CA1292692C - Dispersion of water dispersible or alcohol soluble substances in low cloud point lipoidal materials - Google Patents
Dispersion of water dispersible or alcohol soluble substances in low cloud point lipoidal materialsInfo
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- CA1292692C CA1292692C CA000539048A CA539048A CA1292692C CA 1292692 C CA1292692 C CA 1292692C CA 000539048 A CA000539048 A CA 000539048A CA 539048 A CA539048 A CA 539048A CA 1292692 C CA1292692 C CA 1292692C
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Abstract
ABSTRACT:
An improved low cloud point lipid carrier for polar, water dispersible or alcohol-soluble substances, and to lipid compositions containing such substances.
An improved low cloud point lipid carrier for polar, water dispersible or alcohol-soluble substances, and to lipid compositions containing such substances.
Description
12~?Z6~32 DISPERSION OF WATER DISPERSIBLE OR ALCOHOL SOLUBLE
SUBSTANCES IN LOW CLOUD POINT LIPOIDAL MATERIALS
TECHNICAL FIELD
The present invention relates to an improved low cloud point lipid carrier for polar, water dispersible or alcohol-soluble substances, and to lipid compositions containing such substances. The present invention is particularly applicable to foods, and the dispersion of polar substances which are food approved in a low cloud point lipid or oil medium. The present invention is also applicable to the preparation of cosmetics and toiletries such as creams, lotions and makeup (e.g., lipsticks).
For purposes of the present application, the terms "dispersion" and "solution", and their various genders, shall be considered synonymous and be used interchangeably. In actuality, in the practice of the present invention, the end-products hereof (lipid carrier plus polar substance) are for a substantial part true solutions, although portions of the substances added, depend-ing upon ingredients involved and loading, may be in a dispersed state. Principal characteristics of the composition of the present invention, in addition ,~
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to its ability to disperse polar substances, are its low cloud point and its high stability against oiling-off when blended with polar materials.
At lower loadings, the end product will have the appearance of a true solution free of visible precipitation. With higher loadings, for instance up to about 50~, the end product will be in the form of a smooth homogeneous paste. On standing, no material or visible phase separation, e.g., oiling-off or separation of solids, occurs.
Examples of polar substances within the scope of the present invention are water-soluble aolorants, pigments, lakes, flavors, fragrances, antioxidants and chelating agents. The term "polar" in the present application means, broadly, dispersible or miscible in an aqueous or alcohol medium, and, re narrowly, an electrolyte, or capable of ionization when dispersed in an aqueous or alaohol medium.
Also, for purposes of the present application, the terms "lipid" and "lipoidal" include such materials as normally liquid oils and liquid waxes. A wax is distinguishable fram an oil or fat in that it is a fatty acid ester of a high molecular weight mono-aloohol having 12-24 carbon atoms, other than glycerol. ~he term "normally liquid" means fluid or flowable at roam temperature, as oontrasted with a normally solid or plastic shortening-type product.
8ACE~D ~r Often, in food, pharmaceutical and cosmetic products, difficulties are encountered when attempting to inaorporate a polar or water soluble material into non-polar or water insoluble hydrocarbons. The incompatibility can be overoome by forming micellar dispersions with crown ethers, quaternary ammonium salts, or medium chain alcohols with ionic surfactants, or by forming a water-in-oil (w/o) emulsion. The micellar forming agents are often toxic or dermatological irritants and water-in-oil emulsions limit applications to water-tolerant systems.
Also, the typical opaque emulsion appearance of such dispersions may be objectionable.
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Prior United States patent 3,489,573 to Brankamp describes a method of mixing water soluble-oil insoluble dyes with a fatty acid ester of polyglycerol such as decaglycerol trilino-leate or tetraglycerol monooleate and then mixing the dye-polyglycerol ester mixture with a liquid fatty triglyceride.
Examples of water soluble-oil insoluble dyes within the scope of the patent are "FD&C" dyes such as FD&C Blue No. 2. One purpose of the method of the '573 patent is utilization of "dyes" which are heat-stable. It is pointed out in the patent that none of the other materials tried, such as lecithin, glycerine, monoglycerides of fatty acids, and various fatty acid esters of sorbitan, gave the same results as the '573 method.
The base compositions of the '573 patent are either plastic shortenings or suspended solids liquid shortenings. The latter are described in prior United States patents Nos. 2,815,286 and 2,815,285, referenced in the '573 patent. In addition, all of the polyglycerol esters listed in the patent in column 5, lines 25-30, are either dispersed solids in the oil or fat medium, or incompletely soluble or dispersible, at the level used, so that the end product would not `ae a clear solution or dispersion for this reason.
Prior United States patent 3,677,691 to Kach relates to a method for conversion of water soluble color additives to oil soluble color compositions involving dissolving the water soluble color additives in a solution of a polyhydric alcohol, such as glycerine, and then admixing this solution with a second solution of a polyglycerol fatty acid ester while heating to 150C, .,.,~
lZ5~?Z692 - 3a -followed by stirring for at least 5 minutes during cooling. This patent seems to deal primarily with FD~C colors, and preferred esters appear to be those of hexaglycerol, octaglycerol, and deca-glycerol. Preferred fatty acids listed are oleic, linoleic, stearic and lauric. The disclosure of the patent is not a sugges-tion of the present invention. Predissolving the dye in the poly-hydric alcohol is critical in the practice of the Koch method.
There is no disclosure of a lipid carrier capable of accepting polar substances without pretreatment.
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Also in the prior art are Todd et al~ patents Nos. 4,343,823 and A~ 4,315,947~ The 'a23 patent describes homogeneous, liquid, condimental compositions useful in flavoring or coloring foods and beverages and being dispersible in both oil and water. The compositions comprise a blend of monoglyceride of caproic and/or caprylic and/or lauric acid;
polyglycerol ester of at least one fatty acid; and one or more condiments selected from edible flavorings and colorings, the ratio by weight of acid plus ester to condiment being at least 1:4. Examples given of condiments are spice oleoresins, essential oils, and edible colorings. The '947 patent is similar in disclosure, but more specific as to polyglycerol ester and condiment contemplated.
In the Todd et al patents, the only condiments or colorants disclosed are oleoresins which are normally oil dispersible and non-polar (column 9, line 44 of the '823 patent). The principal purpose therefore is to make these substances also water dispersible, and for this purpose, Todd et al propose treating the oleoresin with the combination of a polyglycerol ester, which is normally immiscible with the oleoresin (column 7, line 66 of the '823 patent), and a mono-digylceride, which probably serves as a coupling aid to disperse the oleoresin in the polyglycerol ester (column 8, line 19+ of the '823 patent).
