JP5209816B1 - Method for producing O / W emulsion composition - Google Patents

Abstract

An O / W emulsified composition having a fine emulsified particle size using an anionic surfactant that forms an α-gel in water and a higher aliphatic alcohol is excellent in simplicity, economy, and environmental compatibility. Provide in a different way.
A method for producing an O / W emulsion composition according to the present invention comprises: (A) an oil phase containing a higher aliphatic alcohol having 12 to 26 carbon atoms, and (B) an oil component; A part of an aqueous phase (first aqueous phase) comprising (A) an anionic surfactant capable of forming an α-gel in water, (D) a specific alkylene oxide derivative, and (E) water. Is cooled by mixing the emulsified part with the remaining aqueous phase (second aqueous phase) at 10 to 35 ° C. while stirring the mixture at a temperature of 80 ° C. or higher to prepare an O / W emulsified part. And (D) the alkylene oxide derivative is 1 to 30% by mass in the emulsified part.
[Selection figure] None

Description

  The present invention relates to a method for producing an O / W emulsion composition, in particular, an O / W emulsion composition using an anionic surfactant that forms an α-gel in water and a higher aliphatic alcohol. The present invention relates to a method capable of producing an O / W emulsion composition having a fine emulsion particle diameter by a method having excellent environmental compatibility.

  Conventionally, O / W emulsion compositions using α-gel formed in water by higher alcohols and anionic surfactants are used in external compositions such as cosmetics, pharmaceuticals, and quasi drugs. (Patent Documents 1 to 4).

  As a method for preparing such an O / W emulsion composition, an oil phase of 80 ° C. or higher in which a higher aliphatic alcohol is dissolved is usually added to an aqueous phase of 80 ° C. or higher in which an anionic surfactant is dissolved. The method of cooling what was emulsified with the homogenizer etc. to about 35 degreeC with coolers, such as an onlator, has been used. In such an O / W emulsified composition, the higher aliphatic alcohol dissolved in the emulsified particles that are high-temperature oil droplets emerges on the surface of the emulsified particles as the temperature decreases due to cooling, and is present in the water. An aggregate (α-gel) is formed together with the active agent to surround the interface of the emulsified particles and contribute to the stabilization of the O / W emulsion composition (Non-patent Document 1).

  However, the conventional method of cooling after emulsification at 80 ° C. or higher is wasteful because it requires energy by heating components or using a heat exchanger. In addition, a large amount of water is used for cleaning after use of a cooler such as an onlator, resulting in a high environmental load.

  Therefore, it is hoped to develop a method that can economically and easily produce an O / W emulsion composition without heating all components or using a cooling device such as an ontrator as in the prior art. It was rare.

In recent years, an oil phase comprising a nonionic surfactant, a linear higher alcohol capable of forming an α-gel in water together with the nonionic surfactant, an oil component, and a part of the aqueous phase A method for preparing an O / W emulsified composition by emulsifying at 70 ° C or higher to prepare a high concentration O / W emulsified part and mixing the emulsified part with the remaining aqueous phase at 10 to 35 ° C while stirring is reported. (Patent Document 5).
This method does not need to heat all components and can produce an O / W emulsion composition without using a cooling device such as an on-lator, and thus is excellent in simplicity, economy, and environmental compatibility.

However, Patent Document 5 has not studied a case where an anionic surfactant capable of forming an α-gel in water and a higher fatty acid alcohol are used.
And when the present inventors examined, an anionic surfactant which can form an alpha gel in water, a higher aliphatic alcohol, an oil component, and a high concentration O / W emulsified part using a part of water phase When an O / W emulsified composition is obtained by mixing and cooling the emulsified part with a low-temperature remaining aqueous phase and cooling it, an O / W emulsified composition having a fine emulsified particle diameter is obtained. Turned out to be very difficult.

JP 2001-348325 A JP 2005-132808 A JP 2008-44866 A Japanese Patent No. 4767352 JP 2011-74071 A

Manabu Seneo, “Chemistry and Application of Surface Activity”, Dai Nippon Books, 1995, p. 159-160

  The present invention has been made in view of the circumstances of the background art described above, and its purpose is to use an anionic surfactant that forms an α-gel in water and a higher aliphatic alcohol, and has a fine emulsion particle size. The object is to provide an O / W emulsified composition by a method excellent in convenience, economy and environmental compatibility.

  As a result of studies by the present inventors, an anionic surfactant capable of forming an α-gel in water, a higher aliphatic alcohol, an oil component, and a high concentration O / W emulsified part using a part of the aqueous phase When preparing an O / W emulsified composition by using a specific amount of alkylene oxide derivative and mixing the emulsified part with a low-temperature remaining aqueous phase and cooling to prepare a fine emulsified particle size The inventors have found that an O / W emulsion composition can be obtained, and have completed the present invention.

