JP6630067B2 - W / O / W emulsion composition - Google Patents

Description

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

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

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

  In addition, Patent Document 2 discloses that a W / O / W / O / which contains a polysaccharide derivative having a specific side chain, has good spreadability at the time of application to the skin, imparts a moist feeling, and has no stickiness or oiliness. It is disclosed that a W-type emulsion composition can be provided.

  By the way, a technique for imparting a rich feeling of use to an emulsion composition has been proposed. For example, Patent Literature 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 in use”.

  Further, according to Patent Document 4, according to 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, emulsified cosmetics It is disclosed that a rich feeling of use can be imparted to water.

  On the other hand, Patent Literature 5 describes a gel lotion that has a viscosity by being mixed with a specific thickener in a specific amount, but has good elongation when applied to the skin and is not sticky.

JP 2002-275029 A JP 2007-284354 A JP-A-9-255529 JP 2007-106678 A JP 2013-103920 A

  As shown in Patent Documents 3 and 4, in order to impart a rich feeling of use to emulsified cosmetics, it is necessary to add a certain amount of a thickener such as a carboxyvinyl polymer. There is a problem that the growth of the product becomes worse.

  Further, as described in Patent Document 5, it has been studied to provide a gel-like cosmetic having viscosity with a good feeling of elongation by adjusting the compounding of the thickener used. Such studies have never been made in emulsified cosmetics.

In view of such a situation, the present invention has a rich and dense tactile sensation (richness) from before the application to the skin to the initial stage of the application, and spreads smoothly on the skin as the application proceeds, giving a comfortable feeling of use. It is an object of the present invention to provide a W / O / W type emulsified composition having a unique feeling of use (gap feeling) that gives a (feeling of good elongation).
Another object of the present invention is to provide a W / O / W type emulsified composition which has a feeling of gap and is hardly sticky.
Further, in a preferred embodiment of the present invention, it is an object to provide a W / O / W type emulsified composition having a feeling of gap, and excellent in moisturizing feeling and firmness.
Further, in a preferred embodiment of the present invention, it is an object to provide a W / O / W emulsion composition having a sense of gap and excellent in high-temperature stability.

The present invention that solves the above-mentioned problem is a W / O / W / O1 particle in which oil phase droplets including an aqueous phase and O2 particles that are oil phase droplets not including an aqueous phase are dispersed in an external aqueous phase. A W-type emulsion composition,
The content of the W / O1 particles is 15% by mass or more, and the ratio of the average particle size of the W / O1 particles to the O2 particles is 100: 1 to 2: 1. / W type emulsion composition.

  The W / O / W type emulsified composition of the present invention has a rich and dense tactile sensation, that is, richness, from before the application to the skin to the initial stage of the application, and spreads gently to the skin from the middle stage to the end stage of the application. It has a unique feeling of use that gives a pleasant feeling of use (feeling of elongation), that is, a gap.

In a preferred embodiment of the present invention, the W / O1 particles have an average particle size of 10 μm or more.
By setting the average particle diameter of the W / O1 particles in the above range, the richness felt before application to the skin and in the initial stage of application can be improved. In addition, it is possible to improve the feeling of use that stretches well from the middle stage to the final stage of application to the skin.
In other words, by setting the average particle diameter of the W / O1 particles in the above range, a unique feeling of use having a large difference between a rich feeling and a good feeling of use, that is, a large feeling of gap can be realized.

In a preferred embodiment of the present invention, the content of the W / O1 particles is 0.6 parts by mass or more when the content of the O2 particles is 1 part by mass.
By setting the content of the W / O1 particles in the above range, a W / O / W emulsion composition having a stronger gap can be obtained.

In a preferred embodiment of the present invention, the total content of the W / O1 particles and the O2 particles is 30 to 50% by mass.
By setting the total of the W / O1 particles and the O2 particles dispersed in the external aqueous phase within the above range, a W / O / W emulsion composition having a larger gap feeling can be obtained.

In a preferred embodiment of the present invention, the storage modulus G at a stress of 1 Pa is obtained by measuring the storage modulus G ′ with a rheometer while measuring the oscillation and increasing the stress under the conditions of a gap of 1 mm, 1 Hz and 20 ° C. 'Is 2000 Pa or more.
The W / O / W type emulsified composition having such physical properties has particularly good richness and good elongation, and exhibits an excellent gap feeling.

In a preferred embodiment of the present invention, an oil-soluble humectant is contained.
By adopting such a form, a W / O / W type emulsified composition having a comfortable gap feeling that provides a moisturizing feeling and firmness 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, an α-gel formed by a hydrophilic surfactant and a higher alcohol is contained in the outer aqueous phase.
By adopting such a form, it is possible to provide a W / O / W emulsion composition that maintains an excellent gap feeling even after long-term storage at a high temperature.

The present invention also relates to a cosmetic containing the above-mentioned W / O / W emulsion composition.
The cosmetic containing the W / O / W emulsion composition of the present invention has a gap.

According to the present invention, W / O / has a rich feeling in the initial stage of application from before the application to the skin, and turns into a feeling of good elongation as the application proceeds, that is, W / O / A W-type emulsion composition and a cosmetic containing the same can be provided.
Further, in a preferred embodiment of the present invention, it is possible to provide a W / O / W emulsion composition having a gap feeling, a moisturizing feeling and a firm feeling, and a cosmetic containing the same.
Further, in a preferred embodiment of the present invention, it is possible to provide a W / O / W emulsion composition having a gap feeling and excellent in high-temperature stability, and a cosmetic containing the same.

It is the schematic of a W / O / W type emulsion composition. It is a conceptual diagram of change of storage elastic modulus G 'with respect to an increase in stress, when measuring storage elastic modulus G' while increasing the stress applied with respect to a W / O / W type emulsion composition. For Examples 1 and 4 and Comparative Examples 3 to 5, oscillation was measured using a rheometer, the stress was changed under the conditions of a gap of 1 mm, 1 Hz, and 20 ° C., and the storage elastic modulus G ′ was measured. A graph in which the storage elastic modulus G 'is plotted on the vertical axis is shown.

In the W / O / W emulsion composition of the present invention, the content of W / O1 particles is 15% by mass or more, and the ratio of the average particle diameter of the W / O1 particles to the O2 particles is 100: 1 to 2: It is characterized by being 1.
Hereinafter, the present invention will be described in more detail.

