JP5464587B2 - Oil-in-water emulsified cosmetic - Google Patents

Description

  The present invention relates to an oil-in-water emulsified cosmetic that has a good emulsified state, has little change due to high temperature and time, and is smooth and fresh on the skin at the time of application, particularly a metal oxide. It is related with what contains.

Oil-in-water emulsified cosmetics have been conventionally provided as a form of cosmetics that is smooth and fresh on the skin when applied, and has a refreshing feeling.
Thickeners are used for the purpose of adjusting the viscosity of the oil-in-water emulsified cosmetic to an easy-to-use viscosity or for maintaining the stability of the system. This thickener has a great impact on the feel when using the product, and it is preferred to use ionic water-soluble polymer compounds such as carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer in order to obtain a fresh and refreshing feeling. Has been.

  However, ionic water-soluble polymer compounds such as carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer are low in salt resistance and ion resistance, so that when a large amount of drug components and salts are added, the viscosity of the system is reduced. There were drawbacks.

  Metal oxides such as titanium oxide, zinc oxide, and iron oxide, which are generally used as pigments, are blended in cosmetics for the purpose of obtaining effects such as coloring and UV protection, but they are thickened with ionic water-soluble polymer compounds. When added to the aqueous phase, due to the interaction between the pigment-derived metal ions and the ionic water-soluble polymer compound, the viscosity decreases or rises as a whole or locally, or aggregation of metal oxides occurs. It was difficult to provide a fresh and refreshing feeling of use due to the thickening effect of the ionic water-soluble polymer compound and the original effect of the metal oxide while maintaining stability.

As a means to solve this problem, in a system using an alkyl-modified carboxyvinyl polymer, an oil-in-water solution in which a powder in which a metal oxide is coated with silicic acid is added to reduce the interaction of an ionic water-soluble polymer compound. A mold cosmetic (Patent Document 1) is disclosed. Moreover, although the method and formulation (patent document 2) which suppress liquid separation by mix | blending silicic acid anhydride with the oil-in-water cosmetics containing a metal oxide are disclosed, all are pulled after application | coating. There are drawbacks such as a feeling of dryness and a feeling of dryness and a lack of fresh feeling.
Further, the powder particles to be added are made into hydrophobic powder particles, and by forming a oil-in-water emulsion using a specific polyether-modified silicone, the hydrophobic powder particles, including their elution components, Although the technique (patent document 3) stopped in an oil phase for a long time is disclosed, the stability of the change by high temperature and time passage is inadequate.

On the other hand, vegetable polysaccharides such as guar gum, locust bean gum and carrageenan, and microbial polysaccharides such as xanthan gum, dextran and curdlan are used as other water-soluble polymer thickeners used to adjust the viscosity. ing.
For example, there is a technique for solidifying an aqueous phase by using ι-carrageenan in combination with xanthan gum and / or locust bean gum (Patent Document 4). However, when a polysaccharide is used as a thickener, Although stability in a system in which salts are blended simultaneously is excellent, there are drawbacks in terms of usability such as stickiness.

  As a means to solve this, the technology using agar microgel as a thickener (Patent Document 5), using a water-soluble polymer having a galactomannan skeleton, and adding a small amount of agar or agarose improves gelling ability. Although the technique (patent document 6) to do is disclosed, all are fresh on the skin at the time of application | coating, and the refreshing feeling of use is inadequate.

  Metal oxides such as titanium oxide, zinc oxide, and iron oxide are used with their surfaces covered with silicone or the like. Triethoxycaprylylsilane has also been used frequently. (Patent Documents 7 and 8)

  Polyoxyethylene hydrogenated castor oil is a highly safe nonionic surfactant obtained by adding ethylene oxide to hydrogenated castor oil.

  However, by containing triethoxycaprylylsilane-coated metal oxide in the oil phase and using xanthan gum and carrageenan in combination with polyoxyethylene hydrogenated castor oil in the outer water phase, there is little change due to high temperature and time, and during application It has not been known at all that an oil-in-water emulsified cosmetic containing a metal oxide, which is smooth and fresh on the skin, is refreshing to use.

