JP3891982B2 - Self-emulsifying oily liquid cosmetic - Google Patents

Description

  The present invention relates to a self-emulsifying type oily liquid cosmetic based on a specific polyglycerin fatty acid ester and an oily component, and more specifically, there is no concern about safety to the human body and excellent storage stability. In addition, the present invention relates to a self-emulsifying type oily liquid cosmetic which has excellent dispersibility in water by being easily self-emulsified and also has a good feeling in use.

  Self-emulsifying oily liquid cosmetics are those that undergo phase inversion upon contact with water to produce oil-in-water emulsions. As typical examples of self-emulsifying oily liquid cosmetics, cleansing cosmetics and bath cosmetics Etc.

In recent years, makeup cosmetics are demanded to be hard to fall off, and the preference for thick-coated makeup is increasing due to the trend. For this reason, cleansing cosmetics intended to remove makeup cosmetics such as foundations and lipsticks based on oily ingredients are required to have a strong detergency.
Cleansing cosmetics are available in various dosage forms on the market, for example, water-based, oil-based, polyhydric alcohol-based, liquid crystal-based liquid, gel-like, and cream-like types based on surfactants. Can be mentioned. Among them, oil-based liquid cleansing cosmetics are known to have the highest detergency because they have excellent compatibility with cosmetic oil components. As a result, the most widely distributed product on the market is a self-emulsifying type oily product comprising a mixed system of an oily component and a surfactant. This product has the property that phase inversion occurs quickly when it comes in contact with water. First, the stain is transferred to the oily component by blending cleansing cosmetics and makeup stains, and then soiled by contact with water. An oil-in-water emulsion containing oily components is produced and poured into water as it is to remove makeup.

Such a self-emulsifying type oily liquid cosmetic needs to contain a surfactant having a high concentration of 8 to 30% by mass in order to quickly self-emulsify when it comes into contact with water. Polyoxyethylene sorbitan branched fatty acid esters, polyethylene glycol branched fatty acid esters, polyoxyethylene branched alkyl ethers and the like are used as general surfactants used in self-emulsifying oily liquid cosmetics. Conventional surfactants are known to have safety concerns. Self-emulsifying oily liquid cleansing cosmetics formulated with a high concentration of this polyoxyethylene-based surfactant may cause problems such as a strong sensation after washing and skin problems when applied directly to the skin. There were concerns about safety. For example, in order to solve the problems of cosmetics using polyoxyethylene-based surfactants, cosmetics using polyglycerol fatty acid esters have been disclosed (Patent Document 1). Also, as a disadvantage of polyoxyethylene surfactants, it tastes bad and smells when mixed in the mouth, and when used on the face, especially when removing lipstick etc. In many cleansing cosmetics, discomfort was prominent.

  Polyglycerin fatty acid ester is a surfactant that is high in safety, has no flavor unpleasantness, and is widely used in foods. Generally, those having a high HLB of polyglycerol fatty acid ester are difficult to dissolve in oily components. Polyglycerin fatty acid esters having a low HLB value that are easily dissolved in oily components have poor water dispersibility and are not suitable for self-emulsification. Therefore, even if such a self-emulsifying oil-based cleansing cosmetic comprising a polyglycerin fatty acid ester and an oil component is prepared, the storage stability of the product is deteriorated due to solubility problems, or the dispersibility in water is poor. As a result, the dirt cannot be washed away, and the oily component remains on the skin, resulting in a very sticky feeling. Therefore, in the self-emulsifying oil-based cleansing cosmetic, the polyglycerin fatty acid ester is only used as an emulsification aid.

 On the other hand, conventional self-emulsifying oil-based liquid cleansing cosmetics are soiled by blending with these makeups when washing hard-coated cosmetics such as thick-coated foundations and mascara containing oil-resistant and water-resistant ingredients. In the process of lifting up, there was a problem that the skin was apt to be rubbed by all means, causing skin troubles and missing eyelashes. And in the process of self-emulsification in contact with water, which is the next step, it will disperse in water via liquid crystal and white gel, but since it is difficult to disperse quickly in water, it will remain as a slimy feeling on the skin forever However, there was a problem that it took time to rinse.

Next, bath cosmetics are often used during bathing in order to prevent rough skin, cracks and tears, and to improve the skin condition. Examples of bath cosmetic preparations include bath salt, bath oil, and herbal medicine. Among them, self-emulsifying oil-based bath oil type products consisting of a mixture of oily components and surfactants are self-emulsified in a hot water bath and the fine oily components are uniformly dispersed in the hot water. However, various improvement effects such as emollient, moisturizing property, anti-inflammation, warm bath, etc. that the oil component originally possesses can be expected.
However, conventional self-emulsifying oil-based bath cosmetics composed of a mixture of an oil component and a surfactant have insufficient dispersibility in hot water, and remain in the bath cosmetic formulation without self-emulsification. There was a problem that floated. As a result, there is a problem that not only the feeling of skin after bathing is deteriorated but also the cosmetic for bath adheres to the bathtub wall due to the sticky feeling.

Further, for the same reason as cleansing cosmetics, polyglycerin fatty acid esters are hardly used as surfactants, and are only used as emulsification aids even when blended.
JP 58-185537 A

  The present invention improves the above problems, has no concern for safety to the human body, has excellent storage stability, easily self-emulsified, has excellent dispersibility in water, and has a good feeling of use. A self-emulsifying type oily liquid cosmetic is provided. The self-emulsifying oily liquid cosmetic of the present invention includes quasi drugs.

  As a result of intensive studies to solve the above problems, the present inventors have found that a self-emulsifying oily liquid cosmetic based on a specific polyglycerin fatty acid ester and an oil component can solve the above problems, and the present invention. It came to complete.

