(en)A cosmetic composition and an emulsion composition respectively comprising 0.1 to 99 weight % of an oily component and 99.9 to 1 weight % of a watery component are provided and the oily component in the compositions comprises 85 or more weight % of cis-Δ9-octadecenoic acid or derivatives thereof and contains 90 weight % or more of a cis-Δ9-alkenoic acid or derivatives thereof and 10 weight % or less of fatty adds other than the cis-Δ9-alkenoic acid, derivatives thereof or other oily components. The cosmetic composition showing superior feeling in use and superior storage stability than conventional products and the emulsion composition showing superior stability of emulsion than conventional products can be provided because the oily component contains cis-Δ9-octadecenoic acid or derivatives thereof in a high concentration.

1.ApplicationNumber: US-6601793-A
1.PublishNumber: US-5589515-A
2.Date Publish: 19961231
3.Inventor: SUZUKI; MASAO
SAITO; KOICHI
NAKATA; MASAHIDE

4.Inventor Harmonized: SUZUKI MASAO(JP)
SAITO KOICHI(JP)
NAKATA MASAHIDE(JP)

5.Country: US
6.Claims:
(en)A cosmetic composition and an emulsion composition respectively comprising 0.1 to 99 weight % of an oily component and 99.9 to 1 weight % of a watery component are provided and the oily component in the compositions comprises 85 or more weight % of cis-Δ9-octadecenoic acid or derivatives thereof and contains 90 weight % or more of a cis-Δ9-alkenoic acid or derivatives thereof and 10 weight % or less of fatty adds other than the cis-Δ9-alkenoic acid, derivatives thereof or other oily components. The cosmetic composition showing superior feeling in use and superior storage stability than conventional products and the emulsion composition showing superior stability of emulsion than conventional products can be provided because the oily component contains cis-Δ9-octadecenoic acid or derivatives thereof in a high concentration.

7.Description:
(en)TECHNICAL FIELD
The present invention relates to a cosmetic composition and an emulsion composition comprising cis-Δ9-octadecenoic acid or derivatives thereof in the oily component in a high concentration.
BACKGROUND ART
A cosmetic composition containing cis-Δ9-octadecenoic acid (oleic acid) or derivatives thereof in a high concentration has not been known heretofore.
Conventional oleic acids and derivatives thereof have a bad smell, are colored, cause skin irritation, have a poor feel in use and have poor storage stability tending to further increase the poor smell color and described above.
A method of production of a high purity oleic acid was disclosed in Japanese Patent Application Laid Open No. 1986-297 (Japanese Patent Publication No. 1990-57120). The following methods of production of derivatives of the high purity oleic acid were also disclosed: a method of production of glycerol monooleate in Japanese Patent Application Laid Open No. 1987-132841, a method of production of propylene glycol monooleate in Japanese Patent Application Laid Open No. 1987-138451, a method of production of polyalkylene glycol monooleate in Japanese Patent Application Laid Open No. 1987-138452, a method of production of sorbitan monooleate in Japanese Patent Application Laid Open No. 1987-142141, a method of production of polyalkylene glycol alkyl ether oleate in Japanese Patent Application Laid Open No. 1987-153250, a method of production of polyoxyalkylene polyalcohol oleate in Japanese Patent Application Laid Open No. 1987-153251, a method of production of polyoxyalkylene polyalcohol oleate in Japanese Patent Application Laid Open No. 1987-153252, a method of production of oleic esters in Japanese Patent Application Laid Open No. 1987-153253, a method of production of polyalkylene glycol oleate in Japanese Patent Application Laid Open No. 1987-153254, a method of production of polyoxyalkylene glycol monooleate in Japanese Patent Application Laid Open No. 1987-153255 and a method of production of polyglycerol oleate in Japanese Patent Application Laid Open No. 1987-153256. It has been suggested that these high purity oleic acids and derivatives thereof have no color, no smell, are stable, cause little skin irritation and can be utilized in the field of pharmaceuticals, cosmetics, foods, synthetic resins, lubricants, biochemicals and the like. However no description can be found on specific cosmetic compositions.
The present invention has the object to provide a cosmetic composition and an emulsion composition both comprising cis-Δ9-octadecenoic acid or derivatives thereof in a high concentration and to provide a cosmetic composition having superior feeling in use and superior storage stability than conventional products and an emulsion composition showing superior emulsion stability than conventional products.
DISCLOSURE OF THE INVENTION
The present invention provides a cosmetic composition which comprises 0.1 to 99 weight % of an oily component and 99.9 to 1 weight % of a watery component, the oily component comprising 85 or more weight % of cis-Δ9-octadecenoic acid or derivatives thereof and containing 90 weight % or more of a cis-Δ9-alkenoic acid or derivatives thereof and 10 weight % or less of fatty acids other than the cis-Δ9-alkenoic acid, derivatives thereof or other oily components.
The present invention also provides an emulsion composition which comprises 0.1 to 99 weight % of an oily component and 99.9 to 1 weight % of a watery component, the oily component comprising 85 or more weight % of cis-Δ9-octadecenoic acid or derivatives thereof, containing 90 weight % or more of a cis-Δ9-alkenoic acid or derivatives thereof and 10 weight % or less of fatty acids other than the cis-Δ9-alkenoic acid, derivatives thereof or other oily components and having an oily substance insoluble in the watery component and a surfactant which is dissolved or emulsified in the watery component.


THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION
The invention is described in more detail in the following.
The ratio of the oily component and the watery component is 0.1 to 99 weight %:99.9 to 1 weight %. However, this ratio is adopted for general cosmetic compositions and the ratio is different depending on the kind of the cosmetic composition. For example, the following ratios can be adopted: for skin lotion, 0.5 to 20 weight %:99.5 to 80 weight %; for skin cream, 10 to 85 weight %:90 to 15 weight %; for milk lotion, 3 to 50 weight %:97 to 50 weight %; and for cleansing foam, 30 to 70 weight %: 70 to 30 weight %.
The cis-Δ9-alkenoic acid in the invention is a fatty acid having one cis-unsaturated bond at the 9-position, such as cis-Δ9-octadecenoic acid (generally called oleic acid), cis-Δ9-hexadecenoic acid (generally called palmitoleic acid) and the like.
The derivatives of the cis-Δ9-alkenoic acid (including cis-Δ9-octadecenoic acid) comprise the following derivatives:
(1) Salts: salts of alkali metals, such as sodium, potassium and the like; ammonium salts; morpholine salts; salts of alkylamines, such as methylamine, ethylamine, butylamine and the like; salts of alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol; salts of basic amino acids, such as arginine and the like; and the like salts;
(2) Amides (these amides are cis-Δ9-alkenoic acid amides): amides with alkylamines or alkenylamines, such as methylamine, ethylamine, butylamine, cis-Δ9-alkenyl amines and the like; amides with alkanolamines, such as monoethanolamine, diethanolamine, isopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and the like; polyoxyethylated compounds and polyoxypropylated compounds of these amides; amides and salts of amides of amino acids, such as glutamic acid and the like; amides with sodium N-methyltaurine; cis-Δ9-alkenoyl peptides, such as cis-Δ9-alkenoyl collagen and the like; and the like amides;
(3) Esters: esters with monohydric alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, neopentanol, hexanol, octanol, 2-ethylhexanol, nonanol, isononanol, decanol, dodecanol, isotridecanol, tetradecanol, hexadecanol, isohexadecanol, hexyldecanol, octadecanol, isooctadecanol, eicosanol, 2-octyldodecanol, docosanol, octacosanol, triacontanol, aryl alcohol, hexadecenol, cis-Δ9-octadecenol, decocenol, cyclohexanol, lanolin alcohol, terpene alcohol, benzyl alcohol and the like, and esters with polyoxyethylated compounds or polyoxypropylated compounds of the monohydric alcohols; esters with polyhydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, glycerol, polyglycerols, trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan and the like, and esters with polyoxyethylated compounds or polyoxypropylated compounds of the polyhydric alcohols; esters with sugars, such as glucose, sucrose and the like; esters with sterols, such as cholesterol, cholestanol, sitosterol and the like; esters and salts with other hydroxyl compounds, such as tocopherol, oryzanol, guaiacol, gossypol, terpene alcohols, fiuoroalcohols, isethionic acid and the like; phospholipids in which the acyl group of a cis-Δ9-alkenoic acid is introduced; and the like esters;
(4) Derivatives of cis-Δ9-alkenols: cis-Δ9-alkenols derived from cis-Δ9alkenoic acids; phosphoric esters, sulfuric esters, polyoxyethylated compounds, polyoxypropylated compounds, polyoxyethylated phosphoric esters, polyoxyethylated sulfuric esters, polyoxypropylated phosphoric esters and polyoxypropylated sulfuric esters of the cis-Δ9-alkenols and salts of these compounds; esters, partial esters and partial ester salts of cis-Δ9-alkenyl alcohols with saturated, unsaturated, straight chain, branched chain, monovalent or polyvalent carboxylic acids or hydroxylated carboxylic acids derived from these carboxylic acid, such as ethanoic acid, butanoic acid, 2-ethylhexanoic acid, dodecanoic acid, octadecanoic acid, cis-Δ9-octadecenoic acid, succinic acid, adipic acid, sebacic acid, maleic acid, oxalic acid, citric acid, malic acid and the like; ethers of cis-Δ9-alkenols with alcohols, sugars or hydroxyl compounds described in (3) in the above; and the like compounds; and
(5) Derivatives of cis-Δ9-alkenylamines: salts of cis-Δ9-alkenylamines derived from cis-Δ9-alkenoic acids with acids, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, ethanoic acid and the like; quaternary ammonium salts having a cis-Δ9-alkenyl group; quaternary ammonium betaine having a cis-Δ9-alkenyl group; and the like compounds.
As shown in the above, the derivatives of cis-Δ9-alkenoic acid of the oily component of the invention is an oily substance insoluble in the watery component or a surfactant which is dissolved or emulsified in the watery component. Therefore, the cosmetic composition of the invention includes a composition having two separated layers composed of the oily substance and the watery component, a homogeneous composition composed of the surfactant and the watery component and a homogeneous transparent or turbid composition having the oily substance dissolved, emulsified or dispersed in the watery component by the effect of the surface active agent.
Preferable examples of the derivatives of the cis-Δ9-alkenoic acids as the oily substance are esters of cis-Δ9-octadecenoic acid with ethanol, isopropanol, cis-Δ9-hexadecenol, cis-Δ9-octadecenol, isooctadecanol, cholesterol and tocopherol; glycerol tri-cis-Δ9-octadecenoate; cis-Δ9-octadecenoic acid; cis-Δ9-octadecenol and the like. Preferable examples of the derivatives of the cis-Δ9-alkenoic acids as the surfactant are monoesters of cis-Δ9-octadecenoic acid and glycerol or polyglycerol, sorbitan mono- or sesqui-cis-Δ9-octadecenoate, polyoxyethylated sorbitan mono-cis-Δ9-octadecenoate, polyoxyethylated sorbitol tri- or tetra-cis-Δ9-octadecenoate, polyoxyethylene glycol mono-cis-Δ9-octadecenoate and polyoxyethylated cis-Δ9-octadecenyl ether. The particularly preferable examples for both of the oily substance and the surfactant are esters of cis-Δ9-octadecenoic acid.
In the invention, cis-Δ9-alkenoic acid and the derivative thereof which are the oily component insoluble in the watery component can be solubilized or emulsified in the watery component much more easily by using the surfactant of the derivatives of cis-Δ9-alkenoic acid in comparison to using other surface active agents and the stability is much more excellent. The weight ratio of the oily substance and the surfactant in this case is varied depending on the kinds and the ratio of the oily component and the surfactant, other additives and the like. The ratio is generally in the range of 99 to 1:1 to 99 and preferably in the range of 97 to3:3 to 97.