The disclosure of these patents differ from the present invention in several respects. The patents are not concerned with adding a polar substance to an oil medium or carrier, the subject matter of the present invention. Second, the patents teach treating the oleoresin or additive ingredient, rather than the carrier medium (water), whereas the present invention is concerned with the preparation of an oil carrier to accept a variety of the polar additive ingredients. The blends of Tcdd et al would not accamplish the results sought in the present invention.
M SCL06UR~ oF INvENrIoN
The present invention relates to an improved lipid carrier for polar, water dispersible or alcohol soluble substances; to such carrier 12't2~i92 containing a water dispersible or aloohol soluble substance; and to a method for making the same.
More particularly, the present invention relates to a clear, lipidcarrier for polar, water dispersible or alcohol soluble substances comprising a) a normally liquid high stability oil or wax having an AoM
stability of at least 100 hours and a cloud point below about 55F; b) a dispersing agent dispersed in said oil or wax in the ratio of about 6-12 parts dispersing agent to about 94-88 parts medium, said dispersing agent aomprising; 1) a liquid, non-ionic, strong primary surfactant having both hydrophilic and lipophilic properties which is a fatty acid ester of oleic or linoleic acid and a polyglycerol having saponification and hydroxyl numbers which are approximately equal and in the range of about 140 to about 165, the polyglycerol comprising about 6-10 glycerol units; and 2) a liquid secondary surfactant which is a fatty acid ester of oleic or linoleic acid and a polyol selected from the group consisting of polyglycerol having about 2-5 glycerol units, sorbitol, and sucrose, said ester having an hydroxyl number in the range of about 195-250 and a saponification number in the range of about 140-160.
Preferably, the ratio of primary surfactant to secondary surfactant is in the range of about 2:1 to about 9:1.
For purposes of the present application, the hydroxyl number is an indication of the numker of free hydroxyl groups present in an oil or emulsifier. This is determined by measuring the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of sample.
The saponification number is an indication of the amount of fatty acidspresent in an oil. The number of milligrams of potassium hydroxide which will react with one gram of sample at elevated tempertures gives this value. The saponification number measures both the free fatty 12~Z~2 acids and combined fatty acids in an oil.
The present invention also resides in cosmetic, food and pharmaoe utical products prepared utilizing the carrier of the present invention, and to methods for making the same.
BEST MODE oF c~RRyrNG OUT THE
INVENTION AND INDUSTRIAL APPLIC~BILITY
The Carrier Oil or Wax:
The edible oils or fats which are useful in the product of thisinvention are normally liquid triglyceride oompositions derived from animal, vegetable or marine sources, including, by way of example, naturally occurring triglyceride oils such as cottonseed oil, soybean oil, peanut oil, palm kernel oil, olive oil, corn oil, rapeseed oil, sunflower seed oil, sesame seed oil, safflower oilr sardine oil, and the like. Also, suitable liquid fractions obtained from palm oil, lard and tallow as, for example, by fractional crystallization or interesterification can be used. Mixtures of oils can also be used.
The oils, particularly for food applications, should have good flavor stability, preferably, a bland flavor, and be odor free. Oils predaminating in triglycerides of unsaturated acids may require partial hydrogenation to make them oxidative stable. A number of hydrogenated cottonseed and soybean oils are satisfactory. For non-food uses, an oil of petroleum origin may be used.
The waxes of the present invention can be natural or synthetic and in general are defined as an ester of a fatty acid with a high molecular weight alcohol other than glycerol. An example of a natural wax within the scope of the present invention is that derived from jojoba oil or orange roughy oil.
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For purposes of the present application, the term "oil" when used aloneshall be deemed to emhrace both oils and waxes.
Tw~ properties have to be met in the selection o~ the proper oil or wax, one being AoM stability, the other cloud point. AOM stability is defined as the oxidative stability of an oil. More specifically, it is the number of hours needed for an oil to obtain a peroxide value of 100 under standard conditions, as determined by the Active Oxygen Method, AOCS No.Cc 13b-45. It is desirable that the oil have high oxidative stability for storage at room temperature (including storage stability of end-use products), and for this purpose the oil is preferably a C16-C18 partially hydrogenated triglyceride having an AoM stability of at least 100 hours. ~igh AOM stability can be achieved by well known procedures, for instance hydrogenation and fractionation. Although antioxidants can be added, the composition of the present invention is preferably free of antioxidants, the above AoM stability being inherent in the oil. Oils of this type are known as "high-stability" oils.
A critical feature of the present invention is prolonged clarity of thecarrier composition at rocm or ordinary storage temperatures. The "cloud point" for purposes of the present application is defined as that temperature at which the carrier composition becomes hazy or turbid.
Preferably, the carrier oompositions, and of necessity, also, the base oil of the present invention, have a cloud point below about 55F
(12.8C). In this regard, it is also essential that the carrier oompositions of the present invention are not only clear initially, but also remain clear when stored at this temperature or higher temperatures.This latter requirement can be referred to as the cloud stability.
To achieve a low cloud point known procedures can be employed such as winterization or solvent fractionation of the carrier triglyceride.
In the disclosure and examples of this application, tbe oil used throughout was a partially hydrogenated, fractionated and winterized vegetable oil (cottonseed, soybean~. It is a clear, stable oil which is liquid at normal room temperature having a cloud point less than about 55F, and a Mettler Drop Point less than 16C (60.8F).
The oil was obtained by subjecting Durkex 500, a normally "high stability", (high AoM) hydrogenated and fractionated vegetable oil marketed by 5CM Corporation, having a Wiley Melting Point of about 73F
maximum, to winterization. Durkex S00 also has an rv of about 74-81 and an AaM stability of at least about 350 hours. This oil is normally used in prepared foods as a coating agent, or release agent, and in cosmetics and pharmaceuticals where high stability is desired. It is also used in snack frying and nut roasting. Winterization was carried out by subjecting Durkex 500 to cooling to 56-5~F and holding it at that temperature for 6-8 hours, at which time the oil was filtered in a Bird filter, giving a yield of 70-75%.
