JP2011001295A - Water-in-oil type emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable water-in-oil type emulsion composition having excellent sense of use without substantially using decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane.SOLUTION: The water-in-oil type emulsion composition contains the following components (1)-(4). The components are as follows: (1) a glycerol fatty acid ester and/or a polyglycerol fatty acid ester; (2) an oil phase which contains oil having viscosity of ≤50 cps at 25°C (hereinafter referred to as low viscosity oil) in an amount of ≥65 mass% of all oil excluding surfactants and does not substantially contains decamethylcyclopentasiloxane and/or octamethylcyclotetrasiloxane; (3) a wax being solid at 25°C and having a melting temperature of ≥60°C; and (4) water phase.

Description

  The present invention relates to an external composition that can be used in cosmetics and the like, more specifically, an invention relating to a water-in-oil emulsion composition.

  Decamethylcyclopentasiloxane (D-5) and octamethylcyclotetrasiloxane (D-4), volatile cyclic silicone oils, are used for personal care products such as cosmetics because of their excellent usability and safety to the human body. (For example, Patent Document 1). In particular, it is particularly preferred for makeup cosmetics and sunscreen agents that are light and light and are preferred for non-stickiness. However, formulations using volatile cyclic silicone oils tend to have the same feeling of use. Therefore, in cosmetics that require various feelings of use, it has been required to develop a base that has a feeling of use different from the formulation using volatile cyclic silicone oil and that is excellent in emulsion stability.

  On the other hand, glycerin fatty acid esters and polyglycerin fatty acid esters are surfactants that have been used in various fields including the cosmetic field for a long time.

JP 2000-219609 A

  The present invention provides a water-in-oil emulsion composition having excellent stability and feeling of use without substantially using the decamethylcyclopentasiloxane (D-5) and octamethylcyclotetrasiloxane (D-4). It is invention which makes it a subject to provide.

  The present inventor has found that the above problems can be solved by providing the following invention.

That is, this invention is invention which provides the water-in-oil type emulsion composition (henceforth the composition of this invention) containing the following component (1)-(4).
(1) Glycerin fatty acid ester and / or polyglycerin fatty acid ester (2) An oil component having a viscosity of 50 cps or less at 25 ° C. (hereinafter also referred to as a low-viscosity oil component) accounts for 65% by mass or more of the total oil component excluding the surfactant. Oil phase and an oil phase substantially free of octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane (3) A wax having a solid form at 25 ° C and a melting point of 60 ° C or higher (4) Aqueous Phase In the composition of the present invention, the low-viscosity oil of item (2) preferably contains one or more selected from the group consisting of the following components (a) to (f).
(A) Volatile alkyl-modified silicone (b) Dodecamethylcyclohexasiloxane (c) Dimethicone (d) Volatile hydrocarbon oil (e) Non-volatile hydrocarbon oil (f) Monovalent with an IOB value of less than 0.3 Carboxylic acid alkyl ester

  In addition, the wax of item (3) that is solid at 25 ° C. and having a melting point of 60 ° C. or higher is preferably a polyethylene wax, and the aqueous phase of item (4) contains a humectant and has a composition. It is preferable to occupy 65% by mass or more of the product.

  It is preferable that the composition of the present invention further contains a hydrophobic powder.

  According to the present invention, the water-in-oil has excellent stability and usability even though the volatile cyclic silicone oils decamethylcyclopentasiloxane (D-5) and octamethylcyclotetrasiloxane (D-4) are not used. A mold emulsion composition is provided.

<Essential ingredients>
(1) Glycerin fatty acid ester and / or polyglycerin fatty acid ester As an emulsifier to be blended in the composition of the present invention, by blending glycerin fatty acid ester and / or polyglycerin fatty acid ester, a high internal water phase can be achieved.

  Examples of the glycerin fatty acid ester include glyceryl monostearate, glyceryl distearate, glyceryl monoisostearate, eicosane diacid behenate, and glyceryl monoisostearate is preferable. These glycerin fatty acid esters can be synthesized by a conventional method, and commercially available products are also provided. For example, as a commercial product of glyceryl monoisostearate, Sunsoft 8004 (manufactured by Taiyo Kagaku Co., Ltd.) can be mentioned.