Japanese Patent No. 3409194 JP 2010-6777 A Japanese Patent No. 4276169 JP-A-4-279509 JP 2009-203200 A Japanese Patent No. 3816871 Japanese Patent No. 2729636 JP 2001-181136 A

  An object of the present invention is to provide an oil-in-water emulsified cosmetic containing a metal oxide that has little change due to high temperature and time, and is smooth and fresh on the skin when applied, and a refreshing feeling can be obtained. That is.

  More specifically, by containing triethoxycaprylylsilane-coated metal oxide in the oil phase and using xanthan gum, carrageenan, and polyoxyethylene hydrogenated castor oil in the outer water phase, there is little change due to high temperature and time. Another object of the present invention is to provide an oil-in-water emulsified cosmetic containing a metal oxide that can be applied on the skin smoothly, freshly and freshly when applied.

  The inventors of the present invention have been diligently studied to solve the above-mentioned problems. The oil phase contains a triethoxycaprylylsilane-coated metal oxide, and the outer aqueous phase contains xanthan gum, carrageenan, and polyoxyethylene. Oil-in-water emulsified cosmetics containing metal oxides that can be used in combination with hardened castor oil, so that there is little change due to high temperatures and aging, and smooth, fresh and refreshing feeling on the skin when applied. Found that it is possible to obtain. The present invention has been developed based on such knowledge.

  According to the present invention, it is possible to obtain an oil-in-water emulsified cosmetic containing a metal oxide that has little change due to high temperature or aging, and is smooth and fresh on the skin at the time of application. Can do.

  The oil-in-water emulsified cosmetic according to the present invention can be provided in the form of cream, emulsion, etc., and is particularly suitably provided as a makeup cosmetic such as foundation, makeup base, concealer, control color, eye shadow, and cheek color. it can.

Triethoxycaprylylsilane used for the component (A) is a compound represented by (CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₇ CH ₃ and is processed into powder by a silane coupling reaction.

  The coating amount of triethoxycaprylylsilane is not particularly limited, but is preferably 0.5 to 30% by weight, particularly preferably 1 to 15% by weight, based on the metal oxide to be coated. In addition, it does not restrict | limit especially as a coating processing method, A conventionally well-known method can be selected suitably and can be performed.

  Specific examples of the metal oxide used in the component (A) include titanium oxide, zinc oxide, cerium oxide, zirconium oxide, magnesium oxide, aluminum oxide, bengara, yellow iron oxide, black iron oxide, titanium oxide, Examples include iron oxide composite pigments, mica titanium, iron oxide-coated mica titanium, and the shape (spherical, rod-like, needle-like, plate-like, irregular shape, scale-like, spindle-like, petal-like, etc.) and crystal form are particularly limited However, titanium oxide, zinc oxide, bengara, yellow iron oxide, and black iron oxide are preferable because they can impart cosmetic effects such as coloring and UV protection.

The average primary particle diameter of the metal oxide can be freely selected from 2 nm to 30 μm, but 10 nm to 1 μm is particularly preferable from the viewpoint of emulsion stability.
In the present invention, the average primary particle diameter means the diameter of primary particles measured by a commonly used method. Specifically, from a transmission electron micrograph, It is obtained as an arithmetic average of minor axes.

  Commercially available metal oxides coated with triethoxycaprylylsilane include OTS-2 TiO2 (triethoxycaprylylsilane 2%, titanium oxide 98%), OTS-2 RED R-516-L (triethoxycapri) Rilsilane 2%, Bengala 98%), OTS-2 YELLOW LLXLO (triethoxycaprylylsilane 2%, yellow iron oxide 98%), OTS-2 BLACK BL-100 (triethoxycaprylylsilane 2%, black iron oxide) 98%) (above, manufactured by Daito Kasei Kogyo Co., Ltd.), ALS-T-400 (5%) (5% triethoxycaprylylsilane, 76.95% titanium oxide, 10.45% aluminum hydroxide, 7 stearic acid .6%), ALT-T-300 (12%) (12% triethoxycaprylylsilane, 73.4 titanium oxide) %, Aluminum hydroxide 14.52%), ALIS-Z-031 (6%) (triethoxycaprylylsilane 2.0%, zinc oxide 94.0%, isostearic acid 4.0%) Etc.). One or more of these can be appropriately selected and used.