That is, the method for producing an O / W emulsion composition according to the present invention includes:
(A) a higher aliphatic alcohol having 12 to 26 carbon atoms;
(B) oil and
(C) an anionic surfactant capable of forming an α-gel in water with the (A),
(D) an alkylene oxide derivative represented by the following general formula (1);
(E) water and
A method for producing an O / W emulsion composition comprising
(A) The higher aliphatic alcohol having 12 to 26 carbon atoms is 0.05 to 10% by mass in the O / W emulsion composition,
(B) Oil content contains 1 or more types chosen from hydrocarbon oil, ester oil, and silicone oil, and is 0.1-20 mass% in O / W emulsion composition,
(C) The anionic surfactant capable of forming an α-gel in water with (A) is selected from N-acyl sulfonate type anionic surfactants and N-acyl glutamate type anionic surfactants. One or more selected from 0.01 to 5% by mass in the O / W emulsion composition,
(A) The total amount of the higher aliphatic alcohol having 12 to 26 carbon atoms and (C) the anionic surfactant is 0.5 to 10 parts by mass with respect to 10 parts by mass of (B) oil,
(A) a higher aliphatic alcohol having 12 to 26 carbon atoms;
(B) oil and
An oil phase containing,
(C) an anionic surfactant capable of forming an α-gel in water with the (A),
(D) an alkylene oxide derivative represented by the following general formula (1);
(E) a part of water,
A step of preparing an O / W emulsified part by emulsifying a first aqueous phase containing
Cooling the emulsified part by mixing with stirring the second aqueous phase containing the remaining (E) water at 10 to 35 ° C., and
The (D) alkylene oxide derivative is 1 to 30% by mass in the emulsified part, and is a method for producing an O / W emulsion composition.

_{^{R 1 O - [(AO)}} m (EO) n] -R 2 (1)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70 The ratio of the oxyalkylene group to the total of the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by weight, and the oxyalkylene group and oxyethylene group having 3 to 4 carbon atoms. is .R ^{1, R 2,} appended to the random form is the same or different and an alkyl group having 1 to 4 carbon atoms.)

Moreover, this invention is the method in any one of the said, The said 2nd aqueous phase is 40-75 mass% in O / W emulsion composition whole quantity, The manufacturing method of the O / W emulsion composition characterized by the above-mentioned. Provide .

  According to the method of the present invention, it is not necessary to heat all the components of the target O / W emulsion composition, and an O / W emulsion composition can be produced without using a cooling device such as an onlator. Excellent in convenience, economy and environmental compatibility. And the O / W emulsion composition of a fine emulsion particle diameter can be easily obtained by including a specific amount of alkylene oxide derivative in the 1st water phase which prepares an emulsification part.

The method for producing an O / W emulsion composition according to the present invention includes the following first step and second step in the method for producing an O / W emulsion composition in which an oil phase is emulsified in an aqueous phase. With one feature.
(1) 1st process (high concentration emulsified parts preparation process):
A step of preparing an O / W emulsified part by emulsifying an oil phase and a part of the aqueous phase (first aqueous phase) at a temperature of 80 ° C. or higher.
(2) Second step (cooling step):
The step of cooling by mixing the emulsified part and the remaining aqueous phase (second aqueous phase) at 10 to 35 ° C. while stirring.
The oil phase contains (A) a higher aliphatic alcohol having 12 to 26 carbon atoms and (B) an oil component.
The first aqueous phase contains (C) an anionic surfactant that forms an α-gel in water with (A), (D) an alkylene oxide derivative, and (E) water.

In the method of the present invention, the (D) alkylene oxide derivative is also contained in the emulsified part in an amount of 1 to 30% by mass, preferably 3 to 25% by mass.
An α-gel is formed at the emulsion particle interface of the thus obtained O / W emulsion composition. The α-gel refers to an aggregate composed of a lamellar bimolecular film formed by a surfactant together with a higher alcohol in the presence of water.

  Conventionally, an oil phase containing (A) a higher aliphatic alcohol, and (C) an aqueous phase containing (A) and an anionic surfactant capable of forming an α-gel in water at a temperature of 80 ° C. or higher. O / W emulsified composition was obtained by the process of emulsifying and cooling this. However, it is economical and environmentally friendly if a cooling device such as an on-lator is used. There was a problem that would be loaded.

  On the other hand, in the present invention, O / W emulsification emulsified at a high concentration using a part of the aqueous phase component (first aqueous phase) of the target O / W emulsion composition and the oil phase component. The parts are prepared at 80 ° C. or higher (preferably 80 to 85 ° C.), and the emulsified parts and the remaining low-temperature aqueous phase component (second aqueous phase) at 10 to 35 ° C. are gradually mixed with stirring. As a result, the high-temperature emulsified part is diluted and cooled, and the higher aliphatic alcohol dissolved in the emulsified particles of the high-temperature emulsified part comes out, and the α-gel together with the anionic surfactant and water at the emulsified particle interface And an O / W emulsion composition is obtained. When the emulsification temperature is less than 80 ° C., the emulsified parts may not be dissolved. An apparatus used for emulsification, stirring and the like may be appropriately selected from those normally used, and the apparatus used so far can be used as it is, and no special equipment is required. The mixing order of the emulsified part and the second aqueous phase is not particularly limited.

Therefore, according to the production method of the present invention, it is not necessary to heat a large amount of the aqueous phase without using a cooler such as an onlator during emulsification. Can be manufactured.
And in this invention, the emulsion particle diameter of the obtained O / W emulsion composition is 10 micrometers by making (D) alkylene oxide derivative into 1-30 mass% in an emulsification part, Preferably it is 3-25 mass%. Thereafter, it can be further refined to 5 μm or less. If the alkylene oxide derivative in the emulsified part is too little or too much, an O / W emulsion composition having a fine emulsion particle size cannot be obtained. Even if another aqueous solvent is used in place of the alkylene oxide derivative, a fine O / W emulsion composition cannot be obtained.

