less than 177 is termed heavy white mineral oil. While either of these mineral oils or mixtures thereof may advantageously be utilized in this composition, as an especially preferred embodiment herein, light white mineral oil is utilized herein.
When suitable standards for mildness, toxicity and odor are followed, other oils can be substituted for the mineral oil. Examples of other oils which can be used beneficially in the composition of this invention are vegetable oils such as sesame oil, cottonseed oil or corn oil. Other acceptable vegetable oils are sweet almond oil, olive oil, wheat germ oil, rice bran oil and peanut oil. Animal oils that may be utilized in this bath oil composition are lanolin, neats foot oil, bone oil, sperm oil, cod liver oil, and the like.
All of these oils may be used either alone or in conjunction -with each other. They may be mixed in any suitable ratio and may be specifically formulated for particular uses.
The oil component should be used at a level of from about 20% to about by weight of the total composition. As a preferred embodiment of this invention, the oil component is added in amounts of from about 25% to about 60% by weight of the total composition. In the preferred range, the product has little greasy feeling and is optimumly suited for retarding moisture loss from the skin.
According to a preferred embodiment of this invention, a nonionic surface active agent is present in this composition. The nonionic surfactants which are broadly suitable for use in this invention may be defined as those surfactants which do not ionize in water solution.
For example, a well known class of nonionic surfactants is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1100 to 2500. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where polyoxyethylene content is about 5 0% of the total weight of the condensation product.
Other suitable nonionic surfactants include:
(1) The polyethylene oxide condensates of alkylphenols, e.g., the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, n-octene, or n-nonene, for example.
(2) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with about 3 to 50 moles of ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
(3) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40% to about 80% poly oxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylenediamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000, are satisfactory.
(4) Fatty acid esters of polyoxyethylene sorbitan containing from about to about 40 oxyethylene units per molecule and containing fatty acid groups having from about 8 to about 18 carbon atoms.
(5) Long chain tertiary amine oxides corresponding to the following general formula, R R R 0, wherein R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are selected from methyl, ethyl, hydroxymethyl and hydroxyethyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecylamine oxide, diethyloctylamine oxide, dimethyldecylamine oxide, diethyltetradecyla-mine oxide, dimethylhexadecylamine oxide, di- (hydroxymethyl)dodecylamine oxide, di(hydroxymethyl) tetradecylamine oxide, di(hydroxyethyl)octy1amine oxide, di(hydroxyethyl)decylamine oxide.
(6) The ammonia, monoethanol, and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms. These acyl moieties are normally derived from naturally occurring glycerides (e.g., coconut oil, palm oil, soybean oil, and tallow), but can be derived synthetically (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer- Tropsch process).
These nonionic surface active agents act both as an emulsifier and as a dispersant. They assist in retarding the formation of the objectionable bathtub ring and assist in dispersing the ester and oil mixture over the surface of the water.
As a further preferred embodiment of this invention, the ethoxylated nonionics described in 1) through (4) above are utilized in the composition of this invention. In addition to performing the function related above, these ethoxylated nonionics are mild when contacted with the skin. They allow the maximum amounts of the emollient to be adsorbed on the surface of the skin.
Specific examples of these preferred ethoxylated nonionic surface active agents are the following: The condensation product of one mole of dodecylphenol with about 20 moles of ethylene oxide, the condensation prodduct of one mole of nonylphenol with about 9.5 moles of ethylene oxide, the condensation product of one mole of hexylphenol with about 10 moles of ethylene oxide. the condensation product of decylphenol with about 16 moles of ethylene oxide, the condensation product of octylphenol with about 8 moles of ethylene oxide, the condensation product of octadecanol with about 30 moles of ethylene oxide, the condensation product of dodecanol with about moles of ethylene oxide, the condensation product of octanol with about 10 moles of ethylene oxide, the condensation product of tetradecanol with about 18 moles of ethylene oxide, the condensation product of sorbitan dodecanate with about 20 moles of ethylene oxide, the condensation product of sorbitan tetradecanate with about moles of ethylene oxide, the condensation product of sorbitan octanate with about 15 moles of ethylene oxide, and the condensation product of sorbitan hexadecanate with about moles of ethylene oxide.