  Examples of the polyglycerol fatty acid ester include polyglycerol monostearate, polyglycerol monooleate, diglyceryl diisostearate, and diglyceryl diisostearate is preferable. These polyglycerol fatty acid esters can be synthesized by a conventional method, and commercially available products are also provided. For example, as a commercially available product of diglyceryl diisostearate, WOGEL-18DV (manufactured by Matsumoto Pharmaceutical Co., Ltd.) can be mentioned.

  The glycerin fatty acid ester and the polyglycerin fatty acid ester can be blended in the composition of the present invention either individually or in combination of both. 0.5-5 mass% is suitable for the compounding quantity with respect to a composition, Most preferably, it is 1-3 mass%.

(2) Oil phase The oil phase in the present invention is a general term for components excluding the components constituting the aqueous phase described later, and includes all lipophilic components among the powder, surfactants, etc. in addition to oil components. . The oil phase in the composition of the present invention has the following characteristics.

(Exclusion of specific volatile cyclic silicones)
As described above, the oil phase of the composition of the present invention is substantially free of octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane. Here, “substantially not contained” means that, in principle, these volatile cyclic silicones are not blended at all, and even if they are blended, the effects of blending them will affect the composition of the present invention. This means that the amount is such that it does not appear. Specifically, the amount is such that the upper limit is 0.01% by mass of the composition.

(Low viscosity oil)
The blending amount of the low-viscosity oil in the composition of the present invention is 65% by mass or more of the total oil excluding the surfactant, and the low-viscosity oil is one or two of the following components (a) to (f): It is suitable to contain seeds or more.
(A) Volatile alkyl-modified silicone As the volatile alkyl-modified silicone, caprylyl methicone is suitable.
(B) Dodecamethylcyclohexasiloxane (c) Dimethicone (d) Volatile hydrocarbon oil As the volatile hydrocarbon oil, isododecane and isohexadecane are suitable.
(E) Nonvolatile hydrocarbon oil As the non-volatile hydrocarbon oil, liquid paraffin and squalane are suitable.
(F) Monovalent carboxylic acid alkyl ester having an IOB value of less than 0.3

  Suitable examples of the carboxylic acid alkyl ester include 2-ethylhexanoic acid-2-ethylhexyl, isononyl isononanoate, cetyl octoate and the like.

  In addition, the IOB value (abbreviation of Inorganic Organic Balance) is, so to speak, its oil content (meaning oil content in a broad sense), not to mention oil content in a narrow sense such as fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, esters, etc. , An index indicating the degree of polarity of general alcohol, fatty acid, and the like.) A value indicating the ratio of inorganic to organic [an organic value for one carbon atom in the molecule of the oil “20” and “Inorganic value” for one hydroxyl group as 100, values calculated based on the inorganic values of other substituents (inorganic groups) based on this: [(1) Fujita “Organic Analysis” (1930) Kaniya Shoten, (2) “Prediction of Organic Compounds and Organic Conceptual Diagram (Chemistry Domain 11-10)” (1957) 719-725, (3) Fujita and Akatsuka Author “Systematic Organic Qualitative Analysis ( Pp. 487 (1970) Kazama Shoten, (4) Koda, “Organic Conceptual Diagram-Fundamentals and Applications”, page 227 (1984) Sankyo Publishing, (5) Yaguchi, “Emulsion Formulation Design Using Organic Conceptual Diagram” 98 (1985) Nippon Emulsion Co., Ltd. (6) RHEwell, JMHarrison, L. Berg: Ind Eng Chem 36,871 (1944)], specifically, IOB value = inorganic value of the oil / Represented by the organic value of the oil.

  The low-viscosity oil component includes all the oil components having a predetermined viscosity property in addition to the above (a) to (f). Examples thereof include methylphenyl silicone and isostearyl alcohol disclosed in Examples described later.