As mentioned above, the manufacturing method of the O / W emulsion composition concerning this invention is 10-35 degreeC in the high concentration O / W emulsion part manufactured previously at 80 degreeC or more using the specific amount alkylene oxide derivative. By simply adding the remaining aqueous phase, an O / W emulsion composition having a fine emulsified particle size can be obtained, so that the production process that has been used in the past can be greatly simplified, making it economical and environmentally compatible. Is also excellent.
Hereinafter, the components used in the present invention will be described.

<(A) Higher aliphatic alcohol having 12 to 26 carbon atoms>
In the present invention, the higher aliphatic alcohol having 12 to 26 carbon atoms, which is the component (A), is a component that forms an α-gel in water with the anionic surfactant as the component (C) described later.
The formation of α-gel in water can be confirmed by DSC (inspection scanning calorimetry). That is, the endothermic peak of a sample obtained by mixing a higher aliphatic alcohol and an anionic surfactant that form an α-gel with water dissolves the higher aliphatic alcohol and the anionic surfactant in water independently. Alternatively, since a single peak is shown on the higher temperature side than the endothermic peak obtained with the dispersed sample, formation of α-gel can be confirmed.

  Examples of the higher aliphatic alcohol used in the present invention include those generally used for external compositions such as cosmetics, pharmaceuticals, and quasi drugs. For example, saturated linear monohydric alcohols include dodecanol (= lauryl alcohol), tridecanol, tetradecanol (= myristyl alcohol), pentadecanol, hexadecanol (= cetyl alcohol), heptadecanol, octadecanol ( = Stearyl alcohol), nonadecanol, icosanol (= aralkyl alcohol), heicosanol, docosanol (= behenyl alcohol), tricosanol, tetracosanol (= carnerville alcohol), pentacosanol, hexacosanol (= seryl alcohol) It is done. Examples of unsaturated monohydric alcohols include elaidyl alcohol. From the viewpoint of stability over time, a saturated linear monohydric alcohol having 12 to 26 carbon atoms (preferably 18 to 22 carbon atoms) is preferable.

  (A) 1 type (s) or 2 or more types can be used for a higher aliphatic alcohol, Preferably the mixture of 2 or more types of higher aliphatic alcohol is used. From the viewpoint of temperature stability of the O / W emulsion composition, a combination such that the melting point of the mixture is 60 ° C. or higher is more preferable. An example of a suitable combination is a combination of stearyl alcohol and behenyl alcohol.

(A) As for higher aliphatic alcohol, it is desirable for the average carbon number obtained by a carbon number arithmetic average to be 18 or more. When the average carbon number is less than 18, the melting point of the O / W emulsion composition becomes low, and the high temperature stability may not be sufficient. The upper limit of the average carbon number is not particularly limited, but is preferably about 22 carbon atoms.
In this invention, the compounding quantity of (A) higher aliphatic alcohol is 0.05-10 mass% normally in the O / W emulsion composition whole quantity, Preferably it is 0.1-6 mass%.

<(B) Oil>
The oil component used in the present invention is not particularly limited, and those generally used in external compositions such as cosmetics, pharmaceuticals, and quasi drugs are preferably used. For example, polar oils such as hydrocarbon oils and ester oils, silicone oils, liquid oils and the like are preferable, but not limited thereto.

  Examples of the hydrocarbon oil include liquid paraffin, squalane, squalene, paraffin, isoparaffin, ceresin and the like.

  Examples of the silicone oil include chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; Examples thereof include silicone resin and silicone rubber forming a network structure.

  Polar oils such as ester oils include pentaerythrityl tetraethylhexanoate, cetyl ethylhexanoate, jojoba oil, dilauroyl glutamate (phytosteryl / octyldodecyl), triisostearin, glyceryl diisostearate, triethylhexanoin, dimer dilinoleic acid ( Phytosteryl / behenyl), dimer linoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), isopropyl palmitate, macadamia nut fatty acid phytosteryl, tetra (behenic acid / benzoic acid / ethylhexanoic acid) pentaerythrityl, ethylhexyl palmitate, Examples include myristyl myristate and tripropylene glycol dipivalate.

  Liquid oils include linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut Examples thereof include oil, triglycerin, glycerin trioctanoate, and glycerin triisopalmitate.

The oil can be used alone or in combination of two or more.
In the present invention, the blending amount of the oil is not particularly limited, but is usually 0.1 to 20% by mass, preferably 0.2 to 15% by mass in the total amount of the O / W emulsion composition.

<(C) Anionic surfactant>
In the present invention, the anionic surfactant of component (C) is a component that forms an α-gel in water with the higher aliphatic alcohol of component (A).

  Examples of the anionic surfactant used in the present invention include those generally used in external compositions such as cosmetics, pharmaceuticals, and quasi drugs. For example, fatty acid soap (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate); alkyl ether sulfates (eg, POE-lauryl sulfate triethanolamine) , POE-sodium lauryl sulfate, etc.); N-acyl sarcosine acid (eg, sodium lauroyl sarcosine, etc.); Phosphoric acid ester salt (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphoric acid, etc.); sulfosuccinate (eg, di-2-ethylhexyl sulfate) Sodium succinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkylbenzene sulfonates (eg, sodium lineardodecylbenzenesulfonate, triethanolamine lineardodecylbenzenesulfonate, lineardodecyl) Higher fatty acid ester sulfate (for example, hydrogenated coconut oil fatty acid sodium glyceryl sulfate); N-acyl glutamate (for example, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl) -L-glutamic acid monosodium etc.); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether cal Α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; lauroyl monoethanolamide sodium succinate; N-palmitoyl aspartate ditriethanolamine ; Sodium caseinate and the like.

