JP2012184167A - Oil-in-water type skin cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-in-water type skin cosmetic having no stickiness during application, high moist feeling after application, and improved freeze restoration stability.SOLUTION: The oil-in-water type skin cosmetic contains (A) 5-25 mass% hydrocarbon oil, (B) a water-swellable clay mineral, (C) a polyglycerol fatty acid ester and (D) 0.1-5 mass% oligosaccharide, wherein the mass ratio (B/C) of the content of the (B) component water-swellable clay mineral to the content of the (C) component polyglycerol fatty acid ester is 0.1-3.

Description

  The present invention relates to an oil-in-water skin cosmetic that does not have stickiness during application, has a moist feeling after application, and has improved freeze-recovery stability.

  Oil-in-water skin cosmetics contain an oil-soluble component and a water-soluble component, and have the advantage that both components can be applied at once, and are often used for skin external preparations and the like. As a feeling of use of the external preparation for skin, a feeling of use with a high moist feeling without stickiness at the time of application is required. In order to obtain such a moist feeling, the content of oil components such as hydrocarbons is increased. However, when the content of oil components such as hydrocarbons is increased, the stickiness becomes stronger. In order to suppress the sticky feeling, it has been proposed to add a powder such as bentonite (see Patent Document 1) or to use silicone oil together (see Patent Document 2).

However, when bentonite is added, sufficient stability cannot be obtained, and when it is exposed to below freezing in the distribution stage, water separation, separation, etc. occur, and there is a problem in freeze / restoration stability. Here, freeze-restoration stability means that water separation, separation, etc. do not occur even if freeze-thawing is repeated. Even in Japan, in Hokkaido, Tohoku region, and the like, the temperature may fall below −10 ° C. in the middle of winter, so that there is a strong demand for freeze / restoration stability at the distribution stage or in use. Therefore, it is conceivable to add a thickener to improve freeze / restoration stability and prevent water separation and separation. However, if a thickener is added to an oil-in-water skin cosmetic, stickiness at the time of application increases. There is a problem.
On the other hand, when silicone oil is added, there is a problem that a moist feeling after application is difficult to be imparted because a specific skin slip feeling is developed. In addition, silicone oil has a problem of low compatibility with oily components such as hydrocarbon oil, and adversely affects emulsion stability.

  Therefore, the present situation is that it is desired to provide an oil-in-water skin cosmetic that has no stickiness at the time of application, has a moist feeling after application, and has improved freeze-restoration stability.

JP 2001-151635 A JP 2009-132638 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide an oil-in-water skin cosmetic that has no stickiness at the time of application, has a moist feeling after application, and has improved freeze-restoration stability.

As a result of intensive studies by the present inventors in order to solve the above problems, (A) hydrocarbon oil 5 mass% to 25 mass%, (B) water-swellable clay mineral, (C) polyglycerin fatty acid ester, and (D) 0.1% by mass to 5% by mass of an oligosaccharide, the content of the water-swellable clay mineral as the component (B) and the content of the polyglycerin fatty acid ester as the component (C) The oil-in-water skin cosmetic with a mass ratio (B / C) of 0.1 to 3 has no stickiness at the time of application, increases the moist feeling after application, and improves the freeze-recovery stability. I found out.
In particular, it has been found that, preferably, when at least one selected from (E) xanthan gum and carboxymethylcellulose salt is added, the freeze-recovery stability is further improved by the formation of a network.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> (A) 5% by mass to 25% by mass of hydrocarbon oil,
(B) a water-swellable clay mineral,
(C) polyglycerol fatty acid ester, and (D) 0.1% by mass to 5% by mass of oligosaccharide,
Containing
The mass ratio (B / C) between the content of the water-swellable clay mineral of the component (B) and the content of the polyglycerin fatty acid ester of the component (C) is 0.1 to 3, It is an oil-in-water type skin cosmetic.
<2> The oil-in-water skin cosmetic according to <1>, further comprising (E) 0.1% by mass to 1% by mass of at least one selected from xanthan gum and carboxymethylcellulose salt.
<3> The oil-in-water skin cosmetic according to any one of <1> to <2>, wherein the polyglycerin fatty acid of component (C) is at least one of diisostearyl polyglycerin and isostearyl polyglycerin. It is.
<4> The oil-in-water type skin cosmetic according to any one of <1> to <3>, wherein the swelling power of the water-swellable clay mineral (B) is 20 mL / 2 g or more.
<5> The oil-in-water skin cosmetic according to any one of <1> to <4>, wherein the HLB of the polyglycerin fatty acid of component (C) is 8 to 16.
<6> The oil-in-water skin cosmetic according to any one of <1> to <5>, wherein the oligosaccharide of component (D) is maltotetraose.
<7> The oil-in-water skin cosmetic according to any one of <2> to <6>, wherein the carboxymethylcellulose salt of component (E) has a weight average molecular weight of 10,000 to 300,000.

