JP6679224B2 - W / O / W type emulsion composition - Google Patents

Description

  The present invention relates to a W / O / W type emulsion composition.

Conventionally, as an emulsified cosmetic, an O / W type emulsion composition in which an oil phase is dispersed in an aqueous phase and a W / O type emulsion composition in which an aqueous phase is dispersed in an oil phase have been widely used. However, in recent years, a W / O / W type emulsion composition obtained by further dispersing a W / O type emulsion composition in an aqueous phase has been applied to cosmetics.
The W / O / W type emulsion composition can give a feeling of use different from that of the conventional O / W type emulsion composition and the conventional W / O type emulsion composition.

  For example, Patent Document 1 provides a W / O / W type emulsion composition exhibiting a fresh feeling and stability over time by blending an electrolyte in an inner water phase and an alkyl-modified carboxyvinyl polymer in an outer water phase. It is disclosed that this can be done.

  Further, in Patent Document 2, by containing a polysaccharide derivative having a specific side chain, W / O / which spreads well on the skin and gives a moist feeling, and is not sticky or oily It is disclosed that a W-type emulsion composition can be provided.

  By the way, a technique for imparting a rich feeling in use to an emulsion composition has been proposed. For example, Patent Document 3 describes that an oil-in-water emulsion composition containing an alkyl-modified carboxyvinyl polymer and an oily component that is solid at room temperature is excellent in "feeling of richness in use".

  In Patent Document 4, an emulsifier comprising a complex of a carboxyl group-containing polymer and a polyether compound having a number average molecular weight of less than 6000, which is formed in an aqueous solution whose pH is adjusted to 5 or less, has an emulsified cosmetic composition. It is disclosed that it is possible to impart a rich feel to the water.

  On the other hand, Patent Document 5 describes a gel lotion which has a viscosity by blending a specific amount of a specific thickener, but has good elongation and is not sticky when applied to the skin.

JP, 2002-275029, A JP, 2007-284354, A Japanese Unexamined Patent Publication No. 9-255529 JP, 2007-106678, A JP, 2013-103920, A

  As shown in Patent Documents 3 and 4, it is necessary to add a certain amount or more of a thickening agent such as carboxyvinyl polymer in order to give the emulsified cosmetic body a rich feeling of use. There was a problem that the growth of the rice would become poor.

  Further, as described in Patent Document 5, it has been examined to give a gel-like cosmetic having a viscosity a feeling of use with good elongation by adjusting the composition of a thickener used. With regard to emulsified cosmetics, such a study has never been conducted.

In view of such a situation, the present invention has a rich and dense tactile sensation (body feel) from before application to the skin to the initial stage of application, and as the application proceeds, it spreads lightly on the skin and provides a comfortable feeling of use. An object of the present invention is to provide a W / O / W type emulsion composition having a unique feeling of use (gap feeling) that gives (feeling of good stretchability).
Further, in a preferred embodiment of the present invention, it is an object to provide a W / O / W type emulsion composition having a gap feeling and being less likely to cause stickiness.
Further, in a preferred embodiment of the present invention, it is an object to provide a W / O / W type emulsion composition having a gap feeling and an excellent moisturizing feeling and firmness feeling.
Furthermore, it is an object of a preferred embodiment of the present invention to provide a W / O / W type emulsion composition having a gap feeling and excellent in high temperature stability.

MEANS TO SOLVE THE PROBLEM This invention which solves the said subject WHEREIN: Oscillation measurement by a rheometer, storage elasticity in the stress of 1 Pa when measuring storage elastic modulus G'while increasing stress under conditions of 1 mm of gap, 1 Hz, and 20 degreeC. The rate G ′ is 2000 Pa or more,
The W / O / W type emulsion composition is characterized by containing 15% by mass or more of W / O particles.

  The W / O / W type emulsion composition of the present invention has a rich and dense tactile sensation (body feel) from before application to the skin to the initial stage of application, and spreads lightly on the skin from the middle stage to the final stage of application. It has a unique feeling of giving a comfortable feeling (feeling of stretch), that is, a gap feeling.

In a preferred embodiment of the present invention, the W / O particles have an average particle size of 10 μm or more.
By setting the average particle diameter of the W / O particles within the above range, it is possible to improve the feeling of richness felt before the application to the skin and during the initial stage of the application. In addition, it is possible to improve the feeling of use when the application to the skin is good, from the middle stage to the final stage.
That is, by setting the average particle diameter of the W / O particles within the above range, it is possible to realize a unique feeling of use in which the difference between the feeling of use and the feeling of use with good elongation is large, that is, the feeling of gap is large.

In a preferred embodiment of the present invention, the amount of change in the storage elastic modulus G ′ when the storage elastic modulus G ′ is measured by a rheometer while measuring the oscillation and increasing the stress under the conditions of a gap of 1 mm, 1 Hz and 20 ° C. Satisfies the following conditions (a) and (b).
(A) In the stress range of 1 Pa to 80 Pa, the decrease amount of the storage elastic modulus G ′ is 500 Pa or less. (B) In the stress range of more than 80 Pa, the decrease amount of the storage elastic modulus G ′ with respect to the increase amount of the stress of 100 Pa is There is a range of 2000 Pa or more

  With such a configuration, a W / O / W type emulsion composition having a unique feeling of use, in which the magnitude of the change from a rich feeling to a feeling of good use, that is, a feeling of a gap, can be more significantly felt. You can provide things.

In a preferred aspect of the present invention, the amount of change in the storage elastic modulus G ′ further satisfies the following condition (c).
(C) In the range of stress exceeding 80 Pa, there is a range in which the decrease amount of the storage elastic modulus G ′ with respect to the increase amount of stress is 50 Pa or more.
By providing such a form, it is possible to provide a W / O / W type emulsion composition having a remarkable gap feeling, which is not found in conventional cosmetics, that is, a sharp feeling is rapidly changed to a feeling of good use. can do.

In a preferred embodiment of the present invention, the content of the optionally modified carboxyvinyl polymer is 0.3% by mass or less.
By adopting such a form, it is possible to suppress stickiness from the middle stage to the final stage of application to the skin.

In a preferred embodiment of the present invention, the W / O particles do not contain an electrolyte.
With such a form, stickiness can be suppressed.

In a preferred embodiment of the present invention, the W / O particles contain an organically modified clay mineral.
With such a form, the stability of the W / O / W type emulsion composition can be improved.

Further, in a more preferable aspect of the present invention, the W / O particles contain a silicone-based surfactant.
The stability of the W / O / W type emulsion composition can be improved by adopting a form containing a silicone-based surfactant.

In a preferable embodiment of the present invention, an oil-soluble moisturizing agent is contained.
By providing such a form, a W / O / W type emulsion composition having a comfortable gap feeling of exhibiting a moisturizing feeling and a firmness feeling after changing from a rich feeling to a good feeling of use is provided. be able to.

In a preferred embodiment of the present invention, the outer aqueous phase contains an α-gel formed by a hydrophilic surfactant and a higher alcohol.
With such a form, it is possible to provide a W / O / W type emulsion composition that maintains an excellent gap feeling even after long-term storage at high temperature.

ADVANTAGE OF THE INVENTION According to this invention, W / O / which has a feeling of richness from the time of application to the skin to the initial stage of application, and changes into a feeling of use with good elongation as the application progresses, that is, a feeling of gap excellent in W / O / A W-type emulsion composition can be provided.
Further, in a preferred embodiment of the present invention, it is possible to provide a W / O / W type emulsion composition having a gap feeling and being less likely to cause stickiness.
Further, in a preferred embodiment of the present invention, it is possible to provide a W / O / W type emulsion composition having a gap feeling and a moisturizing feeling and a firm feeling.
Further, in a preferred embodiment of the present invention, it is possible to provide a W / O / W type emulsion composition having a gap feeling and excellent in high temperature stability.

It is a schematic diagram of a W / O / W type emulsion composition. It is a conceptual diagram of the change of storage elastic modulus G'with respect to the increase of stress when measuring storage elastic modulus G ', increasing the stress added with respect to a W / O / W type emulsion composition. For Examples 1 to 3 and Comparative Examples 1 and 2, oscillation measurement was performed using a rheometer, the storage elastic modulus G ′ was measured by changing the stress under the conditions of a gap of 1 mm, 1 Hz, and 20 ° C., and the stress was plotted on the horizontal axis. A graph in which the storage elastic modulus G ′ is plotted on the vertical axis is shown.

