JP5815245B2 - Oil-in-polyhydric alcohol composition - Google Patents

Description

The present invention relates to a polyhydric alcohol-in-oil composition in which a specific oil component is dispersed in glycerin without using a surfactant by using a specific anhydrous silica.
By containing the above components at a specific ratio, the stability over time and the spread are excellent. Furthermore, it contains a zeolite in a specific ratio, so that the warm feeling effect is excellent.

Conventionally, cosmetics such as oils, creams and emulsions have been developed for the purpose of moisturizing and protecting skin and hair. Examples of such cosmetics include ointment-type cosmetics composed of oily components, and emulsified cosmetics in which an oily component and an aqueous component are emulsified. Above all, polyhydric alcohol-in-oil cosmetics in which oil is dispersed in polyhydric alcohols such as glycerin without using water are especially specialized for moisturizing effects, such as washing packs, massage fees, cleansing fees, hair conditioners, Suitable for essence and has excellent functions. In addition, compositions containing a large amount of glycerin have been marketed as warm cosmetics because they feel warm due to the heat of hydration when applied to the skin, and are well received in the market.

Therefore, as a polyhydric alcohol-in-oil cosmetic, a polyhydric alcohol-in-oil emulsified cosmetic for the purpose of improving emulsification stability and usability using a specific oligoester (see, for example, Patent Document 1), a specific polyester There is an oil-in-polyhydric alcohol-in-oil external composition (see, for example, Patent Document 2) that has improved emulsion stability using ether-modified silicone. In addition, a polyhydric alcohol-in-oil thermal base that has reduced skin irritation by using a sucrose fatty acid ester (see, for example, Patent Document 3), and a polyvalent that has been stabilized by using hydrogenated lecithin and stevia. An oil-in-oil emulsion composition (for example, see Patent Document 4), a polyhydric alcohol-in-oil emulsion composition that is stabilized by using lysolecithin or hydroxylecithin (for example, Patent Document 5,
6)) has been developed.

JP 2009-126791 A JP 2003-261433 A JP 2001-206817 A JP-A-1-176443 JP-A-62-95132 JP 62-95131 A

However, in any of the above-mentioned patent literatures, although it has been studied to select a surfactant having high safety and to stabilize by using a small amount, the formulation of the surfactant is indispensable. In consideration of the above, it is limited to a method of wiping or washing off after application, and a method of using without removing it as applied is difficult. In addition, when a two-layer separation type composition that mixes an oil phase and a polyhydric alcohol phase at the time of use is prepared without using a surfactant, it is non-uniform because it only exhibits an emulsified state temporarily. The problem remains that it is difficult to use and the same effect as in the case of an oil-in-polyhydric alcohol composition is not obtained.

Under these circumstances, it has been desired to develop a polyhydric alcohol-in-oil type composition that is excellent in stability over time without blending with a surfactant and is excellent in spreading and spreading.

In view of the actual situation, the present inventors have conducted intensive studies, and as a result, related to an oil-in-polyhydric alcohol composition in which a specific oil agent is dispersed in glycerin with specific anhydrous silica, and more specifically, the components are combined at a specific ratio. Even if it does not contain a surfactant, it is excellent in stability over time,
The present inventors have found that an oil-in-polyhydric alcohol composition excellent in elongation and spread can be obtained. The specific anhydrous silica is a component that coordinates at the interface between a specific oil agent and glycerin and acts to stabilize the oil-in-polyhydric alcohol composition.
Furthermore, it has been found that by combining zeolite in a specific ratio, an oil-in-polyhydric alcohol composition having a high warming effect, excellent stability over time, and excellent spread and spread can be obtained.