As an example of a preferable anionic surfactant, a long-chain acyl sulfonate type anionic surfactant represented by the following general formula (I) may be mentioned.
_{R 1 CO-a- (CH 2} ) n SO 3 M 1 (I)

In the general formula (I), R ₁ CO— represents a saturated or unsaturated aliphatic acyl group having 10 to 22 carbon atoms. As R ₁ CO, C ₁₁ H ₂₃ CO, C ₁₂ H ₂₅ CO, C ₁₃ H ₂₇ CO, C ₁₄ H ₂₉ CO, C ₁₅ H ₃₁ CO, C ₁₆ H ₃₃ CO, C ₁₇ H ₃₅ CO, coconut fatty acid residue Group, palm coconut fatty acid residue and the like are exemplified (fatty acid residue means a group obtained by removing OH group from carboxyl group of fatty acid). R ₁ CO is more preferably one having 12 to 22 carbon atoms from the viewpoint of safety or the like.

a represents -O- or -NR- (wherein R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). These are electron donating groups. a is preferably —O—, —NH—, or —N (CH ₃ ) —.

M ₁ represents an alkali metal, an alkaline earth metal, ammonium or an organic amine. Examples of M ₁ include lithium, potassium, sodium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine, sodium taurine, sodium N-methyltaurine, and the like.
n represents an integer of 1 to 3.

  In the general formula (I), a compound in which a represents —O—, that is, a long-chain acyl isethionate type anionic surfactant includes cocoyl isethionate, stearoyl isethionate, lauryl isethionate, Examples include myristoyl isethionate.

  In the above general formula (I), a compound in which a represents —NH—, that is, a long-chain acyl taurine salt type anionic surfactant includes N-lauroyl taurine salt, N-cocoyl-N-ethanol taurine salt, N— Examples include myristoyl taurine salt and N-stearoyl taurine salt.

In the above general formula (I), a compound in which a represents —N (CH ₃ ) —, that is, a long-chain acylmethyl taurate salt type anionic surfactant includes N-lauroyl-N-methyl taurate, N-palmitoyl -N-methyl taurine salt, N-stearoyl-N-methyl taurine salt, N-cocoyl-N-methyl taurine salt and the like are exemplified.

  Of these, long-chain acylmethyl taurate salt type anionic surfactants are preferred, and particularly preferred are N-stearoyl-N-methyl taurine salts such as sodium N-stearoyl-N-methyl taurate.

Moreover, as an example of another preferable anionic surfactant, a long-chain acylglutamate type anionic surfactant represented by the following general formula (II) may also be mentioned.
_{R 2 CO-NH-CH (} COOM 2) -CH 2 CH 2 -COOM 2 (II)

R ₂ CO— represents a saturated or unsaturated aliphatic acyl group having 16 to 22 carbon atoms. M ₂ represents an alkali metal, an alkaline earth metal, ammonium or an organic amine. Examples of M ₁ include lithium, potassium, sodium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine, sodium taurine, sodium N-methyltaurine, and the like.
Representative examples include, for example, sodium N-stearoyl-L-glutamate, sodium N-palmitoyl-L-glutamate, and N-stearoyl glutamic acid-L-triethanolamine.

  In the present invention, the anionic surfactant is 0.01 to 5% by mass, preferably 0.02 to 3% by mass, based on the total amount of the O / W emulsion composition. Anionic surfactants can be used alone or in combination of two or more.

  At the emulsified particle interface of the O / W emulsified composition obtained in the present invention, (A) a higher aliphatic alcohol and (C) an anionic surfactant form an aggregate consisting of a lamellar bimolecular film. The so-called α-gel state is taken.

  Since α-gel contributes to the stabilization of the O / W emulsion composition, the total amount of (A) higher aliphatic alcohol and (C) anionic surfactant is ( B) It is preferable to set it as 0.5-10 mass parts with respect to 10 mass parts of oil components. When the amount is less than 0.5 parts by mass, the amount of α-gel is small, and thus the stability of the obtained O / W emulsion composition may be insufficient. Moreover, when it exceeds 10 mass parts, since there is too much (alpha) -gel, there exists a tendency which is not preferable at the point of a usability | use_condition.

As described above, α-gel exhibits an endothermic peak by DSC measurement, and the endothermic peak temperature can be considered as the melting point of α-gel. Since the α-gel is reduced in viscosity at a temperature equal to or higher than the melting point, it may affect the high temperature stability of the O / W emulsion composition.
Therefore, from the viewpoint of high temperature stability of the O / W emulsion composition, the melting point of the α-gel is preferably high, and is preferably 60 ° C. or higher, and more preferably 65 ° C. or higher.

<(D) Alkylene oxide derivative>
(D) As an alkylene oxide derivative of a component, what is shown by following General formula (1) is mentioned, for example.

_{^{R 1 O - [(AO)}} m (EO) n] -R 2 (1)

In the general formula (1), AO is an oxyalkylene group having 3 to 4 carbon atoms, and specific examples include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxytrimethylene group, and an oxytetramethylene group. It is done. Preferably, an oxypropylene group and an oxybutylene group are mentioned.
In this invention, it is preferable that the ratio of the oxyalkylene group in the sum total of a C3-C4 oxyalkylene group and an oxyethylene group is 20-80 mass%, Furthermore, it is preferable that it is 30-70 mass%. If the proportion of the oxyalkylene group is too small, the effect of refining is reduced, and if it is too large, it does not dissolve in water and is difficult to use.

  m is the average addition mole number of the oxyalkylene group having 3 to 4 carbon atoms, and n is the average addition mole number of the oxyethylene group, each of which can be in the range of 1 to 70, preferably 2 to 60. In addition, since it may become sticky when the sum of m and n is too large, (m + n) is preferably 100 or less.