The oily component other than those described above are all kinds of oily components other than the cis-Δ9-alkenoic acids and the derivatives thereof. Examples are natural and synthetic oily substances, such as fatty acids and derivatives thereof other than the cis-Δ9-alkenoic acids, paraffin, kerosene, squalane, plant oils, animal oils, lanoline, haze wax, hexadecanol, isooctadecanol, silicone oils, fiuorohydrocarbons, polyoxypropylated ethers, cholesterol, tocopherol and the like; surface active agents derived from fatty acids other than the cis-Δ9-alkenoic acids, such as dodecandiethanolamide and the like; other surface active agents like polyoxyethylated alkylphenyl ether; and the like.
The watery component functions as the moisturizing agent and the examples include water, of course, and compounds which can be mixed with water in any ratio, such as alcohols like ethanol, isopropanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycols, glycerol, sorbitol, polyglycerols, polyvinyl alcohols and the like; sugars like glucose, sucrose and the like; mucopolysaccharides like hyaluronic acid and the like; amino acids like glutamic acid and the like; proteins like collagen and the like; and the like compounds.
When other cis-Δ9-alkenoic acids such as palmitoleic acid are present together with cis-Δ9-octadecenoic acid, the other cis-Δ9-alkenoic acids exhibit the same effect as that of cis-Δ9-octadecenoic acid. The oily component contains 85 weight % or more of cis-Δ9-octadecenoic acid and 90 weight % or more of the cis-Δ9-alkenoic acid, preferably 90 weight % or more of cis-Δ9-octadecenoic acid and 93 weight % or more of the cis-Δ9-alkenoic acid, more preferably 95 weight % or more of cis-Δ9-octadecenoic acid and 97 weight % or more of the cis-Δ9-alkenoic acid and most preferably 97 weight % or more of cis-Δ9-octadecenoic acid and 99 weight % or more of the cis-Δ9-alkenoic acid. When the content of cisΔ9-octadecenoic acid is less than 85 weight % or the content of the cis-Δ9-alkenoic acid is less than 90 weight %, the feeling in use of the cosmetic composition is not satisfactory.
The cosmetic composition of the invention may comprise components generally added to cosmetic compositions, such as drugs like vitamins, antibiotics and the like, nutrients, ultraviolet ray absorbents, carbon black, titanium oxide, iron oxide, metallic soaps, calcium carbonate, silica, talc, colors, perfumes and the like, in addition to the oily component and the watery component described above.
The cosmetic composition of the invention takes the form of liquid, cream, gel or solid depending on the mixed composition. It is used as skin lotion, cosmetic oil, milk lotion, lipstick, hair liquid, hair cream, hair growth agent, foundation, various kinds of cream and the like.
The emulsion composition of the invention may comprise various kinds of additives generally added to emulsion compositions.
The method of preparation of the cosmetic composition and the emulsion composition of the invention can be performed by compounding the components described above. The order of the addition of the components is not particularly limited and components can be suitably selected and added. The compounded components are suitably mixed by using various kinds of mixer, various kinds of dispersing machine, various kinds of emulsifying machine or the like to prepare the cosmetic composition and the emulsion composition of the invention.
The reason that the stability of the product in the invention is very excellent when the derivative of cis-Δ9-octadecenoic acid is used as the surfactant to emulsify or solubilize in the watery component cis-Δ9-octadecenoic acid or the derivative which is insoluble in the watery component can be considered as following: when the concentration of cis9-octadecenoic acid or the derivative is high, mutual orientation and cohesion of the cis-Δ9-octadecenoyl group or the cis-Δ9-octadecenyl group in the molecule is considered to be enhanced and the molecular structure proper to the molecule is efficiently exhibited; this is considered to have the effect on the better feeling in use of the cosmetic composition comprising cis-Δ9-octadecenoic acid or the derivative in a high concentration.
The cosmetic composition of the invention comprising cis-Δ9-octadecenoic acid or the derivatives thereof in the oily component in a high concentration provides very excellent feeling in use and the result is remarkably superior than the cosmetic compositions comprising cis-9-octadecenoic acid or the derivatives thereof in a low concentration.
Cosmetic compositions prepared by using commercial oleic acid or derivatives thereof having low concentrations of cis-Δ9-octadecenoic acid as the material are colored or generate smell with passage of time. The cosmetic composition of the invention does not have such drawback.
The emulsion composition of the invention comprising cis-Δ9-octadecenoic acid or the derivative thereof in the oily component in a high concentration has a very excellent stability of the emulsion.
EXAMPLE
The invention is described with reference to examples. However, the invention is by no means limited by the examples.
In Examples and Comparative Examples, oleic acid or oleic acid derivatives containing various kinds of cis-Δ9-octadecenoic acid and derivatives thereof were used as the oily component. The concentration was represented by the purity of cis-Δ9-octadecenoic acid or a cis-Δ9-alkenoic acid in the oleic acid.
When the concentration of cis-Δ9-octadecenoic acid or its derivative is varied in a cornposition using two or more kinds of oleic acid or oleic acid derivatives, the oleic acids or the oleic acid derivatives having the same purity of the cis-Δ9-octadecenoic acid were used for compounding in the composition.
In the Examples and Comparative Examples, "%" means "weight %". The oleic acid or the oleic acid derivative containing 57% of cis-Δ9-octadecenoic acid and 66 weight % of cis-Δ9-alkenoic acid used in Comparative Examples is a commercial oleic acid or a derivative from the commercial oleic acid.
Method of evaluation of the cosmetic composition, method of evaluation of storage stability of an emulsion composition and method of analysis of purity of a cis-Δ9-alkenoic acid containing cis-Δ9-octadecenoic acid are described in the following.
Method of evaluation of the feeling in use
Overall feeling in use including all of smell, extension, refreshing feeling and emollient effect was evaluated by 20 women panellers and the result is shown by the number of the panellers whose answer was good.
Method of evaluation of storage stability of an emulsion composition
An oily component (including oily substances and surfactants) and a watery component were mixed by shaking mildly and then emulsified by using a homogenizer (DX-3 type, a product of Nippon Seiki Seisakusho Co., Ltd.) at 10,000 rpm for 15 minutes. Condition of the emulsion was evaluated by visual observation according to the following criterion:

