JP2021147371A - Method for producing oil-in-water type emulsion composition - Google Patents

Abstract

To provide a method for producing an oil-in-water type emulsion composition capable of forming pickering emulsion particles having a relatively large particle diameter.SOLUTION: There is provided a method for producing an oil-in-water type emulsion composition which comprises: a step 1 of preparing a nonaqueous mixed solution (I) by mixing component (A): a powder which is an octenyl succinic acid starch ester metal salt and/or talc and component (B); an oily component having an IOB value of 0 to 0.45 which is one or more selected from the group consisting of a silicone oil, a hydrocarbon oil, an ester oil and a vegetable oil; a step of preparing a mixed solution (II) by mixing the nonaqueous mixed solution (I), component (C) and component (D); and a step 3 of emulsifying the mixed solution (II), where the mass ratio [component (B)/component (A)] is 0.05 to 12.5, the mass ratio [component (C)/{component (C)+component (D)}] in the mixed solution (II) is 0.20 to 0.99 and the mass ratio [{component (C)+component (D)}/mixed solution (II)] is 0.50 or more.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an oil-in-water emulsified composition.

Liquid cosmetics such as body lotions, refreshing cosmetics, and deodorants have a unique appearance by dispersing visible-sized particles in the liquid, creating new aesthetic value for consumers. It is expected that demand will be greatly stimulated.
Scrubbing agents are examples of particles used in cosmetics, and it is conceivable to use particles having a large size. Further, as a large-sized particle, for example, calcium alginate capsules are known.

However, a large-sized scrubbing agent is irritating when applied to the skin, and further has a problem of remaining on the skin after application and causing discomfort. Calcium alginate capsules also have a problem that aggregates remain on the skin after application and cause discomfort.

On the other hand, so-called pickering emulsions in which oil droplets are stabilized by powder and contain no surfactant or only a small amount are known (for example, Patent Documents 1 to 4).

Japanese Unexamined Patent Publication No. 2000-95638 Japanese Unexamined Patent Publication No. 2000-956639 JP-A-2018-188497 Japanese Unexamined Patent Publication No. 2019-202962

However, the pickering emulsion particles disclosed in Patent Documents 1 to 4 are formed by a method of dispersing the powder in water, then adding an oily component, and stirring the powder. In such a method, the volume particle diameter is increased. There is a problem that only pickling emulsion particles having a diameter of 100 μm or less can be obtained.

Therefore, an object of the present invention is to provide a method for producing an oil-in-water emulsified composition capable of forming relatively large pickering emulsion particles.

As a result of diligent studies to achieve the above object, the present inventors have found that component (A): octenyl succinate starch ester metal salt and / or talc powder, component (B): silicone oil, hydrocarbon oil, ester. An oily component having an IOB value of 0 to 0.45, which is one or more selected from the group consisting of oils and vegetable oils, component (C): ethanol, and component (D): water, components (A) to It has been found that by mixing (D) in a specific order and in a specific mass ratio, relatively large pickering emulsion particles can be obtained in an oil-in-water emulsified composition. The present invention has been completed based on these findings.

That is, in the present invention, the following component (A) and the following component (B) are blended to prepare a non-aqueous mixed solution (I) containing substantially no water, and the step 1
Step 2 to prepare the mixed liquid (II) by blending the non-aqueous mixed liquid (I), the following component (C) and the following component (D), and
It has a step 3 of emulsifying the mixture (II).
The mass ratio [component (B) / component (A)] of the following component (B) to the following component (A) in the non-aqueous mixture (I) is 0.05 to 12.5.
Mass ratio of the following component (C) to the total amount of the following component (C) and the following component (D) in the mixed solution (II) [component (C) / {component (C) + component (D)}] Is 0.25 to 0.99,
Mass ratio of the total amount of the following component (C) and the following component (D) to the mixed solution (II) in the mixed solution (II) [{component (C) + component (D)} / mixed solution ( II)] provides a method for producing an oil-in-water emulsified composition having a value of 0.50 or more.
Component (A): Powder of octenyl succinate starch ester metal salt and / or talc Component (B): 1 or more selected from the group consisting of silicone oil, hydrocarbon oil, ester oil, and vegetable oil, and has an IOB value. Oily component (C): ethanol component (D): water

In the production method of the present invention, polyglyceryl-10 decaisostearate may be further added in step 1.