That is, the present invention
(A) Hydrophobized anhydrous silica having an average primary particle size of 100 nm or less and / or hydrophilic anhydrous silica (C) hydroxyl group having an average primary particle size of 100 nm or less and a BET specific surface area of 300 m ² / g or less , Containing an oily component having no carboxyl group in the molecule and an average IOB of 0.1 to 0.4, and the content of the component (A) and the content of the component (B) are (A) /
(B) = 50 to 10, and the content of component (C), component (A) and component (B
) Is a polyhydric alcohol-in-oil composition characterized in that the total content of (C) / ((A) + (B)) = 6/4 to 3/7 in mass ratio It is.
Further, when the zeolite is contained as the component (D), the content of the component (D) is set to X% by mass.
When the content of the component (C) and the total content of the component (A) and the component (B) are (C) / ((A) + (B)) = (60−1.4X) ) / (40 + 0.4X) to (30−
The present invention provides a polyhydric alcohol-in-oil composition characterized by being in the range of 0.2X) / (70-0.8X).

Furthermore, the oil-in-polyhydric alcohol composition is a massage cosmetic, which provides an oil-in-polyhydric alcohol composition.

Furthermore, the oil-in-polyhydric alcohol composition is characterized by being a warm cosmetic composition.

An oil-in-polyhydric alcohol composition is characterized in that the oil-in-oil composition in a polyhydric alcohol substantially contains no gelling agent or surfactant other than the component (B).

An oil-in-polyhydric alcohol composition is characterized in that the oil-in-polyhydric alcohol composition is substantially free of water.

The polyhydric alcohol-in-oil composition of the present invention is excellent in stability over time even if it contains substantially no surfactant, by combining glycerin and specific anhydrous silica, a specific oil agent at a specific ratio, Moreover, it is excellent in extension and spread. Furthermore, by combining zeolite at a specific ratio, it is a polyhydric alcohol-in-oil composition having a high warming effect, excellent stability over time, and excellent spread and spread.

FIG. 1 is a phase diagram showing the compositional relationship of components (A) to (D) in the present invention.

FIG. 1 is a phase diagram showing the compositional relationship of components (A) to (D) in the present invention, and region A is the region of the present invention. In addition, some examples and comparative examples described later are shown in FIG. 1, and Example 1 is abbreviated as “Real 1” and Comparative Example 1 as “Ratio 1”.

  The present invention will be described in detail below.

The glycerin of component (A) used in the present invention works as a moisturizing agent and is soft on the skin and hair.
It is a moisturizing ingredient. Moreover, although not specifically limited, as a commercial item, P
ALMELA 9091 (manufactured by PALM OLEO) and the like.

Component (B) anhydrous silica used in the present invention is a component that coordinates at the interface between oil and glycerin and acts to stabilize the oil-in-polyhydric alcohol composition. Component (B) is dimethylsilylation treatment with dimethyldichlorosilane, trimethylsilylation treatment with trimethylchlorosilane or hexamethyldisilazane, octylsilylation treatment with octyltrichlorosilane, silicone treatment with dimethylpolysiloxane or methylhydrogenpolysiloxane, etc. In the case where the average primary particle size is 100 nm or less, or the non-hydrophobized one has a low BET surface area of 300 m ² / g or less and has a low hydrophilicity. Is excellent. Although the hydrophobization treatment has been performed, the stability becomes insufficient when the average primary particle diameter exceeds 100 nm or hydrophilic anhydrous silica having a BET surface area exceeding 300 m ² / g is used. Moreover, if a component (B) is in the said range, it will not specifically limit, AEROSIL R-976S (made by Nippon Aerosil Co., Ltd.) etc. are mentioned as a commercial item. Further, the anhydrous silica of the present invention has an average particle diameter of 0.01 μm to 0.1 μm, and the average particle diameter is determined by measuring the specific surface area using the BET method, and the average particle diameter is calculated from the obtained specific surface area. It is a thing.

Content of the component (A) used for this invention and content of a component (B) are mass ratio (A) / (
B) = 50 to 10 range, and in this range, the stability over time and the elongation spread are excellent.
When the anhydrous silica is reduced from this ratio, the emulsion stability is lowered, and when the anhydrous silica is increased, the anhydrous silica is dispersed in addition to the emulsifying interface and the viscosity is increased, so that the feeling of use becomes heavy and the skin after use becomes rough.

