JP4902243B2 - Oil-in-water emulsified cosmetic - Google Patents

Description

  The present invention relates to an oil-in-water emulsified cosmetic comprising a specific phospholipid and a specific ester compound. More specifically, the oil-in-water emulsified cosmetic has a good feeling of use without stickiness, is excellent in moisturizing effect and its sustainability, and is stable over time. The present invention relates to an excellent oil-in-water emulsified cosmetic.

When the barrier function and water retention function of the stratum corneum are reduced by various internal factors or external factors, various skin troubles such as promoting rough skin and aging are caused. In order to improve such troubles, many cosmetics that supplement the skin with moisture have been put on the market. As an emulsifier for such a cosmetic, an emulsified cosmetic (without lotion) that uses a phospholipid and has excellent moisturizing effect and stability over time is disclosed (for example, see Patent Document 1). By combining phospholipids and other ingredients, cosmetics (skin lotion, beauty serum) excellent in emollient feeling and moisturizing effect can be obtained (for example, refer to Patent Document 2), lotions containing phospholipids, etc. In cosmetics, it is disclosed that a fine feeling of use is obtained and storage stability is improved by making the particle size fine (see, for example, Patent Documents 3 and 4).
On the other hand, oils and fats that have functions to increase flexibility, lubricity, gloss, or to form a hydrophobic film on the skin surface, to prevent invasion of harmful substances and moisture evaporation, and to promote percutaneous absorption of active ingredients. Among them, in recent years, dimer acid and dimer diol derivatives are effective as moisturizers because of their high moisturizing power and durability, stability, and safety. Creams and the like have been proposed (see, for example, Patent Documents 5, 6, and 7). Furthermore, an emulsion and cream containing phospholipid and dimer diol are also disclosed (for example, see Patent Document 8).
Japanese Patent Laid-Open No. 2002-284737 JP 2002-255730 A JP-A-6-24999 JP 2004-269502 A JP 2003-313149 A JP 2001-199937 A JP 2001-72530 A JP 2002-275024 A

However, the cosmetics containing phospholipids and the like as shown in Patent Documents 1, 3, and 4 cannot be said to be sufficient in terms of the durability of the moisturizing effect. However, cosmetics in which phospholipids and other moisturizing agents are combined have the disadvantage that stickiness is caused by other components and that formulation is required. In addition, the cosmetics containing dimer diol derivatives and dimer diol derivatives disclosed in Patent Documents 5 to 7 have a drawback in that when applied to the skin, particularly when the application is completed, stickiness with a sense of incongruity occurs and the feeling of use is impaired. Had.
On the other hand, when a large amount of solid oil or paste oil is blended in cosmetics in anticipation of a moisturizing effect, aggregation of emulsion droplets, coalescence, crystal precipitation, etc. are likely to occur, and it is difficult to ensure stability over time. In particular, in a low-viscosity dosage form such as lotion, this phenomenon is remarkable, and it is difficult to ensure stability over time, and it is necessary to adopt a stabilization method as shown in Patent Document 4.

  For this reason, it has an excellent moisturizing effect and its durability regardless of the viscosity of the composition, and can be easily added to the preparation, has a good feeling of use, and has excellent stability over time. Development of oil-in-water emulsified cosmetics, particularly low-viscosity oil-in-water emulsified cosmetics, has been desired.

  In such a situation, the present inventors have intensively studied, and as a result, contain a compound in which the carboxyl groups at both ends of the oligomeric ester of phospholipid and a specific ester compound, dimer acid and dimer diol, are esterified with isostearyl alcohol. The oil-in-water emulsified cosmetic to solve the above-mentioned problems has led to the completion of the present invention. Furthermore, by setting the average particle size of the emulsified droplets to 0.05 to 5 μm, the permeability to the skin was improved, the moisturizing effect was maintained, and a cosmetic with good temporal stability was obtained. Furthermore, even with a low viscosity of less than 5000 mPa · s at 30 ° C., we developed a cosmetic that has good stability over time, has a very high moisturizing effect and its sustainability, and does not feel sticky. It came to do.