______________________________________stable: emulsified in a stable conditionslightly separated: slightly separatedseparated: completely separated into two phases______________________________________

Method of analysis of purity
Analysis was conducted by using an apparatus for gas chromatography (GC-9A, a product of Shimazu Seisakusho Co., Ltd.) equipped with capillary columns which can separate isomers having different positions of a double bond and different steric structures (SP-2560:0.25 mm×100 m, a product of Supelco Inc.).
Examples 1 to 5 and Comparative Examples 1 to 3
Skin lotions were prepared by using N-oleoyl-L-glutamic acids which are oleic acid derivatives having different purities shown in Table 1 as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 1.

______________________________________Formulation______________________________________oily componentsurfactant: N-oleoyl-L-glutamic acid 3%watery componentsethanol 10%purified water 85%sorbitol 2%______________________________________


TABLE 1______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 1 99.9 100 19Example 2 99 99.5 17Example 3 95 97 15Example 4 90 93 15Example 5 85 90 13Comparative 80 86 7Example 1Comparative 70 78 1Example 2Comparative 57 66 0Example 3______________________________________

Examples 6 to 10 and Comparative Examples 4 to 6
Cleansing creams were prepared by using monosodium N-oleoylglutamates which are oleic acid derivatives having different purities shown in Table 2 as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 2.

______________________________________Formulation______________________________________oily componentsurfactant: monosodium N-oleoylglutamate 45%watery componentspurified water 50%polyethylene glycol 5%______________________________________


TABLE 2______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 6 99.9 100 20Example 7 99 99.5 18Example 8 95 97 16Example 9 90 93 15Example 10 85 90 13Comparative 80 86 10Example 4Comparative 70 78 7Example 5Comparative 57 66 0Example 6______________________________________

Examples 11 to 15 and Comparative Examples 7 to 9
Skin lotions were prepared by using glycerol monooleates which are oleic acid derivatives having different purities shown in Table 3 and polyoxyethylated (25 mols) oleyl ethers which are oleic acid derivatives having the same purities as those of the corresponding glycerol monooleates as the surfactants according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 3.

______________________________________Formulation______________________________________oily componentsurfactants: glycerol monooleate 3%polyoxyethylated (25 mols) oleyl ether 2%watery componentsethanol 10%purified water 82%sorbitol 3%______________________________________


TABLE 3______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 11 99.9 100 20Example 12 99 99.5 19Example 13 95 97 18Example 14 90 93 18Example 15 85 90 15Comparative 80 86 9Example 7Comparative 70 78 0Example 8Comparative 57 66 0Example 9______________________________________

Examples 16 to 20 and Comparative Examples 10 to 12
Skin lotions were prepared by using L-α-dioleoyl phosphatidyl cholines which are oleic acid derivatives having different purities shown in Table 4 and polyoxyethylated (20 mols) sorbitan monooleates which are oleic acid derivatives having the same purities as those of the corresponding L-α-dioleoyl phosphatidyl cholines as the surfactants according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 4.

______________________________________Formulation______________________________________oily componentsurfactants: L-α-dioleoyl phosphatidyl choline 2%polyoxyethylated (20 mols) sorbitan 1%monooleatewatery componentsethanol 15%purified water 80%propylene glycol 2%______________________________________


TABLE 4______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 16 99.9 100 20Example 17 99 99.5 20Example 18 95 97 18Example 19 90 93 15Example 20 85 90 13Comparative 80 86 8Example 10Comparative 70 78 0Example 11Comparative 57 66 0Example 12______________________________________

Examples 21 to 25 and Comparative Examples 13 to 15
Skin lotions were prepared by using N-oleoyl-L-glutamic acids which are oleic acid derivatives having different purities shown in Table 5 and hexaglycerol monooleates which are oleic acid derivatives having the same purities as those of the corresponding N-oleoyl-L-glutamic acids as the surfactants according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 5.

______________________________________Formulation______________________________________oily componentsurfactants: N-oleoyl-L-glutamic acid 2%hexaglycerol monooleate 3%watery componentsethanol 10%purified water 85%______________________________________


TABLE 5______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 21 99.9 100 20Example 22 99 99.5 19Example 23 95 97 16Example 24 90 93 14Example 25 85 90 11Comparative 80 86 3Example 13Comparative 70 78 0Example 14Comparative 57 66 0Example 15______________________________________

Examples 26 to 30 and Comparative Examples 16 to 18
Shaking lotions separated to two phases were prepared by using isooctadecanyl oleates which are oleic acid derivatives having different purities shown in Table 6 as the oily substance and polyoxyethylated (20 mols) sorbitan tetraoleates which are oleic acid derivatives having the same purities as those of the corresponding isooctadecanyl oleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 6.