The W / O / W type emulsion composition of the present invention is characterized by having a storage elastic modulus G'at a stress of 1 Pa of 2000 Pa or more and containing W / O particles in an amount of 15% by mass or more.
Here, the storage elastic modulus G ′ is a value measured by a rheometer while performing oscillation measurement and increasing stress under conditions of a gap of 1 mm, 1 Hz, and 20 ° C.
Hereinafter, the present invention will be described in more detail.

  In the present invention, the W / O / W type emulsion composition means an emulsion composition in which a W / O type emulsion composition (also referred to as a primary emulsion) is further dispersed in an aqueous phase. The oil droplets that encapsulate the water phase (inner water phase) dispersed in the outermost water phase (outer water phase) in the W / O / W emulsion composition are called W / O particles.

In the present invention, the oil droplets that do not include the aqueous phase may be further dispersed in the external aqueous phase.
Hereinafter, in the present specification, as shown in FIG. 1, the inner water phase is referred to as W1, the outer water phase is referred to as W2, the oil phase containing the water phase is referred to as O1, and the oil phase not containing the water phase is referred to as O2.
Further, in the present specification, a W / O / W type emulsion composition in which oil droplets not containing a water phase are further dispersed in an outer water phase, particularly a (W / O1 + O2) / W type emulsion composition Say.

In the present specification, the "gap feeling" refers to a unique feeling of use that has a rich feeling from before the application to the skin to in the initial stage of the application, and changes to a feeling of use with good elongation as the application progresses.
In addition, the richness is a rich and dense tactile sensation, and the feeling of good stretch is a comfortable feeling of lightly spreading on the skin.
The gap feeling can be evaluated by sensory evaluation. Specifically, it can be evaluated by performing a sensory evaluation on the feeling of richness and the feeling of use with good elongation.
The feeling of gap can also be evaluated using a commercially available rheometer. Specifically, it can be evaluated by measuring the storage elastic modulus G ′ when the stress is changed.

Hereinafter, the W / O / W type emulsion composition of the present invention will be described with reference to FIG. FIG. 2 is a conceptual diagram of changes in the storage elastic modulus G ′ with increasing stress when the storage elastic modulus G ′ is measured while increasing the stress applied to the W / O / W type emulsion composition. Here, the storage elastic modulus G ′ is measured by a rheometer while increasing the stress under conditions of oscillation measurement and a gap of 1 mm, 1 Hz, and 20 ° C.
As shown in FIG. 2, the storage modulus G ′ of the W / O / W type emulsion composition of the present invention is 2000 Pa or more when the stress is 1 Pa. The storage elastic modulus G ′ of the W / O / W type emulsion composition of the present invention is preferably 3000 Pa or more, more preferably 4000 to 10000 Pa when the stress is 1 Pa. That is, the W / O / W type emulsion composition of the present invention is an emulsion composition having a hardness of a certain level or more before being applied to the skin.
In order to adjust the storage elastic modulus G ′ at a stress of 1 Pa within the above range, the viscosity of the outer water phase may be adjusted. The higher the viscosity of the outer water phase, the higher the storage elastic modulus G'at a stress of 1 Pa.
As a method for adjusting the viscosity of the outer water phase, specifically, the concentration of the thickener in the outer water phase is adjusted, and the amount of W / O particles dispersed in the outer water phase or the amount of the oil phase that does not include the water phase. And the formation of α-gel by the higher alcohol and hydrophilic surfactant in the external water phase.
The formation of α-gel in the external water phase will be described in detail later.

By the way, when the W / O / W type emulsion composition is applied to the skin, stress is naturally applied to the composition, and the W / O / W type emulsion composition has a viscoelasticity corresponding to the applied stress. Indicates.
The present inventors have found that the relationship between the stress measured under the above conditions and the storage elastic modulus G ′ indicates the change in feel from the initial stage of application to the final stage of application when the W / O / W type emulsion composition is applied to the skin. I found that it really shows.
Specifically, it has been found that the step of applying a stress up to about 1 to 100 Pa can be assumed to be the stress applied to the W / O / W type emulsion composition in the initial step of application to the skin (FIG. 2). ). Further, the step of applying a stress of more than 80 Pa, for example, a stress of more than 90 Pa or a stress of more than 100 Pa can be assumed to be the stress applied to the W / O / W type emulsion composition after the middle stage of application to the skin. Was found (Fig. 2).
When stress is applied to the W / O / W type emulsion composition of the present invention under the above conditions, the storage elastic modulus G ′ shows a change in stress in a range where the applied stress is relatively small, for example, in the range of about 1 to 100 Pa. Hardly affected. However, when a certain stress is exceeded, for example, in a range of more than 80 Pa, the storage elastic modulus G ′ significantly decreases as the stress increases (FIG. 2). This remarkable decrease in the storage elastic modulus G ′ affects the gap feeling that characterizes the unique feeling of use of the present invention.

The W / O / W type emulsion composition of the present invention preferably has a storage elastic modulus G ′ of 2000 Pa or more, and preferably 3000 Pa or more, in the initial stage of application, that is, in a stress range of 1 to 80 Pa. , And more preferably 4000 Pa or more.
By setting the storage elastic modulus G ′ at a stress of 1 to 80 Pa within the above range, it is possible to provide a W / O / W type emulsion composition that exhibits an excellent richness in the initial stage of application to the skin.

The W / O / W emulsion composition of the present invention preferably has a form exhibiting a large storage elastic modulus G ′ even when a larger stress is applied. Specifically, the W / O / W type emulsion composition of the present invention, when the storage elastic modulus G ′ is measured under the above conditions, more preferably has a storage elastic modulus G ′ of 2000 Pa or more at a stress of 90 Pa, The storage elastic modulus G ′ is more preferably 2000 Pa or more at a stress of 100 Pa, and the storage elastic modulus G ′ is more preferably 2000 Pa or more at 120 Pa.
In this way, even when a larger stress is applied, by providing a form that exhibits a large storage elastic modulus G ′, W / which gives a sufficient richness during a certain period in the initial stage of application to the skin. An O / W type emulsion composition can be provided.
In order to adjust the storage elastic modulus G ′ at the stress within the above range, the viscosity of the outer water phase may be adjusted. The higher the viscosity of the outer water phase, the higher the storage elastic modulus G '.
As a method for adjusting the viscosity of the outer water phase, specifically, the concentration of the thickener in the outer water phase is adjusted, and the amount of W / O particles dispersed in the outer water phase or the amount of the oil phase that does not include the water phase. And the formation of α-gel by the higher alcohol and hydrophilic surfactant in the external water phase.
The formation of α-gel in the external water phase will be described in detail later.

Further, in the W / O / W type emulsion composition, when the storage elastic modulus G ′ is measured by the above-mentioned method, the decrease amount of the storage elastic modulus G ′ is 500 Pa or less in the stress range of 1 to 80 Pa. It is preferably 300 Pa or less, more preferably 150 Pa or less.
Further, even in a stress range of preferably 1 to 90 Pa, and more preferably 1 to 100 Pa, the decrease amount of the storage elastic modulus G ′ is preferably in the above range.
By setting the amount of decrease of the storage elastic modulus G ′ in the above stress range to the above range, it is possible to maintain an excellent richness during the operation in the initial stage of application to the skin, which will be described later. It is possible to noticeably change the feeling of use.

In order to adjust the decrease amount of the storage elastic modulus G ′ in the above stress range to the above range, the content of W / O particles and the particle diameter of W / O particles may be adjusted. The higher the W / O particle content, the smaller the decrease in the storage elastic modulus G ′ in the stress range. Further, the larger the particle size of the W / O particles, the smaller the decrease amount of the storage elastic modulus G ′ at the stress of 1 to 80 Pa.
Specifically, it can be realized by adjusting the content of W / O particles, preferably the particle size of W / O particles in addition to this, within the range described below.

