JP6766625B2 - W / O type emulsion composition - Google Patents

Description

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

Emulsions are classified into water-in-oil type (W / O) and oil-in-water type (O / W). Generally, W / O type emulsions evaporate water from the skin more than O / W type emulsions. It is known to have the characteristics of suppressing and moisturizing. On the other hand, it has been extremely difficult to secure high-temperature storage stability and low-temperature storage stability, especially in harsh storage conditions and in freeze-thaw. So far, in order to ensure the stability of the W / O type emulsion, the amount of solid oily base has been increased, or an oil gelling agent (Patent Document 1: International Publication WO99 / 25310) has been used to increase the oil phase viscosity. Measures such as raising were taken. However, all of them have problems such as sticky feeling and difficulty in spreading. On the other hand, in a high internal water phase ratio with less stickiness, the ease of spreading is improved by lowering the viscosity, but the low viscosity emulsion W / O type emulsified composition is extremely difficult to stabilize. , A technique for achieving both excellent stability over time and low viscosity has not been established.

International release WO99 / 25310

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a W / O type emulsion composition having both excellent stability over time and low viscosity.

As a result of diligent studies to achieve the above object, the present inventors have found that (A) specific polyoxyethylene hydrogenated castor oil, specific (B) (poly) glycerin fatty acid ester, and (C) branched higher alcohol. It has been found that the above-mentioned problems can be solved by using the liquid ester oil (D), and the present invention has been achieved.

Therefore, the present invention provides the following W / O type emulsion composition.
[1]. (A) One or more selected from polyoxyethylene cured castor oil having an average polyoxyethylene addition mole number of 5 to 20
(B) One or more selected from monoglycerin fatty acid ester and polyglycerin fatty acid ester, which are ester compounds of fatty acid having 12 to 22 carbon atoms and (poly) glycerin.
A W / O type milky liquid composition containing (C) a branched higher alcohol and (D) a liquid ester oil.
[2]. Further, the W / O type emulsion composition according to [1], which contains (E) dimethylpolysiloxane.
[3]. Further, the W / O type emulsion composition according to [1] or [2], which contains (F) acidic mucopolysaccharide.
[4]. The W / O type emulsion composition according to any one of [1] to [3], wherein the component (C) is octyldodecanol.
[5]. The W / O type emulsion composition according to any one of [1] to [4], wherein the component (D) is isopropyl myristate.
[6]. The W / O type emulsion composition according to any one of [1] to [5], wherein the ratio of the aqueous phase component to the composition is 50% by mass or more.

According to the present invention, it is possible to provide a W / O type emulsion composition having both excellent stability over time and low viscosity.

Hereinafter, the present invention will be described in detail.
[(A) component]
The component (A) is one or more selected from polyoxyethylene hardened castor oil having an average polyoxyethylene addition mole number of 5 to 20, and can be used alone or in combination of two or more. .. Examples of the component (A) include polyoxyethylene cured castor oil (5EO), polyoxyethylene cured castor oil (7EO), polyoxyethylene cured castor oil (10EO), and polyoxy. Ethylene-hardened castor oil (20EO) and the like can be mentioned. Among them, polyoxyethylene (EO) having an average added mole number of 7 to 20 is preferable, and polyoxyethylene cured castor oil having an average added mole number of 10 is preferable.

The HLB of the component (A) is preferably 6 to 11. The feature of the present invention is that a specific component (A) is used, and even if HLBs 6 to 11 other than the component (A) are used, the effect of the present invention cannot be obtained. In the present invention, HLB means a value obtained by Griffin's method (see Yoshida, Shindo, Ogaki, Yamanaka, "New Edition Surfactant Handbook", Engineering Books Co., Ltd., 1991, p. 234. ).

[(B) component]
The component (B) is one or more selected from monoglycerin fatty acid ester and polyglycerin fatty acid ester, which are ester compounds of fatty acids having 12 to 22 carbon atoms and (poly) glycerin, and one kind alone or two or more kinds. Can be used in appropriate combinations. Specific examples of the monoglycerin fatty acid ester, which is an ester compound of a fatty acid having 12 to 22 carbon atoms and glycerin, include glyceryl monooleate, glyceryl monomyristate, glyceryl monopalmitate, glyceryl monostearate, and glyceryl monoisostearate. And so on.

