JP6474744B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

The present invention relates to a water-in-oil cosmetic, and more specifically, in a low-viscosity water-in-oil cosmetic having a viscosity of 10 mPa · s to 20,000 mPa · s, has a high caking-inhibiting effect, and further has good elongation and familiarity. The present invention relates to a water-in-oil cosmetic that is excellent in feeling of use such as no stickiness after use.

Conventionally, water-in-oil (W / O) emulsified cosmetics have a higher affinity for skin compared to oil-in-water (O / W) emulsified cosmetics, preventing moisture transpiration, It has high skin improvement effects such as protection from dryness and imparting treatment effects to the skin, and it is applied to various cosmetics. Above all, water-in-oil emulsified cosmetics adjusted to a low viscosity of 20,000 mPa · s or less are very popular in the market in recent years by improving the weight and stickiness of elongation, which are disadvantages of conventional water-in-oil emulsified products. Has gained popularity. However, low-viscosity water-in-oil emulsified cosmetics have a problem in that the powder tends to agglomerate when the powder is blended, and the agglomerated powder settles (caking phenomenon). In particular, it was very difficult to suppress the caking phenomenon in a high temperature environment or for a long time.

Conventionally, various studies have been made to suppress the caking phenomenon of low-viscosity water-in-oil emulsified cosmetics. For example, technology for hydrophobizing metal oxides by surface treatment with dimethicone / methicone copolymer (Patent Document 1), technology for hydrophobizing powders by surface treatment with specific silicone that reacts with organic groups (Patent Document) 2) etc. are proposed. In addition, an oil-in-water emulsified cosmetic (Patent Document 3) using 10 to 30% by mass of a specific acrylic silicone has been proposed in order to improve the dispersibility of the powder in the oil phase. However, it is complicated to perform surface treatment on all powder raw materials, and it is highly possible that the characteristics of the powder cannot be used effectively if the surface of the powder having a shape such as a porous shape is covered. Moreover, when 10-30 mass% of acrylic silicone is used, the dispersibility of the powder is good, but stickiness peculiar to the acrylic polymer may occur, and there is a problem in terms of usability.
Based on the above, in low-viscosity water-in-oil emulsified cosmetics, the formulation technology that achieves both a good feeling of use such as suppression of caking, good elongation and no stickiness, high safety and stability, There are restrictions on the type, and it has been difficult to achieve by only increasing the amount of surfactants and the surface stabilization technology so far, and further improvements have been required.

Polyoxyethylene dipolyhydroxystearate is a known component that is widely used as an emulsifier capable of preparing a water-in-oil emulsified cosmetic (Non-Patent Document 1).
The silylated peptide / silane compound copolymer is one or more of silylated peptides having two or more hydroxyl groups directly bonded to silicon atoms, and one kind of silane compound that generates two or more hydroxyl groups directly bonded to silicon atoms by hydrolysis. It is a copolymer obtained by polycondensation of the above (Patent Document 4). It is known that the peptide site is hydrophilic, the alkyl group, the silicone site has lipophilic performance, and has surface activity. It is a known component.
However, it has not been disclosed or suggested so far to combine polyoxyethylene dipolyhydroxystearate with a silylated peptide / silane compound copolymer in order to suppress caking when the powder is blended.

JP 2003-95655 A JP 2001-72891 A JP 2005-247722 A JP 2003-104847 A

"FRAGRANCE JOURNAL" September 1999 P83-86

The present invention is a water-in-oil type (W / O type) emulsified cosmetic having a viscosity of 10 mPa · s to 20,000 mPa · s, which has a high caking-inhibiting effect, is light in elongation, has no stickiness, etc. An object of the present invention is to provide an emulsified cosmetic that can achieve satisfactory usability, high safety, and stability over time.

In order to achieve the above object, the present inventors have intensively studied, and as a result, component (A) dipolyhydroxystearate polyoxyethylene and component (B) silylated peptide / silane compound copolymer, component (C) powder. In order to complete the present invention, it has been found that by combining the body, a preparation having a high caking-inhibiting effect can be realized in a preparation having a viscosity of 10 mPa · s to 20,000 mPa · s without impairing safety and feeling of use. It came.

That is, the present invention
The following ingredients,
(A) polyoxyethylene dipolyhydroxystearate (B) silylated peptide / silane compound copolymer (C): oil containing powder and having a viscosity range at 20 ° C. of 10 mPa · s to 20,000 mPa · s A water-in-water emulsified cosmetic is provided.

According to the present invention, it is a low-viscosity water-in-oil emulsified cosmetic having a viscosity of 10 mPa · s to 20,000 mPa · s in a 20 ° C. environment, has a high caking inhibiting effect, has good elongation, and is not sticky. A preparation having a feeling of use and high safety can be provided.