That is, the present invention includes the following components (a) and (b):
(A) Phospholipid (b) Compound R3OCO-R1-(-COO-R2-OCO) obtained by esterifying carboxyl groups at both ends of oligomeric ester of dimer acid and dimer diol represented by the following chemical formula (1) with isostearyl alcohol -R1-) n-COOR3 (1)
(In the formula, R ¹ represents a dimer acid residue, R ² represents a dimer diol residue, R ³ represents an isostearyl alcohol residue, and n represents a number of 4 to 6.)
An oil-in-water emulsified cosmetic is provided.
Furthermore, an oil-in-water emulsified cosmetic with an average particle diameter of emulsified droplets of 0.05 to 5 μm is provided, and an oil-in-water emulsified cosmetic with a viscosity at 30 ° C. of 5000 mPa · s or less is also provided. It is to provide.

  The oil-in-water emulsified cosmetic of the present invention is excellent in moisturizing effect, its durability, and feeling of use, and is excellent in stability over time.

  The component (a) phospholipid used in the present invention functions as an emulsifier in the oil-in-water emulsion cosmetic of the present invention, and any phospholipid used in normal cosmetics is used. be able to. Specifically, soybean-derived phospholipid, soybean-derived hydrogenated phospholipid, soybean-derived lysophospholipid, soybean-derived hydrogenated lysophospholipid, egg yolk-derived phospholipid, egg yolk-derived hydrogenated phospholipid, egg yolk-derived lysophospholipid, egg yolk-derived hydrogenated Examples thereof include lysophospholipids, and one or more of them can be used. Soybean-derived hydrogenated phospholipid, soybean-derived hydrogenated lysophospholipid, egg yolk-derived hydrogenated phospholipid, and egg yolk-derived hydrogenated lysophospholipid are preferred.

  In the oil-in-water emulsified cosmetic of the present invention, the blending amount of the component (a) phospholipid is preferably 0.01 to 5% by mass (hereinafter simply referred to as “%”), more preferably 0.1 to 3%. preferable. If it is this range, the favorable thing excellent in the moisturizing effect and the emulsion stability will be obtained.

The compound obtained by esterifying the carboxyl groups at both ends of the oligomeric ester of the dimer acid and dimer diol of component (b) used in the present invention with isostearyl alcohol (hereinafter sometimes simply referred to as “ester compound”), It can be represented by the following general formula (1).
R3OCO-R1-(-COO-R2-OCO-R1-) n-COOR3 (1)
(In the formula, R ¹ represents a dimer acid residue, R ² represents a dimer diol residue, R ³ represents an isostearyl alcohol residue, and n represents a number of 4 to 6.)

The ester compound of component (b) used in the present invention is a compound obtained by esterifying carboxyl groups present at both ends of an oligomer ester obtained from dimer acid and dimer diol with isostearyl alcohol.
Dimer acid, which is a starting material, is obtained by an intermolecular polymerization reaction of unsaturated fatty acid, but is obtained by dimerizing unsaturated fatty acid having 11 to 22 carbon atoms, and mainly a dibasic acid having about 36 carbon atoms. It is an ingredient. The CAS number corresponds to 61788-89-4. Further, in the dimerization reaction, hydrogenated dimer acid obtained by hydrogenating double bonds is preferable. Examples of commercially available products include PRIPOL 1006, 1009, 1015, and 1025 (manufactured by Unikema).
The dimer diol is mainly composed of a diol having about 36 carbon atoms in which the dimer acid and / or lower alcohol ester thereof is hydrogenated in the presence of a catalyst and the carboxylic acid portion of the dimer acid is an alcohol. Examples of commercially available products include PRIPOL 2033 (manufactured by Unikema).
Isostearyl alcohol includes those obtained by reducing fatty acids obtained from dimer acid by-products, those obtained by the garvet method, those obtained by the aldol condensation method, and the like. Things can also be used. Examples of commercially available products include Speziol C18 ISOC (manufactured by Cognis).