That is, the first invention of the present invention is a self-emulsifying oily liquid cosmetic characterized in that the blending amount of the following component A is 8 to 30% by mass and the blending amount of component B is 50 to 92% by mass. Is:
Component A: HLB value is 11.0 to 15.0, and 50 to 100% by mass of all the constituent fatty acid residues is a branched fatty acid residue having 16 to 18 carbon atoms and / or straight chain unsaturated having 16 to 18 carbon atoms. A polyglycerin fatty acid ester which is a fatty acid residue, and in the polyglycerin constituting the polyglycerin fatty acid ester, the total composition ratio of dimer and trimer polyglycerin cyclic product is 0 to 3 in the total polyglycerin. %, The total composition ratio of polyglycerin of 11-mer or more is 10 to 30% in the total polyglycerin, and the composition ratio of 4 to 10-mer polyglycerin is 4 to 20% in the total polyglycerin. Glycerin fatty acid ester.
Component B: Oily component.

  According to a second aspect of the present invention, the branched fatty acid residue having 16 to 18 carbon atoms is an isostearic acid residue, and the linear unsaturated fatty acid residue having 16 to 18 carbon atoms is an oleic acid residue. The self-emulsifying oily liquid cosmetic described.

  A third invention of the present invention is the self-emulsifying oily liquid cosmetic composition according to the first invention or the second invention, wherein the compounding amount of the component A is 10 to 25% by mass.

  A fourth invention of the present invention is the self-emulsifying oily liquid makeup according to any one of the first to third inventions, wherein the blending amount of the component B is 65 to 85% by mass. It is a fee.

  According to a fifth aspect of the present invention, there is provided the self-emulsifying oily liquid cosmetic composition according to any one of the first to fourth aspects, wherein water is not blended.

  According to a sixth aspect of the present invention, the electrical conductivity at 25 ° C. is not more than 0.1 μS / cm and is uniformly dissolved and dispersed in a hydrocarbon solvent. The self-emulsifying oily liquid cosmetic composition according to any one of the above.

  The seventh invention of the present invention is a self-emulsifying type according to any one of the first to sixth inventions, wherein lecithin is further blended in an amount of 1 to 10% by mass of component A. It is an oily liquid cosmetic.

  The eighth invention of the present invention is characterized in that the blending amount of the hydrocarbon oil in the oil component of component B is an amount that is less than 10% by mass of the self-emulsifying oily liquid cosmetic. To a self-emulsifying oily liquid cosmetic composition according to any one of the seventh to seventh inventions.

  A ninth invention of the present invention is the self-emulsifying oily liquid cosmetic according to any one of the first to eighth inventions, which is a cleansing cosmetic.

  A tenth aspect of the present invention is the self-emulsifying oily liquid cosmetic composition described in any one of the first to eighth aspects, which is a bath cosmetic composition.

11th invention of this invention is a case where the polyglycerin fatty acid ester whose HLB value is 12.0-14.0 among the following components A is used, Comprising: HLB value is 12.0-14.0. The amount of component A, which is a polyglycerin fatty acid ester, is 8 to 30% by mass, the amount of component B is 65 to 90% by mass, and the amount of component C is HLB value 12.0 to 14.0. A self-emulsifying oily liquid cosmetic characterized by being 0.1 to 100% by mass based on the amount of component A, which is a polyglycerin fatty acid ester:
Component A: HLB value is 11.0 to 15.0, and 50 to 100% by mass of all the constituent fatty acid residues is a branched fatty acid residue having 16 to 18 carbon atoms and / or straight chain unsaturated having 16 to 18 carbon atoms. A polyglycerin fatty acid ester which is a fatty acid residue, and in the polyglycerin constituting the polyglycerin fatty acid ester, the total composition ratio of dimer and trimer polyglycerin cyclic product is 0 to 3 in the total polyglycerin. %, The total composition ratio of polyglycerin of 11-mer or more is 10 to 30% in the total polyglycerin, and the composition ratio of 4 to 10-mer polyglycerin is 4 to 20% in the total polyglycerin. Glycerin fatty acid ester.
Component B: Oily component.
Component C: A surfactant having an HLB value of 2.0 to 10.0.

  The twelfth invention of the present invention is the eleventh invention characterized in that the blending amount of component A which is a polyglycerin fatty acid ester having an HLB value of 12.0 to 14.0 is 10 to 25% by mass. Is a self-emulsifying oily liquid cosmetic.

  A thirteenth aspect of the present invention is the self-emulsifying oily liquid cosmetic composition according to the eleventh aspect or the twelfth aspect, wherein the amount of component B is 65 to 85% by mass.

  A fourteenth invention of the present invention is the self-emulsifying oily liquid cosmetic composition according to any one of the eleventh to thirteenth inventions, wherein water is not blended.

  According to a fifteenth aspect of the present invention, the electrical conductivity at 25 ° C. is not more than 0.1 μS / cm and is uniformly dissolved and dispersed in a hydrocarbon solvent. The self-emulsifying oily liquid cosmetic composition according to any one of the above.

  The sixteenth aspect of the present invention is an eleventh aspect characterized in that lecithin is further blended in an amount of 1 to 10% by mass of component A which is a polyglycerin fatty acid ester having an HLB value of 12.0 to 14.0. The self-emulsifying oily liquid cosmetic composition according to any one of the invention to the fifteenth invention.

  A seventeenth aspect of the present invention is an eleventh aspect characterized in that the blending amount of the hydrocarbon oil in the oily component B is an amount that is less than 10% by mass of the self-emulsifying oily liquid cosmetic. To a self-emulsifying oily liquid cosmetic composition according to any one of the sixteenth invention.