  Hereinafter, the present invention will be described in more detail.

  The component (A) used in the present invention is widely used as an emulsifier capable of preparing a water-in-oil emulsified cosmetic. The polyoxyethylene dipolyhydroxystearate of component (A) is prepared by reacting acid chloride prepared by reacting poly (12-hydroxystearic acid) with a halogenating agent such as thionyl chloride and polyethylene glycol in the presence of an alkali. Can be obtained. Some of such polyoxyethylene dipolyhydroxystearates are already commercially available, and such commercially available products can also be used in the present invention. Among such commercially available products, specifically, “CITHROL DPHS” commercially available from Croda Japan is mentioned. This is a diester of poly (12-hydroxystearic acid) of polyethylene glycol (degree of polymerization 30).

Although the compounding quantity of the component (A) used for this invention is not specifically limited, 0.01%-5.0% are preferable and 0.1%-3% are preferable. In this range, the stability over time is very good.

  Component (B) used in the present invention is a copolymer synthesized by condensing a silylated peptide and a silane compound in an aqueous solution. It has the characteristics that a peptide site | part shows hydrophilic property and an alkyl group and a silicone part show lipophilicity. Although it is difficult to obtain a stable emulsifying ability with a low surface active ability with this component alone, in the present invention, a very good caking inhibiting effect was found by chance when combined with the component (A). A commercial item can be used as a silylated peptide / silane compound copolymer of a component (B). Commercially available products from Seiwa Kasei Co., Ltd. “Protecil W / O ((hydrolyzed silk / PGpropylmethylsilanediol) crosspolymer)” “Protecil FN ((hydrolyzed silk / PGpropylmethylsilanediol) crosspolymer) ”,“ Protecil LH ((hydrolyzed silk / PGpropylmethylsilanediol) crosspolymer) ”,“ Protecil ULH ((trimethylsilylhydrolyzed collagen / PGpropylmethylsilanediol) crosspolymer) ”, etc. Is mentioned. In particular, the (hydrolyzed silk / PGpropylmethylsilanediol) crosspolymer showed good stability when combined with component (A). A component (B) can also contain 1 type in the water-in-oil emulsion cosmetics of this invention, and can also contain it in combination of 2 or more type.

Although the compounding quantity of the component (B) used for this invention is not specifically limited, 0.1%-3% are preferable. Furthermore, 0.4% to 2% is preferable from the viewpoint of stability over time. Within this range, the caking inhibiting effect and the feeling of use are very good.

Component (C) “powder” in the present invention is generally used as a component of cosmetics, and includes white and colored pigments, ultraviolet scattering agents, and extender pigments. White pigments and colored pigments are used for coloring cosmetics, while extender pigments are used for improving the feel of cosmetics, and can be used without any particular limitation. One type or two or more types of powders can be blended.

  The shape of the powder (spherical, rod-like, needle-like, plate-like, irregular shape, spindle shape, etc.) and particle structure (porous, nonporous, etc.) are not limited in any way, but the average primary particle diameter Is more preferably in the range of 1 μm to 50 μm. In addition, the average particle diameter of the powder particles is measured by a particle size distribution measuring device using a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, measurement is performed with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.) using ethanol as a dispersion medium.

  Examples of the powder include inorganic powder, organic powder, surfactant metal salt powder (metal soap), colored pigment, pearl pigment, metal powder pigment, and the like. In addition, it is also possible to use a material obtained by coating with a silicone resin or the like, or by combining two or more types. Specifically, as the inorganic powder, titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, Muscovite, synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, sodium silicate, sodium magnesium silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate Barium silicate, strontium silicate, metal tungstate, hydroxyapatite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, etc .; organic powders include polyamide powder, polyester powder, Ethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate powder, cellulose powder, silk powder, nylon powder, 12 nylon, 6 nylon, silicone powder, spherical Silicone rubber powder, polymethylsilsesquioxane spherical powder, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, acrylic resin, epoxy resin, polycarbonate resin , Fiber powder, lauroyl lysine, etc .; surfactant metal salt powders include zinc stearate, aluminum stearate, calcium stearate , Magnesium stearate, zinc myristate, magnesium myristate, zinc palmitate, zinc laurate, zinc cetyl phosphate, calcium cetyl phosphate, sodium cetyl phosphate, etc .; Colored pigments include bengara, iron oxide, iron titanate, yellow Iron oxide, ocher, black iron oxide, carbon black, manganese violet, cobalt violet, chromium hydroxide, chromium oxide, cobalt oxide, cobalt titanate, bitumen, ultramarine, red No. 3, red 104, red 106, red 201 No., Red 202, Red 204, Red 205, Red 220, Red 226, Red 227, Red 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, yellow 203, yellow 204, yellow 401, blue 1 Color No. 201, Blue No. 404, Green No. 3, Green No. 201, Orange No. 201, Orange No. 203, Orange No. 204, etc .; As pearl pigments, titanium oxide coated mica, mica titanium, iron oxide treated mica titanium , Titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, fish scale foil, titanium oxide coated colored mica, etc .; metal powder pigments include metal powders such as aluminum, gold, silver and platinum Can be mentioned.