Although the manufacturing method of the ester compound of a component (b) is not specifically limited, For example, after esterifying dimer acid and dimer diol and obtaining oligomer ester, it obtains by esterifying a carboxyl group with isostearyl alcohol further. be able to. It can also be obtained by esterifying dimer acid, dimer diol and isostearyl alcohol at once.
In the production of component (b), when an oligomer ester is obtained as an intermediate, the oligomer ester of dimer acid and dimer diol, which is an intermediate, can be obtained by changing the respective feed ratios, The average molecular weight can be adjusted. The range of the charging ratio is preferably 0.4 to 0.9 molar equivalent of dimer diol with respect to 1 molar equivalent of dimer acid. Furthermore, when esterifying with isostearyl alcohol, it is preferable that it is 0.8-1.5 mol with respect to the remaining carboxyl group.

  The conditions for the esterification reaction for obtaining the ester compound of component (b) are not particularly limited, and are carried out by a commonly used method. For example, paratoluenesulfonic acid, sulfuric acid, hydrochloric acid, methanesulfonic acid, boron trifluoride diethyl ether complex or the like is used as a catalyst, and heptane, hexane, cyclohexane, toluene, xylene or the like is used as a solvent at 50 to 260 ° C. be able to. Alternatively, esterification can be carried out at 100 to 260 ° C. even without solvent and without catalyst.

  The ester compound of component (b) preferably has a viscosity at 25 ° C. of 10,000 to 20,000 mPa · s. Examples of such ester compounds include LUSPLAN DA-DD-IS (manufactured by Nippon Seika Co., Ltd.). The viscosity was measured using a cone plate viscometer (ROTO visco1 manufactured by Haake Co.) under the conditions of a shear rate of 100 (1 / s), a cone diameter of 35 mm, and an angle of 2 °.

  0.01-5% is preferable and, as for the compounding quantity of the ester compound of the component (b) in the oil-in-water type emulsion cosmetics of this invention, 0.05-3% is especially preferable. If it is this range, the favorable usability without stickiness and the high moisturizing effect will be acquired, and the favorable thing excellent also in the sustainability of the moisturizing effect will be obtained.

  The oil-in-water emulsified cosmetic of the present invention includes water necessary for making an oil-in-water emulsified cosmetic other than the above essential components, and aqueous components such as glycerin, propylene glycol, 1,3-butylene glycol, and polyethylene glycol. , Hydrocarbons, oil components such as ester oils and fatty acids other than component (b) are blended, and, in addition, components blended in ordinary cosmetics within a qualitative and quantitative range that does not impede the effects of the present invention. That is, alcohols, powders, water-soluble polymers, film-forming agents, surfactants, oil-soluble gelling agents, organically modified clay minerals, resins, UV absorbers, antiseptics, antibacterial agents, perfumes, antioxidants , PH adjusters, chelating agents, and the like can be appropriately blended.

The oil-in-water emulsified cosmetic of the present invention is produced by a conventional method. For example, an aqueous phase composed of an aqueous component and an oil phase composed of an oil component are heated and mixed, and then emulsified, and a polymer, a fragrance and the like are added as appropriate.
The average particle size of the emulsified droplets of the oil-in-water emulsified cosmetic of the present invention produced in this way is not particularly limited, but is 0.05 to 5 μm (measured with a Beckman Coulter Coulter Counter). Those having excellent stability over time are obtained, and those having a stability of 0.1 to 1 μm are preferred because those having even better stability over time are obtained.
Of the oil-in-water emulsified cosmetics of the present invention thus produced, those having a lotion-like dosage form with a viscosity at 30 ° C. of 5000 mPa · s or less have been difficult to achieve in the past. It has excellent moisturizing effect, good usability and stability over time.