  The compounding amount of the metal oxide coated with triethoxycaprylylsilane used in the cosmetic of the present invention depends on the specific form and use of the oil-in-water emulsified cosmetic, the type of metal oxide, etc. It can be appropriately selected depending on the situation and is not particularly limited. Usually, it may be 1 to 5% by weight based on the total oil-in-water emulsified cosmetic, and if this content is less than 1% by weight based on the total oil-in-water emulsified cosmetic, cosmetic effects such as coloring and UV protection can be obtained. Therefore, there are few merits to mix | blend a metal oxide. If it exceeds 5% by weight, there may be a problem in usability such as loss of freshness in an oil-in-water emulsified cosmetic due to excessive blending of powder.

  Xanthan gum used for the component (B) is a polysaccharide obtained by fermentation using a carbohydrate such as starch using a microorganism such as Xanthomonas. As xanthan gum, commercially available products that have been refined, dried and powdered, Echo Gum, Echo Gum BT, Echo Gum F, Echo Gum GM, Echo Gum RD, Echo Gum SF, Echo Gum T, Echo Gum TF, Monato Gum GS, Keldent (above, Dainippon Sumitomo Pharma Co., Ltd.) Company), xanthan gum (Merck Japan Co., Ltd.), San Ace (San-Eigen FFI Co., Ltd.), Neosoft XK (Taiyo Kagaku Co., Ltd.), etc., one or more of these Can be appropriately selected and used.

  The carrageenan used for the component (B) is a polysaccharide composed of D-galactose and 3,6-anhydrogalactose obtained by extraction from red algae with hot alkali. Carrageenan includes a water gel formation type, a protein reaction type, and a thickening type. In the present invention, a thickening type can be used. Examples of commercially available products include carrageenan, Genugel, Genubisco JJ (above, Copenhagen Pectin), Takaragen G-30, Takaragen G-50 (above, manufactured by Takaragen Co., Ltd.), and the like. The above can be appropriately selected and used.

  The total amount of xanthan gum and carrageenan as component (B) is preferably 0.05 to 0.3% by weight with respect to the total oil-in-water emulsified cosmetic, and if less than 0.05% by weight, the emulsion stability effect is weak In addition, if it exceeds 0.3% by weight, sliminess and stickiness occur, and a refreshing feeling of use cannot be obtained.

  Furthermore, the component ratio of the xanthan gum and carrageenan of the component (B) is preferably 3: 2 to 2: 3 by weight ratio.

  The polyoxyethylene average addition mole number of the polyoxyethylene hydrogenated castor oil used for the component (C) is preferably 80 to 100, more preferably 100. Examples of commercially available products include NIKKOL HCO-80, NIKKOL HCO-100 (manufactured by Nikko Chemicals Co., Ltd.) and the like, and one or two or more of these can be appropriately selected and used.

  As the blending amount of polyoxyethylene hydrogenated castor oil having an average addition number of polyoxyethylene of 80 to 100 used for component (C), 0.1 to 1.0% by weight is sufficiently stable in oil-in-water emulsification. Cosmetics can be obtained

  As the oily component used in the present invention, solid oils, semisolid oils, liquid oils, volatile oils, activators and the like that are generally used in cosmetics can be used. Regardless of animal oil, vegetable oil, mineral oil, synthetic oil, fats, waxes, hydrocarbons, fatty acids, alkyl glyceryl ethers, esters, silicone oils, fluorine oils, lipophilic surfactants, etc. Can be mentioned. Specifically, oils and fats such as olive oil, coconut oil, avocado oil, castor oil, safflower oil, hydrogenated oil, mink oil, horse oil and the like. Waxes such as lanolin, whale wax, beeswax, carnauba wax, jojoba oil, and candelilla wax. Hydrocarbons such as liquid paraffin, paraffin, microcrystalline wax, petrolatum, ceresin, polyethylene, polybutene, squalene, squalane. Higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Alkyl glyceryl ethers such as batyl alcohol, chimyl alcohol and seraalkyl alcohol. Ethyl oleate, isopropyl myristate, isopropyl palmitate, cetyl palmitate, myristyl myristate, octyldodecyl oleate, isopropyl isostearate, ethyl isostearate, cetyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, isocetyl isostearate , Octyldodecyl dimethyloctanoate, myristyl lactate, diisostearyl malate, tri (capryl / capric acid) glyceryl, and other esters. Silicones such as high polymerization degree dimethylpolysiloxane, methylphenylpolysiloxane, alkoxy-modified polysiloxane, and crosslinked organopolysiloxane. Fluorine oils such as perfluoropolyether, perfluorodecane, and fluorine-modified silicone. Examples include lipophilic surfactants such as condensed polyglyceryl ricinoleate, polyglyceryl monostearate, and sorbitan monostearate, and one or more of these can be used.