(3) Wax The wax blended in the composition of the present invention is a solid having a melting point of 25 ° C. and a melting point of 60 ° C. or higher. The wax is not particularly limited as long as it has such properties and is usually used in a composition for external use such as cosmetics, and ester wax such as carnauba wax and candelilla wax; Hydrocarbon waxes such as microcrystalline wax, paraffin wax and polyethylene wax; natural waxes such as rice wax and beeswax can be exemplified, but among these, polyethylene wax is a non-polar wax having a high melting point and a composition at around 50 ° C. This is suitable in that it can prevent an increase in the viscosity of the product.

  The blending amount of the wax is preferably 0.5 to 2% of the composition.

(4) Aqueous phase It is preferable that the aqueous phase accounts for 60% by mass or more of the composition of the present invention in order to increase the ratio of the internal aqueous phase and suppress the sticky feeling and oily feeling due to the oil phase. is there. In addition to water, other water-soluble components can be blended in the aqueous phase. In particular, glycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, polyethylene glycol, sorbitol, lactic acid It is preferable to add a humectant such as sodium or sodium pyrrolidonecarboxylate.

<Selective ingredients>
(1) Hydrophobic powder Hydrophobic powder can be added to the composition of the present invention from the viewpoints of coloring, stabilization of the composition itself, and the like. The hydrophobic powder is itself a powder of a hydrophobic material, for example, nylon powder, polymethacrylic acid powder, polyurethane powder, polyethylene powder, polystyrene powder, methylsiloxane network powder, boron nitride powder, organopolysiloxane elastomer powder Etc. Furthermore, the hydrophobized powder is also in the category of the hydrophobic powder, and the core particles are hydrophobic powder particles of the above-mentioned hydrophobic material, or mica, talc, sericite, kaolin, titanium oxide powder, iron oxide powder, Using conventional methods to prepare hydrophobized powders used in cosmetics as non-hydrophobic powder particles such as zinc oxide powder, mica titanium powder, barium sulfate powder, silica powder, apatite powder, calcium phosphate powder, zeolite powder, etc. For example, higher fatty acids, surfactants (including any of anionic, cationic, and nonionic surfactants), metal soaps, fats and oils, waxes, silicones, fluorine compounds, hydrocarbons The desired hydrophobization treatment is carried out by treating the surface of the powder particles with one or more substances such as dextrin fatty acid ester according to a conventional method. It is possible to prepare the end.

  As the particle diameter of the hydrophobic powder and the hydrophobized powder, those suitable for the specific embodiment of the composition of the present invention can be used, and generally about 0.001 to 100 μm. Is about 0.01 to 50 μm. In addition, the particle shape can be selected according to the specific form of the present powder cosmetic, and those having a particle shape such as a spherical shape, a plate shape, an indefinite shape, and a needle shape can be used. It is.

  And the said hydrophobic powder can contain the 1 type (s) or 2 or more types in the composition of this invention, Although the compounding quantity is not specifically limited, It is about 1-30 mass with respect to a composition. % Is preferred.

(2) Other components In addition to the various components described above, components used in external compositions such as cosmetics, if necessary, within a quantitative or qualitative range that does not extremely impair the effects of the present invention. Can be blended. Specifically, water-soluble components, moisturizers, oils, surfactants, thickeners, various powders, pigments, pH adjusters, UV absorbers (octyl methoxycinnamate, diparamethoxy cinnamon) other than those listed above Acid mono-2-ethylhexanoate glyceryl, 4-t-butyl-4′-methoxydibenzoylmethane, etc.), antifading agents, antifoaming agents, chemicals, fragrances and the like.

<Composition of the present invention>
The composition of this invention can be manufactured by the manufacturing method of a normal water-in-oil type emulsion composition, for example, the emulsifier method in oil, the alternate addition method, etc.

  Further, the dosage form / form of the composition of the present invention is not particularly limited as long as it is a dosage form that can be taken by the water-in-oil emulsion composition, cream, emulsion, gel, essence, pack mask, W / O emulsification. It can be used in mold foundations, lipsticks, blushers, eyebrows, hair cosmetics and the like.

  Examples of the present invention will be described below, but the present invention is not limited thereto. The blending amount is mass% unless otherwise specified.

<Test method>
Disclosed is a test method conducted to verify the effects of the present invention. These tests were not conducted in all test systems, but were appropriately selected according to the properties of the set test systems.