  In the present invention, the W / O / W emulsion composition refers to an emulsion composition in which a W / O emulsion composition (also referred to as a primary emulsion) is further dispersed in an aqueous phase. Oil droplets dispersed in the outermost aqueous phase (outer aqueous phase) of the W / O / W type emulsified composition and containing the aqueous phase (inner aqueous phase) are referred to as W / O1 particles.

In the present invention, oil droplets not including an aqueous phase are further dispersed in an external aqueous phase.
Hereinafter, in this specification, as shown in FIG. 1, the internal aqueous phase is referred to as W1, the external aqueous phase is referred to as W2, the oil phase including the aqueous phase is referred to as O1, and the oil phase not including the aqueous phase is referred to as O2. Further, in the present specification, a W / O / W type emulsified composition in which oil droplets not including an aqueous phase are further dispersed in an external aqueous phase, particularly a (W / O1 + O2) / W type emulsified composition That.

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 in the initial stage of the application, and turns to a good feeling of elongation as the application proceeds.
In addition, richness refers to a rich and dense tactile sensation, and good stretchability refers to a comfortable sensation that spreads lightly over the skin.
The sense of gap can be evaluated by sensory evaluation. Specifically, it can be evaluated by performing a sensory evaluation on a rich feeling and a feeling of use with good elongation.

The W / O / W emulsion composition of the present invention is characterized in that the content of W / O1 particles is 15% by mass or more. Further, the content of W / O1 particles is preferably 15 to 30% by mass, more preferably 15 to 20% by mass, and still more preferably 16 to 18% by mass.
By setting the content of the W / O1 particles in the above range, the usability with good elongation can be improved from the middle stage to the late stage of application to the skin.
The amount of the W / O emulsion composition (primary emulsion) to be added to the external aqueous phase in the step of preparing the W / O / W emulsion composition described below is determined by the W / O / W emulsion composition. / O1 particle content. That is, by adjusting the amount of the primary emulsion dispersed in the external aqueous phase, the desired content of W / O1 particles can be obtained.

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

Further, the total content of the W / O1 particles and the O2 particles is preferably 20 to 70% by mass, more preferably 25 to 60% by mass, and still more 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 still more preferably 0.6 parts by mass or more. Not less than parts by mass.
By setting the total and ratio of the W / O1 particles and the O2 particles in the above range, the gap feeling can be further improved.

The ratio of the average particle diameter of the W / O1 particles to the O2 particles is 100: 1 to 2: 1, preferably 20: 1 to 3: 1, more preferably 10: 1 to 4: 1. is there.
By setting the ratio of the average particle diameter of the W / O1 particles to the average particle diameter of the O2 particles in the above range, an excellent gap feeling can be realized.

The average particle diameter of the W / O1 particles is preferably 10 μm or more, more preferably 10 to 30 μm, and still more preferably 10 to 20 μm.
The average particle diameter 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.
By setting the average particle diameters of the W / O1 particles and the O2 particles in the above range, it is possible to improve the richness felt 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 that stretches well from the middle stage to the final stage of application to the skin. That is, the W / O / W type emulsified composition of the embodiment is excellent in a unique feeling of use having a large difference between a rich feeling and a good feeling of elongation.

As will be described later, the particle diameters of the W / O1 particles and the O2 particles are determined by combining the stirring conditions such as the type of stirring and mixing device used for dispersing the primary emulsion and the oil phase in the external aqueous phase, the number of rotations, and the stirring time. In this case, the particle size can be controlled to a target range.
Further, as described later, when the primary emulsion and the oil phase are dispersed in the external aqueous phase by the membrane emulsification method, the particle diameters of the W / O1 particles and the O2 particles are determined by the pore diameter of the porous membrane used for membrane emulsification. Can be adjusted.

  The average particle size of the W / O1 particles and the O2 particles in the present specification refers to the particle size of about 100 W / O1 particles arbitrarily selected in a micrograph of the W / O / W emulsion composition. The value measured and averaged.

In the embodiment of the present invention, the mass ratio of W1 to O1 in the W / O / W emulsion composition is preferably from 10: 1 to 1:10, more preferably from 5: 1 to 1: 5, still more preferably. 2: 1-1: 2.
By setting the mass ratio of the aqueous phase to the oil phase within the above range, it is possible to improve the feeling of use, which has good elongation from the middle stage to the late stage of application to the skin.

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

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

The mass ratio between O2 and O1 is preferably 5: 1 to 1: 1, more preferably 4: 1 to 1.5: 1, and still more preferably 3: 1 to 2: 1.
By setting the mass ratio of O1 and O2 to the above range, the richness felt before application to the skin and in the initial stage of application can be improved.

The gap feeling can also be evaluated using a commercially available rheometer. Specifically, the evaluation can be made by measuring the storage elastic modulus G ′ when the stress is changed.
In a preferred embodiment of the present invention, a rheometer is used to measure the oscillation and to measure the storage elastic modulus G ′ while increasing the stress under the conditions of a gap of 1 mm, 1 Hz, and 20 ° C., at a stress of 1 Pa. The storage elastic modulus G ′ is 2000 Pa or more.

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

By the way, when the W / O / W emulsion composition is applied to the skin, stress is naturally applied to the composition, and the W / O / W emulsion composition has a viscoelasticity corresponding to the applied stress. Is shown.
The inventors of the present invention have found that the relationship between the stress measured under the above conditions and the storage elastic modulus G ′ indicates a change in the feel from the initial stage of application to the end of application when the W / O / W emulsion composition is applied to the skin. It was found that it expressed it.
Specifically, it has been found that the stage in which a stress of about 1 to 100 Pa is applied can be simulated as the stress applied to the W / O / W emulsion composition in the initial stage of application to the skin (FIG. 2). ). In addition, a stage in which a stress greater than 80 Pa, for example, a stress greater than 90 Pa or a stress greater than 100 Pa is applied, can be simulated as a stress applied to the W / O / W type emulsified composition after the middle stage of application to the skin. (FIG. 2).
When stress is applied to the W / O / W type emulsified composition of the present invention under the above conditions, the storage elastic modulus G ′ is a change in stress in a range where the applied stress is relatively small, for example, in a range of about 1 to 100 Pa. Hardly affected. However, at a point in time when the stress exceeds a certain level, for example, in a range exceeding 80 Pa, the storage elastic modulus G ′ decreases significantly with an increase in the stress (FIG. 2). This remarkable decrease in the storage modulus G 'affects the gap feeling that characterizes the unique feeling of use of the present invention.