  The order of adding ethylene oxide and alkylene oxide having 3 to 4 carbon atoms is not particularly specified. Further, the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms may be added in a block shape or in a random shape. The block shape includes not only two-stage blocks but also three or more stages. Preferably, those added randomly are listed.

R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. A methyl group and an ethyl group are preferred. When the number of hydrocarbon groups is 5 or more, the hydrophilicity is lowered and the water is hardly dissolved. R ¹ and R ² may be the same or different.

  The alkylene oxide derivative of the present invention can be produced by a known method. For example, it can be obtained by subjecting a compound having a hydroxyl group to addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms, and then subjecting an alkyl halide to an ether reaction in the presence of an alkali catalyst.

  Preferable examples of the alkylene oxide derivative of the general formula (1) include, for example, POE (14) POP (7) dimethyl ether, POE (36) POP (41) dimethyl ether, POE (55) POP (28) dimethyl ether, POE ( 22) POP (40) dimethyl ether, POE (35) POP (40) dimethyl ether, POE (50) POP (40) dimethyl ether, POE (11) POP (9) dimethyl ether, etc., but are not limited thereto. Absent.

In this invention, 1-30 mass%, Preferably 3-25 mass% of (D) alkylene oxide derivatives are mix | blended in an emulsification part.
(D) As long as it is 1-30 mass% in an emulsion part, an alkylene oxide derivative can be mix | blended also in a 2nd aqueous phase. Therefore, the amount of the alkylene oxide derivative in the O / W emulsion composition obtained in the present invention is hardly limited.

<(E) Water>
In the present invention, water is contained in at least the first aqueous phase used for preparing the emulsified parts. The amount of water contained in the first aqueous phase may be adjusted so that the emulsifying part can be adjusted, and is usually 55 to 90% by mass, preferably 60 to 85% by mass in the emulsifying part.
Moreover, it is preferable that it is contained also in the 2nd water phase for cooling an emulsification part.
Although the total amount of water in the O / W emulsion composition obtained in the present invention is not particularly limited, it is usually 40 to 95% by mass in the total amount of the O / W emulsion composition.

The first aqueous phase is preferably from 25 to 50 mass%, more preferably from 30 to 45 mass%, based on the total amount of the O / W emulsion composition. If the first aqueous phase is too small, a stable O / W emulsified composition may not be obtained, and if the first aqueous phase is too much, the second aqueous phase for cooling the emulsified parts will be reduced. Inferior.
Moreover, 40-75 mass% is preferable in a 2nd aqueous phase with respect to O / W emulsion composition whole quantity, and 45-70 mass% is more preferable. If the second aqueous phase is less than 40% by mass, a sufficient cooling effect cannot be obtained, and an extra amount of cooling energy is required. Moreover, since the 1st aqueous phase which prepares O / W emulsification parts will decrease when it exceeds 75 mass%, it exists in the tendency for preparation of a stable O / W emulsification composition to become difficult.

  Moreover, 10-35 degreeC is preferable and, as for the temperature of the 2nd water phase (remaining water phase) added to O / W emulsification parts, it is especially preferable that it is 15-30 degreeC. If it is less than 10 ° C., excessive energy for cooling the second aqueous phase is required, and the economy tends to be inferior. Moreover, when it exceeds 35 degreeC, since sufficient cooling effect is not acquired and extra cooling energy is needed by that much, it is inferior to economical efficiency.

<Other ingredients>
In the O / W emulsion composition according to the present invention, in addition to the above essential components, components usually used in cosmetics, pharmaceuticals and the like can be blended within a range not impairing the effects of the present invention. Examples of such components include the following, but are not limited thereto.

  1,3-butylene glycol, dipropylene glycol, isoprene glycol, 1,2-pentane glycol, 1,2-hexane glycol, 2-methyl-1,3-propanol, ethyl carbitol, 1,2-butylene glycol, glycerin An aqueous solvent such as

  Moisturizing of polyethylene glycol and its mono- or di-alkyl ether, polyethylene glycol / polypropylene glycol copolymer and its mono- or di-alkyl ether, sorbitol, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, chitosan, etc. Agent.

Thickeners such as methylcellulose, ethylcellulose, gum arabic, and polyvinyl alcohol.
Organic solvents such as ethanol.
Antioxidants such as butylhydroxytoluene, tocopherol and phytic acid.
Antibacterial preservatives such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid esters (such as ethylparaben and butylparaben), and hexachlorophene.

Amino acids and salts thereof such as glycine, alanine, valine, leucine, serine, threonine, phenylalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine, histidine.
Organic acids such as acyl sarcosine acid (eg, lauroyl sarcosine sodium), glutathione, citric acid, malic acid, tartaric acid, lactic acid, and salts thereof.

  Vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B such as vitamin B12, vitamin B15 and its derivatives, ascorbic acid, ascorbic acid phosphate ( Salt), vitamin C such as ascorbic acid dipalmitate, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin E nicotinate and other vitamin E, vitamin D, vitamin H, pantothenic acid, pantethine, etc. Vitamins.