Although the compounding quantity of the component (C) used for this invention is not specifically limited, 0.1%-10% are preferable. Furthermore, 3 to 6% is preferable from the viewpoint of stability over time. In this range, the stability over time and the feeling in use are very good.

The water-in-oil emulsified cosmetic of the present invention can further contain an aqueous solvent that can be usually blended in cosmetics. The aqueous solvent in the present specification means alcohols having 1 to 3 hydroxyl groups, and particularly those having a solubility in 100 g of water at 20 ° C. of 10 g or more. In the present specification, water is not included when it is described as an aqueous solvent. Specific examples of such an aqueous solvent include lower alcohols such as ethanol and 2-propanol, and polyhydric alcohols such as glycerin, 1,3-butylene glycol, dipropylene glycol, propylene glycol, and sorbitol. These may be used alone or in combination of two or more. In addition, what is described as 1,3-BG in this specification means 1,3-butylene glycol.

In the water-in-oil emulsified cosmetic of the present invention, the blending amount of the aqueous solvent is not particularly limited, but the stability is good when the total of water and the aqueous solvent is 15% or more and 80% or less.

In addition to the above components, the water-in-oil emulsified cosmetic of the present invention can be blended with components generally used in cosmetics and the like as necessary. For example, as oily components, hydrocarbons, fats and oils, waxes, hardened oils, regardless of the origin, such as animal oils, vegetable oils, synthetic oils, and properties such as solid oils, semi-solid oils, liquid oils, volatile oils, etc. And oil agents such as fatty acids, higher alcohols, silicone oils, fluorine oils, lanolin derivatives and the like. Examples of the water-soluble component include polysaccharides and water-soluble polymers in addition to the aqueous solvent. These components may be used alone or in combination of two or more.

Regarding the water-in-oil type emulsified cosmetic of the present invention, the viscosity is measured using a B-type viscometer: VISCOMETER TVB-10M (manufactured by Tokyo Keiki Co., Ltd., measurement conditions: rotor, rotation speed, and measurement time are changed according to the viscosity) Was used. The rotor measured the value of the measurement time of 60 seconds with the rotation number of 6-30 rpm suitably using TM2 and TM3 rotor according to the viscosity range of the sample.

The present invention will be further described with reference to the following examples. However, these examples do not limit the present invention. In Tables 1 and 2, the blending amounts are displayed so that the total amount of the water-in-oil emulsified cosmetic is 100%. The numerical values of the amounts are all mass%.

The effect was measured by the following evaluation method.
[Emulsification stability evaluation method]
Each sample was filled in a container, allowed to stand at 40 ° C. for 1 month, and then checked visually or with an optical microscope.
[Emulsification stability evaluation criteria]
A: Very good (no separation)
○: Good (produces fine droplets that are difficult to distinguish visually)
Δ: Slightly bad (slight separation occurs)
×: bad (separation occurs, there is a problem as a preparation)

[Evaluation method for good elongation]
Each sample 0.1g was apply | coated on skin and sensory evaluation was performed and evaluated.

[Evaluation criteria for good growth]
◎: Very good ○: Good △: Somewhat bad ×: Bad

[Evaluation method for stickiness]
Each sample 0.1g was apply | coated on skin and sensory evaluation was performed and evaluated.

[Evaluation criteria for stickiness]
◎: Very little ○: Less △: Slightly more ×: Many

[Caking evaluation method]
Each sample was allowed to stand in an 80 ml PET container at 5 ° C. for 1 month, and the bottom was confirmed visually or with a microscope. When caking occurred, the redispersibility when the sample was shaken by hand 10 times in a container was evaluated.