______________________________________Formulation______________________________________oily componentsoily substance: isooctadecanyl oleate 8 %surfactant: polyoxyethylated (20 mols) sorbitan 0.2 %tetraoleatewatery componentspurified water 79.8 %ethanol 10 %sorbitol 1 %glycerol 1 %______________________________________


TABLE 6______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 26 99.9 100 20Example 27 99 99.5 20Example 28 95 97 18Example 29 90 93 17Example 30 85 90 13Comparative 80 86 4Example 16Comparative 70 78 0Example 17Comparative 57 66 0Example 18______________________________________

Examples 31 to 35 and Comparative Examples 19 to 21
Skin creams were prepared by using hexadecenyl oleates which are oleic acid derivatives having different purities shown in Table 7 as the oily substance and polyoxyethylated (10 mols) oleyl ethers which are oleic acid derivatives having the same purities as those of the corresponding hexadecenyl oleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 7.

______________________________________Formulation______________________________________oily componentsoily substance: hexadecenyl oleate 70%surfactant: polyoxyethylated (10 mols) oleyl ether 5%watery componentspurified water 22%glycerol 3%______________________________________


TABLE 7______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 31 99.9 100 20Example 32 99 99.5 20Example 33 95 97 19Example 34 90 93 18Example 35 85 90 13Comparative 80 86 7Example 19Comparative 70 78 0Example 20Comparative 57 66 0Example 21______________________________________

Examples 36 to 40 and Comparative Examples 12 to 24
Skin creams were prepared by using ethyl oleates which are oleic acid derivatives having different purities shown in Table 8 as the oily substance and diglycerol monooleates which are oleic acid derivatives having the same purities as those of the corresponding ethyl oleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 8.

______________________________________Formulation______________________________________oily componentsoily substance: ethyl oleate 65%surfactant: diglycerol monooleate 5%watery componentpurified water 30%______________________________________


TABLE 8______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 36 99.9 100 20Example 37 99 99.5 20Example 38 95 97 18Example 39 90 93 18Example 40 85 90 14Comparative 80 86 7Example 22Comparative 70 78 1Example 23Comparative 57 66 0Example 24______________________________________

Examples 41 to 45 and Comparative Examples 25 to 27
Oleyl oleates of different purities were prepared by esterification of oleic acids having different purities shown in Table 9 with oleyl alcohols having the same purities as those of the corresponding oleic acids which were prepared by reduction of the oleic acids. Skin creams were prepared by using the oleyl oleates as the oily substance and glycerol monooleates and sucrose monooleates which are oleic acid derivatives having the same purities as those of the corresponding oleyl oleates, respectively, as the surfactants according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 9.

______________________________________Formulation______________________________________oily componentsoily substance: oleyl oleate 40%surfactants: glycerol monooleate 2.5%sucrose monooleate 1.5watery componentspurified water 53%propylene glycol 3%______________________________________


TABLE 9______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 41 99.9 100 20Example 42 99 99.5 19Example 43 95 97 18Example 44 90 93 16Example 45 85 90 13Comparative 80 86 8Example 25Comparative 70 78 0Example 26Comparative 57 66 0Example 27______________________________________

Examples 46 to 50 and Comparative Examples 28 to 30
Skin creams were prepared by using glycerol trioleates which are oleic acid derivatives having different purities shown in Table 10 as the oily substance and sorbitan sesquioleates and polyoxyethylated (20 mols) sorbitan monooleates which are oleic acid derivatives having the same purities as those of the corresponding glycerol trioleates, respectively, as the surfactants according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 10.

______________________________________Formulation______________________________________oily componentsoily substance: glycerol trioleate 75%surfactants: sorbitan sesquioleate 3.5%polyoxyethylated (20 mols) sorbitan 1.5%monooleatewatery componentspurified water 17%sorbitol 3%______________________________________


TABLE 10______________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)______________________________________Example 46 99.9 100 19Example 47 99 99.5 19Example 48 95 97 18Example 49 90 93 15Example 50 85 90 13Comparative 80 86 7Example 28Comparative 70 78 0Example 29Comparative 57 66 0Example 30______________________________________

Examples 51 to 55 and Comparative Examples 31 to 33
Skin creams were prepared by using 2-octyldodecyl oleates which are oleic acid derivatives having different purities shown in Table 11 as the oily substance and pentaerythritol monooleates and polyoxyethylated (20 mols) oleyl ethers which are oleic acid derivatives having the same purities as those of the corresponding 2-octyldodecyl oleates, respectively, as the surfactants according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 11.

______________________________________Formulation______________________________________oily componentsoily substance: 2-octyldodecyl oleate 20%surfactants: pentaerythritol monooleate 2%polyoxyethylated (20 mols) oleyl 1%etherwatery componentspurified water 72%glycerol 5%______________________________________


TABLE 11______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 51 99.9 100 20Example 52 99 99.5 19Example 53 95 97 18Example 54 90 93 18Example 55 85 90 14Comparative Example 31 80 86 9Comparative Example 32 70 78 7Comparative Example 33 57 66 0______________________________________

Examples 56 to 60 and Comparative Examples 34 to 36
Milk lotions were prepared by using oleic acids having different purities shown in Table 12 and cholesterol oleates which are derivatives of these oleic acids as the oily substances and L-α-dioleoyl phosphatidyl cholines which are oleic acid derivatives having the same purities as those of the corresponding oleic acids as the surfactant according to the formulation described below and the feeling in use was evaluated, The results are shown in Table 12.