  The emulsion composition of the present invention can further contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include lower alcohols such as ethanol and isopropanol, glycols such as ethylene glycol, propylene glycol, dipropylene glycol, isoprene glycol, 1,3-butylene glycol, and polyethylene glycol (average molecular weight 200 to 1540). Examples thereof include polyhydric alcohols such as polyoxyethylene methyl glucoside, glycerin and diglycerin, tris (2- (2-ethoxyethoxy) ethyl) phosphate, and the like. One or more of these can be used.

  Furthermore, the oil-in-water emulsified cosmetic of the present invention is not particularly limited as long as it is used as a normal cosmetic raw material. For example, animal and plant extracts, amino acids and peptides, vitamins, antioxidants, sequestering metal ions Agents, bactericides / preservatives, ultraviolet absorbers, pH adjusters and the like can be blended within a range that does not impair the effects of the present invention.

  Hereinafter, although an example is given and explained in detail, the present invention is not limited to these. In addition, all% in implementation means weight%.

[Evaluation items and evaluation methods]
(1) Usability (smoothness, freshness, refreshing feeling)
Evaluation items related to the feeling of use were evaluated by 15 female specialist panels based on the following evaluation criteria.
1. Smooth and smooth ◎: Very smooth and smooth.
○: Smooth and smooth.
Δ: Slightly smooth.
X: The spread is bad.
2. Freshness ◎: Very fresh.
○: Fresh.
Δ: Slightly fresh
×: Not fresh.
3. Refreshing feeling ◎: Very refreshing.
○: Refreshing Δ: Slightly refreshing
X: There is no refreshing feeling.

(2) Emulsification stability The makeup base was left at 50 ° C. and room temperature for 1 month, and the stability was evaluated by appearance observation.
○: No appearance abnormality.
X: The oil phase is separated.

  In Tables 1 to 3, “usability” describes the feeling of use on the day after preparation of the oil-in-water emulsified cosmetic, and “emulsification stability” refers to an oil-in-water type that was allowed to stand for 1 month at 50 ° C. and room temperature. The emulsification stability of the emulsified cosmetic was evaluated.

  The HLB values listed in Tables 1 to 3 are methods generally used for evaluating the properties of surfactants. These are added to lipophilic groups for ethylene oxide addition-type nonionic surfactants. Considering a hypothetical compound having an infinitely long hydrophilic group and the greatest hydrophilicity, the HLB value of this compound is set to 20, and for an oleophilic compound having no hydrophilic group, this HLB value is set to 0 and It is an index representing the balance between lipophilicity and hydrophilicity as a relative value.

  The oil-in-water emulsified cosmetics of the present invention described in Table 1 and the comparative products shown in Tables 2 and 3 were prepared, respectively, and the feeling of use (smoothness, freshness, refreshing feeling) and emulsion stability. (Evaluated for 1 month at 50 ° C. and room temperature). The results are also shown in Table 1, Table 2, and Table 3.

(Production method)
A: Components 9 to 14 are heated to 80 ° C., components 1 to 8 are added, uniformly dispersed with a homomixer, and kept at 80 ° C.
B: Components 15 to 29 are mixed uniformly with a homomixer and heated to 80 ° C.
C: A is added to B and emulsified.
D: C is cooled to 68 ° C. and component 30 is added.
E: Further cooling to 30 ° C. to obtain an emulsion makeup base.

  As the results shown in Table 1, the oil-in-water emulsified cosmetics of Formulation Examples 1 to 10 according to the present invention have a smoothness, a refreshing feeling and a freshness, and are excellent in use feeling and stable. The property was also excellent.