  An eighteenth aspect of the present invention is the self-emulsifying oily liquid cosmetic according to any one of the eleventh to seventeenth aspects, which is a cleansing cosmetic.

  A nineteenth aspect of the present invention is the self-emulsifying oily liquid cosmetic according to any one of the eleventh to seventeenth aspects, which is a cosmetic for bath.

The self-emulsifying type oily liquid cosmetic composition of the present invention has no safety concerns, is excellent in water dispersibility, easily self-emulsifies, and has good storage stability.
Further, when the self-emulsifying type oily liquid cosmetic composition of the present invention is used as a cleansing cosmetic composition, since the oily component does not remain on the skin, the generation of acne and pimples due to the remaining oily component can be eliminated. Furthermore, the self-emulsifying oily liquid cosmetic of the present invention can be applied to cosmetics (including quasi-drugs) such as cosmetic oil, hair cleansing, massage oil, or hair treatment, and pharmaceuticals. The present invention can be said to be a very excellent self-emulsifying oily liquid cosmetic.

First, component A will be described.
Component A used in the present invention has an HLB value of 11.0 to 15.0, preferably 12.0 to 14.0. When the HLB value is less than 11.0, the self-emulsifying oily liquid cosmetic composition obtained has low self-emulsifying property, so the dispersibility in water is poor and the purpose as a self-emulsifying oily liquid cosmetic composition cannot be achieved. It is.

  In the present invention, when a polyglycerin fatty acid ester having an HLB value of 12.0 to 14.0 is used, a surfactant having an HLB value of 2.0 to 10.0 can be used in combination. The amount of the surfactant having an HLB value of 2.0 to 10.0 in the self-emulsifying oily liquid cosmetic is 0.1 to 100% by weight, preferably 1 to 70% by weight, of the component A to be blended. Preferably it is 5-70 mass%. Examples of the surfactant having an HLB value of 2.0 to 10.0 include glycerin fatty acid ester, sorbitan fatty acid ester, diglycerin fatty acid ester, and polyglycerin fatty acid ester.

 The measurement of the HLB value described in the present invention can be determined by the Atlas method, and is calculated by determining the saponification value (S) of the polyglycerol fatty acid ester and the acid value of the constituent fatty acid. HLB value = 20 × [1- (S / A)]

Next, 50 to 100% by mass, preferably 5 to 100% by mass, and most preferably 60 to 100% by mass of the total fatty acid residues of the polyglycerin fatty acid ester of Component A is the residue of branched fatty acids having 16 to 18 carbon atoms. Group and / or a linear unsaturated fatty acid residue having 16 to 18 carbon atoms. The branched fatty acid constituting these may be either a branched saturated fatty acid or a branched unsaturated fatty acid, but a branched saturated fatty acid is preferred because it is easier to obtain.
Polyglycerin fatty acid esters obtained by using straight chain saturated fatty acids having 50 to 100% by mass of all the constituent fatty acids are not suitable because they do not become liquid at room temperature or low temperature.
Further, when the fatty acid residue having 15 or less carbon atoms is 50 to 100% by mass of the total fatty acid residue, the self-emulsifying property of the resulting self-emulsifying oily liquid cosmetic composition is lowered, and the fatty acid residue having 19 or more carbon atoms is left. Those whose group is 50 to 100% by mass of the total fatty acid residues are not suitable because they are insoluble in oil components.

 As a branched fatty acid residue having 16 to 18 carbon atoms, an isostearic acid residue (16-methylheptadecanoyl group, 15-methylheptadecanoyl group, 10-methylheptadecanoyl group, multi-branched isostearic acid residue), An isopalmitic acid residue (14-methylpentadecanoyl group) and the like can be mentioned, and an isostearic acid residue is preferable, and a 16-methylheptadecanoyl group is particularly preferable.

Examples of the linear unsaturated fatty acid residue having 16 to 18 carbon atoms include unsaturated monohydroxy acid residues such as oleic acid residue, palmitooleic acid residue, ricinoleic acid residue, etc. Groups are preferred. This also includes mixed fatty acid residues derived from palm oil or the like containing 50% by mass or more of oleic acid residues.

  The polyglycerin constituting the polyglycerin fatty acid ester of component A needs to have a total composition ratio of 0 to 3%, more preferably 0 to 2% of the dimer or trimer polyglycerin cyclic product. Most preferred is 0 to 1%. Because, when the total composition ratio of the diglyceride or trimer polyglycerin cyclic product is more than 3%, the self-emulsification property of the resulting self-emulsifying oily liquid cosmetic is low, so the dispersibility in water is poor, This is because separation occurs during storage. Here, the annular material includes those in which a part thereof is annular.

 In addition, the polyglycerin constituting the polyglycerin fatty acid ester of component A is required to have a total composition ratio of 11 or more polyglycerin of 10 to 30%, more preferably 12 to 28%, most preferably. Is 15-26%. It is because the dispersibility to water will worsen that it is out of the range of 10 to 30% because the self-emulsifying type oily liquid cosmetic composition obtained has a low self-emulsifying property.

  Furthermore, the polyglycerin constituting the polyglycerin fatty acid ester of component A needs to be 4 to 20%, and more preferably 4 to 15%, most preferably 4 to 10-mer polyglycerin. 5 to 12%. Because, when the composition ratio of 4 to 10-mer polyglycerin is out of the range of 4 to 20%, the self-emulsifying property of the resulting self-emulsifying oily liquid cosmetic is low, so the dispersibility in water is poor, This is because separation occurs during storage. In addition, in the polyglycerol fatty acid ester of the component A, a monomer (glycerol) may be included as constituent polyglycerol. Moreover, there is no restriction | limiting in particular in the composition ratio of the polyglycerol non-cyclic material of a dimer and a trimer.