  ADVANTAGE OF THE INVENTION According to this invention, the various problems in the past can be solved, and the oil-in-water type skin cosmetic that has no stickiness at the time of application, has a moist feeling, and has improved freeze-recovery stability can be provided.

  The oil-in-water skin cosmetic of the present invention comprises (A) a hydrocarbon oil, (B) a water-swellable clay mineral, (C) a polyglycerin fatty acid ester, and (D) an oligosaccharide, preferably ( E) It contains at least one selected from xanthan gum and carboxymethylcellulose salt, and further contains other components as necessary.

<(A) Hydrocarbon oil>
The hydrocarbon oil of component (A) is blended for the purpose of improving the moist feeling after coating.
The (A) component hydrocarbon oil is liquid and semi-solid at 25 ° C., and includes synthetic or naturally derived ones.
Examples of the liquid hydrocarbon oil include liquid isoparaffin, liquid lanolin, liquid paraffin, and squalane. Examples of the semi-solid hydrocarbon oil include waxes such as petrolatum and lanolin. Among these, liquid liquid paraffin and squalane are particularly preferable from the viewpoint of non-stickiness during coating and moist feeling after coating.
As the hydrocarbon oil of the component (A), a commercially available product can be used. Examples of the commercially available product include liquid paraffin such as liquid paraffin 350-S (manufactured by Sanko Chemical Co., Ltd.); HIDERM (COGNIS IBERIA) , Sl.) And the like. These may be used alone or in combination of two or more.

  The content of the hydrocarbon oil of the component (A) is 5% by mass to 25% by mass with respect to the whole oil-in-water skin cosmetic, and 10% by mass to 20% by mass from the point of moist feeling after application. % Is more preferable. When the content is less than 5% by mass, moist feeling after coating may be deteriorated, and when the content exceeds 25% by mass, stickiness may occur during coating.

<(B) Water-swellable clay mineral>
The water-swellable clay mineral (B) is added for the purpose of improving stickiness during application, moist feeling after application, and freeze / restoration stability.
The water-swellable clay mineral of component (B) is not particularly limited as long as it has a swelling power of 20 mL / 2 g or more and is not cationized. For example, natural products, purified natural products, natural products And those obtained by modifying the swellability of these.
The swelling force is preferably 20 mL / 2 g or more, more preferably 60 mL / 2 g or more, and particularly preferably 60 mL / 2 g to 90 mL / 2 g from the viewpoint of moist feeling after application and freeze-restoration stability.
When a water-swellable clay mineral having a swelling power of less than 20 mL / 2 g is used, the dispersibility in an oil-in-water cosmetic may be deteriorated, and the moist feeling after application and the freeze / restoration stability may be deteriorated. . The reason for this is unknown, but water-swellable clay minerals with a swelling power of less than 20 mL / 2 g have low water retention, and the stability of freezing and restoring can be improved by the stable emulsified interface film formed with the component (C). Inferred.
Here, the swelling power of the water-swellable clay mineral is expressed in terms of the swelling volume (mL) of 2 g of the water-swellable clay mineral by applying the bentonite test method defined in the 15th revision Japanese Pharmacopoeia. Specifically, 2.0 g of water-swellable clay mineral was taken and added to a 100 mL graduated cylinder containing 100 mL of water in 10 portions, and the apparent volume of the bottom of the vessel when left for 24 hours was calibrated. Read from. When the water-swellable clay mineral is added to water in 10 steps, the next sample is added after most of the previously added sample is deposited.