  Nicotinamide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, hinokitiol, mucidin, bisabolol, eucalyptol, thymol, inositol, saponins (psychosaponin, carrot saponin, loofah) Various drugs such as saponin, muclodisaponin, etc.), pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, cephalanthin, placenta extract.

Bark, Clara, Kouhone, Orange, Sage, Thyme, Yarrow, Zeni-Oyaku, Senkyu, Assembly, Spruce, Spruce, Birch, Horsetail, Loofah, Maronier, Yukishinoshita, Arnica, Lily, Artemisia, Peonies, Aloe, Gardenia, Sawan Natural extract extracted with solvent, alcohol, polyhydric alcohol, water, aqueous alcohol.
Cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, and laurylamine oxide.

  Polyoxyethylene fatty acid glyceryl, polyoxyethylene methylpolysiloxane copolymer, fatty acid polyoxyethylene sorbitan, polyoxyethylene alkyl ether, maltitol hydroxy aliphatic alkyl ether, alkylated polysaccharide, alkyl glucoside, sucrose fatty acid ester, poly Nonionic surfactants such as oxyethylene hydrogenated castor oil glyceryl.

  Metal sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate and gluconic acid. Neutralizing agents such as potassium hydroxide, sodium hydroxide and triethanolamine.

In addition, fragrances, scrub agents, powders, coloring materials, whitening agents, UV protection agents such as UV absorbers and UV scattering agents, and the like can be appropriately blended as long as stability is not impaired.
As for each component, a lipophilic component is usually blended with the oil phase, and a hydrophilic component is blended with the first aqueous phase and / or the second aqueous phase.

  The O / W emulsified composition according to the present invention can be suitably applied to, for example, an external composition that can be applied to the body such as skin and hair in cosmetics, medicines, and quasi drugs. For example, skin care cosmetics such as emulsions, creams, massage creams, cleansing creams, essences and body creams; hair care cosmetics such as hair creams, conditioners and rinses; sunscreen cosmetics such as sunscreens; cleansings, makeup removers, etc. It can be used for makeup cosmetics such as foundations; hair cosmetics such as hair styling.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto. Unless otherwise specified, all compounding amounts are shown in mass%.
First, the test method used in the present invention will be described.

<Emulsified particle size>
The emulsified particle diameter of the O / W emulsified composition immediately after preparation was observed with an electron microscope and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: There are no emulsified particles larger than 5 μm.
Δ: There are no emulsified particles larger than 10 μm.
X: There are emulsified particles larger than 10 μm.

<Viscosity>
The viscosity of the O / W emulsified composition immediately after the preparation was measured at 30 ° C. using a B-type viscometer (rotor number 3, rotor rotation speed 12 rpm).

Test example 1
An O / W emulsion composition having the composition shown in Table 1 below was prepared using a higher aliphatic alcohol that forms an α-gel in water and an anionic surfactant. The manufacturing method is as follows.

<Sample 1-2 to Sample 1-4 (Production Method a)>
(1) The first aqueous phase (components 1 to 6) is heated and mixed and dissolved at 80 to 85 ° C.
(2) The oil phase (components 7 to 11) is heated and mixed and dissolved at 80 to 85 ° C.
(3) The first aqueous phase and the oil phase are stirred and mixed with a homogenizer to prepare an emulsified part.
(4) While stirring the emulsified part with a homogenizer, the second aqueous phase (components 12 to 13) at room temperature (about 20 ° C.) is mixed into the emulsified part to obtain an O / W emulsion composition.

<Sample 1-1 (Production Method b)>
(1) The water phase (components 1 to 6 and components 12 to 13) is heated and mixed and dissolved at 80 to 85 ° C.
(2) The oil phase (components 7 to 11) is heated and mixed and dissolved at 80 to 85 ° C.
(3) The aqueous phase and the oil phase were stirred and mixed with a homogenizer, emulsified, and cooled to 40 ° C. with an on-lator to obtain an O / W emulsion composition.

The composition of Sample 1-1 is a composition capable of obtaining an O / W emulsion composition having a fine emulsion particle diameter by a conventional method (production method b) using an onlator.
Both Sample 1-2 and Sample 1-3 are cases where an O / W emulsion composition having the same composition as Sample 1-1 was prepared by a method of cooling the emulsified part in the second aqueous phase (Production Method a).
If (D) alkylene oxide derivative is not present in the emulsified part as in Sample 1-2, even if (D) alkylene oxide derivative is present in the second aqueous phase for cooling, the emulsified particles An O / W emulsion composition having a fine diameter could not be obtained.

On the other hand, when (D) an alkylene oxide derivative is present in the emulsified part as in Sample 1-3, an O / W emulsion composition having a fine emulsified particle diameter is obtained as in Sample 1-1. I was able to get it. Moreover, about the viscosity, the O / W emulsion composition comparable as the sample 1-1 was able to be obtained.
In addition, even when the anionic surfactant forming the α-gel is different as in Sample 1-4, when (D) an alkylene oxide derivative is present in the emulsified part, as in Sample 1-3. An O / W emulsion composition having a fine emulsion particle size could be obtained.

Test example 2
In Sample 1-3 of Table 1, the (D) alkylene oxide derivative concentration in the emulsified part was changed and examined. The O / W emulsion composition was produced according to the production method a.

As shown in Table 2, the emulsified particle diameter tends to be coarse even if the concentration of the (D) alkylene oxide derivative in the emulsified part is too small or too large. Moreover, a viscosity will fall compared with the O / W emulsion composition of the same composition prepared by the conventional method using an onrator etc.
From such a thing, it was thought that it was suitable that the density | concentration of the (D) alkylene oxide derivative in an emulsified part is 1-30 mass%, Furthermore, it is 3-25 mass%.