In the production method of the present invention, the blending ratio of the surfactant other than polyglyceryl-10 decaisostearate in the oil-in-water emulsified composition is preferably 0.1% by mass or less.

According to the production method of the present invention, an oil-in-water emulsified composition in which relatively large pickering emulsion particles are formed can be efficiently produced.

[Manufacturing method of oil-in-water emulsified composition]
The production method of the present invention is one or more selected from the group consisting of octenyl succinate starch ester metal salt and / or talc powder; silicone oil, hydrocarbon oil, ester oil, and vegetable oil, and has an IOB value of 0. It is a method for producing an oil-in-water emulsified composition, which can obtain an oil-in-water emulsified composition in which relatively large pickering emulsion particles are formed from an oily component having an oil content of ~ 0.45; ethanol; and water. In the present specification, one or more of the octenyl succinic acid starch ester metal salt and / or talc powder selected from the group consisting of "component (A)", silicone oil, hydrocarbon oil, ester oil, and vegetable oil. The oily component having an IOB value of 0 to 0.45 may be referred to as "component (B)", ethanol may be referred to as "component (C)", and water may be referred to as "component (D)". That is, the production method of the present invention uses the above-mentioned component (A), the above-mentioned component (B), the above-mentioned component (C), and the above-mentioned component (D) to obtain an oil-in-water emulsification composition. It is a manufacturing method of goods. Further, in the present specification, the oil-in-water emulsified composition produced by the production method of the present invention may be referred to as "the oil-in-water emulsified composition of the present invention".

In the method for producing an oil-in-water emulsified composition of the present invention, the mass ratio of the above component (B), which is an oily component, and the above component (A), which is a powder, to the above component (A). [Component (B) / Component (A)] Step 1 to prepare a non-aqueous mixed solution (I) that is substantially free of water by mixing in 0.05 to 12.5.
A step of mixing the non-aqueous mixture (I), the component (C) which is ethanol, and the component (D) which is water to prepare a mixture (II), wherein the mixture (II) is prepared. The mass ratio of the component (C) to the total amount of the component (C) and the component (D) [component (C) / {component (C) + component (D)}] is 0.20 to 0. 99, which is the mass ratio of the total amount of the component (C) and the component (D) to the mixed solution (II) in the mixed solution (II) {component (C) + component (D)} / mixing. Liquid (II)] is 0.50 or more in step 2 and
It has a step 3 of emulsifying the mixture (II).

<Step 1>
Step 1 is a step of mixing at least the component (A) and the component (B) to prepare a non-aqueous mixed solution (I) containing substantially no water. Substantially free of water means that the content ratio of water in the non-aqueous mixture is, for example, 0.5% by mass or less, preferably 0.3% by mass or less.

These mixing can be performed by, for example, stirring using a general stirring device or a stirring device (homo mixer, paddle mixer, etc.). The stirring time is not particularly limited and can be appropriately set according to the type of stirring device or stirring device, the type and amount of each component, and the like.

(Ingredient (A))
Ingredient (A) is a powder of octenyl succinate starch ester metal salt and / or talc. The component (A) exerts the effect of blending the powder in the oil-in-water emulsified composition (giving a feeling of low friction to the skin after use, reducing the feeling of powder, giving an appropriate moisturizing feeling, etc.). At the same time, a pickering emulsion can be formed by using it in combination with the components (B) to (D). As the component (A), only one kind may be used, or two or more kinds may be used.

Examples of the octenyl succinic acid starch ester metal salt include aluminum salt, calcium salt, barium salt, iron salt and the like of octenyl succinic acid starch ester. Of these, an aluminum salt (starch aluminum octenyl succinate) is preferable. The octenyl succinate starch aluminum may be referred to as octenyl succinate starch Al or octenyl succinate corn starch aluminum. In addition, the starch aluminum octenyl succinate may be described as ALUMINUM STARCH OCTENYLSUCCINATE in the INCI name.