Further, the W / O / W type emulsion composition of the present invention has a storage elastic modulus G with respect to an increase amount of a stress of 100 Pa in a stress range of more than 80 Pa, when the storage elastic modulus G ′ is measured by the method described above. It is preferable that the amount of decrease of ′ is in the range of 2000 Pa or more (FIG. 2).
Further, in the W / O / W type emulsion composition of the present invention, the decrease amount of the storage elastic modulus G ′ with respect to the increase amount of stress of 100 Pa is preferably 3000 Pa or more, and more preferably 4000 Pa or more.
By adopting such a form, it is possible to provide a W / O / W type emulsion composition which has a large difference in tactile sensation from the initial stage of application to the skin and after the middle stage and which has a more unique usability.
In order to adjust the decrease amount of the storage elastic modulus G ′ in the above stress range to the above range, the content of W / O particles and the particle diameter of W / O particles may be adjusted. The higher the W / O particle content, the smaller the decrease in the storage elastic modulus G ′ in the stress range. Further, the larger the particle size of the W / O particles, the smaller the decrease amount of the storage elastic modulus G ′ at the stress of 1 to 80 Pa.
Specifically, it can be realized by adjusting the content of W / O particles, preferably the particle size of W / O particles in addition to this, within the range described below.

  By the way, as shown in FIG. 2, assuming that the amount of change in stress is ΔX and the amount of change in storage elastic modulus G ′ is ΔY, the numerical value obtained by dividing ΔY by ΔX (ΔY / ΔX) depends on the amount of change in stress. It represents the amount of change in the storage elastic modulus G '. That is, the larger the value of (ΔY / ΔX) in the negative direction, the larger the decrease amount of the storage elastic modulus G ′ according to the increase amount of stress, that is, the sharp decrease of the storage elastic modulus G ′. The present inventors have found that the gap feeling can be extremely remarkably exhibited by setting the value of (ΔY / ΔX) within the following range.

That is, in the W / O / W type emulsion composition of the present invention, in a stress range of more than 80 Pa, preferably 90 Pa, more preferably 100 Pa, the decrease amount of the storage elastic modulus G ′ with respect to the increase amount of stress is 50 Pa or more ( The value of (ΔY / ΔX) is -50 or less).
Further, it is preferable that the amount of decrease in the storage elastic modulus G ′ is in the range of 55 Pa or more ((ΔY / ΔX) value is −55 or less).
As described above, the W / O / W type emulsion composition of the present invention in a form in which the storage elastic modulus G'decreases sharply in response to an increase in stress changes from a rich feeling to a feeling of use with good elongation. It shows a drastic change in usability and has a very unique usability.
The larger the W / O particle content, the smaller the value of (ΔY / ΔX). Therefore, by adjusting the content of W / O particles, it is possible to provide a W / O / W type emulsion composition having a value of (ΔY / ΔX) in the above range.

In the W / O / W type emulsion composition of the present invention, the content of W / O particles is 15% by mass or more, preferably 15 to 30% by mass, more preferably 15 to 20% by mass, and further It is preferably 16 to 18% by mass.
By setting the content of the W / O particles within the above range, it is possible to improve the feeling of use with good elongation from the middle stage to the final stage of application to the skin.
The amount of the W / O type emulsion composition (primary emulsion) added to the outer aqueous phase in the step of preparing the W / O / W type emulsion composition described below is determined by the W in the W / O / W type emulsion composition. It can be regarded as the content of / O particles. That is, the content of the desired W / O particles can be adjusted by adjusting the amount of the primary emulsion dispersed in the outer water phase.

In the W / O / W type emulsion composition of the present invention, the average particle size of W / O particles is preferably 10 µm or more, more preferably 10 to 30 µm, and further preferably 10 to 20 µm.
By setting the average particle diameter of the W / O particles within the above range, it is possible to improve the feeling of richness felt before the application to the skin and during the initial stage of the application. In addition, it is possible to improve the feeling of use when the application to the skin is good, from the middle stage to the final stage. That is, the W / O / W type emulsion composition of such an embodiment has a unique feeling of use with a large difference between a feeling of richness and a feeling of use with good elongation.

The particle size of the W / O particles is determined by compounding the stirring conditions such as the type of stirring / mixing device used to disperse the primary emulsion in the external water phase, the number of revolutions, and the stirring time, as described later. The particle size can be controlled within a desired range.
Further, as described later, when the primary emulsion is dispersed in the outer aqueous phase by the film emulsification method, the particle size of the W / O particles can be adjusted by the pore size of the porous film used for the film emulsification.

  The average particle diameter of W / O particles in the present specification means the average particle diameter of about 100 W / O particles arbitrarily selected in a micrograph of a W / O / W type emulsion composition. I say the value that I did.

In the embodiment of the present invention, the mass ratio of W1 and O1 in the W / O / W type emulsion composition is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and further preferably It is 2: 1 to 1: 2.
By setting the mass ratio of the water phase and the oil phase within the above range, it is possible to improve the usability with good elongation from the middle stage to the final stage of application to the skin.

In the embodiment of the present invention, the mass ratio of W1 and W2 in the W / O / W type emulsion composition is preferably 1: 4 to 1:10, more preferably 1: 5 to 1: 9, and further preferably 1. : 6 to 1: 8.
By setting the mass ratio of W1 and W2 in the W / O / W type emulsion composition to be in the above range, it is possible to improve the feeling of use with good elongation from the middle stage to the final stage of application to the skin.

In the embodiment of the present invention, the mass ratio of the total amount of the aqueous phase and the total amount of the oil phase in the W / O / W type emulsion composition is preferably 20: 1 to 0.5: 1, more preferably 10: 1. ˜1: 1, more preferably 5: 1 to 1.5: 1.
By setting the mass ratio of the water phase and the oil phase in the W / O / W type emulsion composition to be in the above range, it is possible to improve the feeling of richness before the application to the skin and in the initial stage of the application. In addition, it is possible to improve the feeling of use when the application to the skin is good, from the middle stage to the final stage.

When the present invention is a (W / O1 + O2) / W type emulsion composition, the mass ratio of O2 and O1 is preferably 5: 1 to 1: 1, more preferably 4: 1 to 1.5: 1. , And more preferably 3: 1 to 2: 1.
By setting the mass ratio of O1 and O2 to be in the above range, it is possible to improve the richness that is felt before the application to the skin and during the initial stage of the application.

The content of O2 particles is preferably 15% by mass or more, more preferably 15 to 30% by mass, and further preferably 18 to 25% by mass.
The amount of the oil phase added separately from the primary emulsion added to the external water phase in the step of preparing the W / O / W type emulsion composition described below is determined by the amount of O2 particles in the W / O / W type emulsion composition. It can be regarded as the content. That is, the desired O2 particle content can be obtained by adjusting the amount of the primary emulsion dispersed in the outer aqueous phase.

The total content of W / O1 particles and O2 particles is preferably 20 to 70% by mass, more preferably 25 to 60% by mass, and further preferably 30 to 50% by mass.
When the content of O2 particles is 1 part by mass, the content of the W / O1 particles is preferably 0.2 parts by mass or more, more preferably 0.4 parts by mass or more, and further preferably 0.6. It is at least part by mass.
By setting the total amount and the ratio of the W / O1 particles and the O2 particles within the above ranges, the gap feeling can be further improved.

The average particle size of the O2 particles is preferably 0.1 to 5 μm, more preferably 0.5 to 3.5 μm, and further preferably 1 to 2.5 μm.
The ratio of the average particle size of W / O1 particles and O2 particles is 100: 1 to 2: 1, preferably 20: 1 to 3: 1 and more preferably 10: 1 to 4: 1. is there.
By setting the ratio of the average particle diameters of W / O1 particles and O2 particles within the above range, excellent gap feeling can be realized.

  The oil component contained in the oil phase is not particularly limited, and liquid oil, solid oil, wax, hydrocarbon oil, higher fatty acid, higher alcohol, synthetic ester oil, silicone oil and the like can be used.

  Examples of liquid oils and fats include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern oil, castor oil, linseed oil. , Safflower oil, cottonseed oil, eno oil, meadowfoam oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese chili oil, jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, Examples thereof include glycerin triisopalmitate.

  Examples of solid oils and fats include cacao butter, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, lard, beef bone fat, sorghum kernel oil, hardened oil, and beef tallow. , Syrup, hydrogenated castor oil, and the like.

  Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivota wax, whale wax, montan wax, nukarou, lanolin, capok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, jojo. Examples include barow, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.

  Examples of the hydrocarbon oil include liquid paraffin, ozokerite, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax and the like.

  Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenin) acid, 12-hydroxystearic acid, undecylenic acid, tallic acid and the like.

  Examples of higher alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, batyl alcohol, myristyl alcohol, cetostearyl alcohol and the like.

  Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate. , Lanolin acetate, isocetyl stearate, isocetyl isostearate, sucrose stearate, sucrose oleate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, Neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, tri-2-ethyl Trimethylolpropane xylate, Trimethylolpropane triisostearate, Pentaneerythritol tetra-2-ethylhexylate, Glycerin tri-2-ethylhexylate, Trimethylolpropane triisostearate, Cetyl 2-ethylhexanoate, 2-Ethylhexyl palmitate , Glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, cetyl palmitate, diisobutyl adipate, N- Lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethyl sebacate Hexyl myristate 2-hexyl decyl palmitate, 2-hexyldecyl, 2-hexyldecyl adipate, sebacic acid diisopropyl, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, and triethyl citrate.

  Examples of the silicone oil include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, and cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane and tetramethyltetrahydrogenpolysiloxane. Is mentioned.

  The oil component may be used alone or in combination of two or more.

In the embodiment of the present invention, it is usually preferable to contain an emulsifier used when forming an emulsion composition.
As the emulsifier in the present invention, either an ionic surfactant or a nonionic surfactant can be used without limitation.

  Examples of the ionic surfactant include fatty acid soaps such as sodium laurate, sodium stearate, potassium stearate and potassium palmitate, higher alkyl sulfate ester salts such as sodium lauryl sulfate and potassium lauryl sulfate, and polyoxyethylene lauryl sulfate. Alkyl ether sulfate ester salts such as triliethanolamine, N-acyl sarcosinic acid such as sodium lauroyl sarcosine, higher fatty acid amide sulfonates such as sodium N-myristoyl-N-methyltaurine, sodium polyoxyethylene oleyl ether phosphate, Phosphate ester salts such as polyoxyethylene stearyl ether phosphate, sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate, sodium dodecylbenzenesulfonate , Alkylbenzenesulfonates such as dodecylbenzenesulfonic acid triethanolamine and dodecylbenzenesulfonic acid, N-acylglutamates such as monosodium N-lauroylglutamate, disodium N-stearoylglutamate and monosodium N-myristoyl-L-glutamate Etc.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether type active agents such as polyoxyethylene oleyl ether, ester type active agents such as polyoxyethylene hydrogenated castor oil, and polyoxyethylene glyceryl monoisostear. Ethylene oxide addition type surfactants such as ether / ester type surfactants such as oleate, glycerin fatty acid esters such as glyceryl monostearate, sorbitan fatty acid esters such as sorbitan monolaurate, and polyhydric alcohol fatty acid ester type surfactants such as Is mentioned. In addition, examples of the silicone-based surfactant include polyether-modified silicone.
In a more preferred embodiment of the present invention, a silicone surfactant is used as the emulsifier.

In the embodiment of the present invention, the content of the surfactant in the W / O / W type emulsion composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and further preferably It is 0.5 to 2 mass%.
By setting the content of the surfactant within the above range, it becomes possible to improve the stability of the W / O / W type emulsion composition.

In the embodiment of the present invention, when the W / O type emulsion composition which is the primary emulsion is prepared (the primary emulsification step described below), it is preferably 1 to 10 with respect to the entire W / O type emulsion composition. %, More preferably 2-7% by weight of surfactant is added.
By adjusting the amount of the surfactant added during the preparation of the W / O type emulsion composition to the above range, the stability of the W / O type emulsion composition, and by extension, the stability of the W / O / W type emulsion composition It will be possible to improve.

In the embodiment of the present invention, when the W / O type emulsion composition is dispersed in the outer aqueous phase to prepare the W / O / W type emulsion composition (second emulsification step described later), W / O / The surfactant is preferably added in an amount of 0.1 to 2% by mass, and more preferably 0.3 to 1% by mass, based on the entire W-type emulsion composition.
By adjusting the amount of the surfactant added during the preparation of the W / O / W type emulsion composition to the above range, the stability of the W / O / W type emulsion composition can be improved. .

A preferred embodiment of the present invention contains an organically modified clay mineral.
By containing the organically modified clay mineral, it becomes possible to further improve the stability of the W / O / W type emulsion composition.

Further, in a more preferred embodiment of the present invention, the W / O particles contain an organically modified clay mineral.
Since the W / O particles contain the organically modified clay mineral, the stability of the W / O / W type emulsion composition can be further improved.

The organically modified clay mineral is a clay mineral in which a part of an organic compound is bonded to a part of the clay mineral through a covalent bond or an ionic bond. Examples of clay minerals include smetite-type hectorite, bentonite, montrilillonite, kaolinite, illite, marine clay mineral (sea mud), desert rose clay mineral, and pascalite.
Examples of the organic compound include compounds having a quaternary amino group. Specifically, stearyl trimethyl ammonium chloride, dimethyl distearyl ammonium chloride, etc. are mentioned.
In the embodiment of the present invention, it is preferable to use dimethyl distearyl ammonium chloride modified hectorite (distearyl dimonium hectorite) as the organic modified clay mineral.
By containing dimethyl distearyl ammonium chloride modified hectorite, the stability of the W / O / W type emulsion composition is further improved.
Further, it becomes possible to improve the gap feeling of the W / O / W type emulsion composition.

In a preferred embodiment of the present invention, the W / O particles contain a silicone surfactant.
By making the W / O particles contain a silicone-based surfactant, the stability of the W / O / W type emulsion composition can be improved.

In a more preferred embodiment of the present invention, the W / O particles contain an organically modified clay mineral and a silicone surfactant.
The stability of the W / O / W type emulsion composition can be improved by making the W / O particles contain an organically modified clay mineral and a silicone-based surfactant.

In a preferred embodiment of the present invention, the content of the water-soluble polymer is preferably 0.3% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less.
By setting the content of the water-soluble polymer in the above range, stickiness of the W / O / W type emulsion composition can be suppressed.

  Here, the water-soluble polymer refers to those having a viscosity imparting effect, arabia gum, tragacanth gum, karaya gum, xanthan gum, tamarind gum, guar gum, hydroxypropyl guar gum, locust bean gum, quince seed, gellan gum, native gellan gum, polyacrylic acid. , Polymethacrylic acid, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, Nn-butoxymethylacrylamide, N-iso-butoxy. Acrylamide, tert-butylacrylamide sulfonic acid, dimethylaminopropylmethacrylic Mido, or a copolymer of these polymerizable monomer raw materials with other polymerizable monomers, or methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, alginic acid, carrageenan, hyaluronic acid, chondroitin sulfate, dermatan sulfate, collagen, chitin Examples thereof include derivatives, pectin, gelatin, carboxyvinyl polymers, acrylic acid / alkyl methacrylate copolymers and salts thereof.

In a preferred embodiment of the present invention, the content of the optionally modified carboxyvinyl polymer in the water-soluble polymer is preferably 0.3% by mass or less, more preferably 0.03% by mass or less. is there.
Further, a further preferred embodiment of the present invention does not include an optionally modified carboxyvinyl polymer.
By setting the content of the optionally modified carboxyvinyl polymer in the above range, the stickiness of the W / O / W type emulsion composition can be suppressed.

In a preferred embodiment of the present invention, the inner aqueous phase contains no electrolyte.
By making the internal water phase contain no electrolyte, the stickiness of the W / O / W type emulsion composition can be suppressed.

A preferred embodiment of the present invention comprises an oil soluble moisturizer.
By containing an oil-soluble moisturizing agent, it imparts a pleasant gap feeling to the W / O / W type emulsion composition, which exhibits a moisturizing feeling and a firm feeling after changing from a rich feeling to a good feeling of use. be able to.

In a preferred embodiment of the present invention, the oil-soluble humectant comprises dimer dilinoleate di (isostearyl / phytosteryl).
By containing dimer dilinoleic acid di (isostearyl / phytosteryl) as an oil-soluble moisturizer, it is possible to further improve the moisturizing feeling and the firmness feeling, thereby making a more comfortable gap feeling W / O / It can be applied to the W-type emulsion composition.

  In the present invention, dimer dilinoleic acid di (isostearyl / phytosteryl) may be purchased from Nippon Seika Co., Ltd. under the trademark “LUSPLAN PI-DA” and used.