In addition to winterization, the subject oil of the present invention also contained a crystallization inhibitor. A function of the crystallization inhibitor was for cloud stability, i.e., to extend the period free of cloud. A number of crystallization inhibitors are available on the market. That used in the present invention was Caprol ET, a polyglycerol ester marketed by Capital City Products, obtained by direct esterification of polyglycerol with a blend of lauric and domestic fats. These polyglycerol ester crystallization inhibitors preferably have saponification numbers in the range of about 180-195, and hydroxyl numbers in the range of about 20-50. The fatty acid distribution is primarily C12, C16, C18 0 and Clg 1. These compositions are covered by Title 21 of the Food & Drug Administration Regulations, Section 172.854 (c). Another suitable crystallization inhibitor is an oxystearin as covered by the Food & Drug Administration Regulation, Section 172.818 (b). These sections of the regulations are incorporated by reference herein. Normally, a crystallization inhibitor will be used in a small amount, e.g., .05%-.25%, basis total lipid weight, such amount being effective for cloud-free storage stability. The desire for clarity and cloud-free stability, with regard to use of the carrier compositions of the present invention in end-use fluid applications, i2~Z6g2 e.g. fluid solutions or dispersions, should be evident. However, even in the preparation of highly loaded end-use plastic compositions, which are clearly opa~ue, clarity and cloud-free stability are important. If precipitation of lipid occurs, the lipid solids show up as small specks in the dispersion, presenting a mottled, unsightly appearance.
A test was carried out to show the effectiveness of use of a crystallization inhibitor with a winterized "high stability" oil in the practice of the present invention. A sample of winterized Durkex 500 (high stability~ oil with no additives, at 50F, showed 0% precipitated lipid solids at the end of 24 hours and three days storage, but 1% lipid solids at the end of seven days storage. With .05% Caprol ET, the same showed no solids even at the end of seven days. Similar results were obtained with the use of .05% oxystearin.
Another suitable low melting point oil useful in the practice of the present invention is winterized Durkex 100 (trademark SCM Corporation).
Durkex 100 is a partially hydrogenated and fractionated soybean oil having a Wiley Melting Point of about 67F and an SFI at 50F of about 11 maximum. This oil has an rv of about 85-92 maximum, It has an AoM
stability of about 100 hours minimum, and a maximum lovibond color of about 1.5R. This product, as with Durkex 500, is bland in flavor. It can also be winterized to have a cloud p~int less than about 55F.
An alternative to a winterized, high stability vegetable oil is a natural high AoM oil having a cloud point below about 55F. These are oils from new strains of sunflower seeds, described in published literature.
Active Ingredient The water dispersible or alcohol soluble materials which are normally non-dispersible or non-soluble in oil, in the practice of the present 12~9Z
invention, can be either liquid or solid, and include such water dispersible or alcohol soluble/oil insoluble dyes as those approved by the Food and Drug Commission for use in food, drug and cosmetic products, generally referred to as "FDhC dyes". Typical examples of dyes and oolorants useful in the present invention are FD&C Blue #1, FD&C Red #40, lakes and caramel color. Examples of flavorants useful in the process of the present invention are ethyl vanillin (a crystalline solid), terpinenes (liquids) and caffeine (a white solid). Alcohol soluble/oil insoluble fragrances useful in the practice of the present invention are synthetic lemon oil, cinnamaldehyde, citral;
pharmaceuticals are ethyl salicylate, menthol and para-aminobenzoic acid; cosmetic agents are ferric oxide pigments, TiO2; emollients are lactic salts; all by way of example. Others will be well apparent to those skilled in the art.
In the preparation of such compositions as cosmetics, foods and the like, the dispersing agents of the present invention have been found to increase the dispersibility of water dispersible or alcohol soluble/oil insoluble materials up to 60-200 fold.
In this regard, the amount of water dispersible material or alcohol soluble material dispersed in oil depends upon the particular material in question and end-use application. For fluid end-use applications, the amount dispersed within an oil or wax medium will be in the range of about 1-25% (depending upon active ingredient involved) based upon the weight of the oil or wax. In the case of plastic dispersions, the loading can be up to about 50% before the saturation limit is reached, again depending upon active ingredient involved.
The Solvati~ or Dispersing Agent:
The solvating or dispersing agent of the present invention oomprises a blend of what can be referred to as a primary surfactant, and a second ingredient which can be referred to as a secondary dispersing agent.
The primary surfactant is a liquid, non-ionic, strong surfactant havingboth hydrophilic and lipophilic characteristics. For food applications, it should be food approved. Surfactants found to be particularly suitable are the polyglycerol esters of oleic or linoleic acid which have saponification and hydroxyl numbers which are approximately equal and in the range of about 140 to about 165. The number of glyoerol units is in the range of about 6-10. A preferred fatty acid esterified with polyglycerol is oleic acid. The polyglycerol esters are normally prepared by reacting the previously prepared polyglycerol with the fatty acid, either in a direct esterification process or by interesterification with a triglyceride esterified with the desired fatty acid units. Both reactions are well known and not a part of the present invention.
Polyglycerol esters of fatty acids having an hydroxyl value above about165 are not sufficiently solubilized in the base or carrier oil to provide a clear composition at temperatures down to about 55F. Those with hydroxyl values below about 140 do not provide sufficient solubilization, at the levels used, for the active ingredients or polar substances tested. The same constraints apply to the saponification values.
Similarly, with regard to the fatty acid component of the polyglycerol esters, it was found that such fatty acid esters as palmitates and stearates give a cloudy appearance, at the level of ester used, whereas the oleate and linoleate esters are liquid and give a clear appearance at the level used. In this regard, the amounts called for are a solubilizing or dispersing amount to achieve active ingredient loading desired.
Two suitable polyglycerol esters within the soope of the present invention are an octaglycerol pentaoleate and a decaglyceryl hexaoleate.
Both oompositions have hydroxyl numbers in the range of about 145-160 and saponification numbers in the range of about 145-150. They are in norm31ly liquid form.
The secondary dispersing agent o~ the present invention is a liquid fatty acid ester of oleic or linoleic acid and a polyol selected from the group consisting of polyglycerol, having about 2-5 glycerol units, sorbitol, and sucrose, said ester having an hydroxyl value in the range of about 195-250 and a saponification value in the range of about 140-160.
Examples of suitable secondary surfactants are a triglycerol dioleate, which has a hydroxyl number of about 215 plus~minus 15, and a saponification number of about 150 plus/minus 10; and sorbitan monooleate, which has a hydroxyl number of about 214 and a saponification number of about 152. Another such surfactant is sucrose trioleate, which has a hydroxyl number of about 250 and a saponification number of about 150.