Examples of the water-swellable clay mineral of the component (B) include natural or synthesized montmorillonite, beidellite, nontronite, saponite, sauconite, hectorite, stevensite and other smectite group clay minerals having the swelling power, vermiculite Swellable synthetic fluorine mica (Na-type, Li-type synthetic mica) and the like. Moreover, the high metal ion substitution clay mineral etc. which performed the ion exchange reaction of the said clay mineral and improved the swelling property can also be used. These may be used individually by 1 type and may use 2 or more types together.
The water-swellable clay mineral having the swelling power contains exchangeable ions that hydrate and take in water molecules between layers, and has properties such as swelling, adsorptive properties, binding properties, suspension properties, and thickening properties. And exhibit properties different from other clay minerals.
Among these water-swellable clay minerals, bentonite mainly composed of smectite group or smectite group montmorillonite is particularly preferable.
Specifically, as this commercial item, for example, polar gel (swelling power: 20 mL / 2 g, manufactured by American Colloid Co., Ltd.), laponite (manufactured by Nippon Silica Industry Co., Ltd.), Bengel (swelling power: 35 mL / 2 g, Toyshun Mining) Co., Ltd.), Lucentite (Coop Chemical Co., Ltd.), Kunipia F (swelling power: 70 mL / 2 g, Kunimine Kogyo Co., Ltd.), Kunipia G (swelling power: 86 mL / 2 g, Kunimine Kogyo Co., Ltd.), Benclay (Made by Mizusawa Chemical Co., Ltd.), bee gum (made by Vanderbilt) and the like. Among these, Kunipia F and Kunipia G are particularly preferable from the viewpoint of moist feeling after coating.

  The content of the water-swellable clay mineral as the component (B) is preferably 0.1% by mass to 3% by mass and more preferably 0.5% by mass to 2% by mass with respect to the entire oil-in-water skin cosmetic. preferable. When the content is less than 0.1% by mass, no stickiness at the time of application and freeze-recovery stability may be insufficient. When it exceeds 3% by mass, the moist feeling after application decreases. May end up.

<(C) Polyglycerol fatty acid ester>
The polyglycerin fatty acid ester of the component (C) is added for the purpose of improving stickiness at the time of coating, moist feeling after coating, and freeze / restoration stability.
8-16 are preferable and, as for HLB of the polyglycerol fatty acid ester of the said (C) component, 10-12 are more preferable. When the HLB is less than 8 or more than 16, freeze / restoration stability may be deteriorated.

Here, the HLB value is a value indicating the balance of strength between the hydrophilic group constituting the surfactant and the hydrophobic group. Generally, 1 to 8 is hydrophobic, and more than 8 and less than 10 are hydrophilic. 10 or more are hydrophilic, but may differ depending on the structure of the surfactant.
The measurement method of HLB is based on the measurement of HLB value by the emulsification method described in “Handbook-Cosmetics / Formulation raw materials-Revised edition”, Nikko Chemicals Co., Ltd., revised February 1, 1977, page 854-855. To do. As a specific method for obtaining the HLB value of the polyglycerin fatty acid ester of the component (C), the component (C) and sorbitan monostearate (NIKKOL SS-10, HLB 4.7) as a standard substance for an emulsifier are used. In combination, the total amount of these two emulsifiers is kept constant, only the ratio is changed to emulsify the liquid paraffin (HLB10.1) to be emulsified, and after standing overnight, the creaming amount, white turbidity, lower layer water separation, etc. From the above, the optimum proportion of the emulsifier having stability is obtained, and the HLB value x of the component (C) is calculated by the following formula (1).
y = (x × used amount (mass%) + z × used amount (mass%)) / 100 Formula (1)
In the formula (1), “x” represents the HLB value of the component (C), “y” represents the HLB value of liquid paraffin, and “z” represents sorbitan monostearate (NIKKOL SS). The HLB value of -10) is shown.
In addition, the HLB value of the said liquid paraffin is the same method by the combination of monostearic acid sorbitan (NIKKOL SS-10, HLB4.7) and monostearic acid POE sorbitan (NIKKOL TS-10, HLB14.9). Can be sought.