The oil component of the component (C) used in the present invention does not have a hydroxyl group or a carboxyl group in the molecule, and the average value of IOB of each oil component blended (hereinafter abbreviated as “average IOB”) is 0. It is a component that gives a moisturizing effect and a smooth feel to the skin and hair. When the average IOB is less than 0.1, anhydrous silica aggregates in the oil component and does not orientate at the interface, so emulsification cannot be performed. Also, when the average IOB is higher than 0.4, the hydroxyl group and / or carboxyl group may be incorporated in the molecule. In the case where it is included, the hydrophilicity is high, so that it is compatible with glycerin and tends to coalesce the emulsified droplets. The component (C) is not particularly limited as long as it is usually used for cosmetics, but if specifically exemplified, glyceryl tri-2-ethylhexanoate, dipentaerythrityl tetra-2-ethylhexanoate, Tri (capryl / capric acid) glyceryl, 2-ethylhexyl paramethoxycinnamate, dialkyl carbonate (C14, 1
5), neopentyl glycol dicaprate, propylene glycol dicaprate, isononyl isononanoate, diglyceryl tetraisostearate, glyceryl triisostearate, trimethylolpropane triisostearate, ethyl oleate, isotridecyl isononanoate, cetyl isooctanoate, etc. In addition, safflower oil, wheat germ oil, palm oil, palm kernel oil, coconut oil, rice bran oil, olive oil, sesame oil, soybean oil, corn oil, etc., which are vegetable oils that have substantially no hydroxyl group or carboxyl group in the molecule Are mentioned,
One type or two or more types can be selected and used. Specifically, Quasi-drug raw material standard 20
A vegetable oil having an acid value measured by the acid value measuring method described in 06 of 1 or less and a hydroxyl value measured by the hydroxyl value measuring method described in the Quasi-drug Raw Material Standard 2006 by 50 or less is preferable.

Zeolite component (D) used in the present invention is a component that gives warming sensation to the skin by hydration heat during use, commonly _{Me 2 / xO · Al 2 O} 3 · mSiO 2 · nH 2 O (Me : X
In addition to those produced by ordinary methods, those subjected to special treatment such as ion exchange treatment can be used. The average particle size of zeolite is preferably 0.1 to 100 μm from the viewpoint of heat generation rate, usability and the like.

Since the oil-in-polyhydric alcohol composition of the present invention is excellent in spreading and warming effects, the effects of the present invention are more easily exhibited when used in cosmetics applied to the skin. Among the cosmetics, when used in massage cosmetics and warm cosmetics, the effect is further exhibited.

The content of component (C) used in the present invention and the total content of component (A) and component (B) are:
The mass ratio is in the range of (C) / ((A) + (B)) = 6/4 to 3/7. When this ratio is satisfied, the emulsion stability is excellent and the spread is good. From this ratio, when the total content of the component (A) and the component (B) is increased, the components are separated, and when the component (C) is increased from this ratio, the phase tends to invert to the polyhydric alcohol type in oil.

Further, when the component (D) zeolite is contained, when the zeolite content is X mass% (hereinafter abbreviated as “%”), the mass ratio (C) / ((A) + (B) ) = (60-1.
4X) / (40 + 0.4X) to (30-0.2X) / (70-0.8X),
At this ratio, the emulsification stability is excellent and the spread is good and the warm feeling effect is high. From this ratio, the component (A) and the component (B) are separated when the total content increases, and from this ratio, the component (C
) Tends to invert to the polyhydric alcohol type in oil.

The oil-in-polyhydric alcohol composition of the present invention preferably contains substantially no gelling agent other than (B), a surfactant, and water. Further, in the present invention, “substantially does not contain a gelling agent other than (B) and a surfactant” does not contain at all or contains an amount that does not sufficiently exhibit the effect. The phrase “substantially does not contain water” means that water other than water contained in a minute amount in the raw material and water mixed during production is not contained.

The oil-in-polyhydric alcohol composition of the present invention may be used alone or in combination with other components, and can be used as a skin external preparation or cosmetic.