Examples of the polyglycerin fatty acid ester, which is an ester compound of a fatty acid having 12 to 22 carbon atoms and polyglycerin, include polyglyceryl trioleate, polyglyceryl pentaoleate, polyglyceryl pentastearate, polyglyceryl heptaoleate, and polyglyceryl condensed ricinoleate. Be done. Among them, polyglycerin fatty acid esters having 2 or more glycerin addition moles such as polyglyceryl trioleate, polyglyceryl pentaoleate, polyglyceryl pentastearate, and polyglyceryl condensed lysinorainate are preferable, and preferably 5 glycerin addition moles Examples include 10 to 10 polyglycerin fatty acid esters. More preferably, 3 to 10 fatty acid chains having 12 to 22 carbon atoms are ester-bonded, such as a polyglycerin fatty acid ester containing an unsaturated fatty acid in an ester such as polyglyceryl trioleate or polyglyceryl pentaoleate. preferable.

From the viewpoint of high temperature stability, polyglycerin fatty acid ester is preferable to monoglycerin fatty acid ester. Further, from the viewpoint of obtaining high temperature stability and low viscosity emulsion, those having an unsaturated fatty acid chain are preferable.

The HLB of the component (B) is preferably 2 to 7. The feature of the present invention is that a specific component (B) is used, and even if HLBs 2 to 7 other than the component (A) are used, the effect of the present invention cannot be obtained.

As for the content of the component (A) and the component (B), the total amount of the component (A) and the component (B) ((A) + (B)) is preferably 6 to 15% by mass with respect to the entire composition, and 8 ~ 12% by mass is more preferable. When the content is 6 to 15% by mass, a milky liquid composition having better high temperature stability and low viscosity can be obtained, and when the content is 8 to 12% by mass, the high temperature stability and freeze-thaw stability are particularly excellent. A low-viscosity emulsion composition can be obtained.

The content mass ratio (A): (B) of the component (A) to the component (B) is preferably 1: 3 to 3: 1, more preferably 1: 1 to 3: 1. The closer (A): (B) = 3: 1 is, the more excellent the emulsion composition is obtained with high temperature stability, and the closer (A): (B) = 1: 3 is, the lower the viscosity of the emulsion is obtained. Be done.

[Component (C)]
The component (C) is a branched higher alcohol, and one type can be used alone or two or more types can be used in combination as appropriate. Branched higher alcohols include those having 10 to 40 carbon atoms, such as hexyldecanol, octyldodecanol, decyltetradecanol, dodecylhexadecanol, tetradecyloctadecanol, hexadecyleicosanol, and isopalmityl alcohol. , Isostearyl alcohol, isoeicosanol and the like. Among them, hexyldecanol and octyldodecanol are preferable from the viewpoint that a milky liquid composition having excellent high temperature stability and low viscosity can be obtained, and octyldodecanol is more preferable from the viewpoint of being particularly excellent in high temperature stability.

The content of the component (C) is preferably 4 to 12% by mass, more preferably 5 to 12% by mass, based on the entire composition, from the viewpoint of obtaining a milky liquid composition having particularly excellent high temperature stability and low viscosity. , 6-10% by mass is more preferable. By setting the content to 4 to 12% by mass, a milky liquid composition having better high temperature stability and low viscosity can be obtained.

Further, the content of the component (C) is preferably 15% by mass or more and less than 60% by mass, and 20% by mass or more and 60% by mass in the oil phase from the viewpoint of obtaining a milky liquid composition having excellent high temperature stability and low viscosity. % Is more preferable, and 30% by mass or more and less than 50% by mass is further preferable.

[(D) component]
The liquid ester oil (D) component is a liquid ester oil, which can be used alone or in combination of two or more. The liquid is liquid at 25 ° C., for example, decyl laurate, caprylyl laurate, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, cetyl 2-ethylhexanoate, olein. Monoesters such as ethyl acid, 2-ethylhexyl stearate, hexyldecyl stearate, ethyl linoleate, 2-octyldodecyl pivalate, diethyl sebacate, diisopropyl adipate, diisostearyl malate, propylene glycol dicaprate, dicaprylic acid Examples thereof include diesters such as propylene glycol, tri-ethylhexyl citrate, diglyceryl triisostearate, glyceryl tri2-ethylhexanoate, and triesters such as tri (capryl capric acid) glyceryl. Of these, monoesters are preferable from the viewpoint of high temperature stability. From the viewpoint of obtaining a milky liquid composition having a lower viscosity, a short chain such as isopropyl myristate or isopropyl palmitate is more preferable than a long chain such as cetyl ethylhexanoate or hexyldecyl isostearate, and high temperature stability is obtained. Isopropyl myristate is more preferable from the viewpoint of obtaining a milky liquid composition having particularly excellent freeze-thaw stability and low viscosity.