   A suitable method for measuring the composition ratio of polyglycerin is to use polyglycerin as a polyglycerin derivative, and separate and determine the polyglycerin derivative by the GC method (gas chromatographic method). The analysis by the GC method can be easily carried out if a temperature rising analysis is performed at 10 ° C./min from 100 ° C. to 250 ° C. using a fused silica capillary tube in which a low polar liquid phase such as methyl silicon is chemically bonded. Can do. In addition, a gas chromatograph is introduced into a double-focusing mass spectrograph, ionized and measured by a method such as chemical ionization, and then the molecular weight of the peak on the gas chromatogram is obtained from the molecular weight of its parent ion. This can be done easily by determining the degree of polymerization of glycerin. However, it is not restricted to these methods.

 The blending amount (content) of component A in the self-emulsifying oily liquid cosmetic of the present invention is 8 to 30% by mass, preferably 10 to 25% by mass, and most preferably 12 to 20% by mass. This is because if it is less than 8% by mass, the self-emulsification becomes poor, and if it exceeds 30% by mass, the dispersibility in water becomes poor.

 The polyglycerin constituting the polyglycerin fatty acid ester of component A may be of the composition ratio described above, and may be produced by dehydration condensation, a known epichlorohydrin or a synthesis and purification method using glycidol as a starting material, and is commercially available. Product can be used. Examples of commercially available products include Great Oil D-10, Great Oil D-11, and Great Oil D-12 manufactured by Taiyo Kagaku Co., Ltd.

 The oil component of component B used in the present invention is usually composed mainly of a liquid or paste oil component that can be used in cosmetics. Examples include natural animal and vegetable oils, semi-synthetic oils and fats, hydrocarbon oils, higher fatty acids, ester oils, silicone oils, animal and plant and synthetic essential oil components, fat-soluble vitamins, and the like, one or two of these The above can be used.

 Specifically, natural animal and vegetable oils and semi-synthetic oils and fats include avocado oil, linseed oil, almond oil, olive oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, safflower oil, soybean oil, evening primrose oil, corn Oil, rapeseed oil, horse fat, palm oil, palm kernel oil, castor oil, sunflower oil, jojoba oil, macadamia nut oil, coconut oil, hardened coconut oil, peanut oil, lanolin and the like.

Examples of the hydrocarbon include squalane, squalene, liquid paraffin, and petroleum jelly.
Ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, isostearyl isostearate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, di-2-ethyl Neopentyl glycol hexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octoate, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, 2-ethylhexyl succinate, isocetyl stearate, butyl stearate, diisopropyl sebacate, cetyl lactate, tetradecyl lactate, 2-ethylhexyl palmitate, 2-hexyl palmitate Syl, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, phytosteryl oleate, diisostearyl malate, paramethoxycinnamate, pentaerythritol tetrarosinate, glyceryl triisostearate, glyceryl triisopalmitate Glyceryl tri-2-ethylhexanoate, glyceryl tritetradecanoate, diparamethoxycinnamic acid, glyceryl monoisooctylate, and the like.

  Silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclopentasiloxane, decamethylcyclohexasiloxane, stearoxy silicone and other higher alkoxy modified silicones, alkyl modified silicones, higher fatty acid ester modified Examples of silicone and fat-soluble vitamins include tocopherol and its derivatives, retinol and its derivatives.

  The oil component which is Component B used in the present invention is not limited to the specific examples described above. Moreover, even if it is a solid oily component, it can be mix | blended if it is a grade which does not have influence on liquid state maintenance. In addition, although there is no problem in storage stability such as decomposition and precipitation, hydrocarbon oils such as liquid paraffin, squalane and petrolatum should be self-emulsifying oily when it may be cloudy in appearance at 0 ° C or lower. It is good to mix | blend so that it may become less than 10 mass% in liquid cosmetics.

 When the component C is not blended, the blending amount (content) of the component B in the self-emulsifying oily liquid cosmetic composition of the present invention is 50 to 92% by mass, preferably 65 to 85% by mass. Preferably it is 75-85 mass%. This is because when the amount is less than 50% by mass, the dispersibility in water becomes poor, and when the amount is more than 92% by mass, self-emulsification becomes poor.

 The blending amount (content) of the component B oil component in the self-emulsifying oily liquid cosmetic composition of the present invention is 65 to 90% by mass, preferably 65 to 85% by mass when component C is blended. Preferably it is 65-80 mass%.

Component C in the self-emulsifying oily liquid cosmetic composition of the present invention is a surfactant having an HLB value of 2.0 to 10.0. When this component C is used, a polyglycerol fatty acid ester having an HLB value of 12.0 to 14.0 is used as the component A.
The compounding amount of Component C is 0.1 to 100% by mass, preferably 1 to 70% by mass, more preferably 5 to 70% by mass of Component A which is a polyglycerin fatty acid ester having an HLB value of 12.0 to 14.0. %.
Examples of the surfactant having an HLB value of 2.0 to 10.0 include glycerin fatty acid ester, sorbitan fatty acid ester, diglycerin fatty acid ester, and polyglycerin fatty acid ester.

  In this invention, it is preferable not to mix | blend water as a raw material. However, when inconvenience arises in terms of viscosity adjustment and usability of the product, it may be blended within the range not impairing the object of the present invention, and is preferably suppressed to 0 to 2% by mass, more preferably 0 to 1% by mass. %. If blended in an amount of 2% by mass or more, the storage stability of the product may be impaired, and it may become a gel and the water dispersibility may be deteriorated. The water mentioned here includes water extracts of animals and plants in addition to purified water used in cosmetics. In addition, for example, the moisture contained in the polyglycerin fatty acid ester or the like that is absorbed in production or management is excluded.