The warm sensation cosmetic in the present invention is a cosmetic that feels warmth due to the heat of hydration of the ingredients when applied to the skin.

In the oil-in-polyhydric composition of the present invention, in addition to the above components, components usually used in cosmetics such as powder, oil gelling agent, aqueous component, polymer, antioxidant, antibacterial agent Agents, ultraviolet absorbers, film forming agents, preservatives, vitamins, cosmetic ingredients, fragrances, and the like can be appropriately blended within a range that does not impair the effects of the present invention.

The oil-in-polyhydric alcohol composition of the present invention is liquid to paste-like and can be applied to moisturizing and whitening cosmetic liquids, packs, creams, massage creams, and the like.

  EXAMPLES Next, although an Example is given and this invention is further demonstrated, this invention is not limited at all.

Examples 1 to 21 and Comparative Examples 1 to 26: Oil-in-polyol composition in polyhydric alcohol Oil-in-polyhydric alcohol compositions having the compositions shown in Tables 1 to 7 were prepared by the following production method. For each item of “unification of emulsified droplets at high temperature”, “goodness of spreading”, and “warmth effect”, the evaluation method and determination criteria shown below are evaluated and determined, and the results are also shown in Tables 1 to 7, It was shown in FIG.

Note 1: PALMERA G 9091 (manufactured by PALM OLEO)
Note 2: AEROSIL R-976S (Nippon Aerosil Co., Ltd.)
Note 3: AEROSIL R-972S (Nippon Aerosil Co., Ltd.)
Note 4: AEROSIL 200 (Nippon Aerosil Co., Ltd.)
Note 5: AEROSIL 380S (Nippon Aerosil Co., Ltd.)
Note 6: Zeorum A-3 100 # (manufactured by Tosoh Zeorum)
Note 7: TIO (Nisshin Oillio Co., Ltd.)
Note 8: UVINUL MC80 (BASF)
Note 9: Super Nucoa H (manufactured by NOF Corporation)
Note 10: Rice salad oil (manufactured by Tsukino Food Industry Co., Ltd.)
Note 11: Cosmall 44V (Nisshin Oillio Group)
Note 12: CLEARBRIGHT E-81S (manufactured by NOF Corporation)
Note 13: Saracos 6318V (Nisshin Oilio Co., Ltd.)
Note 14: Saracos 913 (Nisshin Oilio Co., Ltd.)
Note 15: Cosmall 41V (Nisshin Oillio Group)
Note 16: Technol MH (manufactured by Yokoseki Yushi Co., Ltd.)
Note 17: Isostearic acid EX (manufactured by Higher Alcohol Industry)
Note 18: Cosmall 42V (Nisshin Oillio Group)
Note 19: Cosmall 222 (Nisshin Oillio Group)
Note 20: Cosmall 43V (Nisshin Oillio Group)
Note 21: KIS-1010 (Sakamoto Pharmaceutical Co., Ltd.)
Note 22: CRODAMOL OO-V (manufactured by Croda)
Note 23: Refined jojoba oil (manufactured by Higher Alcohol Industry)
Note 24: SQUALANE (manufactured by Kishimoto Special Liver Oil Industry Co., Ltd.)
Note 25: High call K-350 (manufactured by Kaneda)
Note 26: High call K-230 (manufactured by Kaneda)
Note 27: Silicon KF-96A (6CS) (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A: Components 1 to 6 are mixed uniformly and dispersed with three rollers.
B: Components 7 to 27 mixed uniformly were added to A and emulsified with a desktop despa to obtain an oil-in-polyhydric alcohol composition.

[Evaluation item 1: Separation at high temperature]
Filling glass standard bottles with the oil-in-polyhydric composition of Examples and Comparative Examples and observing the degree of separation (separation rate) of the “high temperature separation” of one month stored at 50 ° C. Evaluation was made based on the evaluation criteria.