In the W / O / W type emulsion composition of the present invention, the oil-soluble humectant can be contained in the oil phase.
When the present invention is a (W / O1 + O2) / W type emulsion composition, the oil-soluble humectant may be contained in either O1 or O2.
In a preferred embodiment of the present invention, an oil-soluble humectant is contained in O2. In particular, when dimer dilinolenate di (isostearyl / phytosteryl) is contained in O2, a W / O / W type emulsion composition excellent in moisturizing feeling and firmness can be provided.

In the embodiment of the present invention, the content of the oil-soluble humectant is preferably 1 to 10% by mass, more preferably 2 to 5% by mass.
By setting the content of the oil-soluble humectant within the above range, it is possible to improve the moisturizing feeling and the firmness feeling when using the W / O / W type emulsion composition.

In a preferred embodiment of the present invention, the outer aqueous phase contains an α-gel formed by a hydrophilic surfactant and a higher alcohol.
According to such an embodiment, the W / O particles are prevented from coalescing or draining due to the action of the α-gel formed in the outer water phase, and the W / O / W type emulsification excellent in high temperature stability is obtained. A composition can be provided. That is, the W / O / W emulsion composition of the present invention in such an embodiment maintains a feeling of use with a gap even after being stored at a high temperature.

In a more preferred embodiment of the present invention, at least an ionic surfactant is contained as the hydrophilic surfactant.
By using the ionic surfactant, the high temperature stability of the W / O / W type emulsion composition can be further improved.

The ionic surfactant is not particularly limited, but sodium laurate, sodium stearate, potassium stearate, fatty acid salts such as potassium palmitate, polyoxyethylene alkyl ether phosphoric acid and salts thereof, alkaroyl alkyl taurine salt, Preferable examples include alkaloyl glutamate, alkaloyl lactate, alkyltrimethylammonium chloride, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, polyoxyethylene alkyl ether sulfate, alkylamidoamine and salts thereof. it can.
In a preferred embodiment of the present invention, a fatty acid salt is contained as the ionic surfactant.

In a more preferred embodiment of the present invention, the hydrophilic surfactant has a HLB of 8 or more, more preferably 10 or more, still more preferably 12 or more, still more preferably 14 or more, still more preferably 16 or more. Contains a surfactant.
By using such a highly hydrophilic surfactant, the high temperature stability of the W / O / W type emulsion composition can be further improved.
In addition, the HLB in the present specification refers to the HLB calculated by the Griffin method.

  The above-mentioned nonionic surfactant is not particularly limited as long as it can form an α-gel with a higher alcohol, and a lipophilic surfactant that does not form an α-gel is used in the range where an α-gel structure can be formed. It is also possible to use polyoxyethylene alkyl ether, polyoxyethylene / polyoxypropylene alkyl ether, sorbitan fatty acid ester, glycerin monoalkyl ester, polyether fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, Polyoxyethylene glycerin alkyl ester, polyoxyethylene alkyl ether alkyl ester, polyoxyethylene sorbitan alkyl ester, polyglycerin alkyl ester, pyroglutamic acid ester, dimethicone copolyol, polyether Sex dimethicone, and the like.

In a preferred embodiment of the present invention, the content of the hydrophilic surfactant is preferably 0.01 to 5 mass%, more preferably 0.1 to 3 mass%, still more preferably 0.5 to 2 mass%. %.
By setting the content of the hydrophilic surfactant within the above range, a W / O / W type emulsion composition exhibiting an excellent gap feeling even after storage for a longer period at high temperature is obtained. Can be provided.

In a preferred embodiment of the present invention, the carbon number of the higher alcohol is preferably 8 to 22, more preferably 16 to 22, and even more preferably 16 to 18.
By using a higher alcohol having a carbon number within the above range, it is possible to provide a W / O / W emulsion composition that exhibits an excellent gap feeling even after storage at high temperature for a longer period of time. it can.

  The higher alcohol is not particularly limited as long as it can form an α-gel with the hydrophilic surfactant, lauryl alcohol, batyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetanol, etc. Is mentioned.

In a preferred embodiment of the present invention, the content of the higher alcohol is 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and further preferably 2 to 3% by mass.
By setting the content of the higher alcohol in the above range, it is possible to provide a W / O / W type emulsion composition that exhibits an excellent gap feeling even after storage at a high temperature for a longer period of time. it can.

In a preferred embodiment of the present invention, the molar ratio of the higher alcohol to the hydrophilic surfactant is 1: 1 to 20: 1, preferably 1.5: 1 to 10: 1, more preferably 2: 1. ~ 5: 1.
By setting the molar ratio of the higher alcohol to the hydrophilic surfactant within the above range, a W / O / W type emulsion composition exhibiting an excellent gap feeling even after storage for a longer period at high temperature. You can provide things.

In a preferred embodiment of the present invention, the mass ratio of the content of W / O particles dispersed in the external water phase to the total amount of the hydrophilic surfactant and the higher alcohol is preferably 1: 1 to 10: 1. , More preferably 2: 1 to 7: 1, still more preferably 3: 1 to 5: 1.
By setting the mass ratio of W / O particles to the hydrophilic surfactant and higher alcohol within the above range, W / O exhibiting an excellent gap feeling even after storage at high temperature for a longer period of time. A / W type emulsion composition can be provided.

  The W / O / W type emulsified cosmetic composition of the present invention may contain optional additives which are usually contained in cosmetic compositions, within a range that does not impair the effects of the present invention. Examples of such additive components include moisturizing agents such as polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol; lower alcohols such as ethanol; butylhydroxytoluene, tocopherol, phytin, etc. Antioxidants; antibacterial agents such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid alkyl ester, hexachlorophen; paraaminobenzoic acid (hereinafter abbreviated as "PABA"), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester , N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA methyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl P Benzoic acid-based UV absorbers such as BA2-ethylhexyl ester; Anthranilic acid-based UV absorbers such as homomenthyl-N-acetylanthranilate; Amyl salicylate, Menthyl salicylate, Homomenthyl salicylate, Octyl salicylate, Phenyl salicylate, Benzyl salicylate, p -Salicylic acid type UV absorbers such as isopropanol phenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4- Diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy cinnamate, isoamyl-p-methoxy cinnamate, octyl-p-methoxy Cinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α- Cinnamic acid-based UV absorbers such as cyano-β-phenylcinnamate and glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate; [3-bis (trimethylsiloxy) methylsilyl-1-methylpropyl] -3, 4,5-Trimethoxycinnamate, [3-bis (trimethylsiloxy) methylsilyl-3-methylpropyl] -3,4,5-trimethoxycinnamate, [3-bis (trimethylsiloxy) methylsilylpropyl] -3 , 4,5-trimethoxycinnamate, [3-bis (to Methylsiloxy) methylsilylbutyl] -3,4,5-trimethoxycinnamate, [3-tris (trimethylsiloxy) silylbutyl] -3,4,5-trimethoxycinnamate, [3-tris (trimethylsiloxy) silylbutyl ] -3,4,5-Trimethoxycinnamate, [3-tris (trimethylsiloxy) silyl-1-methylpropyl] -3,4-dimethoxycinnamate, etc. Silicone cinnamic acid UV absorbers; 2,4 -Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxy-4'-me Rubenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone , 4-hydroxy-3-carboxybenzophenone and other benzophenone-based UV absorbers; 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid ethyl ester, 2- Phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy- 5'-methylphenyl) benzotriazo UV absorbers such as benzyl, dibenzalazine, dianisoylmethane, 4-methoxy-4′-t-butyldibenzoylmethane, 5- (3,3′dimethyl-2-norbornylidene) -3-pentan-2-one; acyl Organic acids such as sarcosine acid (eg sodium lauroyl sarcosine), glutathione, citric acid, malic acid, tartaric acid, lactic acid; vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its Derivatives, vitamin B12 such as vitamin B12, vitamin B15 and its derivatives, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E such as vitamin E acetate, vitamin Ds, vitamin H, pantothenic acid, pantethine, nicotine Acid amide Vitamins such as benzyl titanate; γ-oryzanol, allantoin, glycyrrhizinic acid (salt), glycyrrhetinic acid and its derivatives, tranexamic acid and its derivatives (as a tranexamic acid derivative, a dimer of tranexamic acid (for example, trans-hydrochloride 4- (trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid, etc.), ester form of tranexamic acid and hydroquinone (for example, trans-4-aminomethylcyclohexanecarboxylic acid 4′-hydroxyphenyl ester, etc.), tranexamic acid And gentisic acid ester (for example, 2- (trans-4-aminomethylcyclohexylcarbonyloxy) -5-hydroxybenzoic acid and salts thereof, etc.), tranexamic acid amide (for example, tran Su-4-Aminomethylsicolohexanecarboxylic acid methylamide and salts thereof, trans-4- (P-methoxybinzoyl) aminomethylcyclohexanecarboxylic acid and salts thereof, trans-4-guanidinomethylcyclohexanecarboxylic acid and salts thereof, and the like) ], Hinokitiol, bisabolol, eucalptone, thymol, inositol, saponins such as saikosaponin, carrot saponin, hemimasaponin, muclodisaponin, pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, arbutin, cepharanthin, placenta extract, etc. Drugs: Rumex, Clara, Kohone, orange, sage, yarrow, mallow, sembly, thyme, touki, spruce, birch, horsetail, loofah, horse chestnut, yukinoshi , Extracts of plants such as Arnica, lily, mugwort, peony, aloe, gardenia and sawara; pigments; porous and / or water-absorbing powders (for example, starches obtained from corn and potatoes, silicic acid anhydride, talc) Powders such as kaolin, magnesium aluminum silicate and calcium alginate); neutralizing agents; preservatives; fragrances; pigments and the like.