In the production method of the present invention, the component (A) is a powder. The octenyl succinate starch ester metal salt is hydrophilized and gelled (so-called gelatinization and gelatinization) by heating to a relatively high temperature (for example, 60 ° C. or higher) and is no longer in a powder state, and can be used as a thickener. May be used. The oil-in-water emulsified composition of the present invention is characterized by being contained in a powder state. Therefore, the manufacturing process including step 1 is preferably performed at a temperature lower than 60 ° C. (more preferably less than 55 ° C.).

The talc is not particularly limited, and talc generally used in cosmetic compositions can be used. The above talc is an INCI name and is written as TALC.

The oil absorption of the talc is not particularly limited, but is preferably 18 to 50 ml / 100 g. The average particle size D50 of the talc is not particularly limited, but is preferably 0.5 to 25.0 μm.

In this specification, the oil absorption amount of talc is a value measured according to the measuring method described in JIS K5101. Further, in the present specification, the average particle size D50 of talc is a value measured by a laser diffraction method.

A commercially available product can also be used as the component (A). Commercially available products of the octenyl succinate starch ester metal salt include, for example, the product name "DRY-FLO PURE", the product name "DRY-FLO PC" (above, manufactured by Nouryon), and the product name "Octier" (Nichijo Chemical Co., Ltd.). (Made) and so on. Examples of commercially available talc products include the trade name "talc MS" (manufactured by Nippon Talc Co., Ltd.).

(Component (B))
The component (B) is one or more selected from the group consisting of silicone oil, hydrocarbon oil, ester oil, and vegetable oil, and is an oily component having an IOB value of 0 to 0.45. By blending the component (B), in the use of the oil-in-water emulsified composition, the powdery feeling (drying feeling and catching feeling) derived from the component (A) can be reduced, and the friction feeling reducing effect can be imparted. As the component (B), only one kind may be used, or two or more kinds may be used.

Since the component (B) has an IOB value of 0 to 0.45 and is hydrophobic, the particle size of the pickering emulsion is formed to be relatively large. The IOB (Inorganicity Organicity) value is a value obtained by dividing an inorganic value (Inorganicity) by an organic value (Organicity). The IOB value of each oily component can be obtained based on, for example, Yoshio Koda, "Organic Conceptual Diagram-Basics and Applications-", Sankyo Publishing, 1984 (p11-17).

Examples of the silicone oil include dimethylsilicone oils such as methylpolysiloxane (dimethicone) and highly polymerized methylpolysiloxane; and methylphenylsilicone oils such as methylphenylpolysiloxane.

Examples of the hydrocarbon oil include isoparaffin, light isoparaffin, light liquid isoparaffin, squalane, synthetic squalane, vegetable squalane, liquid isoparaffin, liquid paraffin, hydrogenated polyisobutene, isododecane and the like.

Examples of the ester oil include isopropyl myristate, isopropyl palmitate, myristyl myristate, cetyl palmitate, 2-ethylhexyl palmitate, octyldodecyl myristate, isopropyl isostearate, cetyl 2-ethylhexanoate, and tri2-ethyl. Examples thereof include glyceryl hexanoate, tri (caprylic acid / capric acid) glyceryl, isononyl isononanoate, diisopropyl adipate, pentaerythrityl tetraoctanoate, diisostearyl malate, dipentaerythrityl hexahydroxystearate and the like. Among them, isononyl isononanoate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, isopropyl myristate, and octyldodecyl myristate are preferable from the viewpoint of being more excellent in safety to the skin.

Examples of the vegetable oil include macadamia nut oil, olive oil, palm oil, shea butter, sunflower oil, jojoba oil, and argan oil.

The component (B) is preferably liquid at 25 ° C. The viscosity η of the component (B) measured at 25 ° C. using a Brookfield type rotational viscometer is preferably 30,000 mPa · s or less (for example, 0.1 to 30,000 mPa · s), and more preferably 1.0 to 10,000 mPa.・ S.

In step 1, the mass ratio [component (B) / component (A)] of the component (B) to the component (A) in the non-aqueous mixture (I) is 0.05 to 12.5. Yes, preferably 0.50 to 10.0. When the mass ratio is 0.05 or more, the powder on the oil phase side of the outer peripheral portion of the emulsion particles becomes sufficient and the curvature of the particles tends to be small, so that the pickering emulsion particles tend to be relatively large. When the mass ratio is 12.5 or less, the powder that does not contribute to emulsion formation tends to be less likely to be released from the emulsion particles, so that the oil-in-water emulsified composition is less likely to become cloudy.