Test example 3
An O / W emulsion composition having the composition shown in Table 3 was prepared according to production method a.

As can be seen from Samples 3-1 to 3-3, in the emulsified part, (D) O / W emulsified composition having a fine emulsified particle diameter even when other aqueous solvent or glycol is used instead of alkylene oxide derivative. Can't get.
In addition, Sample 3-4 and Sample 3-5 may have a viscosity stabilizing effect in an O / W emulsion composition using an anionic surfactant that forms an α-gel in water and a higher aliphatic alcohol. This is the case where known salts and cationic surfactants are blended in the emulsified part, but even if these components are used, the particle size of the emulsified particles cannot be reduced.
Therefore, the effect of refining the emulsified particle size of the O / W emulsion composition in the method of preparing a high-concentration emulsified part and mixing the low-temperature remaining aqueous phase thereto (Production Method a) is as follows: It is understood to be specific.

Test example 4
Furthermore, (D) The alkylene oxide derivative was changed and examined. The O / W emulsion composition was produced according to the production method a.

As shown in Table 4, when the alkylene oxide derivative represented by the general formula (1) was used, the effect of miniaturization was obtained. However, when the ratio of the oxyalkylene group in the total of the oxyethylene group and the oxyalkylene group was reduced, the refinement was achieved. The effect tended to decrease. Moreover, when the said ratio became large, the alkylene oxide derivative became difficult to melt | dissolve in water and it became difficult to use it.
From this, it was considered that the ratio of the oxyalkylene group to the total of the oxyethylene group and the oxyalkylene group was preferably 20 to 80% by mass, and more preferably 30 to 70% by mass.

Test Example 5
The O / W emulsion composition was manufactured according to the manufacturing method a using the prescription of the following Table 5. In any case, a fine O / W emulsion composition having an emulsified particle size of 5 μm or less could be obtained.

Example 1 Emulsion <second aqueous phase>
1. Purified water to 100 mass%
2. Dipropylene glycol 7.0
3. Xanthan gum 0.1
<First water phase>
4). Purified water 42.0
5. EDTA-2Na · 2H ₂ O 0.1
6). Citric acid 0.01
7). Sodium citrate 0.09
8). N-stearoyl-N-methyltaurine sodium 0.2
9. POE (14) POP (7) Dimethyl ether (random) 3.0
<Oil phase>
10. Distearyldimethylammonium chloride 0.07
11. Stearyl alcohol 0.3
12 Behenyl alcohol 1.1
13. Pentaerythrityl tetraethylhexanoate 1.0
14 Dimethicone 3.0
15. Hydrogenated polydecene 1.0

<Manufacturing method>
(1) The second aqueous phase (components 1 to 3) is mixed and dissolved at room temperature.
(2) The first aqueous phase (components 4 to 9) is dissolved at 80 to 85 ° C.
(3) The oil phase (components 10 to 15) is dissolved at 80 to 85 ° C.
(4) The first aqueous phase and the oil phase are stirred and mixed with a homogenizer to prepare an emulsified part.
(5) The second aqueous phase is added and mixed while stirring the emulsified part with a homogenizer to obtain an O / W emulsion.

  In Example 1, the concentration of component 9 in the emulsified parts (components 4 to 15) is 5.8% by mass, the viscosity of the obtained emulsion is 3,770 mPa · s / 30 ° C., and the emulsified particle size is 1 to 5 μm. It was in range.

Example 2 Emulsion <second aqueous phase>
1. Purified water to 100 mass%
2. Xylitol 1.0
3. Dipropylene glycol 3.0
4). Glycerin 5.0
5. Butylene glycol 3.0
6). Xanthan gum 0.1
7). Dipotassium glycyrrhizinate 0.05
8). Ethanol 4.0
9. Phenoxyethanol 0.5
<First water phase>
10. Purified water 30.0
11. EDTA-2Na · 2H ₂ O 0.1
12 Citric acid 0.01
13. Sodium citrate 0.09
14 N-stearoyl-N-methyltaurine sodium 0.2
15. POE (14) POP (7) Dimethyl ether (random) 1.0
<Oil phase>
16. Stearyl alcohol 0.3
17. Behenyl alcohol 1.1
18. Pentaerythrityl tetraethylhexanoate 1.0
19. Dimethicone 3.0
20. Hydrogenated polydecene 1.0
21. Tocopherol acetate 0.05

<Manufacturing method>
(1) The second aqueous phase (components 1 to 9) is mixed and dissolved at room temperature.
(2) The first aqueous phase (components 10 to 15) is dissolved at 80 to 85 ° C.
(3) The oil phase (components 16 to 21) is dissolved at 80 to 85 ° C.
(4) The first aqueous phase and the oil phase are stirred and mixed with a homogenizer to prepare an emulsified part.
(5) The second aqueous phase is added and mixed while stirring the emulsified part with a homogenizer to obtain an O / W emulsion.

  In Example 2, the concentration of component 15 in the emulsified parts (component 10 to component 21) is 2.6% by mass, the viscosity of the obtained emulsion is 3,820 mPa · s / 30 ° C., and the emulsified particle size is 1 to 5 μm. Met.