Separation rate = (height of separated phase ÷ height of packed phase) × 100

Evaluation criteria (separation rate):
[Score result]: [Judgment]
Less than 2%: ◎
2% to less than 4%: ○
4% or more and less than 10%: △
10% or more: ×

[Evaluation item 2: coalescence of emulsified droplets at high temperature]
Fill the glass standard bottle with the oil-in-polyhydric composition of Examples and Comparative Examples, and observe the average particle size of the emulsified droplets stored for 1 month at 50 ° C. for “union of emulsified droplets at high temperature”. Then, the following particle size change rate was obtained and evaluated according to the following evaluation criteria. The average particle size was measured by applying each sample to a slide glass, visually observing the particles using a microscope BX51-P (manufactured by OLYMPUS), and calculating the average particle size.

Change rate of particle size = (average particle diameter of products stored at 50 ° C. for one month ÷ average particle diameter immediately after preparation) × 100

Evaluation criteria (particle size change rate):
[Score result]: [Judgment]
Less than 150%: ◎
150% to less than 200%: ○
200% to less than 300%: △
300% or more: ×

[Evaluation Item 3: Good Elongation], [Evaluation Item 4: Warm Effect]
Ten panelists specializing in cosmetics evaluation use the oil-in-polyhydric alcohol compositions of the examples and comparative examples on their entire faces, and each of them has the following evaluation criteria for “goodness of spreading” and “warmth effect” In accordance with the following criteria, the average score of all panels was determined according to the following criteria.

Evaluation criteria:
[Evaluation Result]: [Score]
Very good: 5 points Good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point

Judgment criteria:
[Average score]: [Judgment]
4.5 or more: ◎
3.5 or more and less than 4.5: ○
1.5 or more and less than 3.5: △
Less than 1.5: ×

As is apparent from the results of Tables 1 to 7 and FIG. 1, Examples 1 to 8 of the present invention containing no component (D) were “separation at high temperature” and “union of emulsified droplets at high temperature”. The oil-in-polyhydric alcohol composition was excellent in all items of “extended and spread”.
In addition, the products 9 to 21 of the present invention containing the component (D) are those of “separation at high temperature”, “unification of emulsified droplets at high temperature”, “goodness of spreading”, “warmth effect”. It was a polyhydric alcohol-in-oil composition excellent in all items.
On the other hand, in Comparative Example 1 in which the mass ratio (A) / (B) of the content of component (A) and the content of (B) is 57.0 and there are few anhydrous silicas, “separation at high temperature”, “ In Comparative Example 2 in which (A) / (B) is 8.1 and a large amount of anhydrous silica is present, the anhydrous silica is dispersed in addition to the emulsified interface and the viscosity is increased. Became heavier and was particularly inferior in “goodness of extension”.
Further, when the content of the zeolite of the component (D) is X%, the ratio of the content of the component (C) and the total content of the component (A) and the component (B) is (C) / ((A) + Comparative Example 3 in which the ratio of component (C) is small from the range of (B)) from (60-1.4X) / (40 + 0.4X) to (30-0.2X) / (70-0.8X), 6, 8, and 11 had a tendency to separate, while Comparative Examples 4, 7, 9, 10, and 12 with a large proportion of component (C) tended to phase-invert to the polyhydric alcohol type in oil .
Further, in place of the specific anhydrous silica of component (B), Comparative Example 5 using an anhydrous silica that has not been hydrophobized and has a BET surface area of greater than 300 m ² / g has high hydrophilicity, and therefore has an interface. Dispersed in glycerin without orientation, it works as a gelling agent of glycerin only, and is inferior to all items of "high temperature separation", "high temperature emulsified droplet coalescence" and "good elongation" It was a thing.
Further, in place of the specific oil agent of component (C), in Comparative Examples 14 to 26 in which an oil agent whose average IOB is not in the range of 0.1 to 0.4, or an oil agent having a hydroxyl group or a carboxyl group in the molecule is blended. Neither was good in “separation at high temperature” and “union of emulsified droplets at high temperature”. When an oil agent having an average IOB greater than 0.4 or an oil agent having a hydroxyl group or a carboxyl group in the molecule is used, the emulsion has a tendency to be compatible with glycerin because of its high hydrophilicity, Conversely, when an oil agent with an IOB of less than 0.1 is used, the anhydrous silica of the component (B) present at the interface between the oil and the polyhydric alcohol collects in the oil phase and aggregates to cause coalescence. There was a tendency for emulsification to become impossible.