The content of the component (D) is preferably 1 to 10% by mass, more preferably 3 to 5% by mass, based on the entire composition. When the content is 1 to 10% by mass, a milky liquid composition having better high temperature stability and low viscosity can be obtained, and when the content is 3 to 5% by mass, the high temperature stability is particularly excellent and the viscosity is low. A milky liquid composition can be obtained.

Further, the content of the component (D) is preferably 4% by mass or more and less than 50% by mass, and 10% by mass or more and 30% by mass in the oil phase from the viewpoint of obtaining a milky liquid composition having excellent high temperature stability and low viscosity. More preferably less than%.

[(E) component]
From the viewpoint of freeze-thaw stability, the composition of the present invention preferably further contains (E) dimethylpolysiloxane. The viscosity of dimethylpolyxane is not particularly specified, and a viscosity of 20 to 50,000 mPa · s at 25 ° C. can be used, but a viscosity of 20 to 5,000 mPa · s is preferable, and a viscosity of 20 to 1,000 mPa · s is preferable. The one of s is more preferable. The viscosity is measured at 25 ° C. and 12 rpm using a B-type viscometer, for example, a rotary viscometer RB-80L manufactured by Tokisan Co., Ltd.

When the component (E) is blended, the content of the component (E) is preferably 0.1 to 5% by mass, more preferably 0.5 to 1% by mass, based on the entire composition. When the content is 0.1 to 5% by mass, a milky liquid composition having better high temperature stability and low viscosity can be obtained, and when the content is 0.5 to 1% by mass, the high temperature stability is particularly excellent. , And a low viscosity emulsion composition can be obtained.

When the component (E) is blended, it can be 0.5% by mass or more and less than 23% by mass in the oil phase, preferably 0.5% by mass or more and less than 15% by mass, and 2% by mass or more and less than 5% by mass. More preferred. When the content is 0.5% by mass or more and less than 15% by mass, an emulsion composition having excellent high temperature stability and low viscosity can be obtained, and when the content is 2% by mass or more and less than 5% by mass, it is particularly low. An emulsion having a high viscosity and excellent high-temperature stability can be obtained.

[(F) component]
The composition of the present invention preferably further contains (F) acidic mucopolysaccharide from the viewpoint of further improving high temperature stability. The acidic mucopolysaccharide may be used alone or in combination of two or more. Examples of the acidic mucopolysaccharide include chondroitin sulfate, hyaluronic acid, and heparinoid, and heparinoid is preferable. As the heparin-like substance, a commercially available substance can be used, and examples thereof include a heparin-like substance manufactured by Api Co., Ltd.

When the component (F) is blended, the content of the component (F) is preferably 0.01 to 10% by mass, more preferably 0.1 to 1% by mass, based on the entire composition.

In the present invention, it is classified into three components, (1) aqueous phase component, (2) oil phase component, and (3) activator component, according to the properties of each component shown below.

(1) Aqueous phase component In the present invention, as the component corresponding to the aqueous phase component, a hydrophilic substance that is uniformly soluble in water, such as component (F), water, water-soluble compounds such as ethanol and a thickener, is used. This includes, for example, water, alcohols, glycerin, polyethylene glycol polyhydric alcohols, sodium pyrosulfite, inorganic salts such as sodium citrate hydrate, organic acid salts, polysaccharides, water-soluble polymer compounds and the like. The water content is preferably 5% by mass or more and less than 80% by mass with respect to the entire composition.

(2) Oil phase components As the components corresponding to the oil phase components in the present invention, all hydrocarbon compounds such as natural animal / vegetable oils, synthetic oils, oily chemicals, etc., which are hardly or completely soluble in the aqueous phase, are applicable, for example. Component (C), component (D), component (E), hydrocarbon oil (squalane, liquid paraffin, etc.), higher alcohol, ester oil, silicon oil, waxes, wax, oily chemicals (diphenhydramine, vitamin A oil, tocopherol) Acetate ester, dibutylhydroxytoluene, etc.), oil gelling agent, fragrance, etc.

(3) Activator component In the present invention, the component corresponding to the activator component corresponds to a substance classified as a surfactant having both a hydrophilic group and a lipophilic group in the molecule, for example, (A). ) Component, (B) component, (polyoxyethylene) sorbitan fatty acid ester, (polyoxyethylene) sorbit fatty acid ester, sucrose fatty acid ester, lecithin derivative, beeswax derivative, polyoxyethylene lanolin, polyoxyethylene (hydrogenated) sterol , Proxin glycol fatty acid esters, polyoxyethylene alkyl ethers, nonionic surfactants such as polyoxyethylene polyoxypropylene alkyl ethers, cationic surfactants such as alkylammonium salts, amphoteric surfactants such as betaine acetate and amidoamine. Examples thereof include anionic surfactants such as agents, fatty acid soaps, (polyoxyethylene) alkyl ether phosphates / phosphates, alkyl sulfates, sulfonates, and polyethylene glycol fatty acid esters.