Example 3 Latex <second aqueous phase>
1. Purified water to 100 mass%
2. Glycerin 7.0
3. Dipropylene glycol 5.0
4). Butylene glycol 5.0
5. Carboxyvinyl polymer 0.14
6). Potassium hydroxide 0.07
7). Ethanol 3.0
8). Phenoxyethanol 0.5
<First water phase>
9. Purified water 34.0
10. EDTA-2Na · 2H ₂ O 0.01
11. N-stearoyl-N-methyltaurine sodium 0.28
12 POE (14) POP (7) Dimethyl ether (random) 3.0
<Oil phase>
13. Stearyl alcohol 0.42
14 Behenyl alcohol 1.54
15. Vaseline 0.2
16. Palm oil 0.5
17. Macadamia nut oil fatty acid phytosteryl 0.1
18. Pentaerythrityl tetraethylhexanoate 4.0
19. Glyceryl diisostearate 0.6
20. Hydrogenated polydecene 2.0
21. Dimethicone 1.0

<Manufacturing method>
(1) The second aqueous phase (components 1 to 8) is mixed and dissolved at room temperature.
(2) The first aqueous phase (components 9 to 12) is dissolved at 80 to 85 ° C.
(3) The oil phase (components 13 to 21) is dissolved at 80 to 85 ° C.
(4) The first aqueous phase and the oil phase are stirred and mixed with a homogenizer to prepare an emulsified part.
(5) The second aqueous phase is added and mixed while stirring the emulsified part with a homogenizer to obtain an O / W emulsion.

  In Example 3, the concentration of component 12 in the emulsified part (components 9 to 21) is 6.3% by mass, the viscosity of the obtained emulsion is 5,130 mPa · s / 30 ° C., and the emulsion particle size is 1 to 5 μm. It was in range.

Example 4 Latex <second aqueous phase>
1. Purified water to 100 mass%
2. Glycerin 5.0
3. Butylene glycol 7.0
4). Polyethylene glycol 1500 1.0
5. Ethanol 5.0
6). Phenoxyethanol 0.5
7). Citric acid 0.02
8). Sodium citrate 0.18
9. Ascorbic acid glucoside 1.0
<First water phase>
10. Purified water 35.0
11. Succinoglucan 0.07
12 Sodium metaphosphate 0.03
13. N-stearoyl-N-methyltaurine sodium 0.2
14 POE (14) POP (7) Dimethyl ether (random) 2.0
<Oil phase>
15. Cetyl alcohol 0.3
16. Stearyl alcohol 1.0
17. Glyceryl monostearate 0.45
18. Polyoxyethylene sorbitan monostearate 0.6
19. Hydrogenated polydecene 2.0
20. Dimethicone 3.0
21. Methylphenylpolysiloxane 1.0

<Manufacturing method>
(1) The second aqueous phase (components 1 to 9) is mixed and dissolved at room temperature.
(2) The first aqueous phase (components 10 to 14) is dissolved at 80 to 85 ° C.
(3) The oil phase (components 15 to 21) is dissolved at 80 to 85 ° C.
(4) The first aqueous phase and the oil phase are stirred and mixed with a homogenizer to prepare an emulsified part.
(5) The second aqueous phase is added and mixed while stirring the emulsified part with a homogenizer to obtain an O / W emulsion.

  In Example 4, the concentration of component 14 in the emulsified part (components 10 to 21) is 4.4 mass%, the viscosity of the obtained emulsion is 4,470 mPa · s / 30 ° C., and the emulsified particle diameter is 1 to 5 μm. It was in range.

Claims (2)

(A) a higher aliphatic alcohol having 12 to 26 carbon atoms;
(B) oil and
(C) an anionic surfactant capable of forming an α-gel in water with the (A),
(D) an alkylene oxide derivative represented by the following general formula (1);
(E) water and
A method for producing an O / W emulsion composition comprising
(A) The higher aliphatic alcohol having 12 to 26 carbon atoms is 0.05 to 10% by mass in the O / W emulsion composition,
(B) Oil content contains 1 or more types chosen from hydrocarbon oil, ester oil, and silicone oil, and is 0.1-20 mass% in O / W emulsion composition,
(C) The anionic surfactant capable of forming an α-gel in water with (A) is selected from N-acyl sulfonate type anionic surfactants and N-acyl glutamate type anionic surfactants. One or more selected from 0.01 to 5% by mass in the O / W emulsion composition,
(A) The total amount of the higher aliphatic alcohol having 12 to 26 carbon atoms and (C) the anionic surfactant is 0.5 to 10 parts by mass with respect to 10 parts by mass of (B) oil,
(A) a higher aliphatic alcohol having 12 to 26 carbon atoms;
(B) oil and
An oil phase containing,
(C) an anionic surfactant capable of forming an α-gel in water with the (A),
(D) an alkylene oxide derivative represented by the following general formula (1);
(E) a part of water,
A step of preparing an O / W emulsified part by emulsifying a first aqueous phase containing
Cooling the emulsified part by mixing with stirring the second aqueous phase containing the remaining (E) water at 10 to 35 ° C., and
The method for producing an O / W emulsified composition, wherein the (D) alkylene oxide derivative is 1 to 30% by mass in the emulsified part.
_{^{R 1 O - [(AO)}} m (EO) n] -R 2 (1)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70 The ratio of the oxyalkylene group to the total of the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by weight, and the oxyalkylene group and oxyethylene group having 3 to 4 carbon atoms. is .R ^{1, R 2,} appended to the random form is the same or different and an alkyl group having 1 to 4 carbon atoms.) The method according to claim 1 , wherein the second aqueous phase is 40 to 75% by mass in the total amount of the O / W emulsion composition.