Preferably, the primary surfactant is used in the ratio of about 6-12 parts by weight surfactant to about 94-98 parts oil carrier. The ratio of primary surfactant to secondary surfactant then is in the range of about 2:1 to about 9:1; or, based on the combined weight of surfactants, the secondary surfactant is about 10-30%.
In the practice of the present invention, it was found that the primarysurfactant, havinq both hydrophilic and lipophilic characteristics, is an essential ingredient in that it has sufficiently strong hydrophilic properties to hold the active ingredient in solution or suspension, and at the same time has sufficient lipophilic characteristics to be capable of substantially oomplete suspension in the lipoidal carrier at the level used. The secondary dispersing agent then acts as a solvent modifier, when used in the proportion of about 10 to about 30 weight percent, based on the weight of the combination of surfactants, completing solubilization of the primary surfactant.
In addition to the above critical ingredients, it is possible to include in the solvating agent formùlation other emulsifiers which have some 2t~3Z
solubility, for instance polysorbate 80 up to a level of about 2~, based on the weight of the entire formulation. ~bove about 2%, some polysorbate 80 precipitates in the oil medium.
ExAMæLE 1 This Example illustrates advantages of the present invention insolubilizing three water soluble materials, ethyl vanillin, ethanol, and benzyl alcohol.
The oomposition tested comprised 92% Durkex 500 winterized vegetable oil, 6% octaglycerol pentaoleate, and 2% of either triglycerol dioleate or sorbitan monooleate.
The alcohols and ethyl vanillin were dissolved by heating the lipid ingredients to 60C and then ultrasonically agitating them for ten minutes. All solutions were stored at 21C, unagitated, for six weeks prior to spectrophotometric analysis. Optical density was measured on a Beckman Model 3600 spectrophotometer for each sample at 630 and 510 nano,meters - light wavelength, and compared against water solution standards for each ingredient.
In the case of 2~ triglycerol dioleate, ethyl vanillin was soluble at the 2% level. Both absolute ethanol and benzyl alcohol were soluble in this composition up to the 103 level. With 2~ of the sorbitan mono~leate, ethyl vanillin was soluble at both the 2% and 5% lévels.
Both alcohols were also soluble in this composition up to the 10~ level.
All soluble materials resulted in clear solutions without visible precipitation.
This Example illustrates use of the present invention with a water soluble dye such as Blue No. 1 Lake. The carrier composition comprised 92 parts of winterized Durkex 500, 6 parts of octaglycerol pentaoleate, A and 2 parts of triglycerol dioleate. The same procedure as in Example 1 was employed. The Blue No. 1 Lake was found to be soluble up to a level of 2.5% without any precipitated dye.
In this Example, essentially the same formulation as used in Example 2 was employed except that the amount of winterized base oil was reduced to 91.75~ and .25~ Caprol ET crystallization inhibitor was added to the formulation. The formulation was tested with 50% loadings of FD&C
Yellow #5, Lake (37~ dye) and FD~C ~ed #40, Lake (38% dye). Both formulations remained stable over prolonged periods of storage, down to about 55F, and showed neither precipitation of lipid nor appreciable oiling-off of lipid. Both formulations were in the form of very smooth, homogeneous pastes. Neither was lumpy nor granular.
Both formulations were frozen at -20F for 18 hours, and then thawed at room temperature for 6 hours. Viscosity readings of 87.5 for the yellow #5 formulation and 92.5 for the ~ed #40 formulation were obtained, using a Brookfield visoometer Model LVF, Spindle #4, Speed 6. The samples were placed in 25 ml. graduated cylinders filled to the 15 ml. mark, to check for separated surface oil. None was present after a~out one month storage.
Similar results were obtained with a formulation which was the same in all respects except that the secondary surfactant was sorbitan monooleate instead of triglycerol dioleate. Samples having loadings of 50% of both dyes were prepared, and similar results were obtained. The Yellow Lake sample gave a viscosity reading of 100; the Red Lake, 88.
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SUBSTANCES IN LOW CLOUD POINT LIPOIDAL MATERIALS
TECHNICAL FIELD
The present invention relates to an improved low cloud point lipid carrier for polar, water dispersible or alcohol-soluble substances, and to lipid compositions containing such substances. The present invention is particularly applicable to foods, and the dispersion of polar substances which are food approved in a low cloud point lipid or oil medium. The present invention is also applicable to the preparation of cosmetics and toiletries such as creams, lotions and makeup (e.g., lipsticks).
For purposes of the present application, the terms "dispersion" and "solution", and their various genders, shall be considered synonymous and be used interchangeably. In actuality, in the practice of the present invention, the end-products hereof (lipid carrier plus polar substance) are for a substantial part true solutions, although portions of the substances added, depend-ing upon ingredients involved and loading, may be in a dispersed state. Principal characteristics of the composition of the present invention, in addition ,~
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to its ability to disperse polar substances, are its low cloud point and its high stability against oiling-off when blended with polar materials.
At lower loadings, the end product will have the appearance of a true solution free of visible precipitation. With higher loadings, for instance up to about 50~, the end product will be in the form of a smooth homogeneous paste. On standing, no material or visible phase separation, e.g., oiling-off or separation of solids, occurs.
Examples of polar substances within the scope of the present invention are water-soluble aolorants, pigments, lakes, flavors, fragrances, antioxidants and chelating agents. The term "polar" in the present application means, broadly, dispersible or miscible in an aqueous or alcohol medium, and, re narrowly, an electrolyte, or capable of ionization when dispersed in an aqueous or alaohol medium.
Also, for purposes of the present application, the terms "lipid" and "lipoidal" include such materials as normally liquid oils and liquid waxes. A wax is distinguishable fram an oil or fat in that it is a fatty acid ester of a high molecular weight mono-aloohol having 12-24 carbon atoms, other than glycerol. ~he term "normally liquid" means fluid or flowable at roam temperature, as oontrasted with a normally solid or plastic shortening-type product.
8ACE~D ~r Often, in food, pharmaceutical and cosmetic products, difficulties are encountered when attempting to inaorporate a polar or water soluble material into non-polar or water insoluble hydrocarbons. The incompatibility can be overoome by forming micellar dispersions with crown ethers, quaternary ammonium salts, or medium chain alcohols with ionic surfactants, or by forming a water-in-oil (w/o) emulsion. The micellar forming agents are often toxic or dermatological irritants and water-in-oil emulsions limit applications to water-tolerant systems.