As another preferred embodiment of this invention, the amides described in 6) above are utilized in the composition of this invention. These particular amides can be utilized alone or in combination with the alcohols and hereinbefore described nonionics of this composition. These amides actually emulsify the oil and ester mixture in the bath water. A stable, cloudy, white emulsion is formed in the bath water and no floating emollient layer can be discerned. With an emulsion of this type, only a controlled amount of the oil and ester mixture is deposited on the skin. This is particularly advantageous for people with greasy or oily skin who desire to take advantage of the softening effect of a bath oil yet do not wish to have more than a controlled amount of oil and ester deposited on their skin. An emulsion of this type is also particularly valuable in reducing and, for all practical purposes, eliminating the bathtub ring as the emulsified oil and ester flow out of the tub with the water.
Specific examples of these amides are the following: N,N diethanoldodecanamide, N,N diethanoltetradecan amide, N,N dicthanolhexadecanamide, N,N diethanoldecanamide, N,N diethanoloctanamide, N ethanoldodecanamide, N ethanoltetradecanamide, N ethanoloctanamide, N ethanolnonanamide, octanamide and decanamide.
These nonionic surface active agents should comprise from about 0% to about 10% of the composition of this invention. The capability of the nonionic to effectively insure adequate dispersion and emulsification of the oil and ester drops off substantially when used at levels below about 2% by weight of the total composition. Above the 10% level the surface active agent does not contribute materially, in proportion to its weight, to the effectiveness of the bath oil composition. Maximum effectiveness of the nonionic surface active agent is attained at about 4% to 8% by weight of the total composition.
As another preferred embodiment of this invention, lower molecular weight alcohols are added to this composition. The addition of these alcohols performs several functions. When the alcohols are admixed with a nonionic surface active agent in this composition, these alcohols act as a coupling agent which pulls the surface active agent into the mixture of oil and ester. In this manner, a homogeneous system is formed. These alcohols also help disperse the oil and ester mixture, thus again causing a decrease in the thickness of the oil and ester layer on the water and again decreasing the greasy feeling of the skin and the formation of objectionable bathtub ring. Physical properties of the composition of this invention, such as viscosity, cloud point and freezing point, can also be advantageously adjusted through the use of these alcohols. Also, these alcohols can be used as a solvent for the higher molecular weight esters of this invention. Lower molecular weight aryl alcohols have the additional advantage of being perfume fixatives.
Alcohols suitable for use in this invention include straight or branched chain saturated aliphatic alcohols having from about 2 to about 6 carbon atoms and aryl and alicylic alcohols having from about 5 to about 10 carbon atoms. Also suitable for use herein are the polyhydric alcohols having from about 2 to about 6 carbon atoms. Alcohols containing from about 2 to about 6 carbon atoms are preferred for use in this invention. Specific examples of suitable alcohols are ethanol, propanol, butanol, hexanol, benzyl alcohol, cyclohexanol, 1,2- ethanediol, 1,2-propanediol. Ethanol is the preferred alcohol of this invention.
These alcohols can be added to this composition in amounts from 0% to about 30% by weight of the total composition. The practical minimum to obtain all of the above-stated advantages is about 2%. The preferred range for the addition of these alcohols is from 5% to 15% by weight of the total composition.
Colors and perfumes well known in the art may be added in measured amounts to suit individual tastes and add aesthetic appeal. Silicone compounds can also be added to create a smoother feeling and prevent foaming of the bath oil. If foaming is desired, sOap or other anionic surface active agents can be added for this purpose. Deodorants and antibacterial agents can be incorporated into the bath oil as a further improvement.
The following specific examples are given in order to further explain and illustrate this invention. They are not intended to limit the scope in any way.