The ratio of the aqueous phase component to the composition is preferably 50% by mass or more, more preferably 50% by mass or more and less than 80% by mass, and further preferably 60% by mass or more and less than 70% by mass. When it is 50% by mass or more, it is less sticky and spreads more easily, and when it is 80% by mass or less, low viscosity and high temperature stability can be further maintained.

The mass ratio represented by the aqueous phase component: the oil phase component is preferably 2 or more and less than 4: 1, more preferably 2.8 to 3.2: 1. When it is 2 or more and 1, it is less sticky and spreads more easily, and when it is less than 4 and 1, it is possible to maintain low viscosity and high temperature stability.

[Production method]
The production method is not particularly limited, but for example, an aqueous phase heated to the same temperature is added to the oil phase heated and dissolved at 50 to 80 ° C. An example is a method of emulsifying at 2,000 to 10,000 rpm with an emulsifier such as a homomixer for 2 to 15 minutes while maintaining the temperature, and then cooling to room temperature while stirring at 50 to 200 rpm with a paddle mixer. ..

[W / O type emulsion composition]
The viscosity of the W / O type emulsion composition of the present invention is less than 10,000 mPa · s at 25 ° C. as a viscosity that is easy to spread, and less than 7,000 mPa · s as a viscosity that is easy to spread over the whole body even in the emulsion. Is preferable, and 5,000 mPa · s or less is preferable from the viewpoint that the resistance at the time of spreading is small and the spreading is easier. On the other hand, if it is less than 2,000 mPa · s, there is no problem in use such as spreading it on the whole body, but the shape retention of the preparation deteriorates and it may be difficult to spread it due to dripping from the affected area. It is preferably 000 mPa · s or more. The viscosity is measured using a B-type viscometer (Tokyo Keiki ASB100 type) under the following conditions.
Rotor: No. 13
Measurement temperature: 25 ° C
Rotation speed 12 rpm

The pH (25 ° C.) of the W / O type emulsified composition of the present invention is preferably 4.5 to 8.5 at 25 ° C., more preferably 6.0 to 7.5.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, unless otherwise specified, "%" of the composition indicates mass%, and the ratio indicates mass ratio.

[Examples, comparative examples]
An aqueous phase heated to the same temperature was added to the oil phase heated and dissolved at 70 ° C. While maintaining the temperature, emulsify with a homomixer (TK AUTO HOMO MIXER manufactured by Tokushu Kagaku Kogyo Co., Ltd.) at 6,000 rpm for 5 minutes, and cool to room temperature while stirring at 100 rpm using a paddle mixer. A W / O type emulsified composition having the composition shown in the table below was obtained. The obtained composition was evaluated as follows. The results are shown in the table.

<High temperature stability>
The emulsified composition was stored at 50 ° C. for 2 months, and the stability was evaluated by visual changes in appearance (oil exudation, water separation, separation). The results are shown by the following evaluation criteria.
(Evaluation criteria)
◎: No change in appearance for 2 months or more ○: No change in appearance for 1 month or more and less than 2 months ●: No change in appearance for 2 weeks or more and less than 1 month ×: Change in appearance in less than 2 weeks ● Passed ..

<Easy to spread>
The viscosity of the emulsified composition was measured using a B-type viscometer (Tokyo Keiki ASB100 type) under the following conditions.
Rotor: No. 13
Measurement temperature: 25 ° C
Rotation speed 12 rpm
From the results of the obtained viscosity, the ease of spreading is shown by the following evaluation criteria.
(Evaluation criteria)
⊚: 2,000 mPa ・ s or more and less than 5,000 mPa ・ s ○: 5,000 mPa ・ s or more and less than 7,000 mPa ・ s ●: 7,000 mPa ・ s or more and less than 10,000 mPa ・ s ×: 10,000 mPa ・ s or more ● Pass the test.

<Freeze-thaw stability>
The emulsified composition was stored at −20 ° C. for 12 hours or longer, and then left at 25 ° C. for 12 hours. This operation was similarly repeated 5 times. The results are shown by the following evaluation criteria from the viscosity maintenance rate before and after the freeze-thaw operation and the change in appearance (oil exudation, water separation, separation).
Viscosity retention rate (%) = viscosity after freeze-thaw / viscosity before freeze-thaw x 100
(Evaluation criteria)
⊚: Viscosity maintenance rate 40% or more ○: Viscosity maintenance rate less than 40% ×: Appearance changes If the viscosity maintenance rate is less than 40%, the shape retention of the liquid deteriorates and it may be difficult to spread it due to dripping from the affected area. However, there is no problem in use such as spreading over the whole body, and when the viscosity retention rate is 40% or more, there is almost no change in the ease of spreading and the high temperature stability.