Also, the typical opaque emulsion appearance of such dispersions may be objectionable.
?Z69Z
Prior United States patent 3,489,573 to Brankamp describes a method of mixing water soluble-oil insoluble dyes with a fatty acid ester of polyglycerol such as decaglycerol trilino-leate or tetraglycerol monooleate and then mixing the dye-polyglycerol ester mixture with a liquid fatty triglyceride.
Examples of water soluble-oil insoluble dyes within the scope of the patent are "FD&C" dyes such as FD&C Blue No. 2. One purpose of the method of the '573 patent is utilization of "dyes" which are heat-stable. It is pointed out in the patent that none of the other materials tried, such as lecithin, glycerine, monoglycerides of fatty acids, and various fatty acid esters of sorbitan, gave the same results as the '573 method.
The base compositions of the '573 patent are either plastic shortenings or suspended solids liquid shortenings. The latter are described in prior United States patents Nos. 2,815,286 and 2,815,285, referenced in the '573 patent. In addition, all of the polyglycerol esters listed in the patent in column 5, lines 25-30, are either dispersed solids in the oil or fat medium, or incompletely soluble or dispersible, at the level used, so that the end product would not `ae a clear solution or dispersion for this reason.
Prior United States patent 3,677,691 to Kach relates to a method for conversion of water soluble color additives to oil soluble color compositions involving dissolving the water soluble color additives in a solution of a polyhydric alcohol, such as glycerine, and then admixing this solution with a second solution of a polyglycerol fatty acid ester while heating to 150C, .,.,~
lZ5~?Z692 - 3a -followed by stirring for at least 5 minutes during cooling. This patent seems to deal primarily with FD~C colors, and preferred esters appear to be those of hexaglycerol, octaglycerol, and deca-glycerol. Preferred fatty acids listed are oleic, linoleic, stearic and lauric. The disclosure of the patent is not a sugges-tion of the present invention. Predissolving the dye in the poly-hydric alcohol is critical in the practice of the Koch method.
There is no disclosure of a lipid carrier capable of accepting polar substances without pretreatment.
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Also in the prior art are Todd et al~ patents Nos. 4,343,823 and A~ 4,315,947~ The 'a23 patent describes homogeneous, liquid, condimental compositions useful in flavoring or coloring foods and beverages and being dispersible in both oil and water. The compositions comprise a blend of monoglyceride of caproic and/or caprylic and/or lauric acid;
polyglycerol ester of at least one fatty acid; and one or more condiments selected from edible flavorings and colorings, the ratio by weight of acid plus ester to condiment being at least 1:4. Examples given of condiments are spice oleoresins, essential oils, and edible colorings. The '947 patent is similar in disclosure, but more specific as to polyglycerol ester and condiment contemplated.
In the Todd et al patents, the only condiments or colorants disclosed are oleoresins which are normally oil dispersible and non-polar (column 9, line 44 of the '823 patent). The principal purpose therefore is to make these substances also water dispersible, and for this purpose, Todd et al propose treating the oleoresin with the combination of a polyglycerol ester, which is normally immiscible with the oleoresin (column 7, line 66 of the '823 patent), and a mono-digylceride, which probably serves as a coupling aid to disperse the oleoresin in the polyglycerol ester (column 8, line 19+ of the '823 patent).
The disclosure of these patents differ from the present invention in several respects. The patents are not concerned with adding a polar substance to an oil medium or carrier, the subject matter of the present invention. Second, the patents teach treating the oleoresin or additive ingredient, rather than the carrier medium (water), whereas the present invention is concerned with the preparation of an oil carrier to accept a variety of the polar additive ingredients. The blends of Tcdd et al would not accamplish the results sought in the present invention.
M SCL06UR~ oF INvENrIoN
The present invention relates to an improved lipid carrier for polar, water dispersible or alcohol soluble substances; to such carrier 12't2~i92 containing a water dispersible or aloohol soluble substance; and to a method for making the same.
More particularly, the present invention relates to a clear, lipidcarrier for polar, water dispersible or alcohol soluble substances comprising a) a normally liquid high stability oil or wax having an AoM
stability of at least 100 hours and a cloud point below about 55F; b) a dispersing agent dispersed in said oil or wax in the ratio of about 6-12 parts dispersing agent to about 94-88 parts medium, said dispersing agent aomprising; 1) a liquid, non-ionic, strong primary surfactant having both hydrophilic and lipophilic properties which is a fatty acid ester of oleic or linoleic acid and a polyglycerol having saponification and hydroxyl numbers which are approximately equal and in the range of about 140 to about 165, the polyglycerol comprising about 6-10 glycerol units; and 2) a liquid secondary surfactant which is a fatty acid ester of oleic or linoleic acid and a polyol selected from the group consisting of polyglycerol having about 2-5 glycerol units, sorbitol, and sucrose, said ester having an hydroxyl number in the range of about 195-250 and a saponification number in the range of about 140-160.
Preferably, the ratio of primary surfactant to secondary surfactant is in the range of about 2:1 to about 9:1.
For purposes of the present application, the hydroxyl number is an indication of the numker of free hydroxyl groups present in an oil or emulsifier. This is determined by measuring the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of sample.
The saponification number is an indication of the amount of fatty acidspresent in an oil. The number of milligrams of potassium hydroxide which will react with one gram of sample at elevated tempertures gives this value. The saponification number measures both the free fatty 12~Z~2 acids and combined fatty acids in an oil.
The present invention also resides in cosmetic, food and pharmaoe utical products prepared utilizing the carrier of the present invention, and to methods for making the same.
BEST MODE oF c~RRyrNG OUT THE
INVENTION AND INDUSTRIAL APPLIC~BILITY
The Carrier Oil or Wax:
The edible oils or fats which are useful in the product of thisinvention are normally liquid triglyceride oompositions derived from animal, vegetable or marine sources, including, by way of example, naturally occurring triglyceride oils such as cottonseed oil, soybean oil, peanut oil, palm kernel oil, olive oil, corn oil, rapeseed oil, sunflower seed oil, sesame seed oil, safflower oilr sardine oil, and the like. Also, suitable liquid fractions obtained from palm oil, lard and tallow as, for example, by fractional crystallization or interesterification can be used. Mixtures of oils can also be used.