  From the results shown in Table 2 and Table 3, as shown in Comparative Example 1, when a non-surface-treated metal oxide is blended, aggregation occurs at the time of emulsification and takes the form of an oil-in-water emulsion cosmetic. I couldn't. Moreover, as shown in Comparative Examples 2 to 3, the surface treatment other than triethoxycaprylylsilane was inferior in freshness, and in Comparative Example 2, the emulsion stability at 50 ° C. was also poor. Therefore, in the present invention, surface treatment of triethoxycaprylylsilane is necessary. In Comparative Example 4, locust bean gum, which is a polysaccharide thickener, was used. However, the smoothness, refreshing feeling and emulsification stability at 50 ° C. were poor. Similarly, Comparative Examples 5 to 8 showed examples in which xanthan gum and carrageenan were not used together, but they were not satisfactory as a feeling of use, and stability at 50 ° C. was also poor. In Comparative Examples 9 to 10 using carboxyvinyl polymer, aggregation occurred at the time of emulsification in the same manner as in Comparative Example 1, and it was not possible to take the form of an oil-in-water emulsified cosmetic. In Comparative Examples 11 to 13, a nonionic surfactant having an average polyoxyethylene addition mole number of 80 to 100 was used, but the emulsion stability at room temperature and 50 ° C. was poor. In Comparative Examples 14 to 15, the triethoxycaprylylsilane-coated metal oxide was 0.6% by weight and 6.4% by weight in the inner oil phase, but it was not sufficient for feeling of use and emulsion stability. Moreover, in Comparative Examples 16-17, although the compounding quantities of xanthan gum and carrageenan were 0.04% by weight and 0.4% by weight, they were not satisfactory in use feeling and emulsion stability. Further, in Comparative Examples 18 to 19, the blended amounts of polyoxyethylene hydrogenated castor oil having a polyoxyethylene average addition mole number of 100 are 0.05% by weight and 1.5% by weight. The emulsion stability was not satisfactory.

  As described above in Formulation Examples 1 to 10, the component (A) triethoxycaprylylsilane-coated metal oxide is contained in the inner oil phase, and the component (B) xanthan gum and carrageenan in the outer water phase, (C) Polyoxyethylene hydrogenated castor oil having an average added mole number of polyoxyethylene of 80 to 100 is contained, and the amount of components (A) to (C) in the oil-in-water emulsified cosmetic composition is the component (A) The oil-in-water emulsified cosmetic characterized by 1 to 5% by weight, component (B) 0.05 to 0.3% by weight, and component (C) 0.1 to 1.0% by weight It became an oil-in-water emulsified cosmetic containing a metal oxide that has little change over time, and is smooth and fresh on the skin at the time of application.

  An oil-in-water emulsified foundation was prepared with the composition shown in Table 4.

(Production method)
A: Components 5 to 10 are heated to 80 ° C., components 1 to 4 are added, and uniformly dispersed with a homomixer, and kept at 80 ° C.
B: Components 11 to 19 are uniformly mixed with a homomixer and heated to 80 ° C.
C: A is added to B and emulsified.
D: C is cooled to 68 ° C. and component 20 is added.
E: Further cooling to 30 ° C. to obtain an emulsion foundation.

  The obtained oil-in-water emulsified foundation had a smooth smoothness, a refreshing feeling and a freshness, an excellent usability, and an excellent stability.

According to the present invention, there is provided an oil-in-water emulsified cosmetic containing a metal oxide that has little change due to high temperature and time and can be applied smoothly on the skin at the time of application, providing a refreshing use feeling. it can.

Claims (4)

  Component (A) contains triethoxycaprylylsilane-coated metal oxide in the inner oil phase, component (B) xanthan gum and carrageenan in the outer aqueous phase, and (C) polyoxyethylene average added mole number is 80 to 100 It contains a certain polyoxyethylene hydrogenated castor oil, and the blending amounts of the components (A) to (C) in the all-in-water emulsion cosmetic are components (A) 1 to 5% by weight, components (B) 0. An oil-in-water emulsified cosmetic comprising 05-0.3 wt% and component (C) 0.1-1.0 wt%.   2. The oil-in-water emulsion cosmetic according to claim 1, wherein the polyoxyethylene hydrogenated castor oil as component (C) has an average polyoxyethylene addition mole number of 100. 3.   The oil-in-water emulsified cosmetic according to claim 1 or 2, wherein the component ratio of xanthan gum and carrageenan is 3: 2 to 2: 3 by weight. The oil-in-water emulsified cosmetic according to any one of claims 1 to 3, which is a makeup cosmetic.