In the W / O / W type emulsified composition of the present invention, the storage elastic modulus G ′ is preferably 2000 Pa or more, and more preferably 3000 Pa or more in the initial stage of application, that is, in the range of stress of 1 to 80 Pa. , 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 emulsified composition exhibiting excellent richness in the initial stage of application to the skin.

Further, it is preferable that the W / O / W type emulsified composition of the present invention has a form showing a large storage modulus G ′ even when a large stress is applied. Specifically, the W / O / W emulsion composition of the present invention, when measured under the above conditions, has a storage elastic modulus G ′ of preferably 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 more preferably 2000 Pa or more at 120 Pa.
As described above, even when a large stress is applied, by adopting a form that shows a large storage elastic modulus G ′, a sufficient richness is exhibited for a certain period in the initial stage of application to the skin. An O / W emulsion composition can be provided.
In order to adjust the storage elastic modulus G ′ under the stress to the above range, the viscosity of the external aqueous phase may be adjusted. The higher the viscosity of the external aqueous phase, the higher the storage modulus G '.
As a method for adjusting the viscosity of the external water phase, specifically, the adjustment of the concentration of the thickener in the external water phase, the adjustment of the amount of W / O1 particles or O2 particles dispersed in the external water phase, Formation of an α-gel by a higher alcohol and a hydrophilic surfactant in the outer aqueous phase.
The formation of the α-gel in the external water phase will be described later in detail.

When the storage elastic modulus G ′ of the W / O / W type emulsified composition is measured by the above-described method, the decrease in the storage elastic modulus G ′ is 500 Pa or less in a stress range of 1 to 80 Pa. Is preferably 300 Pa or less, more preferably 150 Pa or less.
Further, even in a stress range of preferably 1 to 90 Pa, more preferably 1 to 100 Pa, it is preferable that the amount of decrease in the storage modulus G ′ is within the above range.
By setting the amount of decrease in the storage modulus G ′ in the above-mentioned range of stress to the above-mentioned range, an excellent richness can be maintained during the operation of the initial stage of application to the skin. This makes it possible to make the user feel a noticeable change in usability.

In order to adjust the amount of decrease in the storage modulus G ′ in the above-described range of stress to the above range, the content of W / O1 particles and the particle diameter of W / O1 particles and O2 particles may be adjusted. The higher the content of W / O1 particles, the smaller the amount of decrease in storage modulus G 'in the range of the stress. In addition, as the particle size of the W / O1 particles increases, the amount of decrease in the storage elastic modulus G ′ at a stress of 1 to 80 Pa decreases.
Specifically, it can be realized by adjusting the content of the W / O1 particles, preferably the particle diameters of the W / O1 particles and the O2 particles in addition to the above ranges.

When the storage elastic modulus G ′ of the W / O / W emulsion composition of the present invention is measured by the above-described method, the storage elastic modulus G with respect to the increase in the stress of 100 Pa in the range of stress exceeding 80 Pa. It is preferable that the decrease amount of ′ has a range of 2000 Pa or more (FIG. 2).
Further, in the W / O / W emulsion composition of the present invention, the amount of decrease in the storage elastic modulus G ′ with respect to an increase in 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 emulsion composition having a more unique feeling of use, which has a large difference in the tactile sensation felt in the initial stage of application to the skin and in the middle and subsequent stages.
The content of the W / O1 particles and the particle size of the W / O1 particles may be adjusted in order to adjust the amount of decrease in the storage elastic modulus G ′ in the above-described stress range to the above range. The higher the content of W / O1 particles, the smaller the amount of decrease in storage modulus G 'in the range of the stress. In addition, as the particle size of the W / O1 particles increases, the amount of decrease in the storage elastic modulus G ′ at a stress of 1 to 80 Pa decreases.
Specifically, it can be realized by adjusting the content of the W / O1 particles, preferably the particle diameters of the W / O1 particles and the O2 particles in addition to the above ranges.

  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 modulus G ′ is ΔY, the numerical value (ΔY / ΔX) obtained by dividing ΔY by ΔX corresponds to the amount of change in stress. It represents the amount of change in storage modulus G '. That is, the larger the value of (ΔY / ΔX) in the negative direction, the larger the amount of decrease in the storage elastic modulus G ′ according to the increase in the stress, that is, the more rapidly the storage elastic modulus G ′ decreases. The present inventors have found that by setting the value of (ΔY / ΔX) in the following range, a sense of gap can be extremely remarkably exhibited.

That is, in the W / O / W type emulsified composition of the present invention, in the range of stress exceeding 80 Pa, preferably 90 Pa, and more preferably 100 Pa, the amount of decrease in storage modulus G ′ with respect to the increase in 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 a range of 55 Pa or more ((ΔY / ΔX) value is −55 or less).
As described above, the W / O / W type emulsified composition of the present invention in a form in which the storage elastic modulus G ′ rapidly decreases in accordance with the increase in the stress is changed from a rich feeling to a feeling of good elongation in use. It shows a sudden change in usability and has a very unique usability.
The value of (ΔY / ΔX) decreases as the content of W / O1 particles increases. Therefore, by adjusting the content of the W / O1 particles, it is possible to provide a W / O / W emulsion composition having a value of (ΔY / ΔX) in the above range.

  The oil component contained in the oil phase is not particularly limited, and liquid oils and fats, solid oils and fats, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, and the like can be used.

  Examples of liquid fats and oils 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, teaseed oil, kaya oil, rice bran oil, sinagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, glycerin trioctanoate, Glycerin triisopalmitate and the like can be mentioned.

  Solid oils and fats include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep butter, hardened tallow, palm kernel oil, lard, beef bone oil, mocro kernel oil, hardened oil, beef leg fat , Molle, hardened castor oil and the like.

  Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, and jojo. Examples include barrow, 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 the higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic (behenic) acid, 12-hydroxystearic acid, undecylenic acid, and tolic acid.

  Examples of the higher alcohol include cetyl alcohol, stearyl alcohol, behenyl alcohol, butyl alcohol, myristyl alcohol, and cetostearyl alcohol.

  Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, sucrose stearate, sucrose oleate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, fatty acid ester of dipentaerythritol, 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 Glycerin trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleic 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 linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane, and tetramethyltetrahydrogenpolysiloxane. Is mentioned.

  One or more oils can be used.

In the embodiment of the present invention, it is usually preferable to contain an emulsifier used for forming an emulsified composition.
As the emulsifier in the present invention, any of an ionic surfactant and 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 sulfates such as sodium lauryl sulfate and potassium lauryl sulfate; and polyoxyethylene lauryl sulfate. Alkyl ether sulfates such as triliethanolamine; N-acyl sarcosine acids such as lauroyl sarcosine sodium; higher fatty acid amide sulfonates such as N-myristoyl-N-methyltaurine sodium; sodium polyoxyethylene oleyl ether phosphate; Phosphate esters such as polyoxyethylene stearyl ether phosphate, sulfosuccinates such as sodium di-2-ethylhexylsulfosuccinate, sodium dodecylbenzenesulfonate Alkylbenzenesulfonates such as triethanolamine dodecylbenzenesulfonate, dodecylbenzenesulfonate, monosodium N-lauroylglutamate, disodium N-stearoylglutamate, and monosodium N-myristoyl-L-glutamate. And the like.

Examples of nonionic surfactants include, for example, polyoxyethylene alkyl ether-type activators such as polyoxyethylene oleyl ether, and ester-type activators such as polyoxyethylene hydrogenated castor oil, and further, polyoxyethylene glyceryl monoisostearate. Polyhydric alcohol fatty acid ester surfactants, such as ethylene oxide addition type surfactants such as ether / ester type surfactants such as glyceryl monostearate, and sorbitan fatty acid esters such as sorbitan monolaurate Is mentioned. Further, examples of the silicone surfactant include polyether-modified silicone.
In a more preferred embodiment of the present invention, a silicone surfactant is used as an emulsifier.

In the embodiment of the present invention, the content of the surfactant in the W / O / W emulsion composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably. It is 0.5 to 2% by mass.
By setting the content of the surfactant within the above range, the stability of the W / O / W emulsion composition can be improved.

In the embodiment of the present invention, when preparing a W / O-type emulsified composition as a primary emulsified product (a primary emulsification step described later), preferably 1 to 10 % By weight, more preferably 2 to 7% by weight of a surfactant is added.
By adjusting the amount of the surfactant to be added in the preparation of the W / O emulsion composition to the above range, the stability of the W / O emulsion composition, and hence the W / O / W emulsion composition, can be improved. It can be improved.

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

In a preferred embodiment of the present invention, an organically modified clay mineral is contained.
By containing the organically modified clay mineral, it becomes possible to further improve the stability of the W / O / W emulsion composition.

Further, in a more preferred embodiment of the present invention, the W / O1 particles contain an organically modified clay mineral.
When the W / O1 particles contain the organically modified viscosity mineral, the stability of the W / O / W 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 hectorite, bentonite, montrillonite, kaolinite, illite, marine clay mineral (sea mud), desert rose clay mineral, and pascalite.
Examples of the organic compound include a compound having a quaternary amino group. Specifically, stearyl trimethyl ammonium chloride, dimethyl distearyl ammonium chloride and the like can be mentioned.
In the embodiment of the present invention, dimethyl distearyl ammonium chloride-modified hectorite (distearyl dimonium hectorite) is preferably used as the organically modified clay mineral.
By containing dimethyl distearyl ammonium chloride-modified hectorite, the stability of the W / O / W emulsion composition is further improved.
In addition, it is possible to improve the gap feeling of the W / O / W emulsion composition.

In a preferred embodiment of the present invention, the W / O1 particles contain a silicone-based surfactant.
By making the W / O1 particles contain a silicone surfactant, the stability of the W / O / W emulsion composition can be improved.

In a more preferred embodiment of the present invention, the W / O1 particles contain an organically modified clay mineral and a silicone-based surfactant.
When the W / O1 particles contain the organic modified clay mineral and the silicone-based surfactant, the stability of the W / O / W emulsion composition can be improved.

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, and further preferably 0.05% by mass or less.
By setting the content of the water-soluble polymer in the above range, the stickiness of the W / O / W emulsion composition can be suppressed.

  Here, the water-soluble polymer refers to one having a viscosity-imparting effect, and includes arabic gum, tragacanth gum, karaya gum, xanthan gum, tamarind gum, guar gum, hydroxypropyl guar gum, locust bean gum, quince seed, gellan gum, native gellan gum, and 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, dimethylaminopropyl methacryl Amide, or a copolymer of these polymerizable monomer raw materials and other polymerizable monomers, or methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, alginic acid, carrageenan, hyaluronic acid, chondroitin sulfate, dermatan sulfate, collagen, chitin Derivatives, pectin, gelatin, carboxyvinyl polymer, acrylic acid / alkyl methacrylate copolymer and salts thereof, and the like.

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 a carboxyvinyl polymer which may be modified.
By setting the content of the carboxyvinyl polymer which may be modified in the above range, the stickiness of the W / O / W emulsion composition can be suppressed.

In a preferred embodiment of the present invention, the inner aqueous phase contains no electrolyte.
When the inner aqueous phase does not contain an electrolyte, the stickiness of the W / O / W emulsion composition can be suppressed.

In a preferred embodiment of the present invention, an oil-soluble humectant is included.
By including an oil-soluble humectant, the W / O / W-type emulsified composition imparts a comfortable gap feeling that a moisturizing feeling and a firm feeling are exhibited after the feeling of richness is changed to a good feeling of use. be able to.

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

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

In the W / O / W emulsion composition of the present invention, the oil-soluble humectant can be contained in the oil phase.
When the present invention is made into a (W / O1 + O2) / W emulsion composition, the oil-soluble humectant may be contained in either O1 or O2.
In a preferred embodiment of the present invention, O2 contains an oil-soluble humectant. In particular, when the dimer dilinoleic acid di (isostearyl / phytosteryl) is contained in O2, it is possible to provide a W / O / W emulsion composition having excellent moisturizing feeling and firmness.

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 in the above range, the moisturizing feeling and firmness at the time of using the W / O / W emulsion composition can be improved.