In step 1, the mass ratio of the total amount of the above component (A) and the above component (B) to the non-hydraulic mixed solution (I) [{component (A) + component (B)} / mixed solution (I)] Is preferably 0.60 to 1.0, more preferably 0.80 to 1.0. When the mass ratio is within the above range, the component (A) and the component (B) can be easily mixed uniformly, and the stabilization of the interface by the component (A) is not hindered during emulsification, and pickering. Emulsion formation is less likely to be inhibited.

The viscosity η of the non-aqueous mixture (I) measured at 25 ° C. using a Brookfield type rotational viscometer is preferably 50,000 mPa · s or less (for example, 0.1 to 50,000 mPa · s), and more preferably 1. It is 0 to 15000 mPa · s. When the viscosity of the non-aqueous mixture (I) is 50,000 mPa · s or less, the non-aqueous mixture (I) is likely to be dispersed in the component (C) and the component (D) in the step 2 following the step 1.

The blending ratio of the above component (A) and the above component (B) in the non-aqueous mixture (I) of step 1 is the same as that of the component (A) in the oil-in-water emulsified composition of the present invention described later. It is preferable to adjust the content ratio of the component (B).

<Process 2>
Step 2 is at least a step of mixing the non-aqueous mixed solution (I), the component (C), and the component (D) prepared in step 1 to prepare the mixed solution (II). The mixing is preferably carried out by adding the non-aqueous mixed solution (I) to the component (C) and / or the component (D).

These mixing can be performed by, for example, stirring using a general stirring device or a stirring device (homo mixer, paddle mixer, etc.). The stirring time is not particularly limited and can be appropriately set according to the type of stirring device or stirring device, the type and amount of each component, and the like.

(Component (C))
The component (C) is ethanol. By using the above component (C), the polarity of the aqueous phase in the pickering emulsion is lowered and the emulsion particles are stabilized, so that even relatively large pickering emulsion particles are stabilized without coalescing. It is less likely to become oil droplets. In addition, it is possible to impart a quick-drying property and a refreshing feeling to the skin after using the oil-in-water emulsified composition.

(Component (D))
The component (D) is water, and although it is not particularly limited, purified water is preferable.

In step 2, the mass ratio of the component (C) to the total amount of the component (C) and the component (D) in the mixed solution (II) [component (C) / {component (C) + component ( D)}] is 0.25 to 0.99, preferably 0.30 to 0.90, and more preferably 0.40 to 0.80. When the mass ratio is within the above range, the desorption of the component (A) from the interface and the coalescence of the pickering emulsion particles can be suppressed by the polar balance between the aqueous phase and the oil phase, and a relatively large pickering emulsion can be suppressed. Even particles are stabilized.

In step 2, the mass ratio of the total amount of the component (C) and the component (D) to the mixed solution (II) in the mixed solution (II) [{component (C) + component (D)} / Mixed solution (II)] is 0.50 or more, more preferably 0.50 to 0.9995, and even more preferably 0.70 to 0.9995. When the mass ratio is 0.50 or more, the amount of the aqueous phase is sufficient, so that the non-aqueous mixture (I) is likely to be uniformly dispersed in the mixture (II), and is also compared at the time of emulsification. Large pickering emulsion particles are easily formed.

In step 2, the mixed liquid (II) may be prepared by blending and mixing the non-aqueous mixed liquid (I) with the premixed component (C) and the component (D). By doing so, the non-aqueous mixture (I) can be dispersed in the aqueous phase whose polarity has been adjusted in advance, so that relatively large pickling emulsion particles are likely to be formed, and the pickling emulsion particles are easily formed. Is more likely to be stabilized.

Further, in step 2, the non-aqueous mixed liquid (I) and the component (D) are mixed and mixed, and then the component (C) is further mixed and mixed to prepare the mixed liquid (II). You may. By doing so, the non-aqueous mixture (I) can be dispersed in the aqueous phase whose polarity is finally adjusted, so that relatively large pickering emulsion particles are likely to be formed, and pickering. Emulsion particles are easily stabilized.