  In the present invention, the self-emulsifying type oily liquid cosmetic is one in which a surfactant is dissolved in a molecule or micelle in an oily component, or a surfactant is dissolved in a liquid crystal state in an oily component. A non-aqueous liquid obtained by adding an oil phase to a mixture of an aqueous component such as an aqueous polyhydric alcohol and a surfactant introduced in JP-A-9-208444 and JP-A-11-152205. The composition, gel composition or thickening composition differs from the present invention because the continuous phase is based on polyhydric alcohol.

  In order to determine whether it is oil-based, water-based polyhydric alcohol-based, or non-aqueous polyhydric alcohol-based, a method of measuring the electrical conductivity to check the electric conductivity, or polyhydric alcohol-based And a method for examining the solubility in a hydrocarbon-based solvent (for example, hexane, xylene, etc.) that is difficult to dissolve.

  In the present invention, self-emulsification characteristics can be further improved by blending lecithin. Examples of lecithin include, but are not limited to, soybean lecithin, egg yolk lecithin, or hydrogenated lecithin that has been saturated with hydrogen to obtain a commercially available product or reagent. As a compounding quantity, it is preferable that it is 1-10 mass% (of the polyglyceryl fatty acid ester) of the component A used for this invention.

 Moreover, in this invention, it is not essential to mix | blend polyhydric alcohols, such as glycerol and 1.3-butylene glycol (1.3-BG). Moreover, in order to maintain the storage stability, it is possible to produce a gel-like emulsion type or liquid crystal type cosmetic by adding an oily component to a polyhydric alcohol continuous phase containing water. Since the detergency is poor and the dispersibility with respect to water is lowered, it is not the object of the present invention. Therefore, in this invention, it is preferable not to mix | blend a polyhydric alcohol. In addition, unreacted polyglycerin and glycerin remaining in the polyglycerin fatty acid ester (polyglycerin fatty acid ester having an HLB of 11 or more usually contains 0 to 30% by mass thereof) or water-soluble extracts are included. This does not apply to polyhydric alcohols such as 3-BG, glycerin, and propylene glycol.

  As a method of determining that water is not a continuous phase, for example, there is a method of measuring electrical conductivity. Further, as a method for discriminating that the polyhydric alcohol is not a continuous phase, a method of dissolving in a hydrocarbon solvent such as hexane or xylene may be mentioned. The self-emulsifying type oily liquid cosmetic of the present invention is more specifically, for example, by measuring the electric conductivity at 25 ° C. with a commercially available simple electric conductivity meter and the like, and the electric conductivity is substantially zero. Is 0.1 μS / cm or less, and can be confirmed by uniformly dissolving and dispersing in hexane.

  The self-emulsifying type oily liquid cosmetic composition of the present invention can be blended with known ingredients used in those fields as long as the properties of the present invention are not impaired. Examples include pH adjusters, sequestering agents, ultraviolet absorbers, extracts, colorants, fragrances and the like.

  In the method for producing the self-emulsifying cosmetic of the present invention, each component including component A and component B is usually heated to 40 to 90 ° C. and mixed and dissolved, but may be at room temperature if the components are dissolved at room temperature. Furthermore, when mix | blending component C and a lecithin, it can manufacture by heating the component A and component B, the component C, and lecithin to 40-90 degreeC, and carrying out mixing dissolution. Even when components other than the polyglycerin fatty acid ester of component A and the oily component of component B that are essential for the present invention are blended, the procedure for mixing and dissolving is not particularly limited. For example, the polyglycerin fatty acid ester of component A and the oily component of component B used in the present invention and the HLB 3-10 surfactant or lecithin of component C are mixed at the same time, or used as essential in the present invention. The component B polyglycerin fatty acid ester and the component C HLB 3-10 surfactant, lecithin and the like may be mixed and dissolved, and then the component B oil component used in the present invention may be mixed and dissolved. The same applies when other components are blended. Stirring may be a known method, and the apparatus such as a blade-type stirrer, a disper, or a homomixer is not particularly limited.

Specific examples of the self-emulsifying oily liquid cosmetic of the present invention include cleansing cosmetics and bath cosmetics.
The cleansing cosmetic of the present invention has no safety concerns, excellent storage stability, good detergency, no stickiness after being washed, no squeaky feeling, no slimy feeling when washed away, and easy rinsing It has the effect of being.
In addition, the bath cosmetic of the present invention has no concern about safety, has good dispersibility in bath water, is excellent in storage stability, and has a moist feeling.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Table 1 Specific polyglycerin for production of polyglycerin fatty acid ester of adult sentence A used in this example 3 types (Great oil D-10, Great oil D-11, Great oil D-12 manufactured by Taiyo Kagaku Co., Ltd.) And 4 types of polyglycerin for production of polyglycerin fatty acid ester used in Comparative Examples (Great Oil S-10, Great Oil S-11, Great Oil S-12, Great Oil S-13, Taiyo Kagaku Co., Ltd.) Table 1 shows the results of polyglycerin composition analysis measured by the tograph method. Each composition analysis value was calculated by the area percentage method. Moreover, when a dimer or a trimer cyclic | annular thing is included in polyglycerin, the polyglycerin composition analysis value of a dimer and a trimer shows the value which match | combined the non-cyclic thing and the cyclic | annular thing, respectively.

[Analysis Examples and Comparative Examples]
Various polyglycerin product names and analysis examples Great oil D-10 (analysis example 1)
Great oil D-11 (Analysis Example 2)
Great oil D-12 (Analysis Example 3)
Great oil S-10 (Analysis Comparative Example 1)
Great oil S-11 (Analysis Comparative Example 2)
Great oil S-12 (Analysis Comparative Example 3)
Great oil S-13 (Analysis Comparative Example 4)

  Various polyglycerol fatty acid esters were synthesized using the seven types of polyglycerols shown in the analysis examples of Table 1. Table 2 shows the polyglycerol fatty acid esters used in the examples, and Table 3 shows the polyglycerol fatty acid esters used in the comparative examples.