(1) Stability test 2 ml of the test product is put into a 5 ml vial, stoppered, and left at 0 ° C., room temperature (about 25 ° C.), 37 ° C., and 50 ° C. for 2 weeks. The appearance of the test product after the lapse of time was visually observed, and the stability was evaluated. The evaluation criteria were evaluated by using the viscosity change, “separation” in which the liquid component floats on the surface of the base, and the degree of separation, as shown below. The viscosity of the test product was measured using a single-type rotational viscosity viscometer (manufactured by TOKIMEC INC). The sample was kept at 30 ° C., and measurement was performed at 10 rpm using rotor No. 6.

(Evaluation criteria)
A: The change in viscosity at the start and end of the test is less than 20%, and no separation is observed.
○: The change in viscosity at the start and end of the test is less than 20 to 50%, and no separation is observed.
Δ: Viscosity change at start and end of test is 50% or more, and slight separation / separation is observed.
X: Viscosity change at the start and end of the test is 50% or more, and significant separation / separation is observed.

(2) Usability test For 15 female panels, an actual use test was conducted on "lightness of stretch" and "no stickiness" when a test product was applied to the face after washing. The evaluation criteria are as follows.

○: There are more than 12 panelists who answered that the growth was light and there was no stickiness.
Δ: Eight to eleven panel members answered that the elongation was light and there was no stickiness.
X: Less than 7 panelists answered that the growth was light and there was no stickiness.
(3) Hardness test Hardness immediately after preparation of the test article (at the start of the test) and the hardness after standing for 2 weeks at 0 ° C, room temperature (about 25 ° C), 37 ° C, and 50 ° C, At 30 ° C., using a card meter, an 8 mmφ stainless steel needle was entered under a 200 g load and measured.

<Test results, etc.>
(1) Examination of oil content to be blended Among the effects to be exhibited in the present invention, a basic study was conducted as to what kind of oil content the stability was exhibited by selecting. Table 1 shows the formulation used and the results of the stability test. Table 1 also shows the IOB values for each oil.

  In addition, in the test recipe for conducting this examination, in order to clearly grasp the influence on the stability of the oil content, the wax which is an essential component of the composition of the present invention is not blended. In each test example, after the oil and the surfactant were uniformly mixed, water-in-oil emulsification was performed while gradually adding the water phase component using a homogenizer.

  From the results of Table 1, it was revealed that when a monovalent carboxylic acid alkyl ester oil having an IOB of less than 0.3 is used as a main oil component, a relatively stable water-in-oil emulsion composition can be obtained. . On the other hand, it has been clarified that when a highly polar oil having an IOB of 0.3 or more is used as a main oil, the emulsion stability is remarkably lowered.

(2) Examination of the effect of blending wax Next, the test product blended with wax was examined for its effect on usability in combination with stability. As the wax, a rice wax which is a natural wax having a solid form at 25 ° C. and a melting point of 60 ° C. or more was used. In each test example, the oil, wax, hydrophobized powder and surfactant were heated to 85 ° C, mixed uniformly using a homogenizer, and then the aqueous phase component preheated to 85 ° C using the homogenizer was gradually added. Water-in-oil type emulsification while adding to. The mixture was cooled to room temperature while stirring in an ice bath.

  From the results shown in Table 2, it was found that the stability and usability of the system blended with rice wax were good as long as other requirements were met. However, for a system (test example 16) containing dimethicone having a viscosity exceeding 50 cps, a system (test example 20) containing 5% by weight of liquid paraffin, and a system (test example 21) from which caprylyl methicone was removed, There were problems with usability.

(3) Examination of wax suitable for blending Next, the properties (hardness and stability) given to the test product according to the kind of the blended wax were examined (Table 3). The method for producing the test product was in accordance with the example in Table 2.