In all of the following specific examples, the ingredients were added in the order listed below. Between each addition, the product was stir-red to insure uniformity of the final bath oil. Since a major factor in consumer acceptance of this type of product is odor, and in view of the high dilution of the product in usage, relatively high levels of perfume are used in these formulations.
EXAMPLE I The following clear formulation of this invention was compared with a commercially successful bath oil which contained isopropylmyristate.
Percent by weight Essentially octyl dodecanoate 50 Light white mineral oil (graded by United States Pharmacopoeia) 35 Condensation product of nonyl phenol with 9.5 moles of ethylene oxide Isopropyl alcohol 7 Perfume and color 3 The octyl dodecanoate component was prepared by the alcoholysis of a mixture of middle cut coconut methyl ethers with a mixture of light out coconut alcohols. The middl cut coconut fraction contained the following distribution of carbon chain lengths 1% C10, 68% C1 24% C14 and 7% C10. The light out fraction contained 4% Cu, 60% Ca, 35% C and 1% C12.
These two formulations were compared in home use tests. Panelists used these products over a period of time and were then asked to register their preferences. They were not informed of the compositions being tested. There was a decided overall preference for the clear composition of this invention.
EXAMPLE II The following bath oil compositions were prepared. In all the formulations listed below, the product was a clear, homogenous, liquid mixture which, when applied in the normal bathtub manner to the skin, left it feeling smooth, soft and silky. The formation of the bathtub ring was substantially retarded during use of several formulations by using the dispersants and emulsifiers as hereinbefore described.
In the following formulations, the esters, octyl octanoate, octyl dodecanoate, dodecyl octanoate and dodecyl dodecanoate, were prepared from coconut fractions. The octyl octanoate ester is the reaction product of light cut coconut methyl esters and light out coconut alcohols. The octyl dodecanoate ester is the reaction product of middle cut coconut methyl esters and light out coconut alcohols while the dodecyl octanoate ester is the reaction product of light cut coconut methyl esters and middle cut coconut alcohols. Middle cut coocnut methyl esters and middle cut coconut alcohols were utilized in preparing the dodecyl dodecanoate. The terms light and middle have been hereinbefore defined.
Formulation 1: Parts by weight Octyl dodecanoate 50 Light white mineral oil (graded by United States 1,2-propanediol 11 8 Formulation 5: Parts by weight Octyl dodecanoate 43 Light white mineral oil (U.S.P. Grade) 47 The condensation product of a mixture of isomeric linear secondary alcohols containing from 11 to 15 carbon atoms with about 9 moles of ethylene oxide 5 Ethanol 5 Formulation 6:
Octyl dodecanoate 60 Light white mineral oil (U.S.P. Grade) 30 Benzyl alcohol 10 Formulation 7:
Dodecyl octanoate 40 Light white mineral oil (U.S.P. Grade) 50 Hexanol 10 Formulation 8:
Octyl dodecanoate 42 Heavy white mineral oil (U.S.P. Grade) 24 Light white mineral oil (U.S.P. Grade) 24 N,N-diethanoldodecanamide 7 Perfume, color 3 Formulation 9:
Octyl dodecanoate 46 Light white mineral oil (U.S.P. Grade) 35 The condensation product of nonyl phenol with 9.5 moles of ethylene oxide 7 Ethanol 6 N,N-diethanoldodecanamide 6 Formulation 10:
Octyl dodecanoate 60 Light white mineral oil (U.S.P. Grade) 35 N-ethanoloctanamide 5 Formulation 11:
Z-ethylhexyl dodecanoate 60 Light white mineral oil (U.S.P. Grade) 35 Octanamide 5 Formulation 12:
Octyl dodecanoate 50 Light white mineral oil (U.S.P. Grade) 41 N-ethanoloctanamide 4 Ethanol 5 Formulation 13:
Dodecyl octanoate 45 Light white mineral oil (U.S.P. Grade) 22 Heavy white mineral oil (U.S.P. Grade) 23 Tetradacanamide 5 2-propanol 5 Formulation 14:
Octyl octanoate 50 Light white mineral oil (U.S.P. Grade) 40 N,N-diethanoldodecanamide 5 Butanol 5 Formulation 15:
Octyl dodecanoate 46 Light white mineral oil (U.S.P. Grade) 35 The condensation product of nonyl phenol with 9.5 moles of ethylene oxide 7 Ethanol 6 N-ethanoldodecanamide 6 Formulation 16:
Dodecyl octanoate 46 Light white mineral oil (U.S.P. Grade) 36 The condensation product of sorbitan dodecanoate with about 20 moles of ethylene oxide 6 Ethanol 6 Dodecanamide 6 In all of the above formulations, other of the esters in the range hereinbefore delineated may be substituted for the ones mentioned either in a single compound form or at the blends derived from such natural sources as coconut oil. Substitution of higher molecular weight esters results in oilier products, while substitution of lower molecular weight esters results in less oily products. Use of esters beyond the essentially C -C ester results in a very thick product which also tends to increase the problem of the bathtub ring. Below the essentially C -C ester, the product loses therapeutic and emollient value.