______________________________________Formulation______________________________________oily componentsoily substances: oleic acid 2%cholesterol oleate 10surfactant: L-α-dioleoyl phosphatidyl choline 2%watery componentpurified water 86%______________________________________


TABLE 12______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 56 99.9 100 20Example 57 99 99.5 19Example 58 95 97 18Example 59 90 93 18Example 60 85 90 15Comparative Example 34 80 86 10Comparative Example 35 70 78 7Comparative Example 36 57 66 0______________________________________

Examples 61 to 65 and Comparative Examples 37 to 39
Milk lotions were prepared by using glycerol dioleates which are oleic acid derivatives having different purities shown in Table 13 as the oily substance and L-arginine oleates which are oleic acid derivatives having the same purities as those of the corresponding glycerol dioleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 13.

______________________________________Formulation______________________________________oily componentsoily substance: glycerol dioleate 15%surfactant: L-arginine oleate 1%watery componentpurified water 84%______________________________________


TABLE 13______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 61 99.9 100 20Example 62 99 99.5 20Example 63 95 97 18Example 64 90 93 18Example 65 85 90 18Comparative Example 37 80 86 14Comparative Example 38 70 78 9Comparative Example 39 57 66 0______________________________________

Examples 66 to 70 and Comparative Examples 40 to 42
Milk lotions were prepared by using tocopherol oleates which are oleic acid derivatives having different purities shown in Table 14 as the oily substance and sucrose monooleates which are oleic acid derivatives having the same purities as those of the corresponding tocopherol oleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 14.

______________________________________Formulation______________________________________oily componentsoily substance: tocopherol oleate 10%surfactant: sucrose monooleate 3%watery componentspurified water 84%glycerol 3%______________________________________


TABLE 14______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 66 99.9 100 20Example 67 99 99.5 19Example 68 95 97 18Example 69 90 93 15Example 70 85 90 13Comparative Example 40 80 86 7Comparative Example 41 70 78 0Comparative Example 42 57 66 0______________________________________

Examples 71 to 75 and Comparative Examples 43 to 45
Cleansing creams were prepared by using isopropyl oleates which are oleic acid derivatives having different purities shown in Table 15 as the oily substance and polyoxyethylated (20 mols) oleyl ethers and polyoxyethylated (5 mols) sorbitan monooleates which are oleic acid derivatives having the same purities as those of the corresponding isopropyl oleates, respectively, as the surfactants according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 15.

______________________________________Formulation______________________________________oily componentsoily substance: isopropyl oleate 80%surfactants: polyoxyethylated (20 mols) oleyl ether 3%polyoxyethylated (5 mols) sorbitan 2%monooleatewatery componentpurified water 15%______________________________________


TABLE 15______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 71 99.9 100 20Example 72 99 99.5 20Example 73 95 97 18Example 74 90 93 18Example 75 85 90 13Comparative Example 43 80 86 7Comparative Example 44 70 78 0Comparative Example 45 57 66 0______________________________________

Examples 76 to 80 and Comparative Examples 46 to 48
Cleansing foams were prepared by using oleyl alcohols which are oleic acid derivatives having different purities shown in Table 16 as the oily substance and potassium oleates which are oleic acid derivatives having the same purities as those of the corresponding oleyl alcohols as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 16.

______________________________________Formulation______________________________________oily componentsoily substance: oleyl alcohol 3%surfactant: potassium oleate 40%watery componentpurified water 57%______________________________________


TABLE 16______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 76 99.9 100 20Example 77 99 99.5 19Example 78 95 97 18Example 79 90 93 18Example 80 85 90 14Comparative Example 46 80 86 9Comparative Example 47 70 78 0Comparative Example 48 57 66 0______________________________________

Examples 81 to 85 and Comparative Examples 49 to 51
Cleansing foams were prepared by using ethylene glycol monooleates which are oleic acid derivatives having different purities shown in Table 17 as the oily substance and monosodium N-oleoylglutamates which are oleic acid derivatives having the same purities as those of the corresponding ethylene glycol monooleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 17.

______________________________________Formulation______________________________________oily componentsoily substance: ethylene glycol monooleate 5%surfactant: monosodium N-oleoylglutamate 40%watery componentspurified water 50%polyethylene glycol 5%______________________________________


TABLE 17______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 81 99.9 100 20Example 82 99 99.5 19Example 83 95 97 18Example 84 90 93 18Example 85 85 90 14Comparative Example 49 80 86 8Comparative Example 50 70 78 7Comparative Example 51 57 66 0______________________________________

Examples 86 to 90 and Comparative Examples 52 to 54
Foundations of milk lotion were prepared by using isooctadecanyl oleates which are oleic acid derivatives having different purities shown in Table 18 as the oily substance and triethanolamine oleates which are oleic acid derivatives having the same purities as those of the corresponding isooctadecanyl oleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 18.

______________________________________Formulation______________________________________oily componentsoily substance: isooctadecanyl oleate 18%surfactant: triethanolamine oleate 5%watery componentpurified water 64.9%pigmentstitanium dioxide 8%talc 4%color 0.1%______________________________________


TABLE 18______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 86 99.9 100 20Example 87 99 99.5 20Example 88 95 97 18Example 89 90 93 18Example 90 85 90 18Comparative Example 52 80 86 13Comparative Example 53 70 78 8Comparative Example 54 57 66 0______________________________________

Examples 91 to 95 and Comparative Examples 55 to 57
Lipsticks were prepared by using docosenyl oleates and octacosanyl oleates which are oleic acid derivatives having different purities shown in Table 19, respectively, as the oily substances and glycerol monooleates which are oleic acid derivatives having the same purities as those of the corresponding docosenyl oleates and octacosanyl oleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 19.