The polyglycerin fatty acid ester of the component (C) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyglyceryl isostearate-10 (HLB = 12), polyglyceryl diisostearate-10 (HLB = 10), polyglyceryl stearate-10 (HLB = 12), polyglyceryl tristearate-10 (HLB = 7.5), polyglyceryl stearate-6 (HLB = 9), polyglyceryl laurate-10 (HLB = 15. 5) (all manufactured by Nippon Surfactant Co., Ltd.). These may be used alone or in combination of two or more.
0.5 mass%-5 mass% are preferable with respect to the said whole oil-in-water type skin cosmetics, and, as for content of the polyglycerol fatty acid ester of the said (C) component, 1 mass%-3 mass% are more preferable. If the content is less than 0.5% by mass, emulsification is poor and freeze-recovery stability may be inferior. If it exceeds 5% by mass, freeze-restore stability is inferior and may become sticky during application.

  The mass ratio (B / C) between the content of the water-swellable clay mineral of the component (B) and the content of the polyglycerin fatty acid ester of the component (C) is 0.1 to 3, and is frozen and restored. From the viewpoint of stability, 0.75 to 2 is preferable. If the mass ratio (B / C) is too low or too high, the freeze / restoration stability may be lowered.

<(D) oligosaccharide>
The oligosaccharide of the component (D) means a saccharide in which 2 to 10 monosaccharides are linked, and these derivatives are also included.
The oligosaccharide of the component (D) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, sucrose, maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, malto Examples include heptaose, maltooctaose, maltononaose, threitol and raffinose. These may be used individually by 1 type and may use 2 or more types together. Among these, maltotetraose, maltotriose, maltose, raffinose, and maltopentaose are preferable, and maltotetraose is particularly preferable in terms of freeze-recovery stability and non-stickiness during coating.
As the oligosaccharide of the component (D), an appropriately synthesized product or a commercially available product may be used. There is no restriction | limiting in particular as this commercial item, According to the objective, it can select suitably, For example, maltotetraose (brand name: TETRAP-H, a maltotetraose 74% or more containing product, Hayashibara Corporation make), Maltopentaose (trade name: Pentrap, containing 74% or more of maltopentaose, manufactured by Hayashibara Shoji Co., Ltd.), Maltose (Saint malt, containing maltose 89 ± 2%, manufactured by Hayashibara Shoji Co., Ltd.), Maltotriose (Malto) Triose, manufactured by Kishida Chemical Co., Ltd.).
The content of the oligosaccharide of the component (D) is 0.1% by mass to 5% by mass with respect to the whole oil-in-water skin cosmetic, freezing and restoring stability, and no stickiness at the time of application. And 0.5 mass%-3 mass% are preferable. When the content is less than 0.1% by mass, the freeze / restoration stability may be deteriorated, and when it exceeds 5% by mass, the content may be sticky at the time of application.