In a preferred embodiment of the present invention, an α-gel formed by a hydrophilic surfactant and a higher alcohol is contained in the outer aqueous phase.
According to such an embodiment, coalescence and drainage of W / O1 particles are suppressed by the action of the α-gel formed in the external aqueous phase, and W / O / W type emulsification excellent in high-temperature stability is achieved. A composition can be provided. That is, the W / O / W type emulsified composition of the present invention in such an embodiment maintains a feeling of use with a sense of gap even after storage 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 emulsion composition can be further improved.

The ionic surfactant is not particularly limited, but includes fatty acid salts such as sodium laurate, sodium stearate, potassium stearate, and potassium palmitate; polyoxyethylene alkyl ether phosphoric acid and salts thereof; alkaloyl alkyl taurine salts; Preferred 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 nonionic surfactant having an HLB of 8 or more, more preferably 10 or more, further preferably 12 or more, further preferably 14 or more, and still more preferably 16 or more. Contains a surfactant.
By using such a surfactant having a high degree of hydrophilicity, the high-temperature stability of the W / O / W emulsion composition can be further improved.
Note that HLB in this specification refers to HLB calculated by the Griffin method.

  The nonionic surfactant described above is not particularly limited as long as it can form a higher alcohol and an α-gel, and a lipophilic surfactant which does not form an α-gel within a range where an α-gel structure can be formed is used in combination. 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% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.5 to 2% by mass. %.
By setting the content of the hydrophilic surfactant in the above range, a W / O / W emulsion composition exhibiting an excellent gap feeling even after storage at a high temperature for a longer period of time can be obtained. Can be provided.

In a preferred embodiment of the present invention, the higher alcohol has a carbon number of preferably 8 to 22, more preferably 16 to 22, and still more preferably 16 to 18.
By using a higher alcohol having a carbon number in the above range, it is possible to provide a W / O / W emulsion composition that exhibits an excellent gap feeling even after storage at a 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 still more preferably 2 to 3% by mass.
By setting the content of the higher alcohol 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 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. ５5: 1.
By setting the molar ratio between the higher alcohol and the hydrophilic surfactant within the above range, a W / O / W emulsion composition that exhibits an excellent gap feeling even after storage at a high temperature for a longer period of time. Things can be provided.

In a preferred embodiment of the present invention, the mass ratio of the content of the W / O1 particles dispersed in the external aqueous 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, even more preferably 3: 1 to 5: 1.
By setting the mass ratio of the W / O1 particles to the hydrophilic surfactant and the higher alcohol within the above range, the W / O exhibiting an excellent gap feeling even after a long-term storage at a high temperature. / W type emulsified composition can be provided.

  The W / O / W type emulsified cosmetic of the present invention may be blended with any optional components usually added to cosmetics as long as the effects of the present invention are not impaired. Examples of such additional components include humectants such as polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol; lower alcohols such as ethanol; butylhydroxytoluene, tocopherol, phytin and the like. Antioxidants; antibacterial agents such as benzoic acid, salicylic acid, sorbic acid, p-hydroxybenzoic acid alkyl ester, and hexachlorophene; p-aminobenzoic 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 ultraviolet absorbers such as BA2-ethylhexyl ester; anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p Salicylic acid ultraviolet absorbers such as isopropanol phenyl salicylate; octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4- Diisopropyl cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, 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 ultraviolet 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 (g 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 and the like silicone-based cinnamic acid ultraviolet absorbers; -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 Benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone Benzophenone-based ultraviolet absorbers such as 4-hydroxy-3-carboxybenzophenone; 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid ethyl ester, Phenyl-5-methylbenzoxazole, 2,2′-hydroxy-5-methylphenylbenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy- 5'-methylphenyl) benzotriazoe UV absorbers such as benzene, dibenzalazine, dianisoylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 5- (3,3'dimethyl-2-norbornylidene) -3-pentan-2-one; acyl Organic acids such as sarcosine acid (for example, sodium lauroyl sarcosine), glutathione, citric acid, malic acid, tartaric acid, and lactic acid; vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and the like Vitamin B such as derivatives, vitamin B12, vitamin B15 and derivatives thereof, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E such as vitamin E acetate, vitamin D, vitamin H, pantothenic acid, pantethine, nicotine Acid amide, d Vitamins such as benzyl formate; γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, tranexamic acid and its derivatives [Tranexamic acid derivatives include tranexamic acid dimers (eg, trans-hydrochloride). 4- (trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid, etc.), esters of tranexamic acid and hydroquinone (eg, trans-4-aminomethylcyclohexanecarboxylic acid 4′-hydroxyphenyl ester, etc.), tranexamic acid (E.g., 2- (trans-4-aminomethylcyclohexylcarbonyloxy) -5-hydroxybenzoic acid and its salts, etc.) and tranexamic acid amide (e.g., tolane) (S-4-Aminomethylcyclohexanecarboxylic acid methylamide and its salt, trans-4- (P-methoxybinzoyl) aminomethylcyclohexanecarboxylic acid and its salt, trans-4-guanidinomethylcyclohexanecarboxylic acid and its salt, etc.) ), Saponins such as hinokitiol, bisabolol, eucalptone, thymol, inositol, saikosaponin, carrot saponin, hemimasaponin, muclodisaponin, pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, arbutin, cepharanthin, placenta extract, etc. Drugs: Rye, Clara, Kouhone, orange, sage, yarrow, mallow, thyme, thyme, spruce, spruce, birch, horsetail, loofah, marronnier, snowy , Arnica, lily, mugwort, peonies, aloe, gardenia, sawara and other plant extracts; pigments; porous and / or water-absorbing powders (eg, starches obtained from corn, potato, etc., silicic anhydride, talc) , A powder of kaolin, aluminum magnesium silicate, calcium alginate, etc.); a neutralizing agent; a preservative; a perfume;

  The method for producing the W / O / W emulsion composition of the present invention is not particularly limited, and it can be produced, for example, by the following Preparation Method 1 or Preparation Method 2.

(Preparation method 1) An oil-in-water emulsion composition (O2 / W2) is prepared by dispersing O2 in 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 emulsion composition (W1 / O1 / W2). I do. A (W1 / O1 + O2) / W-type emulsion composition is prepared by mixing this emulsion composition and a water-in-oil emulsion composition (O2 / W2) in which O2 is dispersed in W2, which is prepared in advance. can do.