[Caking evaluation criteria]
A: Very good (no caking)
○: Good (secondary particle formation is observed to the extent that visual discrimination is difficult, but there is no problem in quality)
Δ: Slightly bad (caking occurs but can be redispersed by shaking)
×: Poor (caking occurs and cannot be redispersed by shaking)

[Measurement of viscosity at the completion of preparation]
After each sample was prepared, it was allowed to stand for 20 hours in a 20 ° C. environment, and the viscosity was measured. Viscosity measurement uses a B-type viscometer: VISCOMETER TVB-10M, and shows a measurement value of 60 seconds with a TM2 and TM3 rotor, 6 to 30 rpm.

The table of evaluation results is shown below.

Water-in-oil emulsified cosmetics of Examples 1 to 15 and Comparative Examples 1 to 6 having the compositions shown in Tables 1 and 2 were prepared by a conventional method.

As is clear from the examples, the water-in-oil emulsified cosmetics using the ingredients of the present invention do not cause powder caking, but as shown in the comparative examples, caking occurs in formulations that are not of the constitution of the present invention. . In addition, all of the examples had good stability and showed an excellent feeling of use.

In Comparative Examples 1 to 4 and 6 that do not contain the component (A) and Comparative Examples 3 to 5 that do not contain the component (B), the emulsified state was poor, causing problems in stability, and caking occurred. Further, as in Examples 13 and 14, the water-in-oil emulsified cosmetics of the present invention tend to improve in viscosity when the amount of water is increased. However, even if the viscosity is increased, the non-stickiness and elongation are maintained. ing. Conversely, as in Example 15, as the amount of oil increases, the viscosity decreases, but stability and caking properties are not deteriorated.

The water-in-oil type emulsified cosmetic of the present invention can be mainly made into emulsion or cream as a dosage form, and can also be used as a spray type.

<Prescription example>
The composition of each prescription was produced by the conventional method. It was confirmed that the effects of the present invention were achieved in any prescription.
<Emulsion>
Ingredient name Compounding amount (%)
Dipolyhydroxystearic acid PEG-30 0.5
(Hydrolyzed silk / PGpropylmethylsilanediol) Crosspolymer 0.8
Hydrogenated polyisobutene 7.0
Cetyl ethylhexanoate 7.0
Preservative 0.2
Dimethicone 0.5
Polymethyl methacrylate 2.0
Cellulose powder 1.0
Purified water 76.0
Na chloride 1.0
1,3-BG 4.0
Total 100

<Emulsion>
Ingredient name Compounding amount (%)
Dipolyhydroxystearic acid PEG-30 3.0
(Hydrolyzed silk / PGpropylmethylsilanediol) Crosspolymer 0.8
Jojoba oil 27.0
Hydrogenated polyisobutene 25.0
Cetyl ethylhexanoate 17.0
Cholesterol 1.2
(Vinyl Dimethicone / Methicon Silsesquioxane) Cross Polymer 3.0
Preservative 0.2
Dimethicone 3.0
Cyclopentasiloxane 4.0
Purified water 10.0
Na chloride 0.8
Glycerin 5.0
Total 100

<Sunscreen emulsion>
Ingredient name Compounding amount (%)
PEG-30 dipolyhydroxystearic acid 0.2
(Hydrolyzed silk / PGpropylmethylsilanediol) Crosspolymer 1.2
UV absorber 15.0
Pentaerythrityl tetraethylhexanoate 10.0
Isododecane 7.0
Caprylyl Methicone 6.0
Cyclopentasiloxane 6.0
(Vinyl Dimethicone / Methicon Silsesquioxane) Cross Polymer 5.0
Preservative 0.2
Purified water 39.1
Na chloride 0.3
1,3-BG 6.0
Glycerin 4.0
Total 100

Claims (3)

Component (A): Polyoxyethylene dipolyhydroxystearate component (B): Silylated peptide / silane compound copolymer component (C): Contains powder, viscosity range at 20 ° C. is 10 mPa · s to 20, 000 mPa · s water-in-oil emulsified cosmetic. However, hair cosmetics are not included.
Component (A): Polyoxyethylene dipolyhydroxystearate component (B): Silylated peptide / silane compound copolymer component (C): Water-in-oil emulsified cosmetic containing powder, the oil A water-in-oil emulsified cosmetic having a viscosity range of 10 mPa · s to 20,000 mPa · s at 20 ° C. containing 15% to 80% of water in the water-in-water emulsified cosmetic. However, hair cosmetics are not included.
Component (A): Polyoxyethylene dipolyhydroxystearate Component (B): Silylated peptide / silane compound copolymer
Component (C): A water-in-oil emulsified cosmetic containing powder, wherein the water-in-oil emulsified cosmetic has a viscosity at 20 ° C. of 15 to 80% in total of water and an aqueous solvent. A water-in-oil emulsified cosmetic with a range of 10 mPa · s to 20,000 mPa · s. However, hair cosmetics are not included.