The mixing ratio of the component (C) and the component (D) to be blended in the mixed liquid (II) of the step 2 is the component (C) and the component (D) in the oil-in-water emulsified composition of the present invention described later. ) Is preferably adjusted so as to have a content ratio of).

<Step 3>
Step 3 is a step of emulsifying the mixture (II) to produce the composition (III). Emulsification can be performed, for example, by stirring the mixture (II) using a general stirrer or a stirrer (homo mixer, paddle mixer, etc.).

The oil-in-water emulsified composition of the present invention may be the above-mentioned composition (III), and in step 4 described later, the above-mentioned composition (III) is further added to the following polyhydric alcohol, water-soluble polymer, and the like. And other components, as well as components (C), component (D), and the like may be blended.

The production method of the present invention may contain polyglyceryl-10 decaisostearate. Polyglyceryl-10 decaisostearate may be blended in any of steps 1 to 3, but is preferably blended in step 1. Polyglyceryl-10 decaisostearate (INCI name: Polyglyceryl-10 Decaisostearate) has a hydrophilic moiety derived from 2 hydroxyl groups and 10 ester groups per molecule, and a lipophilic moiety derived from an isostearyl group. , The hydrophilic part adheres to the component (A), and the lipophilic part enhances the hydrophobicity of the component (A). Therefore, by blending polyglyceryl-10 decaisostearate, the component (A) is less likely to be released from the emulsion particles, so that the white turbidity of the oil-in-water emulsified composition is reduced. Also, larger size pickering emulsion particles can be formed. Polyglyceryl-10 decaisostearate is preferably blended so as to have a content ratio in the oil-in-water emulsified composition of the present invention described later.

In addition, the production method of the present invention may contain a polyhydric alcohol and / or a water-soluble polymer. The polyhydric alcohol and / or the water-soluble polymer may be blended in any of steps 1 to 3, but is preferably blended in step 2.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, isoprene glycol, 1,2-hexanediol, 1,2-octanediol, and 1, Examples thereof include 2-decanediol, concentrated glycerin, diglycerin and polyglycerin.

Examples of the water-soluble polymer include carboxyvinyl polymers, acrylic acid / alkyl methacrylate copolymers, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, and xanthan gum.

The polyhydric alcohol and / or the water-soluble polymer is preferably blended so as to have a content ratio in the oil-in-water emulsified composition of the present invention described later.

In addition, the production method of the present invention may contain other ingredients usually used in cosmetics and quasi-drugs. Such ingredients may be blended in any of steps 1-3.

Other ingredients include, for example, refreshing agents, bactericides, fragrances, anti-inflammatory agents (glycyrrhizinic acid and its salts, etc.), UV absorbers, antioxidants, preservatives, sequestrants, pigments, pigments, vitamins, etc. , Amino acids, astringents, whitening agents, animal and plant extracts, anti-inflammatory agents, deodorants and the like.

Examples of the refreshing agent include lower alcohols, menthol, menthol derivatives (for example, menthol glyceryl ether, menthol lactate, menthol glycosides, etc.), camphor, icillin, peppermint oil, peppermint oil, eucalyptus oil and the like.

The bactericidal agent is, for example, an agent that suppresses the growth of indigenous skin flora that produces a substance that causes body odor. Examples of the above-mentioned bactericidal agent include isopropylmethylphenol, benzalkonium chloride, benzethonium chloride, chlorhexidine hydrochloride, phenol, trichlorocarbanilide, chlorhexidine gluconate, triclosan, triclocarban, piroctone olamine, zincpyrythion, salicylic acid, and sorbic acid. , Chlorhexidine, etc.

It is preferable that the other components are blended so as to have a content ratio in the oil-in-water emulsified composition of the present invention described later.

Further, in the production method of the present invention, in addition to the above-mentioned polyglyceryl-10 decaisostearate, a surfactant (nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant) is blended. However, the blending ratio of the surfactant may be 0.1% by mass or less with respect to 100% by mass of the oil-in-water emulsified composition of the present invention from the viewpoint of stabilizing large-sized pickering emulsion particles. Is preferable.