<(E) Xanthan gum, carboxymethylcellulose salt>
There is no restriction | limiting in particular as carboxymethylcellulose salt of the said (E) component, Although it can select suitably according to the objective, For example, carboxymethylcellulose sodium, carboxymethylcellulose potassium, etc. are mentioned. Among these, sodium carboxymethyl cellulose is particularly preferable.
The weight average molecular weight of the sodium carboxymethyl cellulose is preferably 10,000 to 300,000, and more preferably 20,000 to 70,000, from the viewpoint of non-stickiness at the time of coating and freeze / restoration stability. If the weight average molecular weight exceeds 300,000, it may become sticky at the time of coating, and if it is less than 10,000, the effect of improving the freeze / restoration stability may not be sufficiently obtained.
Here, the weight average molecular weight can be measured by a method of comparing with a polymer having a known molecular weight by liquid chromatography using a general GPC column. The weight average molecular weight of the sodium carboxymethylcellulose is a value measured using GPC-MALLS, and a sample solution diluted with a mobile phase having a pure polymer concentration of about 1,000 ppm is prepared using a TSK-GELA column (manufactured by Tosoh Corporation). ), A wavelength of about 633 nm is measured with a multi-angle light scattering detector using a 0.5 mol / L sodium perchlorate solution as a mobile phase. As a standard product, polyethylene glycol having a known molecular weight is used.
Commercial products may be used as the xanthan gum and carboxymethylcellulose salt of the component (E). There is no restriction | limiting in particular as this commercial item, According to the objective, it can select suitably, As xanthan gum, brand name: Echo gum T (made by Dainippon Sumitomo Pharma Co., Ltd.), As carboxymethylcellulose sodium, brand name: Serogen F-5A (weight average molecular weight: 13,000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Serogen F-815A (weight average molecular weight: 50,000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. From the viewpoint of stability, a carboxymethyl cellulose salt is more preferable.
The content of at least one selected from xanthan gum and carboxymethylcellulose salt of the component (E) is preferably 0.1% by mass to 1% by mass with respect to the entire oil-in-water skin cosmetic, and moist after application. From the viewpoints of feel, freeze / restoration stability, and non-stickiness during application, 0.2 mass% to 0.7 mass% is more preferable. When the content is less than 0.1% by mass, the moist feeling after application and freeze-recovery stability may be inferior. When the content exceeds 1% by mass, stickiness may occur during application.

<Other ingredients>
The other components are not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected depending on the purpose. For example, the oil and fat component excluding the component (A), an anionic surfactant, Cationic surfactants, amphoteric surfactants, surfactants such as nonionic surfactants excluding component (C), water-insoluble powders such as inorganic powders and organic powders, moisturizers, vitamins, Amino acids, anti-inflammatory agents, ultraviolet absorbers, cooling sensation agents, antioxidants, coloring agents, fragrances, antiperspirants, bactericides, deodorants, preservatives, inclusion compounds, solvents, and the like. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as content of the said other component, According to the objective, it can select suitably.

<Manufacturing method>
There is no restriction | limiting in particular as a manufacturing method of the oil-in-water type skin cosmetics of this invention, Although it can select suitably according to the objective, The method containing the following (1) process to (6) processes is suitable. .
(1) While stirring purified water, component (B) is gradually added thereto to prepare a uniform dispersion.
(2) While stirring purified water, the component (E) is gradually added to the mixture as necessary to prepare a uniform dispersion.
(3) While stirring purified water, component (D) is added to this, and the liquid obtained in (1) and (2) are added thereto to prepare a uniform dispersion. And heat to 60 ° C.
(4) Add component (C) to component (A) and dissolve by heating at 65 ° C.
(5) The liquid obtained in (4) is gradually added to (3) and emulsified with a homomixer.
(6) It cooled to 30 degreeC, stirring, and obtained the oil-in-water type skin cosmetics.

-PH-
The pH of the oil-in-water skin cosmetic is not particularly limited and may be appropriately selected depending on the intended purpose. 0.0 is preferred.
The pH can be measured, for example, according to the cosmetic raw material standard general test method pH measurement method.

-Viscosity-
The viscosity of the oil-in-water skin cosmetic is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 500 mPa · s to 10,000 mPa · s at 25 ° C., and 1,000 mPa · s. Is more preferably 8,000 mPa · s, and further preferably 2,000 mPa · s to 5,000 mPa · s. If the viscosity is less than 500 mPa · s, the freeze / restoration stability is poor, the liquid may easily drip, and the applicability may decrease, and if it exceeds 10,000 mPa · s, it may become sticky during application.
The viscosity at 25 ° C. can be measured, for example, according to the Cosmetic Raw Material Standard General Test Method Viscosity Measurement Method 2 method.