The oils, particularly for food applications, should have good flavor stability, preferably, a bland flavor, and be odor free. Oils predaminating in triglycerides of unsaturated acids may require partial hydrogenation to make them oxidative stable. A number of hydrogenated cottonseed and soybean oils are satisfactory. For non-food uses, an oil of petroleum origin may be used.
The waxes of the present invention can be natural or synthetic and in general are defined as an ester of a fatty acid with a high molecular weight alcohol other than glycerol. An example of a natural wax within the scope of the present invention is that derived from jojoba oil or orange roughy oil.
~ 2ti9;~
For purposes of the present application, the term "oil" when used aloneshall be deemed to emhrace both oils and waxes.
Tw~ properties have to be met in the selection o~ the proper oil or wax, one being AoM stability, the other cloud point. AOM stability is defined as the oxidative stability of an oil. More specifically, it is the number of hours needed for an oil to obtain a peroxide value of 100 under standard conditions, as determined by the Active Oxygen Method, AOCS No.Cc 13b-45. It is desirable that the oil have high oxidative stability for storage at room temperature (including storage stability of end-use products), and for this purpose the oil is preferably a C16-C18 partially hydrogenated triglyceride having an AoM stability of at least 100 hours. ~igh AOM stability can be achieved by well known procedures, for instance hydrogenation and fractionation. Although antioxidants can be added, the composition of the present invention is preferably free of antioxidants, the above AoM stability being inherent in the oil. Oils of this type are known as "high-stability" oils.
A critical feature of the present invention is prolonged clarity of thecarrier composition at rocm or ordinary storage temperatures. The "cloud point" for purposes of the present application is defined as that temperature at which the carrier composition becomes hazy or turbid.
Preferably, the carrier oompositions, and of necessity, also, the base oil of the present invention, have a cloud point below about 55F
(12.8C). In this regard, it is also essential that the carrier oompositions of the present invention are not only clear initially, but also remain clear when stored at this temperature or higher temperatures.This latter requirement can be referred to as the cloud stability.
To achieve a low cloud point known procedures can be employed such as winterization or solvent fractionation of the carrier triglyceride.
In the disclosure and examples of this application, tbe oil used throughout was a partially hydrogenated, fractionated and winterized vegetable oil (cottonseed, soybean~. It is a clear, stable oil which is liquid at normal room temperature having a cloud point less than about 55F, and a Mettler Drop Point less than 16C (60.8F).
The oil was obtained by subjecting Durkex 500, a normally "high stability", (high AoM) hydrogenated and fractionated vegetable oil marketed by 5CM Corporation, having a Wiley Melting Point of about 73F
maximum, to winterization. Durkex S00 also has an rv of about 74-81 and an AaM stability of at least about 350 hours. This oil is normally used in prepared foods as a coating agent, or release agent, and in cosmetics and pharmaceuticals where high stability is desired. It is also used in snack frying and nut roasting. Winterization was carried out by subjecting Durkex 500 to cooling to 56-5~F and holding it at that temperature for 6-8 hours, at which time the oil was filtered in a Bird filter, giving a yield of 70-75%.
In addition to winterization, the subject oil of the present invention also contained a crystallization inhibitor. A function of the crystallization inhibitor was for cloud stability, i.e., to extend the period free of cloud. A number of crystallization inhibitors are available on the market. That used in the present invention was Caprol ET, a polyglycerol ester marketed by Capital City Products, obtained by direct esterification of polyglycerol with a blend of lauric and domestic fats. These polyglycerol ester crystallization inhibitors preferably have saponification numbers in the range of about 180-195, and hydroxyl numbers in the range of about 20-50. The fatty acid distribution is primarily C12, C16, C18 0 and Clg 1. These compositions are covered by Title 21 of the Food & Drug Administration Regulations, Section 172.854 (c). Another suitable crystallization inhibitor is an oxystearin as covered by the Food & Drug Administration Regulation, Section 172.818 (b). These sections of the regulations are incorporated by reference herein. Normally, a crystallization inhibitor will be used in a small amount, e.g., .05%-.25%, basis total lipid weight, such amount being effective for cloud-free storage stability. The desire for clarity and cloud-free stability, with regard to use of the carrier compositions of the present invention in end-use fluid applications, i2~Z6g2 e.g. fluid solutions or dispersions, should be evident. However, even in the preparation of highly loaded end-use plastic compositions, which are clearly opa~ue, clarity and cloud-free stability are important. If precipitation of lipid occurs, the lipid solids show up as small specks in the dispersion, presenting a mottled, unsightly appearance.
A test was carried out to show the effectiveness of use of a crystallization inhibitor with a winterized "high stability" oil in the practice of the present invention. A sample of winterized Durkex 500 (high stability~ oil with no additives, at 50F, showed 0% precipitated lipid solids at the end of 24 hours and three days storage, but 1% lipid solids at the end of seven days storage. With .05% Caprol ET, the same showed no solids even at the end of seven days. Similar results were obtained with the use of .05% oxystearin.
Another suitable low melting point oil useful in the practice of the present invention is winterized Durkex 100 (trademark SCM Corporation).
Durkex 100 is a partially hydrogenated and fractionated soybean oil having a Wiley Melting Point of about 67F and an SFI at 50F of about 11 maximum. This oil has an rv of about 85-92 maximum, It has an AoM
stability of about 100 hours minimum, and a maximum lovibond color of about 1.5R. This product, as with Durkex 500, is bland in flavor. It can also be winterized to have a cloud p~int less than about 55F.
An alternative to a winterized, high stability vegetable oil is a natural high AoM oil having a cloud point below about 55F. These are oils from new strains of sunflower seeds, described in published literature.
Active Ingredient The water dispersible or alcohol soluble materials which are normally non-dispersible or non-soluble in oil, in the practice of the present 12~9Z
invention, can be either liquid or solid, and include such water dispersible or alcohol soluble/oil insoluble dyes as those approved by the Food and Drug Commission for use in food, drug and cosmetic products, generally referred to as "FDhC dyes". Typical examples of dyes and oolorants useful in the present invention are FD&C Blue #1, FD&C Red #40, lakes and caramel color. Examples of flavorants useful in the process of the present invention are ethyl vanillin (a crystalline solid), terpinenes (liquids) and caffeine (a white solid). Alcohol soluble/oil insoluble fragrances useful in the practice of the present invention are synthetic lemon oil, cinnamaldehyde, citral;
pharmaceuticals are ethyl salicylate, menthol and para-aminobenzoic acid; cosmetic agents are ferric oxide pigments, TiO2; emollients are lactic salts; all by way of example. Others will be well apparent to those skilled in the art.