The method for producing the W / O / W type emulsion composition of the present invention is not particularly limited, and for example, it can be produced using a stirring and mixing apparatus as follows.
First, the oil phase component and the internal water phase component are heated and mixed to prepare a uniform mixture. Next, in a state where the mixture of the oil phase component is stirred using a stirring and mixing device, the mixture of the internal water phase component is gradually added to the mixture of the oil phase component to emulsify (primary emulsification step), Prepare the primary emulsion.

  A uniform mixture prepared by heating and mixing the external water phase components is prepared. Next, in a state of stirring the mixture of the external water phase components using a stirring and mixing device, the primary emulsion is gradually added to the mixture of the external water phase components to emulsify (secondary emulsification step), A W / O / W type emulsion composition is prepared.

  When it is in the form of a (W / O1 + O2) / W type emulsion composition, it is not particularly limited, but it can be produced, for example, by the following preparation method 1 or preparation method 2.

(Preparation method 1) O2 is dispersed in W2 to prepare an oil-in-water emulsion composition (O2 / W2). Separately, W1 is dispersed in O1 to prepare a water-in-oil emulsion composition (W1 / O1). By dispersing the water-in-oil emulsion composition (W1 / O1) in the oil-in-water emulsion composition (O2 / W2), a (W1 / O1 + O2) / W emulsion composition can be prepared.

(Preparation method 2) A water-in-oil emulsion composition (W1 / O1) prepared by dispersing W1 in O1 is dispersed in W2 to prepare a W / O / W type emulsion composition (W1 / O1 / W2). To do. A (W1 / O1 + O2) / W type emulsion composition is prepared by mixing this emulsion composition with an oil-in-water emulsion composition (O2 / W2) in which O2 is dispersed in W2, which has been adjusted in advance. be able to.

  In this case, the higher alcohol can be in the form of forming an α-gel in the external water phase, whether added as the O1 component or the O2 component.

The average particle diameter of the W / O particles in the W / O / W type emulsion composition of the present invention can be controlled by various methods, and a method of controlling by the stirring conditions in the secondary emulsification step can be preferably exemplified.
Generally, the larger the number of revolutions of the stirring / mixing device used in the secondary emulsification step and the longer the stirring time, the larger the load due to shearing / collision / cavitation. To do. Therefore, the average particle diameter of the W / O particles of the W / O / W type emulsion composition of the present invention is determined by complexly adjusting the stirring conditions such as the type of stirring / mixing device, the number of revolutions, and the stirring time. The particle size range can be controlled.

  Examples of the stirring and mixing device include a homodisper, a homomixer, a homogenizer, a high-speed emulsifying device such as a microfluidizer, a disper mixer including a saw-toothed stirring blade, and an impeller-type stirring device including a rotary blade. . A W / O / W type emulsified composition containing W / O particles having an average particle size specified in the present invention can be produced by using any of the above stirring and mixing devices, and particularly high-speed emulsification represented by homodisper. It is preferable to use a device.

The W / O / W type emulsion composition of the present invention can also be produced by a membrane emulsification method using a porous membrane having a uniform pore size.
That is, it is also possible to prepare the liquid that becomes the dispersed phase through the porous membrane by pressure injection into the liquid that becomes the continuous phase with nitrogen gas or the like.

  When the W / O / W type emulsion composition of the present invention is a (W / O1 + O2) / W type emulsion composition, the method for adjusting the ratio of the average particle diameters of W / O1 particles and O2 particles is not limited, When the W / O / W type emulsion composition is produced by the preparation method 1 and the preparation method 2, the preparation can be performed as follows.

  When the preparation method 1 is adopted, the average particle size of O2 particles is adjusted in the step of preparing the oil-in-water emulsion composition (O2 / W2) to prepare the (W1 / O1 + O2) / W emulsion composition. By adjusting the average particle diameter of the W / O1 particles in the step, the ratio of the average particle diameters of the W / O1 particles and the O2 particles can be adjusted to the preferable range described above.

  When the preparation method 2 is adopted, the average particle size of the W / O1 particles is adjusted at the stage of preparing the W / O / W type emulsion composition (W1 / O1 / W2), and the oil-in-water emulsion composition (O2 By adjusting the average particle size of the O2 particles in the step of preparing / W2), the ratio of the average particle size of the W / O1 particles and the O2 particles can be adjusted to the above-mentioned preferable range.

  The W / O / W emulsion composition of the present invention can be used as a cosmetic such as an emulsion, a cream, a beauty essence, a sunscreen, a liquid foundation, a skin external preparation, a quasi-drug or a medicine.

<Production Example 1>
The W / O / W type emulsion compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were produced by the following method.
First, each of the O1 component and the W1 component shown in Table 1 was heated and dissolved, and then the W1 component was gradually added to the O1 component with stirring to emulsify and cool to prepare a W / O type primary emulsion.

After the O2 component and the W2 component shown in Table 2 were heated and dissolved, the O2 component was gradually added to a part of the W2 component while stirring to emulsify the O2 / W type emulsion. In addition, the above-mentioned primary emulsion was gradually added to the rest of the W2 component while stirring to emulsify to prepare a W / O1 / W type emulsion composition.
The average particle diameters of the W / O1 particles and the O2 particles were adjusted by adjusting the stress in stirring during the preparation of the O2 / W type emulsion and the W / O1 / W type emulsion composition.
By mixing this O2 / W type emulsion and the W / O1 / W type emulsion composition, the W / O / W type emulsion compositions of Examples 1 to 3 and Comparative Examples 1 and 2 ((W / O1 + 2 ) / W type emulsion composition) was prepared.
The W / O / W type emulsion composition thus prepared was observed under a microscope to measure the average particle size of W / O1 particles and O2 particles. Table 2 shows the average particle size and ratio of each particle.