<Step 4>
Since the pickering emulsion once formed in step 3 is highly stable, in the production method of the present invention, polyhydric alcohols, water-soluble polymers, and other components, as well as component (C) and component (D) are used. ) Can be further added to the composition (III). Then, the feeling of use of the oil-in-water emulsified composition of the present invention may be prepared by the formulation in step 4. The compounding of the polyhydric alcohol, the water-soluble polymer, and other components in step 4 as well as the components (C) and (D) is the content ratio of the oil-in-water emulsified composition of the present invention described later. It is preferably carried out within the range.

[Oil-in-water emulsified composition of the present invention]
The content ratio of each component in the oil-in-water emulsified composition of the present invention is preferably as follows.

The content ratio of the above component (A) in the oil-in-water emulsified composition of the present invention is preferably 0.05 to 10.0% by mass with respect to 100% by mass of the oil-in-water emulsified composition of the present invention. It is preferably 0.1 to 5.0% by mass. When the content ratio is 0.05% by mass or more, relatively large pickering emulsion particles are likely to be formed, and when the content ratio is 10.0% by mass or less, the oil-in-water emulsified composition becomes cloudy. It becomes difficult.

The content ratio of the above component (B) in the oil-in-water emulsified composition of the present invention is preferably 0.01 to 3.0% by mass with respect to 100% by mass of the oil-in-water emulsified composition of the present invention. It is preferably 0.02 to 25.0% by mass. When the above content ratio is 0.01% by mass or more, the skin feels smooth due to the use of the oil-in-water emulsified composition (the friction feels small when rubbing the skin, and the powder feels (dryness and powder). It is possible to give a feeling (feeling of being caught by) suppressed. When the content ratio is 30.0% by mass or less, oil droplets are less likely to be generated due to coalescence of the emulsion particles, so that the aesthetic appearance of the oil-in-water emulsified composition is likely to be impaired.

The content ratio of the above component (C) in the oil-in-water emulsified composition of the present invention is preferably 20.0 to 95.0% by mass with respect to 100% by mass of the oil-in-water emulsified composition of the present invention. It is preferably 30.0 to 70.0% by mass. When the content ratio is within the above range, the polarity of the aqueous phase in the pickering emulsion is lowered and the emulsion particles are stabilized, so that even relatively large pickering emulsion particles are stabilized without coalescence. Therefore, it becomes difficult for oil droplets to form.

The content ratio of the above component (D) in the oil-in-water emulsified composition of the present invention is preferably 0.5 to 85.0% by mass with respect to 100% by mass of the oil-in-water emulsified composition of the present invention. It is preferably 1.0 to 82.0% by mass. When the content ratio is within the above range, the polarity of the aqueous phase does not decrease too much, so that relatively large pickering emulsion particles are likely to be generated, and the pickering emulsion particles are relatively large due to the decrease in polarity of the aqueous phase. However, since it stabilizes without coalescing, it becomes easier to prevent oil floating.

When the polyglyceryl-10 decaisostearate is contained, the content ratio of the polyglyceryl-10 decaisostearate in the oil-in-water emulsified composition of the present invention is 100% by mass with respect to 100% by mass of the oil-in-water emulsified composition of the present invention. It is preferably 0.0005 to 1.0% by mass, more preferably 0.001 to 0.5% by mass, and further preferably 0.001 to 0.3% by mass. When the content ratio is within the above range, the liberation of the component (A) from the pickering emulsion particles can be reduced, so that the oil-in-water emulsified composition is less likely to become cloudy. Also, larger size pickering emulsion particles are formed.

When the polyvalent alcohol is contained, the content ratio of the polyvalent alcohol in the oil-in-water emulsified composition of the present invention is 0.1 to 1% with respect to 100% by mass of the oil-in-water emulsified composition of the present invention. 30.0% by mass is preferable. When the content ratio is within the above range, the viscosity of the aqueous phase does not become too high, and it becomes difficult to inhibit the formation of relatively large pickering emulsion particles.

When the water-soluble polymer is contained, the content ratio of the water-soluble polymer in the oil-in-water emulsified composition of the present invention is 0. 001 to 1.0% by mass is preferable. When the content ratio is within the above range, the viscosity of the aqueous phase does not become too high, and it becomes difficult to inhibit the formation of relatively large pickering emulsion particles.