[Production example of polyglycerol fatty acid ester]
Various polyglycerol fatty acid esters having different hydroxyl values were synthesized using the seven types of polyglycerols shown in Table 1 as raw materials. Below, the manufacture result of the polyglycerol fatty acid ester which used the great oil D-10 (raw material polyglycerol of analysis Example 1) as a raw material is shown.
In a four-necked flask equipped with a stirrer, a thermometer, a gas blowing tube and a water separator, 190 g of polyglycerin, 110 g of oleic acid and 0.1 g of tripotassium phosphate were placed, and these were placed in a nitrogen gas stream at 200 to 250 ° C. And the esterification reaction was carried out. After the reaction, 0.3 ml of phosphoric acid was added to obtain polyglycerin oleate used in Example 1 of HLB 12.5.
The polyglycerin fatty acid ester used in the following examples and comparative examples is charged with various fatty acids and polyglycerin at a ratio that theoretically assumes the value of HLB by the Atlas method, and is esterified in the same process as the above reaction example. It is what went.

[Examples and Comparative Examples of Cleansing Cosmetics]
Examples 1-13, Comparative Examples 1-14
The polyglycerol fatty acid ester used in Examples and Comparative Examples was synthesized in the same manner as described above using polyglycerol having the composition shown in Table 1. Cleansing cosmetics were prepared by adding each component in the formulations shown in Tables 4, 5 and 6 and heating to 70-80 ° C. with sufficient stirring to dissolve, then cooling to room temperature with stirring. .
The following items (1), (2) and (3) were evaluated for each of the cleansing cosmetics obtained above. The results are shown in Tables 4-6. In Tables 4 to 6, analysis examples 1, 2, 3, and analysis comparative examples 1, 2, 3, 4 are the analysis examples 1, 2, 3, analysis comparative example 1, 2, 3, 4 are shown.

(1) Dispersibility in water: Cleansing cosmetic preparation (5 ml) prepared as described above was dispersed in water (50 ml), stirred for 3 seconds, the state was observed, and evaluation was performed according to the following evaluation criteria. .

<Evaluation criteria>
A: Self-emulsified quickly and uniformly dispersed
○: Uniformly dispersed within 10 seconds Δ: Self-emulsified but white gel-like substance is floating □: Self-emulsification is bad and white gel-like substance and oily substance are floating ×: Self-emulsification Oily substance is floating

(2) Sensory evaluation: After applying each cleansing cosmetic to the place where the waterproof mascara was applied to 10 subjects, after gently massaging the 10 reciprocating application parts to the left and right as if sliding gently, the palm Repeat the operation of wetting so that the lukewarm water collected in the application part is applied to the application part three times, and then apply a towel to absorb moisture. In this series of operations, a slimy feeling, a rinsing feeling, a feeling of omission, a sticky feeling after washing, and a squeaky feeling after washing were evaluated in five stages.

Slimy feeling;
<Evaluation point><Average evaluation point>
4 points: No slimy feeling ◎: 3.5 to 4.0 points
3 points: almost no sliminess ○: 3.0 to 3.4 points
2 points: Slightly slim △: 2.0 to 2.9 points
1 point: slimy □: 1.0 to 1.9 points
0 point: Very slimy feeling ×: 0.0-0.9 point Rinse feeling;
<Evaluation point><Average evaluation point>
4 points: very easy to rinse ◎: 3.5 to 4.0 points 3 points: easy to rinse ○: 3.0 to 3.4 points 2 points: difficult to overly easy Δ: 2.0 to 2.9 points 1 point : Hard to rinse □: 1.0 to 1.9 points
0 points: very difficult to rinse ×: 0.0 to 0.9 points
<Evaluation point><Average evaluation point>
4 points: fell very clean ◎: 3.5-4.0 points
3 points: Almost cleanly dropped ○: 3.0 to 3.4 points
2 points: There is a little dirt left. △: 2.0 to 2.9 points
1 point: There is a dirt residue □: 1.0 to 1.9 points
0 point: Dirt is hardly removed ×: 0.0 to 0.9 point Stickiness after washing;
<Evaluation point><Average evaluation point>
4 points: no stickiness ◎: 3.5 to 4.0 points 3 points: little stickiness ○: 3.0 to 3.4 points 2 points: slightly sticky Δ: 2.0 to 2 .9 points 1 point: Sticky feeling □: 1.0 to 1.9 points 0 points: Very sticky feeling ×: 0.0 to 0.9 points Squeezed feeling after washing
<Evaluation point><Average evaluation point>
4 points: no squeaking feeling ◎: 3.5 to 4.0 points 3 points: almost no squeaking feeling ○: 3.0 to 3.4 points 2 points: slightly squeaking feeling Δ: 2.0 to 2 .9 points 1 point: squeaked □: 1.0 to 1.9 points 0 points: Very squeaky ×: 0.0 to 0.9 points

(3) Storage stability: Stored at 5 ° C., 25 ° C., and 40 ° C. for 6 months, and observed for oil layer separation and precipitation.
Stable- ○ Precipitation or two-layer separation- ×

  In addition, in order to confirm that Examples 1 to 13 are oily cosmetics, the electrical conductivity and hexane solubility were examined, and all the electrical conductivity was 0.1 μS / cm and dissolved and dispersed in hexane.

  Moreover, the cleansing material which is not this invention was prepared using the polyglyceryl fatty acid ester similar to Example 1, and the evaluation result was shown in Table 7 (comparative examples 12, 13, and 14).