  The oil-in-water emulsified cosmetic of the present invention can be exemplified by skin care cosmetics such as skin lotions, milky lotions, creams, beauty essences, massages, packs, hand creams, body creams, etc. As the shape, various forms such as liquid, gel, emulsion, cream, and solid can be selected. In addition, the usage method includes a method of taking an appropriate amount in a normal hand, a method of impregnating a nonwoven fabric, etc. Sheet-like cosmetics that are applied to the skin for use are preferred because they provide a higher effect.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

(Synthesis Example 1)
"Dimer acid dimer diol oligomer ester isostearyl alcohol ester compound"
Hydrogenated dimer acid (PRIPOL 1006: manufactured by Unikema) 200 g (0.348 mol) and dimer diol (PRIPOL 2033: manufactured by Unikema) 132 g (0.243 mol) were charged into a reactor and heated to 210-220 ° C. in a nitrogen stream. Then, the esterification reaction was carried out for 5 hours while distilling off the generated water to obtain 323 g of an intermediate dimer acid dimer diol oligomer ester (dimer acid: dimer diol = 1: 0.7). Furthermore, 307 g of the oligomer ester and 59 g (0.217 mol) of isostearyl alcohol (Speziol C18 ISOC: manufactured by Cognis) were charged into a reactor, heated to 210 to 220 ° C. in a nitrogen stream, and the generated water was distilled off. Then, the esterification reaction was performed for 10 hours to obtain 351 g of the target ester compound. The obtained ester compound had a hue Gardner 2, an acid value of 5.2, a saponification value of 111, a viscosity of 15,000 mPa · s, and a refractive index of 1.48.

Examples 1 to 4 and Comparative Examples 1 to 7: Toner lotion Toner lotions having the composition shown in Table 1 are produced by the following production method. No stickiness) and stability over time were evaluated.
Moreover, about each, the particle size and the viscosity in 30 degreeC were measured.
The particle diameter was measured with a Beckman Coulter Coulter Counter (μm), and the viscosity was filled in a glass bottle with a diameter of 30 mm, left at 30 ° C. for 24 hours, and then a single cylindrical rotational viscometer (Shibaura System Co., Ltd.). Measurement (mPa · s) was performed for 60 seconds.

(Production method)
A: Components 1 to 6 are heated to 70 ° C. and mixed uniformly.
B: Components 7 to 10 and 12 are heated to 70 ° C. and mixed uniformly.
C: B is added to A and emulsified and mixed at 70 ° C., and 11 is added.
D: C was cooled to room temperature to obtain a skin lotion.

(Evaluation methods)
A 15-person expert evaluation panel tested the moisturizing effect as a moisturizing effect, and maintained the moisturizing effect and the feeling of use (no stickiness) in five levels from the following evaluation criteria (i). Further, the average score of the scores was obtained and judged according to the following criteria (b).
The stability over time was set in an incubator at 40 ° C., the state after one month was observed with the naked eye, and judged according to the following criteria (c). The results are also shown in Table 1.
[Evaluation criteria (I)]
5 points: Very good.
4 points: Good.
3 points: Normal.
2 points: Somewhat bad.
1 point: Defect.
[Criteria (b)]
◎: Average point 4.5 points or more ○: Average point 3.5 points or more and less than 4.5 points △: Average point 2.5 points or more and less than 3.5 points ×: Average point less than 2.5 points

[Criteria (C)]
A: No change at all.
○: Slight oil floating is observed.
Δ: Slight oil floating is observed.
X: Separated.

As is apparent from the results in Table 1, Examples 1 to 4 according to the present invention are excellent in moisturizing effect and sustainability, have no stickiness and have a good feeling in use, and are excellent in stability over time. It was a thing.
On the other hand, among Comparative Examples 1 to 4 in which other oils were blended in place of component (b), Comparative Examples 1 to 3 in which the blending amount of component (a) was the same as in Example 2 were all sticky and used. Although the feeling is poor and the moisturizing effect and its sustainability are inferior, Comparative Example 4 containing a large amount of the component (a) has a slightly moisturizing effect and its sustainability, but has a poor sticky feeling and stability over time. It was also inferior. Further, among Comparative Examples 5 to 7 in which component (a) is not blended, Comparative Example 5 in which component (b) is not blended is inferior in all items, and in particular, stability over time is extremely poor. Comparative Example 6 in which the blending amount of component (b) was the same as in Example 2 had a slight moisturizing effect (moist feeling during application), but all other items were inferior. Moreover, Comparative Example 7 containing a large amount of component (b) had a moisturizing effect (moist feeling at the time of application) and stability over time, but had a poor moisturizing effect and poor usability. .