When the above other components are contained, the content ratio of the total amount of the above other components in the oil-in-water emulsified composition of the present invention is 0 with respect to 100% by mass of the oil-in-water emulsified composition of the present invention. It is preferably 0.01 to 1.5% by mass, more preferably 0.05 to 1.2% by mass.

The content ratio of the surfactant other than polyglyceryl-10 decaisostearate in the oil-in-water emulsified composition of the present invention is 0.1% by mass or less with respect to 100% by mass of the oil-in-water emulsified composition of the present invention. Is preferable.

The production method in the oil-in-water emulsified composition of the present invention comprises a non-aqueous mixture (I) obtained by premixing the component (A) and the oily component (B) at a specific blending ratio, and the component (C). ) And the component (D) are mixed at a specific blending ratio, and the mixed solution (II) is further emulsified to form relatively large oil-in-water type pickering emulsion particles. Since the non-aqueous mixture (I) is a highly viscous oil phase containing powder, large oil droplets are likely to be formed in the mixture (II). As a result, the pickering emulsion particles in the oil-in-water emulsified composition of the present invention become relatively large. It is considered that by mixing the component (A) and the component (B) in advance to obtain the non-aqueous mixture (I), the component (A) is likely to be present on the oil phase side in the outer peripheral portion of the pickering emulsion particles. However, the tendency can be strengthened by blending the mass ratio of the component (B) to the component (A) [component (B) / component (A)] to be 0.05 to 12.5. .. Further, the mass ratio of the total amount of the component (C) and the component (D) to the mixed solution (II) in the mixed solution (II) [{component (C) + component (D)} / mixed solution (II) ] Is blended so as to be 0.50 or more, the non-aqueous mixture (I) is likely to be uniformly dispersed in the aqueous phase, and relatively large pickering emulsion particles are likely to be formed during emulsification. .. Further, when the aqueous phase (matrix) is only the component (D), the pickering emulsion particles are united to form oil droplets and easily float, but the component (C) and the component (D) relative to the total amount (D). Pickering because the polarity of the aqueous phase can be adjusted by blending the mass ratio of C) [component (C) / {component (C) + component (D)}] so as to be 0.20 to 0.99. The emulsion can be stabilized.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The blending ratio shown in the table is the blending ratio of each component (that is, the blending ratio of the active ingredient in each raw material, so-called pure content), and is represented by "mass%" unless otherwise specified.

Examples 1-19, 21-27, Comparative Examples 1-4
For the components (A) to (D), polyglyceryl-10 decaisostearate, and other components (cooling agent, insecticide, fragrance), each of the examples and comparative examples was used in the blending amounts at the content ratios shown in the table. An oil-in-water emulsified composition was prepared.
First, the component (A), the component (B), polyglyceryl-10 decaisostearate, or other components are uniformly mixed to obtain a non-aqueous mixture (I), and then the non-aqueous mixture is obtained. (I) is added to a water-methanol mixed solution prepared by mixing the component (C) and the component (D) in advance as a dispersion medium and mixed uniformly to obtain a mixed solution (II), and further, the mixed solution is obtained. (II) was stirred using a paddle mixer at 1000 rpm for 10 minutes and emulsified to obtain a sample for evaluation. The above preparation was performed in an environment of 25 ° C.

Example 20
For the components (A) to (D), the oil-in-water emulsified compositions of Examples were prepared at the blending amounts having the content ratios shown in the table.
First, the component (A) and the component (B) are uniformly mixed to obtain a non-aqueous mixture (I), and then the non-aqueous mixture (I) is added to water (component (D)). After uniformly mixing, ethanol (component (C)) was added and further uniformly mixed to obtain a mixed solution (II), and the mixed solution (II) was further emulsified to obtain a sample for evaluation. ..

Comparative Example 5
For the components (A) to (D), the oil-in-water emulsified compositions of Examples were prepared at the blending amounts having the content ratios shown in the table.
First, the component (A), ethanol (component (C)), and water (component (D)) are uniformly mixed to obtain a slurry, and then the component (B) is gradually added to the slurry. The mixture was uniformly mixed to obtain a mixed solution, and the mixed solution was emulsified to obtain a sample for evaluation.

(evaluation)
The samples for each evaluation obtained in Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in the table.