  In this case, whether the higher alcohol is added as an O1 component or as an O2 component, an α-gel can be formed in the external aqueous phase.

The average particle diameter of the W / O1 particles and the O2 particles in the W / O / W emulsion composition of the present invention can be controlled by various methods, but a method controlled by stirring conditions in the emulsification step is preferably exemplified.
In general, as the number of revolutions of the stirring and mixing device used in the emulsification process increases, and as the stirring time increases, the load due to shearing, collision, and cavitation increases. Therefore, the average particle diameter of the W / O1 particles and the O2 particles of the W / O / W emulsion composition of the present invention is determined by complexly adjusting the stirring conditions such as the type of the stirring and mixing device, the number of rotations, and the stirring time. Thereby, it can be controlled to a target particle size range.

  Examples of the stirring and mixing device include a high-speed emulsifying device such as a homodisper, a homomixer, a homogenizer, and a microfluidizer, a disper mixer having a sawtooth-shaped stirring blade, an impeller-type stirring device having a rotating blade, and the like. . The W / O / W emulsion composition containing the W / O1 particles and the O2 particles having the average particle diameter specified in the present invention can be produced by using any of the above stirring and mixing devices, and particularly represented by homodispers. It is preferable to use a high-speed emulsifying device.

Further, the W / O / W 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 by a method of injecting a liquid to be a dispersed phase through a porous membrane into a liquid to be a continuous phase with nitrogen gas or the like.

  The method of adjusting the ratio of the average particle diameter of the W / O1 particles and the O2 particles is not limited. However, when the W / O / W emulsion composition is produced by the above-mentioned Preparation Method 1 and Preparation Method 2, the following method is used. Can be adjusted.

  When the preparation method 1 is adopted, the average particle diameter of the O2 particles is adjusted at the stage of preparing the oil-in-water emulsion composition (O2 / W2) to prepare a (W1 / O1 + O2) / W emulsion composition. By adjusting the average particle diameter of the W / O1 particles at the stage, the ratio of the average particle diameter of the W / O1 particles to the O2 particles can be adjusted to the range specified in the present invention.

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

  The W / O / W type emulsified composition of the present invention can be used as cosmetics such as emulsions, creams, serums, sunscreens, liquid foundations, etc., external preparations for the skin, quasi-drugs and pharmaceuticals.

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

After heating and dissolving the O2 component and the W2 component shown in Table 2, the O2 component was gradually added to a part of the W2 component while stirring to emulsify to prepare an O2 / W emulsion. Further, the above-mentioned primary emulsion was gradually added to the remainder of the W2 component with stirring to emulsify, thereby preparing a W / O1 / W emulsion composition.
In addition, the average particle diameter of W / O1 particles and O2 particles was adjusted by adjusting the stress in stirring at the time of producing the O2 / W emulsion and the W / O1 / W emulsion composition.
By mixing the O2 / W emulsion and the W / O1 / W emulsion composition, the W / O / W emulsion compositions of Examples 1 to 3 and Comparative Examples 1 and 2 ((W / O1 + 2 ) / W-type emulsified composition) was prepared.
The W / O / W emulsion composition thus prepared was observed with a microscope, and the average particle diameter of W / O1 particles and O2 particles was measured. 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 methods.
Twenty panelists applied the W / O / W type emulsified compositions of Examples 1 to 3 and Comparative Examples 1 and 2 in their containers to their own skin. Then, according to the following evaluation criteria, 1 to 5 points regarding the richness felt from scooping up the W / O / W type emulsified composition from the container to the initial stage of application and the good elongation from the middle stage to the end stage of application. And the average was taken.
Then, the gap feeling was evaluated based on the evaluation results of the rich feeling and the good feeling of use.
The results are shown in Table 2.
・ 5 points of richness ... 4 points with very strong richness ... 3 points with strong richness ... 2 points with richness ... 1 point with weakness of richness ... no richness

-5 points of good elongation-4 points with fairly good elongation-3 points with good elongation-2 points with elongation-1 point with slightly poor elongation-very poor elongation

As shown in Table 2, the W / O / W type emulsified compositions of Examples 1 to 3 are more excellent in richness than the W / O / W type emulsified composition of Comparative Example 1, and Excellent in elongation as compared with the W / O / W emulsion composition of Example 2. The W / O / W emulsion compositions of Examples 1 to 3 are superior in the sense of gap as compared with the W / O / W emulsion compositions of Comparative Examples 1 and 2.
This result indicates that the W / O / W emulsion composition in which the ratio of the average particle diameter of the W / O1 particles to the O2 particles is 100: 1 to 2: 1 is excellent in a gap feeling.

<Production Example 2>
A W / O / W emulsion composition having a blending ratio shown in Table 3 was produced in the same manner as in Production Example 1 (Example 4, Comparative Examples 3 to 5).

<Test Example 2>
In the same manner as in Test Example 1, the W / O / W emulsion compositions of Example 4 and Comparative Examples 3 to 5 were evaluated for richness, good elongation, and gap. The results are shown in Table 3 (the evaluation results of Example 1 are also shown for reference).

As shown in Table 3, the content of W / O1 particles in the W / O / W emulsion composition (Examples 1 and 4) in which the content of W / O1 particles is 16% by mass or 20% by mass is as follows. Compared with the W / O / W type emulsified composition of 10% by mass (Comparative Examples 4 and 5), the feeling of body is remarkably strong and the use feeling with good elongation is excellent. The W / O / W emulsion compositions of Examples 1 and 4 have a unique feeling of use with an excellent gap feeling.
From these results, it is found that the W / O / W emulsion composition having a content of W / O1 particles of 15% by mass or more has unique characteristics such as a rich feeling that is difficult to achieve compatibility and a feeling of use with good elongation. Was.

The W / O / W emulsion compositions of Example 1 and Comparative Example 3 each had a content of W / O1 particles of 16% by mass, but the W / O / W emulsion composition of Comparative Example 3 was 16% by mass. Is inferior in the sense of gap as compared with the W / O / W emulsion composition of Example 1.
When the results of Test Example 1 and Test Example 2 are combined, in order to obtain a W / O / W emulsion composition having an extremely good gap feeling, the content of W / O1 particles is 15% by mass or more, Further, it shows that the ratio of the average particle diameter of the W / O1 particles to the O2 particles needs to be 100: 1 to 2: 1.