Electrical conductivity: Measured using a Lacom conductivity meter ECScanPure + manufactured by AS ONE.
Hexane solubility: As for solubility in hexane, 1 or 2 drops of the product of the present invention was dropped into 10 ml of hexane solution with a Komagome pipette, and after lightly stirring, it was observed whether or not it was uniformly dissolved.
From these results, it was confirmed that Examples 1 to 13 were oily, Comparative Example 12 was an oil-in-water cream, and Comparative Example 13 was an aqueous polyhydric alcohol continuous phase. Since Comparative Example 14 was separated immediately, measurement was impossible.

  As shown in Examples 1 to 13, the oily liquid cleansing cosmetic blended with an oily component and a specific polyglycerin fatty acid ester has a good feeling of omission, no sticky feeling after washing, no squeaky feeling, and further slimming The feeling of use was good because there was no feeling and rinsing was easy. Moreover, the storage stability was good at 5 ° C, 25 ° C and 40 ° C. On the other hand, the cleansing cosmetics containing the polyglycerin fatty acid esters shown in Comparative Examples 1 to 11 could not achieve the object of the present invention and did not become good oily liquid cleansing cosmetics. Moreover, it was confirmed that the oily cleansing cosmetic composition of the present invention was very well-familiar with the cosmetic composition and was an excellent cosmetic composition.

[Examples of cleansing cosmetics]
Cleansing cosmetics were prepared by adding each component in the following formulation, heating to 70 to 80 ° C., sufficiently stirring and dissolving, and then cooling to room temperature with stirring.

Example 14
Oily liquid cleansing cosmetic formulation example
(Unit: g)
Polyglycerin oleate 15.0 used in Example 1
Diglycerin oleate (HLB7.0) 2.0
Soy lecithin (PC concentration 60%) 1.0
Palmityl isooctylate 40.0
Neopentyl glycol diisooctylate 20.0
Liquid paraffin 5.0
Isononyl isononanoate 15.0
Cyclotetrapolysiloxane 0.5
Natural vitamin E 1.0
Fragrance 0.5
Total 100.0

  20 expert panelists used the oil-based liquid cleansing cosmetic of the present invention of Example 14. As a result of evaluation of all the feelings of use, ◎ (no sliminess, very easy to rinse, very clean as a condition of omission The storage stability was ○ (stable) at all temperatures.

[Comparative example of cleansing cosmetics]
Comparative Example 15
An oily liquid cleansing cosmetic using polyethylene glycol isostearate (HLB value 12.0) in place of the polyglycerin oleate of Example 14 was prepared. The resulting cleansing cosmetic was ◎ (very beautifully dropped), but the squeaky feeling was x (very squeaky), and the remaining feeling was △ (slightly slimy, somewhat It was hard to rinse and had a slightly sticky feeling).

[Examples and comparative examples of bath cosmetics]
Examples 15-23, Comparative Examples 16-24
The bath cosmetics prepared by the same method as the cleansing cosmetics of Examples 1 to 9 and Comparative Examples 1 to 9 were used as Examples 15 to 23 and Comparative Examples 16 to 24, respectively. About these, the dispersibility to bath water, a feeling of use (moist feeling), and a sticky feeling were evaluated. The evaluation results are shown in Tables 8 and 9.

(1) Dispersibility in bath water: The bath cosmetic (20 ml) prepared as described above is dispersed in 40 ° C. bath water (200 l), stirred for 3 seconds with bare hands, and its state is observed. Evaluation was performed according to the evaluation criteria.

<Evaluation method>
◎: Quickly emulsify and disperse uniformly ○: Disperse uniformly within 10 seconds △: Self-emulsify but white gel-like substance is floating □: Self-emulsification is poor and white gel-like substance Oily substance is floating x: Oily substance is floating without self-emulsification (2) Feeling of use: Ask 10 subjects to take a bath for 5 minutes, and feel moist and sticky after bathing. Evaluation was performed as follows.

Moist feeling;
4 points: feels very moist ◎: 3.5-4.0 points
3 points: feels moist ○: 3.0 to 3.4 points
2 points: feels slightly moist △: 2.0-2.9 points
1 point: not very moist □: 1.0 to 1.9 points
0 points: No moist feeling ×: 0.0 to 0.9 points Stickiness:
<Evaluation point><Average evaluation point>
4 points: no stickiness ◎: 3.5 to 4.0 points 3 points: little stickiness ○: 3.0 to 3.4 points 2 points: slightly sticky Δ: 2.0 to 2 .9 points 1 point: Sticky feeling □: 1.0 to 1.9 points 0 points: Very sticky feeling ×: 0.0 to 0.9 points

  The product of the present invention was excellent in all items, but the comparative product was insufficient in all items.

[Examples of bath cosmetics]
Each component was added in the following composition, heated to 70 to 80 ° C., sufficiently stirred and dissolved, and then cooled to room temperature with stirring to prepare a bath cosmetic.

Example 24
Examples of bath cosmetics
(Unit: g)
Polyglycerin oleate 16.0 used in Example 1
Diglycerin oleate (HLB7.0) 2.0
Soy lecithin (PC concentration 60%) 0.5
Isostearyl palmitate 40.0
Neopentyl glycol dicaprate 20.0
Squalane 5.0
Glyceryl tri (capryl / caprin) 14.5
High oleic safflower oil 1.0
Fragrance 1.0
Total 100.0

  As a result of using the bath preparation of the present invention of Example 24, 20 professional panelists were found to have dispersibility in bath water (quickly self-emulsified and disperse uniformly), moist feeling ◎ (very moist feeling) ), Sticky feeling ◎ (no sticky feeling). The storage stability was also ◯ (stable) at all temperatures.