______________________________________Formulation______________________________________oily componentsoily substances: docosenyl oleate 42%octacosanyl oleate 15%surfactant: glycerol monooleate 30%watery componentglycerol 3%pigmentstitanium dioxide 1%red pigment No. 201 1%red pigment No. 202 1%blue pigment No. 1 aluminum chelate 0.5%mica titanium 6.5%______________________________________


TABLE 19______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 91 99.9 100 20Example 92 99 99.5 19Example 93 95 97 18Example 94 90 93 18Example 95 85 90 14Comparative Example 55 80 86 9Comparative Example 56 70 78 7Comparative Example 57 57 66 0______________________________________

Examples 96 to 100 and Comparative Examples 58 to 60
Hair creams were prepared by using octadecyl oleates which are oleic acid derivatives having different purities shown in Table 20 as the oily substance and polyoxyethylene (10 mols) glycol monooleates which are oleic acid derivatives having the same purities as those of the corresponding octadecyl oleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 20.

______________________________________Formulation______________________________________oily componentsoily substance: octadecyl oleate 15%surfactant: polyoxylethylene (10 mols) glycol 5%monooleatewatery componentspurified water 75%propylene glycol 5%______________________________________


TABLE 20______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 96 99.9 100 20Example 97 99 99.5 19Example 98 95 97 18Example 99 90 93 18Example 100 85 90 13Comparative Example 58 80 86 8Comparative Example 59 70 78 0Comparative Example 60 57 66 0______________________________________

Examples 101 to 105 and Comparative Examples 61 to 63
Hair growth agents were prepared by using ethyl oleates which are oleic acid derivatives having different purities shown in Table 21 as the oily substance and glycerol monooleates which are oleic acid derivatives having the same purities as those of the corresponding ethyl oleates as the surfactant according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 21.

______________________________________Formulation______________________________________oily componentsoily substance: ethyl oleate 3%surfactant: glycerol monooleate 2%watery componentethanol 93.4%hair growth componentscepharanthin 1%hinokitiol 0.1%tocopherol nicotinate 0.5%______________________________________


TABLE 21______________________________________ evaluation purity of purity of of feeling cis-Δ9- cis-Δ9- in use octadecenoic alkenoic (number of acid (%) acid (%) persons)______________________________________Example 101 99.9 100 20Example 102 99 99.5 20Example 103 95 97 19Example 104 90 93 18Example 105 85 90 14Comparative Example 61 80 86 7Comparative Example 62 70 78 1Comparative Example 63 57 66 0______________________________________

Examples 106 to 110 and Comparative Examples 64 to 66
Hair growth agents were prepared by using palmityl oleates which are oleic acid derivatives having different purities shown in Table 22 as the oily substance and polyoxyethylene (10 mols) oleyl ether phosphoric acid sodium salts which are oleic acid derivatives having the same purities as those of the corresponding palmityl oleates as the surfactants according to the formulation described below and the feeling in use was evaluated. The results are shown in Table 22.

______________________________________Formulation______________________________________oily componentsoily substance: palmityl oleate 2%surfactants: polyoxyethylene (10 mols) oleyl ether 2%phosphoric acid sodium saltwatery componentsethanol 70%purified water 24.4%hair growth componentscapronium chloride 1%extract of Japanese green gentian 0.1%α-tocopherol 0.5%______________________________________


TABLE 22__________________________________________________________________________ evaluation of purity of cis-Δ9- purity of cis-Δ9- feeling in use octadecenoic acid alkenoic acid (number of (%) (%) persons)__________________________________________________________________________Example 106 99.9 100 20Example 107 99 99.5 19Example 108 95 97 18Example 109 90 93 18Example 110 85 90 13Comparative Example 64 80 86 9Comparative Example 65 70 78 0Comparative Example 66 57 66 0__________________________________________________________________________

Examples 111 to 115 and Comparative Examples 67 to 69
Emulsion compositions were prepared by using glycerol trioleates which are oleic acid derivatives having different purities shown in Table 23 as the oily substance and sorbitan sesquioleates and polyoxyethylene (20 mols) sorbitan monooleates which are oleic acid derivatives having the same purities as those of the corresponding glycerol trioleates, respectively, as the surfactants according to the formulation described below.

______________________________________Formulation______________________________________oily componentsoily substance: glycerol trioleate 50%surfactants: sorbitan sesquioleate 8.5%polyoxylethylene (20 mols) sorbitan 1.5monooleatewatery componentpurified water 40%______________________________________


TABLE 23______________________________________ purity of cis-Δ9- purity of cis-Δ9- octadecenoic acid alkenoic acid (%) (%)______________________________________Example 111 99.9 100Example 112 99 99.5Example 113 95 97Example 114 90 93Example 115 85 90Comparative Example 67 80 86Comparative Example 68 70 78Comparative Example 69 57 66______________________________________

Storage stability of the emulsion compositions thus prepared was evaluated. The results on the condition of the emulsion and the storage stability on standing are shown in Table 24.