<Test Example 3>
For the W / O / W emulsion compositions of Examples 1 and 4 and Comparative Examples 3 to 5, using a rheometer (TA Instruments AR-G2), a temperature of 20 ° C., an oscillation measurement, and a gap of 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 4 and FIG. 3, the W / O / W emulsion compositions of Examples 1 and 4 and Comparative Examples 3 to 5 all have a storage elastic modulus G ′ of 2000 or more at a stress of 1 Pa.

Further, in the W / O / W type emulsified compositions of Examples 1 and 4, the storage elastic modulus G 'hardly decreases in the range of stress of 1 Pa to 80 Pa.
On the other hand, the W / O / W type emulsified compositions of Comparative Examples 4 and 5 decrease by about 2300 Pa and about 700 Pa, respectively, in the range of stress of 1 Pa to 80 Pa.

  The W / O / W type emulsified compositions of Examples 1 and 4 were subjected to a storage modulus G ′ while the stress was increased by about 100 Pa, about 120 Pa, and about 100 Pa, respectively, while the stress was further increased by 100 Pa. Decreased by about 3600 Pa, about 8700 Pa, and about 3000 Pa, respectively.

From the above results, the W / O / W type emulsified compositions of Examples 1 and 4 showed (a) a stress range of 1 Pa to 80 Pa when the storage elastic modulus G ′ was measured while increasing the stress under the above conditions. In the above, there is a range in which the decrease in the storage elastic modulus G 'is 500 Pa or less, and (b) in the range of the stress exceeding 80 Pa, the decrease in the storage elastic modulus G' with respect to the increase in the stress of 100 Pa is 2000 Pa or more.
When this result and the result of Table 2 are combined, as a result of measurement by a rheometer, the W / O / W type emulsified composition satisfying the above (a) and (b) has a strong feeling of richness and a good feeling of elongation. It is also clear that the gap is strong.

As described above, the W / O / W emulsion compositions of Examples 1 and 4 each have a storage elastic modulus G ′ in the range of 1 Pa to about 100 Pa, 1 Pa to about 120 Pa, and 1 Pa to about 100 Pa. Hardly drops.
When this result is combined with the results in Table 3, the larger the range of the stress at which the storage elastic modulus G ′ hardly decreases, the stronger the richness felt in the initial stage of application of the W / O / W emulsion composition to the skin. It can be seen that the sense of gap tends to increase.

In addition, the W / O / W type emulsified compositions of Examples 1 and 4 have storage elastic moduli G ′ of about 3600 Pa and about 8700 Pa, respectively, when the stress exceeds 100 Pa and the stress exceeds 100 Pa.
When this result is combined with the results in Table 3, it can be seen that the richness tends to increase as the storage elastic modulus G ′ decreases beyond the above range.

Table 4 shows numerical values (ΔX / ΔY) obtained by dividing the change in the storage elastic modulus G ′ by the change in the stress. As shown in Table 4, the W / O / W type emulsified compositions of Examples 1 and 4 have stresses (ΔX / ΔY) of about −58 and about −240, respectively, in the range of stress exceeding 80 Pa. There is a range.
When this result is combined with the results in Table 3, (c) in the range of stress exceeding 80 Pa, there is a range where the amount of decrease in the storage modulus G ′ with respect to the increase in stress is in the range of 50 Pa or more. The object has a strong sense of richness and a strong sense of gap.

  The results of Test Examples 2 and 3 indicate that the W / O / W type emulsified compositions of Examples 1 and 4 have an excellent richness from before the application to the initial stage of the application, but sharply from the middle to the end of the application. It shows a unique feeling of use that turns into a feeling of good elongation, that is, an excellent gap feeling.

<Production Example 4>
W / O / W emulsion compositions having the blending ratios shown in Table 5 were produced in the same manner as in Production Example 1 (Examples 5 to 10). The average particle diameters of W / O1 particles and O2 particles in the W / O / W emulsion compositions of Examples 5 to 10 and their ratios are the same as in Example 1.
As a comparative example, an O / W emulsion composition having the compounding ratio shown in Table 5 was produced (Comparative Example 6). The O / W emulsion composition of Comparative Example 6 was prepared 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 4>
The moisturizing feeling and firmness of the W / O / W emulsion compositions of Examples 5 to 10 and the O / W emulsion composition of Comparative Example 6 were evaluated by the following methods.
Twenty panelists applied the W / O / W emulsion compositions of Examples 5 to 10 and the O / W emulsion composition of Comparative Example 6 to their own skin. Then, the moisturizing feeling and firmness were evaluated according to the following evaluation criteria.
Table 5 shows the results.
・ Moisture feeling ◎ ・ ・ ・ Feel strong moist feeling ○ ・ ・ ・ Feel moist feeling △ ・ ・ ・ Not much moist feeling × ... No moist feeling

・ A feeling of tension ◎ ・ ・ ・ A feeling of tension is strong ○ ・ ・ ・ A feeling of tension is felt △ ・ ・ ・ A feeling of tension is not so much felt × ・ ・ ・ A feeling of tension is not felt

As shown in Table 5, the W / O / W-type emulsified compositions of Examples 5 to 8 containing di (isostearyl / phytosteryl) dimer dilinoleate, which is an oil-soluble humectant, did not contain the compound. As compared with the W / O / W type emulsified compositions of Examples 9 and 10, it was found that they had excellent moisturizing feeling and firmness.
This result indicates that the W / O / W emulsion composition containing the oil-soluble humectant has excellent moisturizing feeling and firmness during use.

In addition, the W / O / W type emulsified compositions of Examples 6 and 7 in which the content of dimer dilinoleic acid di (isostearyl / phytosteryl) is 10% by mass or 14% by mass are sticky.
On the other hand, it is found that the W / O / W emulsion compositions of Examples 5 and 8 in which the content of di (distearyl / phytosteryl) dimer dilinoleate is 2% by mass or 5% by mass do not cause stickiness. Was.
This result indicates that the W / O / W type emulsified composition having an oil-soluble humectant content of 2 to 5% by mass does not cause stickiness while exhibiting a moisturizing feeling and is excellent in use feeling with good elongation. Is shown.