In the preparation of such compositions as cosmetics, foods and the like, the dispersing agents of the present invention have been found to increase the dispersibility of water dispersible or alcohol soluble/oil insoluble materials up to 60-200 fold.
In this regard, the amount of water dispersible material or alcohol soluble material dispersed in oil depends upon the particular material in question and end-use application. For fluid end-use applications, the amount dispersed within an oil or wax medium will be in the range of about 1-25% (depending upon active ingredient involved) based upon the weight of the oil or wax. In the case of plastic dispersions, the loading can be up to about 50% before the saturation limit is reached, again depending upon active ingredient involved.
The Solvati~ or Dispersing Agent:
The solvating or dispersing agent of the present invention oomprises a blend of what can be referred to as a primary surfactant, and a second ingredient which can be referred to as a secondary dispersing agent.
The primary surfactant is a liquid, non-ionic, strong surfactant havingboth hydrophilic and lipophilic characteristics. For food applications, it should be food approved. Surfactants found to be particularly suitable are the polyglycerol esters of oleic or linoleic acid which have saponification and hydroxyl numbers which are approximately equal and in the range of about 140 to about 165. The number of glyoerol units is in the range of about 6-10. A preferred fatty acid esterified with polyglycerol is oleic acid. The polyglycerol esters are normally prepared by reacting the previously prepared polyglycerol with the fatty acid, either in a direct esterification process or by interesterification with a triglyceride esterified with the desired fatty acid units. Both reactions are well known and not a part of the present invention.
Polyglycerol esters of fatty acids having an hydroxyl value above about165 are not sufficiently solubilized in the base or carrier oil to provide a clear composition at temperatures down to about 55F. Those with hydroxyl values below about 140 do not provide sufficient solubilization, at the levels used, for the active ingredients or polar substances tested. The same constraints apply to the saponification values.
Similarly, with regard to the fatty acid component of the polyglycerol esters, it was found that such fatty acid esters as palmitates and stearates give a cloudy appearance, at the level of ester used, whereas the oleate and linoleate esters are liquid and give a clear appearance at the level used. In this regard, the amounts called for are a solubilizing or dispersing amount to achieve active ingredient loading desired.
Two suitable polyglycerol esters within the soope of the present invention are an octaglycerol pentaoleate and a decaglyceryl hexaoleate.
Both oompositions have hydroxyl numbers in the range of about 145-160 and saponification numbers in the range of about 145-150. They are in norm31ly liquid form.
The secondary dispersing agent o~ the present invention is a liquid fatty acid ester of oleic or linoleic acid and a polyol selected from the group consisting of polyglycerol, having about 2-5 glycerol units, sorbitol, and sucrose, said ester having an hydroxyl value in the range of about 195-250 and a saponification value in the range of about 140-160.
Examples of suitable secondary surfactants are a triglycerol dioleate, which has a hydroxyl number of about 215 plus~minus 15, and a saponification number of about 150 plus/minus 10; and sorbitan monooleate, which has a hydroxyl number of about 214 and a saponification number of about 152. Another such surfactant is sucrose trioleate, which has a hydroxyl number of about 250 and a saponification number of about 150.
Preferably, the primary surfactant is used in the ratio of about 6-12 parts by weight surfactant to about 94-98 parts oil carrier. The ratio of primary surfactant to secondary surfactant then is in the range of about 2:1 to about 9:1; or, based on the combined weight of surfactants, the secondary surfactant is about 10-30%.
In the practice of the present invention, it was found that the primarysurfactant, havinq both hydrophilic and lipophilic characteristics, is an essential ingredient in that it has sufficiently strong hydrophilic properties to hold the active ingredient in solution or suspension, and at the same time has sufficient lipophilic characteristics to be capable of substantially oomplete suspension in the lipoidal carrier at the level used. The secondary dispersing agent then acts as a solvent modifier, when used in the proportion of about 10 to about 30 weight percent, based on the weight of the combination of surfactants, completing solubilization of the primary surfactant.
In addition to the above critical ingredients, it is possible to include in the solvating agent formùlation other emulsifiers which have some 2t~3Z
solubility, for instance polysorbate 80 up to a level of about 2~, based on the weight of the entire formulation. ~bove about 2%, some polysorbate 80 precipitates in the oil medium.
ExAMæLE 1 This Example illustrates advantages of the present invention insolubilizing three water soluble materials, ethyl vanillin, ethanol, and benzyl alcohol.
The oomposition tested comprised 92% Durkex 500 winterized vegetable oil, 6% octaglycerol pentaoleate, and 2% of either triglycerol dioleate or sorbitan monooleate.
The alcohols and ethyl vanillin were dissolved by heating the lipid ingredients to 60C and then ultrasonically agitating them for ten minutes. All solutions were stored at 21C, unagitated, for six weeks prior to spectrophotometric analysis. Optical density was measured on a Beckman Model 3600 spectrophotometer for each sample at 630 and 510 nano,meters - light wavelength, and compared against water solution standards for each ingredient.
In the case of 2~ triglycerol dioleate, ethyl vanillin was soluble at the 2% level. Both absolute ethanol and benzyl alcohol were soluble in this composition up to the 103 level. With 2~ of the sorbitan mono~leate, ethyl vanillin was soluble at both the 2% and 5% lévels.
Both alcohols were also soluble in this composition up to the 10~ level.
All soluble materials resulted in clear solutions without visible precipitation.
This Example illustrates use of the present invention with a water soluble dye such as Blue No. 1 Lake. The carrier composition comprised 92 parts of winterized Durkex 500, 6 parts of octaglycerol pentaoleate, A and 2 parts of triglycerol dioleate. The same procedure as in Example 1 was employed. The Blue No. 1 Lake was found to be soluble up to a level of 2.5% without any precipitated dye.
In this Example, essentially the same formulation as used in Example 2 was employed except that the amount of winterized base oil was reduced to 91.75~ and .25~ Caprol ET crystallization inhibitor was added to the formulation. The formulation was tested with 50% loadings of FD&C
Yellow #5, Lake (37~ dye) and FD~C ~ed #40, Lake (38% dye). Both formulations remained stable over prolonged periods of storage, down to about 55F, and showed neither precipitation of lipid nor appreciable oiling-off of lipid. Both formulations were in the form of very smooth, homogeneous pastes. Neither was lumpy nor granular.