TABLE 24__________________________________________________________________________ condition storage stability on standing, after the specified time of emulsion 30 min. 1 hour 5 hours 24 hours 72 hours__________________________________________________________________________Example 111 good stable stable stable stable stableExample 112 good stable stable stable stable stableExample 113 good stable stable stable stable stableExample 114 good stable stable stable stable stableExample 115 good stable stable stable stable slightly separatedComparative good stable stable slightly separated separatedExample 67 separatedComparative good stable slightly separated separated separatedExample 68 separatedComparative good stable slightly separated separated separatedExample 69 separated__________________________________________________________________________

Comparative Examples 70 to 72
Emulsion compositions were prepared by the same method used in Examples 111 to 115 and in Comparative Examples 67 to 69 except that sorbitan sesquioleate and polyoxyethylene (20 mols) sorbitan monooleate as the surfactants were replaced by 8.5% of sorbitan sesquistearate which is a derivative of 99% stearic acid and 1.5% of polyoxyethylene (20 mols) sorbitan monostearate as the surfactants in Comparative Example 70, by 10% of polyoxyethylene (2 mols) nonylphenyl ether as the surfactant in Comparative Example 71 and by 10% of glycerol monolaurate which is a derivative of 99% lauric acid as the surfactant in Comparative Example 72 and the storage stability of emulsion was evaluated. The results are shown in Table 25. The results show that the storage stability of emulsion is inferior when the compounds other than the derivatives of cis-Δ9-octadecenoic acid are used as the surfactant.

TABLE 25______________________________________ condi- tion of storage stability on standing, emul- after the specified time sion 30 min. 1 hour 5 hours 24 hours______________________________________Comparative poor separated separated separated separatedExample 70Comparative poor slightly slightly separated separatedExample 71 separated separatedComparative poor slightly separated separated separatedExample 72 separated______________________________________

Examples 116 to 120 and Comparative Examples 73 to 75
Emulsion compositions were prepared by using ethyl oleates which are oleic acid derivatives having different purities shown in Table 26 as the oily substance and sorbitan sesquioleates and polyoxyethylene (20 mols) sorbitan monooleates which are oleic acid derivatives having the same purities as those of the corresponding ethyl oleates, respectively, as the surfactants according to the formulation described below.

______________________________________Formulation______________________________________oily componentsoily substance: ethyl oleate 50%surfactants: sorbitan sesquioleate 7.5%polyoxylethylene (20 mols) sorbitan 2.5%monooleatewatery componentpurified water 40%______________________________________


TABLE 26______________________________________ purity of cis-Δ9- purity of cis-Δ9- octadecenoic acid alkenoic acid (%) (%)______________________________________Example 116 99.9 100Example 117 99 99.5Example 118 95 97Example 119 90 93Example 120 85 90Comparative Example 73 80 86Comparative Example 74 70 78Comparative Example 75 57 66______________________________________

Storage stability of the emulsion compositions thus prepared was evaluated. The results on the condition of the emulsion and the storage stability on standing are shown in Table 27.

TABLE 27__________________________________________________________________________ condition storage stability on standing, after the specified time of emulsion 30 min. 1 hour 5 hours 24 hours 72 hours__________________________________________________________________________Example 116 good stable stable stable stable stableExample 117 good stable stable stable stable stableExample 118 good stable stable stable stable stableExample 119 good stable stable stable stable slightly separatedExample 120 good stable stable stable stable slightly separatedComparative good stable stable slightly separated separatedExample 73 separatedComparative good stable slightly separated separated separatedExample 74 separatedComparative good stable slightly separated separated separatedExample 75 separated__________________________________________________________________________

Examples 121 to 125 and Comparative Examples 76 to 78
Emulsion compositions were prepared by using oleyl alcohols which are oleic acid derivatives having different purities shown in Table 28 as the oily substance and sorbitan sesquioleates and polyoxyethylene (20 mols) sorbitan monooleates which are oleic acid derivatives having the same purities as those of the corresponding oleyl alcohols, respectively, as the surfactants according to the formulation described below.

______________________________________Formulation______________________________________oily componentsoily substance: oleyl alcohol 50%surfactants: sorbitan sesquioleate 8.5%polyoxylethylene (20 mols) sorbitan 1.5monooleatewatery componentpurified water 40%______________________________________


TABLE 28______________________________________ purity of cis-Δ9- purity of cis-Δ9- octadecenoic acid alkenoic acid (%) (%)______________________________________Example 121 99.9 100Example 122 99 99.5Example 123 95 97Example 124 90 93Example 125 85 90Comparative Example 76 80 86Comparative Example 77 70 78Comparative Example 78 57 66______________________________________

Storage stability of the emulsion compositions thus prepared was evaluated. The results on the condition of the emulsion and the storage stability on standing are shown in Table 29.

TABLE 29__________________________________________________________________________ condition storage stability on standing, after the specified time of emulsion 30 min. 1 hour 5 hours 24 hours 72 hours__________________________________________________________________________Example 121 good stable stable stable stable stableExample 122 good stable stable stable stable stableExample 123 good stable stable stable stable stableExample 124 good stable stable stable stable stableExample 125 good stable stable stable stable stableComparative good stable stable stable stable separatedExample 76Comparative good stable stable stable separated separatedExample 77Comparative good stable stable slightly separated separatedExample 78 separated__________________________________________________________________________

As the results in Tables 24, 25, 27 and 29 show, the emulsion compositions having very excellent storage stability can be prepared by the formulations of Examples 111 to 125, which contain oleic acid or oleic acid derivatives containing cis-Δ-9-octadecenoic acid in high concentrations as the oily substance and oleic acid derivatives containing cis-A9-octadecenoic acid in high concentrations as the surfactant.
INDUSTRIAL APPLICABILITY
As described above, the cosmetic composition of the invention is useful as various kinds of cosmetic materials, such as skin lotion, cream, milk lotion, cleansing foam and the like.
The emulsion composition of the invention can provide an emulsion having excellent storage stability of emulsion. This emulsion can be utilized as a base material for pharmaceuticals, an emulsifying agent for oily materials which are not easily emulsified and the like as well as the cosmetic material.