Further, the W / O / W emulsion composition of Example 5 was compared with the O / W emulsion composition of Comparative Example 6 even though the contained components and the content were the same. It was found that it exhibited remarkably excellent moisture retention and firmness.
The results show that the inclusion of the oil-soluble humectant makes the moisturizing feeling and firmness feel very comfortable when used in combination with the gap feeling of the W / O / W emulsion composition of the present invention. ing.

  As described above, the W / O / W type emulsified composition of the present invention can remarkably enhance the feeling of moisturizing and firmness. Therefore, the W / O / W type emulsifying composition preferably contains an oil-soluble humectant.

<Production Example 3>
W / O / W emulsion compositions having the blending ratios shown in Table 6 were produced in the same manner as in Production Example 1 (Examples 11 to 18).

<Test Example 5>
The high-temperature stability, moisture retention and non-stickiness of the W / O / W emulsion compositions of Examples 11 to 18 were evaluated by the following methods. The results are shown in Table 6.
-High temperature stability The W / O / W type emulsified compositions of Examples 11 to 18 were stored at 40 ° C, and the period of maintaining the W / O / W type observed before the start of the storage test was examined. .
-Moisturizing feeling and non-stickiness The W / O / W type emulsified compositions of Examples 11 to 18 were applied to their own skin to 20 panelists. Then, a score was given for the moisturizing feeling and non-stickiness according to the following evaluation criteria, and the average value was taken.
5 points of moisturizing feeling 4 points of feeling very good moisturizing 3 points of good moisturizing 3 points 2 points of feeling of moisturizing 1 point of almost no feeling of moisturizing・ I do not feel moisturizing

5 points without stickiness 4 points that are not sticky at all 3 points that are almost sticky 2 points that are slightly sticky 1 point that is sticky

The W / O / W emulsion compositions of Examples 11 to 18 contain a higher alcohol and a hydrophilic surfactant, and form an α-gel in the external aqueous phase.
And as shown in Table 6, the W / O / W type emulsified composition of Examples 11-18 has maintained the W / O / W type emulsified form for 1 month or more at 40 degreeC under all. .
This result indicates that the W / O / W emulsion composition containing the α-gel formed by the hydrophilic surfactant and the higher alcohol in the external aqueous phase maintains an excellent gap feeling even after long-term storage at a high temperature. It is shown that.

As shown in Table 6, the W / O / W type emulsified composition of Example 18 can maintain the emulsified form for one month, while the W / O / W type emulsified composition of Examples 11 to 17 has 40%. The W / O / W type emulsified form was maintained for 3 months or more at ℃.
This result indicates that the high-temperature stability of the W / O / W emulsion composition is improved by containing potassium stearate as a hydrophilic surfactant.
In other words, this result shows that the inclusion of an ionic surfactant as a hydrophilic surfactant for the formation of an α-gel provides an excellent gap feeling even after a long-term storage at a high temperature. This shows that a W / O / W type emulsified composition exhibiting the following can be provided.

As shown in Table 6, no matter what kind of higher alcohol is used, the W / O / W type emulsified form should be maintained for 3 months or more as long as the form contains an ionic surfactant. Can be.
Examples 11 to 13 using cetanol (carbon number 16) and behenyl alcohol (carbon number 22) as compared with the W / O / W emulsion composition of Example 17 using lauryl alcohol (carbon number 12). The W / O / W type emulsified composition of (1) 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 6, compared to the W / O / W emulsion composition of Example 14 in which the total content of higher alcohol was 1.3% by mass, the total content of higher alcohol was 2.6% by mass, 3.5% by mass and 2.4% by mass of the W / O / W emulsion compositions of Examples 11 to 13 are excellent in high-temperature stability and moisturizing feeling.
Further, as compared with the W / O / W emulsion composition of Example 12 in which the total content of higher alcohol was 3.5% by mass, Example 10 in which the total content of higher alcohol was 2.6% by mass was Excellent in non-stickiness.
These results indicate that by setting the content of the higher alcohol to 2 to 3% by mass, W / O / which is excellent in high-temperature stability and gives a comfortable gap feeling excellent in moisture retention without causing stickiness. This shows that a W-type emulsion composition can be provided.

Examples 11 to 13 in which the ratio of the total molar amount of the higher alcohol to the total molar amount of the hydrophilic surfactant contained was 3.1: 1, 4.2: 1, 2.7: 1. The W / O / W type emulsified composition of Examples 14 to 17 in which the ratio is 1.6: 1, 1.8: 1, 1.5: 1, 5.8: 1. High temperature stability is superior to W-type emulsion composition.
This result indicates that the W / O / W 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. .

The present invention can be applied to a W / O / W type emulsifying cosmetic.

Claims (8)

W / O / W type emulsification for application to the skin, wherein W / O1 particles as oil phase droplets containing an aqueous phase and O2 particles as oil phase drops not containing an aqueous phase are dispersed in an aqueous phase. A composition,
Before application to the skin, the content of the W / O1 particles is 15% by mass or more, and the ratio of the average particle diameter of the W / O1 particles to the O2 particles is 100: 1 to 2: 1. A W / O / W emulsion composition, which is characterized by the following.   The W / O / W emulsion composition according to claim 1, wherein the average particle diameter of the W / O1 particles is 10 µm or more.   The W / O / W according to claim 1 or 2, wherein the content of the W / O1 particles is 0.6 parts by mass or more when the content of the O2 particles is 1 part by mass. -Type emulsion composition.   The W / O / W type according to any one of claims 1 to 3, wherein the total content of the W / O1 particles and the O2 particles is 30 to 50% by mass or more. Emulsion composition.   When the storage elastic modulus G 'is measured with a rheometer while measuring the oscillation while increasing the stress under the conditions of a gap of 1 mm, 1 Hz, and 20 ° C., the storage elastic modulus G' at a stress of 1 Pa is 2,000 Pa or more. The W / O / W emulsion composition according to any one of claims 1 to 4, characterized in that:   The W / O / W emulsion composition according to any one of claims 1 to 5, further comprising an oil-soluble humectant.   The W / O / W emulsion composition according to any one of claims 1 to 6, wherein an α-gel formed by a hydrophilic surfactant and a higher alcohol is contained in the external aqueous phase.   A cosmetic comprising the W / O / W emulsion composition according to any one of claims 1 to 7.