(1) Preparation of capsules (pickering emulsion particles) 1 mL of uniformly dispersed evaluation sample is dropped onto a 12-well multi-well plate and enlarged using a microscope (all-in-one fluorescence microscope BZ-X800, manufactured by KEYENCE CORPORATION). Pickering emulsion particles in one hole were observed at a multiple of 40 times. 10 pickering emulsion particles in which the entire outer peripheral portion of the emulsion is included in the region between the circumscribed circle of the outer peripheral portion of the emulsion and the concentric circle having a diameter of 50% of the outer peripheral circle are arranged in order from the one having the largest diameter of the outer peripheral portion of the emulsion. Individuals were selected and used as evaluation targets.
[Adjustability criteria]
◯ (Good): The diameter of the circumscribed circle of the pickering emulsion particles is 200 μm or more for all 10 particles.
X (defective): The diameter of the circumscribed circle of the pickering emulsion particles is less than 200 μm for one or more of the ten particles.

(2) Dispersibility The samples for evaluation obtained in Examples and Comparative Examples were visually confirmed.
[Criteria for dispersibility]
◯ (Good): The particles were uniformly dispersed as a whole.
Δ (Slightly defective): A lump in which particles were partially united was observed.
X (defective): The whole was united into one mass, or the particles were totally aggregated and not dispersed.

(3) Oil floating The samples for each evaluation obtained in the examples and comparative examples were put into a glass container, allowed to stand at 25 ° C. for 30 minutes, and then visually observed, and the oil phase formation was evaluated according to the following evaluation criteria. Judged.
[Oil float]
○ (Good): There are no oil droplets on the upper layer.
× (defective): Oil droplets are present in the upper layer.

From the results of Examples 1 to 27, it was shown that the production method of the present invention can stably prepare an oil-in-water emulsified composition having relatively large pickering emulsion particles. In Example 25, larger pickering emulsion particles were formed as compared with Example 19. Further, in Example 26, larger pickering emulsion particles were formed as compared with Example 1. Further, in Example 27, larger pickering emulsion particles were formed as compared with Example 2. As described above, when polyglyceryl-10 decaisostearate was further blended, larger pickering emulsion particles were formed. On the other hand, when the mass ratio of the component (B) to the component (A) is outside the range of the present invention as in Comparative Examples 1 and 2, the pickling emulsion particles are small or oil floating occurs. Further, when the component (D) was not blended in the aqueous phase as in Comparative Example 3, the pickering emulsion particles were small. Further, as in Comparative Example 4, when the blending ratio of the aqueous phase component (C) was small, the dispersion of the pickering emulsion particles was non-uniform. Further, as in Comparative Example 5, when each component was blended and mixed in an order different from that of the present invention, the pickering emulsion particles were small.

Claims (3)

Step 1 to prepare a non-water mixed solution (I) that contains substantially no water by blending the following component (A) and the following component (B).
Step 2 to prepare the mixed liquid (II) by blending the non-aqueous mixed liquid (I), the following component (C) and the following component (D), and
It has a step 3 of emulsifying the mixture (II).
The mass ratio [component (B) / component (A)] of the component (B) to the component (A) in the non-aqueous mixture (I) is 0.05 to 12.5.
Mass ratio of the component (C) to the total amount of the component (C) and the component (D) in the mixed solution (II) [component (C) / {component (C) + component (D)}] Is 0.25 to 0.99,
The mass ratio of the total amount of the component (C) and the component (D) to the mixed solution (II) in the mixed solution (II) [{component (C) + component (D)} / mixed solution ( II)] is 0.50 or more, a method for producing an oil-in-water emulsified composition.
Component (A): Powder of octenyl succinate starch ester metal salt and / or talc Component (B): 1 or more selected from the group consisting of silicone oil, hydrocarbon oil, ester oil, and vegetable oil, and has an IOB value. Oily component (C): ethanol component (D): water The method for producing an oil-in-water emulsified composition according to claim 1, wherein in the step 1, the polyglyceryl-10 decaisostearate is further blended to prepare the non-aqueous mixture (I). 1. A method for producing an oil-in-water emulsified composition, wherein the blending ratio of a surfactant other than polyglyceryl-10 decaisostearate in the oil-in-water emulsified composition is 0.1% by mass or less. Alternatively, the method for producing an oil-in-water emulsified composition according to 2.