Example 5 Latex (component) (%)
1. Hydrogenated soybean phospholipid 2
2. Glyceryl isooctanoate 5
3. Liquid paraffin 5
4). Ester compound (Note 1) 3
5.1.3 Butylene glycol 10
6). Glycerin 10
7). Xanthan gum 0.2
8). Preservative appropriate amount 9. Perfume appropriate amount 10. Purified water remaining

(Production method)
A: Components 1 to 4 are heated to 70 ° C. and mixed uniformly.
B: Components 5-6, 8 and 10 are heated to 70 ° C. and mixed uniformly.
C: B is added to A and emulsified and mixed at 70 ° C.
D: C was cooled to room temperature, and components 7 and 9 were added and mixed to obtain an emulsion.

  The emulsion of Example 5 was an emulsion that was excellent in the moisturizing effect and its sustainability, had a good feeling of use without stickiness, and had excellent stability over time. Moreover, as a result of measuring similarly to Example 1, the average particle diameter was 2 micrometers and the viscosity was 4000 mPa * s.

Example 6 Cream (ingredient) (%)
1. Egg yolk phospholipids 5
2. Stearic acid 1
3. Cetanol 3
4). Vaseline 1.5
5. Glyceryl isooctanoate 10
6). Liquid paraffin 5
7). Dimethylpolysiloxane 2
8). Phytosterol 1.5
9. Ester compound (Note 1) 5
10.1,3-butylene glycol 10
11. Glycerin 10
12 Sodium lactate 2
13. Xanthan gum 0.4
14 Triethanolamine 0.5
15. Preservative appropriate amount 16. Perfume appropriate amount 17. Purified water remaining

(Production method)
A: Components 1 to 9 are heated to 70 ° C. and mixed uniformly.
B: Components 10 to 15 and 17 are heated to 70 ° C. and mixed uniformly.
C: B is added to A and emulsified and mixed at 70 ° C.
D: C was cooled to room temperature, and component 16 was added and mixed to obtain a cream.

  The cream of Example 6 was a cream having an excellent moisturizing effect and its durability, no stickiness, and excellent stability over time. Moreover, as a result of measuring similarly to Example 1, the average particle diameter was 1.5 micrometers and the viscosity was 50000 mPa * s.

Example 7 Sheet Cosmetics A non-woven sheet (cotton (100%) manufactured by Sansho Paper Co., Ltd., density 50 g / m ² , length 20 cm × width 20 cm) was impregnated with 20 g of the lotion of Example 1, and a PET film A sheet-shaped cosmetic was obtained by hermetically packaging in a package made of the above.
The sheet-form cosmetic of Example 7 was excellent in the moisturizing effect and its durability, had no stickiness and had a good feeling of use.

Claims (2)

The following components (a), (b);
(A) Phospholipid (b) Compound R ³ OCO—R ¹ — (— COO) in which the carboxyl groups at both ends of the oligomeric ester of dimer acid and dimer diol represented by the following general formula (1) are esterified with isostearyl alcohol ^{-R 2 -OCO-R 1 -)} n-COOR 3 ··· (1)
(In the formula, R ¹ represents a dimer acid residue, R ² represents a dimer diol residue, R ³ represents an isostearyl alcohol residue, and n represents a number of 4 to 6.)
And an oil-in-water emulsified cosmetic having a viscosity at 30 ° C. of 5000 mPa · s or less ( excluding those containing a nonionic surfactant or an anionic surfactant ).   The oil-in-water emulsified cosmetic according to claim 1, wherein an average particle diameter of the emulsified droplets is 0.05 to 5 µm.