  From the results of Table 3, in the examples (test examples 26 and 27) using candelilla wax and carnauba wax, which are highly polar ester waxes, separation occurred at 50 ° C., and an obvious problem in stability was recognized. In addition, when paraffin wax was used, the time-lapse hardness of the product stored at 50 ° C. was significantly increased (Test Example 25). This is considered to be because the paraffin wax partially dissolved at 50 ° C., and when the temperature was returned to 30 ° C., the crystal growth of the wax was promoted and the hardness increased. In the example using the microcrystalline wax which is a branched paraffin wax (Test Example 23), the solidification power of the wax was inferior. On the other hand, in the test examples (Test Examples 24 and 28) using non-polar polyethylene wax as all or part of the wax, it is clear that the increase in hardness is suppressed and good results can be obtained. It was.

(4) Examination of amount of wax to be blended Next, a suitable blending amount of polyethylene wax, which was clarified as one of the suitable waxes in the present invention from the results of Table 3, was examined (Table 4). The method for producing the test product was in accordance with the example in Table 2.

  From the results shown in Table 4, when the blending amount of the polyethylene wax exceeds 2% by mass of the composition, the evaluation of the feeling of use deteriorates, and the hardness of the product stored at 50 ° C. increases by about 40% from the initial hardness. On the contrary, when the amount of wax was less than 0.5% by mass, separation / separation was observed at 50 ° C. Therefore, it became clear that the suitable compounding quantity of the wax in the composition of this invention is 0.5-2 mass of a composition.

(5) Disclosure of Typical Formulation Next, Table 5 shows a typical formulation of the composition of the present invention and results of each test. The method for producing the test product was in accordance with the example in Table 2.

  The results of the two examples shown in Table 5 were all good, and it was revealed that good results could be obtained even when diglyceryl diisostearate was used instead of glyceryl monoisostearate.

(6) Formulation example Below, the other formulation example of the composition of this invention is described.
[Prescription Example 1] Sunscreen
Compounding component amount (% by mass)
Glyceryl monoisostearate 2.5
Both ends silicone-modified polyglycerin 1.0
Trimethylsiloxysilicate 0.5
Liquid paraffin 0.5
Octyl methoxycinnamate 5.0
Diparamethoxycinnamic acid mono-2-ethylhexanoic acid glyceryl 0.5
4-t-butyl-4'-methoxydibenzoylmethane 0.1
Caprylyl Methicone 5.0
2-ethylhexyl 2-ethylhexanoate 5.0
Polyethylene wax 0.75
Fatty acid aluminum-treated fine particle titanium oxide 8.0
Spherical PMMA 3.0
Spherical silicone resin powder 2.0
Sodium chloride 1.0
Methylparaben 0.2
Dynamite Glycerin 2.5
1,3-butylene glycol 4.0
Dipropylene glycol 1.0
Ion exchange water

<Manufacturing method>
Oil, wax, hydrophobized powder and surfactant are heated to 85 ° C, mixed uniformly using a homogenizer, and then gradually added with water phase components preheated to 85 ° C using a homogenizer. Perform water-in-water emulsification. The mixture was cooled to room temperature while stirring in an ice bath.

[Prescription Example 2] Sunscreen
Compounding component amount (% by mass)
Glyceryl monoisostearate 2.5
Sorbitan sesquiisostearate 1.0
Trimethylsiloxysilicate 0.5
Liquid paraffin 0.5
Octyl methoxycinnamate 5.0
Diparamethoxycinnamate mono-2-ethylhexanoate glyceryl 0.5
4-t-butyl-4'-methoxydibenzoylmethane 0.1
Caprylyl Methicone 5.0
2-ethylhexyl 2-ethylhexanoate 5.0
Polyethylene wax 0.75
Fatty acid aluminum treated fine particle titanium oxide 3.0
Silicone-treated fine particle zinc oxide 5.0
Spherical PMMA 3.0
Spherical silicone resin powder 2.0
Sodium chloride 1.0
Methylparaben 0.2
Dynamite Glycerin 2.5
Ethyl alcohol 2.0
1,3-butylene glycol 2.0
Dipropylene glycol 1.0
Ion exchange water

<Manufacturing method>
Oil, wax, hydrophobized powder and surfactant are heated to 85 ° C, mixed uniformly using a homogenizer, and then gradually added with water phase components preheated to 85 ° C using a homogenizer. Perform water-in-water emulsification. The mixture was cooled to room temperature while stirring in an ice bath.