Both formulations were frozen at -20F for 18 hours, and then thawed at room temperature for 6 hours. Viscosity readings of 87.5 for the yellow #5 formulation and 92.5 for the ~ed #40 formulation were obtained, using a Brookfield visoometer Model LVF, Spindle #4, Speed 6. The samples were placed in 25 ml. graduated cylinders filled to the 15 ml. mark, to check for separated surface oil. None was present after a~out one month storage.
Similar results were obtained with a formulation which was the same in all respects except that the secondary surfactant was sorbitan monooleate instead of triglycerol dioleate. Samples having loadings of 50% of both dyes were prepared, and similar results were obtained. The Yellow Lake sample gave a viscosity reading of 100; the Red Lake, 88.
T;~le- ~r ~
Claims (10)
1. A clear, fluid, lipid carrier for polar, water dispersible or alcohol soluble substances comprising a) a high stability liquid oil or wax having an AOM stability of at least 100 hours and a cloud point below about 55°F;
b) a dispersing agent dispersed in said oil in the ratio of about 6-12 parts dispersing agent to about 94-88 parts oil or wax, said dispersing agent comprising a liquid, non-ionic, strong primary surfactant having both hydrophilic and lipophilic properties and a secondary surfactant;
b.1) said primary surfactant being a fatty acid ester of oleic or linoleic acid and polyglycerol having saponification and hydroxyl numbers which are approximately equal and in the range of about 140 to about 165, the polyglycerol comprising about 6-10 glycerol units;
b.2) said secondary surfactant being a fatty acid ester of oleic or linoleic acid and a polyol selected from the group consisting of polyglycerol having about 2-5 glycerol units, sorbitol and sucrose, said ester having an hydroxyl number in the range of about 195-250 and a saponification number in the range of about 140-160.
the ratio of primary surfactant to secondary surfactant being in the range of about 2:1 to about 9:1.
b) a dispersing agent dispersed in said oil in the ratio of about 6-12 parts dispersing agent to about 94-88 parts oil or wax, said dispersing agent comprising a liquid, non-ionic, strong primary surfactant having both hydrophilic and lipophilic properties and a secondary surfactant;
b.1) said primary surfactant being a fatty acid ester of oleic or linoleic acid and polyglycerol having saponification and hydroxyl numbers which are approximately equal and in the range of about 140 to about 165, the polyglycerol comprising about 6-10 glycerol units;
b.2) said secondary surfactant being a fatty acid ester of oleic or linoleic acid and a polyol selected from the group consisting of polyglycerol having about 2-5 glycerol units, sorbitol and sucrose, said ester having an hydroxyl number in the range of about 195-250 and a saponification number in the range of about 140-160.
the ratio of primary surfactant to secondary surfactant being in the range of about 2:1 to about 9:1.
2. The carrier of claim 1 wherein said oil is a partially hydrogenated winterized C16-C18 soybean and/or cottonseed oil.
3. The carrier of claim 1 further containing a crystallization inhibitor.
4. The carrier of claim 1 wherein said primary surfactant is octaglycerol pentaoleate.
5. A liquid lipoidal dispersion comprising the carrier of claims 1 or 2 or 3 or 4, and a water dispersible or alcohol soluble active ingredient, the proportion of active ingredient being about 1-50%
based on the weight of the carrier, said dispersion being cloud free.
based on the weight of the carrier, said dispersion being cloud free.
6. The dispersion of claim 5 for food applications.
7. The dispersion of claim 5 for cosmetic applications.
8. The dispersion of claim 5 for pharmaceutical applications.
9. The dispersion of claim 5 wherein the amount of dispersing agent in the carrier is a solubilizing amount effective to solubilize the active ingredient.
10. A clear, fluid, lipid carrier for polar, water dispersible or alcohol soluble substances comprising a) a high stability winterized, liquid, C16-C19 oil having an AOM stability of at least 100 hours and a cloud point below about 55°F;
b) a dispersing agent dispersed in said oil in the ratio of about 6-12 parts dispersing agent to about 94-88 parts ail, said dispersing agent comprising a liquid, non-ionic, strong primary surfactant having both hydrophilic and lipophilic properties and a secondary surfactant;
b.1) said primary surfactant being a fatty acid ester of oleic or linoleic acid and polyglycerol having saponification and hydroxyl numbers which are approximately equal and in the range of about 140 to about 165, the polyglycerol comprising about 6-10 glycerol units;
b.2) said secondary surfactant being a fatty acid ester of oleic or linoleic acid and a polyol selected from the group consisting of polyglycerol having about 2-5 glycerol units, sorbitol and sucrose, said ester having an hydroxyl number in the range of about 195-250 and a saponification number in the range of about 140-160;
c) further including a crystallization inhibitor in an amount effective to inhibit crystallization, the ratio of primary surfactant to secondary surfactant being in the range of about 2:1 to about 9:1.
b) a dispersing agent dispersed in said oil in the ratio of about 6-12 parts dispersing agent to about 94-88 parts ail, said dispersing agent comprising a liquid, non-ionic, strong primary surfactant having both hydrophilic and lipophilic properties and a secondary surfactant;
b.1) said primary surfactant being a fatty acid ester of oleic or linoleic acid and polyglycerol having saponification and hydroxyl numbers which are approximately equal and in the range of about 140 to about 165, the polyglycerol comprising about 6-10 glycerol units;
b.2) said secondary surfactant being a fatty acid ester of oleic or linoleic acid and a polyol selected from the group consisting of polyglycerol having about 2-5 glycerol units, sorbitol and sucrose, said ester having an hydroxyl number in the range of about 195-250 and a saponification number in the range of about 140-160;
c) further including a crystallization inhibitor in an amount effective to inhibit crystallization, the ratio of primary surfactant to secondary surfactant being in the range of about 2:1 to about 9:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87380286A | 1986-06-13 | 1986-06-13 | |
| US873,802 | 1986-06-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1292692C true CA1292692C (en) | 1991-12-03 |
Family
ID=25362352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000539048A Expired - Lifetime CA1292692C (en) | 1986-06-13 | 1987-06-08 | Dispersion of water dispersible or alcohol soluble substances in low cloud point lipoidal materials |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1292692C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0660696B1 (en) * | 1992-09-21 | 1997-01-08 | The Procter & Gamble Company | Lipsticks |
-
1987
- 1987-06-08 CA CA000539048A patent/CA1292692C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0660696B1 (en) * | 1992-09-21 | 1997-01-08 | The Procter & Gamble Company | Lipsticks |
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