-Application-
The oil-in-water type skin cosmetic has no stickiness at the time of application, has a high moist feeling after application, and has improved freeze-restoration stability, so that it can be suitably used for, for example, emulsions and creams.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, all the component amount as described in an Example and a comparative example is a pure part conversion.

(Examples 1-40 and Comparative Examples 1-7)
-Preparation of oil-in-water skin cosmetics-
About the composition (unit: mass%) shown in following Table 1, the oil-in-water type skin cosmetics of Examples 1-40 and Comparative Examples 1-7 were prepared by the conventional method. Finally, citric acid was added to adjust the pH to 5.2. The pH was measured by stabilizing a sample at 25 ° C. for 2 minutes using a pH meter (Horiba pH meter D-52, Horiba, Ltd.).
Viscosity is measured using a BH viscometer (specified in quasi-drug material standards, viscosity measurement method, second method, etc.) at 25 ° C., 20 rpm, and 1 minute later. The rotor used was a No. 6 rotor. The BH viscometer used was a Tokyo Keiki BH viscometer.

  Next, each oil-in-water type skin cosmetic obtained was evaluated as follows in terms of feeling of use (no stickiness during application, moistness after application) and freeze-restoration stability. The results are shown in Tables 1 and 2.

<Evaluation method of feeling of use>
For 20 subjects, 0.3 g of the sample was spread by hand on the entire inner part of the forearm, and the non-stickiness when spread and the moist feeling after application were evaluated. Sensory evaluation is performed based on the following evaluation criteria, and the results are shown based on the following criteria based on the sensory evaluation average score of 20 subjects.
-No stickiness during application-
〔Evaluation criteria〕
5 points: no stickiness 4 points: no stickiness 3 points: no stickiness 2 points: sticky 1 point: very sticky-moist after application-
〔Evaluation criteria〕
5 points: very moist 4 points: moist 3 points: slightly moist 2 points: not very moist 1 point: not moist [criteria]
-No stickiness during application and moist feeling after application-
A: The average score of 20 subjects is 4.5 or more and 5 or less B: The average score of 20 subjects is 4.0 or more and less than 4.5 C: The average score of 20 subjects is 3.0 or more Less than 4.0 points D: The average score of 20 subjects is 2.0 points or more and less than 3.0 points E: The average score of 20 subjects is 1.0 points or more and less than 2.0 points

<Frozen recovery stability>
A 450 mL soft transparent glass bottle was filled with 350 g of the oil-in-water type skin cosmetic preparation prepared above, stored at -20 ° C. for 1 day and completely frozen, and then allowed to stand at room temperature for 1 day and naturally thawed. After this operation was repeated 5 times, the freeze / restoration stability was evaluated according to the following criteria.
〔Evaluation criteria〕
A: No water separation or separation is observed B: Water separation is observed only slightly, but no separation is observed C: Water separation is observed, slight separation is observed D: Water separation and separation are completely recognized

In addition, the specific content of the raw material of the oil-in-water type skin cosmetic used in Examples 1-40 and Comparative Examples 1-7 is as showing in following Table 3.

  The oil-in-water skin cosmetic of the present invention has no stickiness at the time of application, has a high moist feeling after application, and has improved freeze-restoration stability. .

Claims (3)

(A) hydrocarbon oil 5 mass% to 25 mass%,
(B) a water-swellable clay mineral,
(C) polyglycerol fatty acid ester, and (D) 0.1% by mass to 5% by mass of oligosaccharide,
Containing
The mass ratio (B / C) between the content of the water-swellable clay mineral of the component (B) and the content of the polyglycerin fatty acid ester of the component (C) is 0.1 to 3, Oil-in-water skin cosmetics.   The oil-in-water skin cosmetic according to claim 1, further comprising 0.1 mass% to 1 mass% of (E) at least one selected from xanthan gum and carboxymethylcellulose salt.   The oil-in-water type skin cosmetic according to any one of claims 1 to 2, wherein the polyglycerin fatty acid as component (C) is at least one of diisostearyl polyglycerin and isostearyl polyglycerin.