Example 22: Massage cosmetic (ingredient) (%)
1. Glycerin (Note 1) 50
2. Hydrophobic anhydrous silica (Note 2) 4
3. Glyceryl tri-2-ethylhexanoate (Note 7) 35
4). Diglyceryl tetraisostearate (Note 11) 10.9
5. Fragrance 0.1

(Production method)
A: Components 1 and 2 are mixed uniformly and dispersed with three rollers.
B: Ingredients 3 to 5 that were uniformly mixed were added to A and emulsified with a desktop despa to obtain a massage cosmetic.

The massage cosmetics of Example 22 are “separation at high temperature”, “union of emulsified droplets at high temperature”, “
It was an excellent massage cosmetic for all items of “goodness of extension”.

Example 23: Warm cosmetic (component) (%)
1. Glycerin (Note 1) 50
2. Hydrophobic anhydrous silica (Note 2) 5
3. Zeolite (Note 6) 20
4). Rice bran oil (Note 10) 20
5. Ethyl oleate (Note 12) 5

(Production method)
A: Components 1 to 3 are mixed uniformly and dispersed with three rollers.
B: Ingredients 4 and 5 mixed uniformly were added to A and emulsified with a desktop despa to obtain a warm cosmetic.

The warm cosmetics of Example 23 are “separation at high temperature”, “union of emulsified droplets at high temperature”, “
It was a warm sensation cosmetic that was excellent in all the items of “goodness of spreading” and “warm sensation effect”.

Claims (6)

The following components (A) to (C);
(A) Hydrophobized anhydrous silica having an average primary particle size of 100 nm or less and / or hydrophilic anhydrous silica (C) hydroxyl group having an average primary particle size of 100 nm or less and a BET specific surface area of 300 m ² / g or less average IOB having no carboxyl groups in the molecule contains a oil component is 0.1 to 0.4, does not contain a surfactant and zeolite satisfy the following condition (1) and (2) An oil-in-polyhydric alcohol composition characterized by the above.
(1) Content of component (A) and content of component (B) in mass ratio (A) / (B) = 50 to 10 (2) Content of component (C) and component (A) And the total content of component (B) is in the mass ratio (C) / ((A) + (B)) = range of 6/4 to 3/7 The following components (A) to (D);
(A) Hydrophobized anhydrous silica having an average primary particle size of 100 nm or less and / or hydrophilic anhydrous silica (C) hydroxyl group having an average primary particle size of 100 nm or less and a BET specific surface area of 300 m ² / g or less An oily component (D) zeolite having an average IOB having no carboxyl group in the molecule of 0.1 to 0.4 is 25% by mass or less (provided that the total oil-in-polyhydric composition is 100% by mass).
A polyhydric alcohol-in-oil composition characterized by satisfying the following conditions (3) and (4).
(3) The content of the component (A) and the content of the component (B) are mass ratios (A) / (B) = 50 to
The range of 10 (4) The content of component (D) is X mass%, and the content of component (C) and the total content of component (A) and component (B) are (C) / (( A) + (B)) = (60−1.4X) / (40 + 0.4X) to (30−0.2X) / (70−0.8X)   The oil-in-polyhydric alcohol composition according to claim 1 or 2, wherein the oil-in-polyhydric alcohol composition is a massage cosmetic.   The oil-in-polyhydric alcohol composition according to any one of claims 1 to 3, wherein the oil-in-polyhydric alcohol composition is a warm cosmetic.   The oil-in-polyhydric alcohol composition according to any one of claims 1 to 4, wherein the oil-in-polyhydric alcohol composition does not contain a gelling agent other than the component (B).   The polyhydric alcohol-in-oil composition according to any one of claims 1 to 5, wherein the polyhydric alcohol-in-oil composition does not contain water.