Additionally, any of the hereinbefore described oils, nonionic surface active agents or alcohols may be substituted in the examples in accordance with this invention. Perfumes and color are added to suit individual taste, but they atfect this invention only by adding aesthetic appeal.
The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.
What is claimed is:
1. A clear, non-aqueous liquid composition containing 60% by Weight of octyl dodecanoate, 30% by Weight of light white mineral oil and 10% by weight of benzyl alcohol.
2. A clear, non-aqueous liquid composition containing 50% by weight of octyl dodecanoate, 37% by weight of light white mineral oil, 6% by weight of the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide and 7% by Weight of ethanol.
3. A clear, non-aqueous liquid composition containing 46% by weight of octyl dodecanoate, 35% by Weight of light white mineral oil, 7% by weight of the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide, 6% by weight of ethanol, and 6% by Weight of N,N-diethan0lododecanamide.
References Cited UNITED STATES PATENTS 2,677,700 5/ 1954 Jackson et al.
2,774,709 12/ 1956 Mayhew et al.
2,834,731 5/1958 Carpenter 106-311 XR 3,035,987 5/ 1962 Wietzel 167-66 XR 3,055,836 9/1962 Masci et al. 167-87 XR 3,175,949 3/1965 Siegal 16785 3,223,647 12/1965 Drew et al 252-152 XR 3,330,730 7/1967 Hernandez 16787 XR 3,330,731 7/1967 Mehafiey 167-85 XR OTHER REFERENCES ALBERT T. MEYERS, Primary Examiner.
D. R. MAHANAND, Assistant Examiner.

Claims (1)

1. A CLEAR, NON-AQUEOUS LIQUID COMPOSITION CONTAINING 60% BY WEIGHT OR OCTYL DODECANOATE, 30% BY WEIGHT OF LIGHT WHITE MINERAL OIL AND 10% BY WEIGHT OF BENZYL ALCOHOL.
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US4035514A (en) * 1976-02-17 1977-07-12 Ici United States Inc. Water washable petrolatum compositions
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US4005210A (en) * 1975-07-03 1977-01-25 Estee Lauder, Inc. Protein containing emollient composition for a skin moisturizer
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US20100024684A1 (en) * 2006-03-03 2010-02-04 Hans Riepe Liquid release agent
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JP2012506393A (en) * 2008-10-21 2012-03-15 コグニス・アイピー・マネージメント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Cosmetic and / or pharmaceutical preparations
WO2010046061A2 (en) * 2008-10-21 2010-04-29 Cognis Ip Management Gmbh Cosmetic and/or pharmaceutical formulations
US20120115949A1 (en) * 2009-06-30 2012-05-10 Cognis Ip Management Gmbh Ester Mixtures And Compositions Comprising Such Ester Mixtures
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US10751271B2 (en) 2015-02-19 2020-08-25 Conopco, Inc. Fast rinsing cleansing composition

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