<Test Example 1>
The W / O / W emulsion compositions of Examples 1 to 3 and Comparative Examples 1 and 2 produced in Production Example 1 were evaluated for richness and good elongation by the following method.
Twenty panelists applied the W / O / W emulsion compositions of Examples 1 to 3 and Comparative Examples 1 and 2 in a container to their skin. Then, according to the following evaluation criteria, the richness felt from the time when the W / O / W type emulsion composition is scooped up from the container to the initial stage of coating and the goodness of the elongation from the middle stage to the final stage of the coating are 1 to 5 points. Was given a score and the average value was taken.
Then, the gap feeling was evaluated based on the evaluation results of the rich feeling and the feeling of use with good elongation.
The results are shown in Table 2.
・ 5 points of richness ・ ・ ・ 4 points of very strong feeling ・ ・ ・ 3 points of strong feeling of feeling ・ ・ ・ 2 points of strong feeling of feeling ・ ・ ・ 1 point of weak feeling of feeling ・ ・ ・ No feeling of feeling of strength

・ Good elongation 5 points ・ ・ ・ Extensively good 4 points ・ ・ ・ Elongation is good 3 points ・ ・ ・ Elongation is 2 points ・ ・ ・ Extension is slightly bad 1 point ・ ・ ・ Extension is very bad

As shown in Table 2, the W / O / W type emulsion compositions (Examples 1 to 3) having a W / O particle content of 16% by mass or 20% by mass have a W / O particle content of Compared with the W / O / W type emulsion composition of 10% by mass (Comparative Examples 1 and 2), it is remarkably strong and has excellent elongation and excellent usability. It was also found that the W / O / W emulsion compositions of Examples 1 to 3 had a unique feeling of use with excellent gap feeling.
From these results, it is found that the W / O / W type emulsion composition having the content of W / O particles of 15% by mass or more has unique characteristics of being hard to be compatible with each other and having a good feeling of use with good elongation. It was

  Further, comparing the W / O / W type emulsion compositions of Example 1 and Example 3 in which the content of W / O particles is 16% by mass, the average particle diameter of W / O particles is 2 μm. Compared with the W / O / W type emulsion composition of Example 3, the W / O / W type emulsion composition of Example 1 in which the average particle diameter of W / O particles is 10 μm has a stronger solid feeling. It was found that the stretch feeling was excellent and the feeling of gap was large.

  In addition, as shown in Table 3, the W / O / W type emulsion compositions of Example 1 and Example 3 each have a W / O1 particle content of 16% by mass. However, the W / O / W type emulsion composition of Example 1 in which the ratio of the average particle size of W / O1 particles and O2 particles is 5: 1 has the W / O / W type emulsion composition of Example 3 in which the ratio is 1: 1. Excellent gap feeling as compared with the O / W type emulsion composition.

<Test Example 2>
Regarding the W / O / W type emulsion compositions of Examples 1 to 3 and Comparative Examples 1 and 2, using a rheometer (TA Instruments AR-G2), temperature 20 ° C., oscillation measurement, gap 1 mm The storage elastic modulus (G ′) was measured while increasing the stress from 1 Pa under the condition of 1 Hz. The results are shown in Table 3 and FIG.
In the rheometer used, the geometry was a 40 mm parallel plate made of stainless steel, and the base was a hard chrome-plated copper Peltier plate.

  As shown in Table 3 and FIG. 3, the W / O / W emulsion compositions of Examples 1 to 3 and Comparative Examples 1 and 2 each have a storage elastic modulus G ′ of 2000 or more at a stress of 1 Pa.

Further, in the W / O / W emulsion compositions of Examples 1 to 3, the storage elastic modulus G ′ hardly decreases in the stress range of 1 Pa to 80 Pa.
On the other hand, in the W / O / W type emulsion compositions of Comparative Examples 1 and 2, in the stress range of 1 Pa to 80 Pa, the pressure drops by about 2300 Pa and about 700 Pa, respectively.

  In addition, the W / O / W emulsion compositions of Examples 1 to 3 have storage elastic modulus G'from when stresses of about 100 Pa, about 120 Pa, and about 100 Pa are applied, respectively, while the stress is further increased by 100 Pa. Are about 3600 Pa, about 8700 Pa, and about 3000 Pa, respectively.

From the above results, the W / O / W type emulsion compositions of Examples 1 to 3 have a stress range of (a) 1 Pa to 80 Pa when the storage elastic modulus G ′ is measured while increasing the stress under the above conditions. In the above, the decrease amount of the storage elastic modulus G ′ is 500 Pa or less, and (b) in the stress range of more than 80 Pa, the decrease amount of the storage elastic modulus G ′ with respect to the increase amount of the stress of 100 Pa is 2000 Pa or more.
When this result is combined with the result in Table 2, the W / O / W type emulsion composition satisfying the above-mentioned (a) and (b) has a strong body feeling and a good feeling of elongation when used by the rheometer. It can be seen that it is also excellent and has a strong sense of gap.

As described above, the W / O / W emulsion compositions of Examples 1 to 3 have storage elastic modulus G ′ in the stress range of 1 Pa to about 100 Pa, 1 Pa to about 120 Pa, and 1 Pa to about 100 Pa, respectively. Hardly decreases.
Combining this result with the result in Table 2, the larger the stress range in which the storage elastic modulus G ′ hardly decreases, the stronger the feeling of bodyiness felt in the initial stage of application of the W / O / W type emulsion composition to the skin. It can be seen that there is a tendency for the sense of gap to strengthen.

In addition, the W / O / W emulsion compositions of Examples 1 to 3 have storage elastic modulus G'reduced by about 3600 Pa, about 8700 Pa, and about 3000 Pa, respectively, while exceeding the above range and applying a stress of 100 Pa. are doing.
When this result is combined with the result in Table 2, it can be seen that the larger the decrease in the storage elastic modulus G'beyond the above range, the stronger the richness tends to be.

Table 3 shows numerical values (ΔX / ΔY) obtained by dividing the amount of change in storage modulus G ′ by the amount of change in stress. As shown in Table 3, the W / O / W type emulsion compositions of Examples 1 to 3 have a value of (ΔX / ΔY) of about −58, about −240, and about −80 in the stress range of more than 80 Pa, respectively. There is a stress range of 78.
Combining this result with the result in Table 2, in the range of (c) the stress exceeding 80 Pa, there is a range in which the decrease amount of the storage elastic modulus G ′ with respect to the increase amount of the stress is 50 Pa or more in the W / O / W type emulsion composition. It can be seen that the object has a strong body feeling and a strong gap feeling.

  The results of Test Examples 1 and 2 show that the W / O / W type emulsion compositions of Examples 1 to 3 have an excellent rich feeling from before application to the initial stage of application, but they rapidly increase from the middle stage to the final stage of application. It shows that it has a unique feeling of use, that is, it has a good stretch feeling, that is, it has a good gap feeling.

<Production Example 2>
W / O / W type emulsion compositions having the compounding ratios shown in Table 4 were produced by the same method as in Production Example 1 (Examples 4 to 9).
Further, as a comparative example, an O / W type emulsion composition having a blending ratio shown in Table 2 was produced (Comparative Example 3). The O / W emulsion composition of Comparative Example 3 was produced by preparing an oil phase component and an aqueous phase component, and gradually adding the oil phase component to the aqueous phase component while stirring.

<Test Example 3>
The moisturizing feeling and firmness of the W / O / W type emulsion compositions of Examples 4 to 9 and the O / W type emulsion composition of Comparative Example 3 were evaluated by the following methods.
20 panelists applied the W / O / W emulsion compositions of Examples 4 to 9 and the O / W emulsion composition of Comparative Example 3 to their own skin. Then, the moisturizing sensation and the firmness sensation were evaluated according to the following evaluation criteria.
The results are shown in Table 4.
・ Moisturizing feeling ◎ ・ ・ ・ I feel a strong moisturizing feeling ○ ・ ・ ・ I feel a moisturizing feeling △ ・ ・ ・ I do not feel a very moisturizing feeling × ・ ・ ・ I do not feel a moisturizing feeling

・ Strongness ◎ ・ ・ ・ Strong feeling ○ ・ ・ ・ Strong feeling △ ・ ・ ・ Not so sharp × ・ ・ ・ No feeling

As shown in Table 4, the W / O / W emulsified compositions of Examples 4 to 7 containing dimer dilinoleic acid di (isostearyl / phytosteryl), which is an oil-soluble moisturizer, were prepared without containing the compound. It was found that compared with the W / O / W type emulsion compositions of Examples 8 and 9, the moisturizing feeling and the firmness feeling were excellent.
This result indicates that the W / O / W type emulsion composition containing the oil-soluble moisturizer has excellent moisturizing feeling and firmness during use.

Moreover, the W / O / W type emulsion compositions of Examples 5 and 6 in which the content of dimer dilinoleic acid di (isostearyl / phytosteryl) was 10% by mass or 14% by mass were sticky.
On the other hand, it was found that the W / O / W emulsion compositions of Examples 4 and 7 in which the content of dimer dilinoleic acid di (isostearyl / phytosteryl) was 2% by mass or 5% by mass did not cause stickiness. It was
This result shows that the W / O / W type emulsion composition having an oil-soluble humectant content of 2 to 5% by mass does not cause stickiness while exhibiting a moisturizing feeling, and has excellent elongation and excellent usability. Is shown.