  As shown in Examples 15 to 24, a bath preparation containing an oil component and a specific polyglycerin fatty acid ester has good dispersibility in hot water, excellent storage stability, and excellent feeling of use such as moist feeling. It was what was. On the other hand, when the polyglycerin fatty acid ester shown in Comparative Examples 16 to 24 was blended, the dispersibility in hot water, stability and feeling of use were poor, and it was poor as a bath preparation.

The self-emulsifying oily liquid cosmetic of the present invention can be widely used in the chemical industry, the pharmaceutical industry, and the like.

Claims (19)

A self-emulsifying oily liquid cosmetic characterized in that the compounding amount of the following component A is 8 to 30% by mass and the compounding amount of component B is 50 to 92% by mass.
Component A: HLB value is 11.0 to 15.0, and 50 to 100% by mass of all the constituent fatty acid residues is a branched fatty acid residue having 16 to 18 carbon atoms and / or straight chain unsaturated having 16 to 18 carbon atoms. A polyglycerin fatty acid ester which is a fatty acid residue, and in the polyglycerin constituting the polyglycerin fatty acid ester, the total composition ratio of dimer and trimer polyglycerin cyclic product is 0 to 3 in the total polyglycerin. %, The total composition ratio of polyglycerin of 11-mer or more is 10 to 30% in the total polyglycerin, and the composition ratio of 4 to 10-mer polyglycerin is 4 to 20% in the total polyglycerin. Glycerin fatty acid ester.
Component B: Oily component.   The self-emulsifying oily liquid cosmetic composition according to claim 1, wherein the branched fatty acid residue having 16 to 18 carbon atoms is an isostearic acid residue, and the linear unsaturated fatty acid residue having 16 to 18 carbon atoms is an oleic acid residue. The self-emulsifying oily liquid cosmetic composition according to claim 1 or 2, wherein the amount of component A is 10 to 25% by mass. The self-emulsifying oily liquid cosmetic composition according to any one of claims 1 to 3, wherein the blending amount of component B is 65 to 85 mass%. The self-emulsifying oily liquid cosmetic composition according to any one of claims 1 to 4, wherein water is not blended. The self-emulsifying oily liquid makeup according to any one of claims 1 to 5, wherein the electrical conductivity at 25 ° C is 0.1 µS / cm or less, and it is uniformly dissolved and dispersed in a hydrocarbon solvent. Fee. Furthermore, lecithin is mix | blended with 1-10 mass% of component A, The self-emulsification type oily liquid cosmetics of any one of Claims 1-6 characterized by the above-mentioned. The amount of the hydrocarbon oil in the oil component of component B is set to an amount that is less than 10% by mass of the self-emulsifying oily liquid cosmetic, according to any one of claims 1 to 7. Self-emulsifying oily liquid cosmetic. The self-emulsifying oily liquid cosmetic composition according to any one of claims 1 to 8, which is a cleansing cosmetic composition. The self-emulsifying oily liquid cosmetic composition according to any one of claims 1 to 8, which is a bath cosmetic composition. Among the following components A, component A, which is a polyglycerol fatty acid ester having an HLB value of 12.0 to 14.0 and having a HLB value of 12.0 to 14.0 Of component A which is a polyglycerin fatty acid ester having an HLB value of 12.0 to 14.0, and a blending amount of component C of 8 to 30% by mass, component B of 65 to 90% by mass, and component C. A self-emulsifying oily liquid cosmetic, characterized in that it is 0.1 to 100% by mass with respect to the blending amount.
Component A: HLB value is 11.0 to 15.0, and 50 to 100% by mass of all the constituent fatty acid residues is a branched fatty acid residue having 16 to 18 carbon atoms and / or straight chain unsaturated having 16 to 18 carbon atoms. A polyglycerin fatty acid ester which is a fatty acid residue, and in the polyglycerin constituting the polyglycerin fatty acid ester, the total composition ratio of dimer and trimer polyglycerin cyclic product is 0 to 3 in the total polyglycerin. %, The total composition ratio of polyglycerin of 11-mer or more is 10 to 30% in the total polyglycerin, and the composition ratio of 4 to 10-mer polyglycerin is 4 to 20% in the total polyglycerin. Glycerin fatty acid ester.
Component B: Oily component.
Component C: A surfactant having an HLB value of 2.0 to 10.0. 12. The self-emulsifying oily liquid cosmetic composition according to claim 11, wherein the blending amount of component A, which is a polyglycerin fatty acid ester having an HLB value of 12.0 to 14.0, is 10 to 25% by mass. 13. The self-emulsifying oily liquid cosmetic composition according to claim 11 or 12, wherein the amount of component B is 65 to 85 mass%. The self-emulsifying oily liquid cosmetic composition according to any one of claims 11 to 13, wherein water is not blended. The self-emulsifying oily liquid makeup according to any one of claims 11 to 14, wherein the electrical conductivity at 25 ° C is 0.1 µS / cm or less, and it is uniformly dissolved and dispersed in a hydrocarbon solvent. Fee. Furthermore, lecithin is mix | blended 1-10 mass% of the component A which is a polyglyceryl fatty acid ester whose HLB value is 12.0-14.0, The any one of Claims 11-15 characterized by the above-mentioned. Self-emulsifying oily liquid cosmetic. The blending amount of the hydrocarbon oil in the oil component of component B is set to an amount that is less than 10% by mass of the self-emulsifying oily liquid cosmetic composition, according to any one of claims 11 to 16. Self-emulsifying oily liquid cosmetic. The self-emulsifying oily liquid cosmetic composition according to any one of claims 11 to 17, which is a cleansing cosmetic composition. The self-emulsifying oily liquid cosmetic composition according to any one of claims 11 to 17, which is a bath cosmetic composition.