The raw materials used in the above example are shown below. Unless otherwise specified, the amount of each component in the table is a net conversion amount.
・ Heparinoid: Api Co., Ltd. External Regulations Heparinoid ・ Vitamin A oil: DSM Nutrition Japan Co., Ltd. Japan Bureau Vitamin A oil (tocopherol addition: 1 million units / g)
・ Tocopherol acetate: DSM Nutrition Japan Co., Ltd. Japan Bureau Tocopherol acetate ・ Polyethylene glycol: Sanyo Chemical Industries, Ltd. Macrogol 20000
-POE hardened castor oil 5: Nikko Chemicals Co., Ltd. NIKKOL HCO-5 Polyoxyethylene hardened castor oil (average number of moles added 5)
-POE hardened castor oil 10: Nikko Chemicals Co., Ltd. NIKKOL HCO-10 Polyoxyethylene hardened castor oil (average number of moles added 10)
-POE hardened castor oil 20: Nikko Chemicals Co., Ltd. NIKKOL HCO-20 Polyoxyethylene hardened castor oil (average number of moles added 20)
-POE hardened castor oil 60: Nikko Chemicals Co., Ltd. NIKKOL HCO-60 Polyoxyethylene hardened castor oil (average number of moles added 60)
・ Glycerin: Sakamoto Yakuhin Kogyo Co., Ltd. Japan Bureau Glycerin / dibutylhydroxytoluene: Wako Pure Chemical Industries, Ltd. Dibutylhydroxytoluene / sodium pyrosulfite: Wako Pure Chemical Industries, Ltd. Sodium pyrosulfite (for production only)
-Sodium citrate hydrate: Three F Co., Ltd. Sodium citrate hydrate-Decaglyceryl pentaoleate: Nikko Chemicals Co., Ltd. NIKKOL Decaglin 5-OV
・ Sorbitan oleate: Nikko Chemicals Co., Ltd. NIKKOL SO10-V
・ Hexildecanol: Higher Alcohol Industry Co., Ltd. Lysonol 16SP
・ Octyldodecanol: Kao Corporation Calcor 200GD
-Stearyl alcohol: Kao Corporation Calcor 8098
・ Oleyl alcohol: Croda Japan Co., Ltd. Noboru-LQ- (JP)
-Isopropyl myristate: Nikko Chemicals Co., Ltd. IPM-EX
-Isopropyl palmitate: Nikko Chemicals Co., Ltd. IPP-EX
-Cetyl ethylhexanoate: Nikko Chemicals Co., Ltd. NIKKOL CIO
・ Hexyldecyl isostearate: Nikko Chemicals Co., Ltd.
-Diisopropyl adipic acid: Nikko Chemicals Co., Ltd. NIKKOL DID
-Diethyl sebacate: Nikko Chemicals Co., Ltd. NIKKOL DES-SP
・ Squalane: Nikko Chemicals Co., Ltd. NIKKOL Squalene

Claims (7)

(A) One or more selected from polyoxyethylene cured castor oil having an average polyoxyethylene addition mole number of 5 to 20
(B) One or more selected from monoglycerin fatty acid ester and polyglycerin fatty acid ester, which are ester compounds of fatty acid having 12 to 22 carbon atoms and (poly) glycerin.
It contains (C) a branched higher alcohol and (D) liquid ester oil, and the total content of the components (A) and (B) is 6 to 15% by mass, and the content of the component (C) is A W / O type emulsion composition having an amount of 4 to 12% by mass and a content of the component (D) of 1 to 10% by mass . The W / O type emulsion composition according to claim 1, further containing (E) dimethylpolysiloxane. The W / O type emulsion composition according to claim 1 or 2, further comprising (F) an acidic mucopolysaccharide. The W / O type emulsion composition according to any one of claims 1 to 3, wherein the component (C) is octyldodecanol. The W / O type emulsion composition according to any one of claims 1 to 4, wherein the component (D) is isopropyl myristate. The W / O type emulsion composition according to any one of claims 1 to 5, wherein the ratio of the aqueous phase component to the composition is 50% by mass or more. The W / O type emulsion composition according to any one of claims 1 to 6, wherein the content mass ratio (A): (B) of the component (A) to the component (B) is 1: 3 to 3: 1. object.