[Prescription Example 3] Foundation
Compounding component amount (% by mass)
Glyceryl monoisostearate 2.5
Sorbitan sesquiisostearate 0.5
Trimethylsiloxysilicate 0.5
Liquid paraffin 0.5
Octyl methoxycinnamate 2.0
Caprylyl Methicone 5.0
Dimethicone 1.0
2-ethylhexyl 2-ethylhexanoate 5.0
Polyethylene wax 0.75
Alkyl-modified silicone resin coated yellow iron oxide 2.0
Alkyl modified silicone resin coated bengara 0.5
Alkyl-modified silicone resin-coated black iron oxide 0.1
Alkyl-modified silicone resin-coated silicic acid 1.0
Alkyl-modified silicone resin-coated titanium oxide 10.0
Silicone treatment red interference pearl mica 0.5
Spherical silicone resin powder 2.0
Sodium chloride 1.0
Methylparaben 0.2
Dynamite Glycerin 2.5
Ethyl alcohol 1.0
1,3-butylene glycol 4.0
Ion exchange water

<Manufacturing method>
Oil, wax, hydrophobized powder and surfactant are heated to 85 ° C, mixed uniformly using a homogenizer, and then gradually added with water phase components preheated to 85 ° C using a homogenizer. Perform water-in-water emulsification. The mixture was cooled to room temperature while stirring in an ice bath.

[Prescription Example 3] Foundation
Compounding component amount (% by mass)
Glyceryl monoisostearate 2.5
Sorbitan sesquiisostearate 0.5
Trimethylsiloxysilicate 0.5
Liquid paraffin 0.5
Octyl methoxycinnamate 2.0
Caprylyl Methicone 5.0
Dimethicone 1.0
2-ethylhexyl 2-ethylhexanoate 5.0
Polyethylene wax 0.75
Alkyl-modified silicone resin coated yellow iron oxide 2.0
Alkyl modified silicone resin coated bengara 0.5
Alkyl-modified silicone resin-coated black iron oxide 0.1
Alkyl-modified silicone resin-coated titanium oxide 10.0
Alkyl-modified silicone resin coated sericite 1.0
Silicone treatment red interference pearl mica 0.5
Spherical silicone resin powder 2.0
Sodium chloride 1.0
Methylparaben 0.2
Dynamite Glycerin 2.5
Ethyl alcohol 1.0
1,3-butylene glycol 4.0
Ion exchange water

<Manufacturing method>
Oil, wax, hydrophobized powder and surfactant are heated to 85 ° C, mixed uniformly using a homogenizer, and then gradually added with water phase components preheated to 85 ° C using a homogenizer. Perform water-in-water emulsification. The mixture was cooled to room temperature while stirring in an ice bath.

Claims (5)

A water-in-oil emulsion composition containing the following components (1) to (4).
(1) Glycerin fatty acid ester and / or polyglycerin fatty acid ester (2) The oil component having a viscosity of 50 cps or less at 25 ° C. is an oil phase occupying 65% by mass or more of the total oil content excluding the surfactant, Oil phase substantially free of methylcyclotetrasiloxane and / or decamethylcyclopentasiloxane (3) A wax that is solid at 25 ° C and has a melting point of 60 ° C or higher (4) Aqueous phase The oil-in-water emulsion composition according to claim 1, wherein the oil component having a viscosity of 50 cps or less at 25 ° C contains one or more selected from the group consisting of the following components (a) to (f). .
(A) Volatile alkyl-modified silicone (b) Dodecamethylcyclohexasiloxane (c) Dimethicone (d) Volatile hydrocarbon oil (e) Non-volatile hydrocarbon oil (f) Monovalent with an IOB value of less than 0.3 Carboxylic acid alkyl ester The water-in-oil emulsion composition according to claim 1 or 2, wherein the wax that is solid at 25 ° C and has a melting point of 60 ° C or higher is polyethylene wax. The water-in-oil emulsion composition according to any one of claims 1 to 3, wherein the aqueous phase contains a humectant and occupies 60% by mass or more of the composition. Furthermore, the water-in-oil type emulsion composition in any one of Claims 1-4 containing hydrophobic powder.