In addition, the W / O / W type emulsion composition of Example 4 was compared with the O / W type emulsion composition of Comparative Example 3 in spite of the same content and the same content rate. It was found that it exhibits remarkably excellent moisturizing properties and firmness.
The results show that the inclusion of the oil-soluble moisturizer provides a moisturizing feeling and a firm feeling together with a gap feeling of the W / O / W type emulsion composition of the present invention, resulting in a very comfortable feeling. ing.

  As described above, since the W / O / W type emulsion composition of the present invention can remarkably enhance the actual feelings of moisturizing feeling and firmness, it is preferable that the composition contains an oil-soluble moisturizing agent.

<Production Example 3>
The W / O / W type emulsion compositions having the compounding ratios shown in Table 5 were produced by the same method as in Production Example 1 (Examples 10 to 17).

<Test Example 4>
The high temperature stability, moisture retention and non-stickiness of the W / O / W type emulsion compositions of Examples 10 to 17 were evaluated by the following methods. The results are shown in Table 5.
High temperature stability The W / O / W type emulsion compositions of Examples 10 to 17 were stored at 40 ° C., and the period for maintaining the W / O / W type observed before the start of the storage test was examined. .
Moisturizing sensation and non-greasiness Twenty panelists applied the W / O / W emulsion compositions of Examples 10 to 17 to their own skin. Then, according to the following evaluation criteria, a moisturizing feeling and non-stickiness were given a rating, and the average value thereof was taken.
Moisturizing sensation 5 points ... Very good moisturizing sensation 4 points ... Good moisturizing sensation 3 points ... Moisturizing sensation 2 points ... Almost no moisturizing sensation 1 point ...・ Does not feel moisturizing

Non-greasy 5 points ... No stickiness at all 4 points ... Almost no stickiness 3 points ... Slightly sticky 2 points ... Sticky 1 point ... Very sticky

The W / O / W type emulsion compositions of Examples 10 to 17 contain a higher alcohol and a hydrophilic surfactant, and form an α-gel in the outer aqueous phase.
And as shown in Table 5, all of the W / O / W type emulsion compositions of Examples 10 to 17 maintain the W / O / W type emulsion form at 40 ° C. for one month or longer. .
This result indicates that the W / O / W type emulsion composition containing the α-gel formed by the hydrophilic surfactant and the higher alcohol in the outer aqueous phase maintains an excellent gap feeling even after long-term storage at high temperature. It is shown that.

As shown in Table 5, the W / O / W type emulsified composition of Example 17 can maintain the emulsified form for 1 month, while the W / O / W type emulsified composition of Examples 10 to 16 is 40%. The emulsified form of W / O / W type was maintained for more than 3 months at 0 ° C.
This result shows that the high temperature stability of the W / O / W type emulsion composition is improved by containing potassium stearate as the hydrophilic surfactant.
That is, this result shows that the inclusion of an ionic surfactant as a hydrophilic surfactant for forming α-gel results in an excellent gap feeling even after storage at high temperature for a longer period of time. It is shown that it is possible to provide a W / O / W type emulsion composition exhibiting

As shown in Table 5, no matter what kind of higher alcohol is used, if the form contains an ionic surfactant, the W / O / W type emulsified form should be maintained for 3 months or longer. You can
Further, in comparison with the W / O / W type emulsion composition of Example 16 using lauryl alcohol (C12), Examples 10 to 12 using cetanol (C16) and behenyl alcohol (C22) were used. The W / O / W type emulsion composition of is more excellent in high temperature stability. This result indicates that it is more preferable to use a higher alcohol having 16 or more carbon atoms.

As shown in Table 5, as compared with the W / O / W type emulsion composition of Example 13 in which the total content of the higher alcohols was 1.3% by mass, the total content of the higher alcohols was 2.6% by mass, 3.5% by mass and 2.4% by mass of the W / O / W type emulsion compositions of Examples 10 to 12 are excellent in high temperature stability and moisturizing feeling.
Further, in comparison with the W / O / W type emulsion composition of Example 11 in which the total content of higher alcohols is 3.5% by mass, Example 10 in which the total content of higher alcohols is 2.6% by mass is Excellent in non-stickiness.
These results show that by setting the content of the higher alcohol to 2 to 3% by mass, the high temperature stability is excellent, and the W / O / which gives a comfortable gap feeling excellent in moisturizing property without causing stickiness. It shows that a W-type emulsion composition can be provided.

Further, Examples 10 to 12 in which the ratio of the total molar amount of the higher alcohol contained to the total molar amount of the hydrophilic surfactant is 3.1: 1, 4.2: 1, 2.7: 1. The W / O / W type emulsified compositions of Example 13 to 16 have the ratio of 1.6: 1, 1.8: 1, 1.5: 1, 5.8: 1. It is excellent in high temperature stability as compared with the W type emulsion composition.
This result shows that the W / O / W type emulsion composition in which the molar ratio of the higher alcohol to the hydrophilic surfactant is 2: 1 to 5: 1 is particularly excellent in high temperature stability. .

<Production Example 4>
By the same method as in Production Example 1, W / O / W type emulsion compositions having the blending ratios and emulsion particle sizes shown in Table 6 were produced (Examples 18 to 21).

<Test Example 5>
By the same method as in Test Example 1, the richness, the good elongation and the gap feeling were evaluated. The results are shown in Table 6 (for reference, the evaluation results of Example 1 are also shown).

As shown in Table 6, the W / O / W type emulsified compositions of Examples 1, 18 and 19 were excellent in richness as compared with the W / O / W type emulsified composition of Example 20, and The excellent elongation is superior to that of the W / O / W type emulsion composition of Example 21. Then, the W / O / W type emulsion compositions of Examples 1, 18 and 19 are excellent in gap feeling as compared with the W / O / W type emulsion compositions of Examples 20 and 21.
This result shows that the W / O / W type emulsion composition in which the ratio of the average particle diameters of W / O1 particles and O2 particles is 100: 1 to 2: 1 is particularly excellent in the gap feeling.

The present invention can be applied to W / O / W type emulsifier type cosmetics.

Claims (10)

The storage modulus G'at a stress of 1 Pa is 2000 Pa or more when the storage modulus G'is measured with a rheometer while increasing the stress under the conditions of an oscillation measurement, a gap of 1 mm, 1 Hz, and 20 ° C. , The change amount of the storage elastic modulus G ′ satisfies the following conditions (a) and (b),
The content of W / O particles is 15% by mass or more , further contains O particles, and the content of the W / O particles is 0.6 parts by mass or more when the content of the O particles is 1 part by mass. A W / O / W type emulsified composition characterized by the following.
(A) In the stress range of 1 Pa to 80 Pa, the decrease amount of the storage elastic modulus G ′ is 500 Pa or less,
(B) In the stress range of more than 80 Pa, the decrease amount of the storage elastic modulus G ′ with respect to the increase amount of the stress of 100 Pa is 2000 Pa or more.   The W / O / W type emulsion composition according to claim 1, wherein the W / O particles have an average particle size of 10 µm or more. The W / O / W type emulsion composition according to claim 1, wherein the amount of change in the storage elastic modulus G ′ further satisfies the following condition (c).
(C) In the range of stress exceeding 80 Pa, there is a range in which the decrease amount of the storage elastic modulus G ′ with respect to the increase amount of stress is 50 Pa or more.   The W / O / W type emulsion composition according to any one of claims 1 to 3, wherein the content of the optionally modified carboxyvinyl polymer is 0.3% by mass or less.   The W / O / W emulsion composition according to any one of claims 1 to 4, wherein the W / O particles do not contain an electrolyte.   The W / O / W type emulsion composition according to any one of claims 1 to 5, wherein the W / O particles contain an organically modified clay mineral.   The W / O / W type emulsion composition according to any one of claims 1 to 6, wherein the W / O particles contain a silicone-based surfactant.   The W / O / W type emulsion composition according to any one of claims 1 to 7, which comprises an oil-soluble humectant.   The W / O / W type emulsion composition according to any one of claims 1 to 8, wherein the outer aqueous phase contains an α-gel formed by a hydrophilic surfactant and a higher alcohol.   Cosmetics containing the W / O / W type emulsion composition as described in any one of Claims 1-9.