JP2006281182A - W/o/w type emulsion composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a W/O/W type emulsion composition which is excellent in aging stability and can be applied for a wide range of products. <P>SOLUTION: A W/O type emulsion composition indispensably comprising a liquid oil component and polyhydric alcohol ester of self condensate of mono-hydroxyl carboxylic acid is prepared beforehand at 25°C. A W/O/W type preliminary emulsion is prepared by further dispersing the obtained W/O type emulsion composition into an aqueous phase. Further, the W/O/W type preliminary emulsion is forced into a fluid mixer composed of a plurality of training unit bodies made by stacking concentrically discs in which small chambers of front-opened honey-comb structures are arranged in such a form that the honey-comb chambers are deviated by a half size thereof, thereby the W/O/W type preliminary emulsion is made finer and, as the result, a W/O/W type emulsion composition excellent in aging stability is obtained. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a W / O / W emulsion composition having excellent temporal stability.

  A W / O / W emulsion composition is a multiphase emulsion composition comprising a water-in-oil emulsion in the water phase. In this emulsion composition, various useful components are encapsulated in the inner aqueous phase of the W / O / W type emulsion, thereby stabilizing the useful components contained therein by preventing oxidation and releasing control by sustained release. It can be used as a functional emulsion composition and is very useful in a wide range of fields such as cosmetics, pharmaceuticals, and foods. However, since the W / O / W type emulsion has a multiphase structure by two-stage emulsification, it is difficult to prepare the emulsion that is stable over time, and there is a problem that useful components in the emulsion internal phase leak. .

  Therefore, various approaches have been made as a method for preparing a stable W / O / W emulsion composition. For example, JP-A-60-199833 discloses a W / O / W emulsion composition characterized by using polyglycerin condensed ricinoleic acid. However, the emulsification method in preparing the W / O / W type emulsion is exclusively by a stirrer such as a homomixer, and can withstand practical use at the cosmetic level unless the external water phase has some viscosity. It has not reached the long-term stability.

  Also, emulsification using a porous glass film having uniform fine pores in JP-A-2-95433, JP-A-2-215881, JP-A-5-220382, JP-A-2001-179077, etc. A method for producing a W / O / W emulsion composition by (hereinafter referred to as membrane emulsification) is disclosed, and it is said that a W / O / W emulsion composition having excellent stability over time can be prepared. However, this porous glass membrane has a high viscosity because the oil component in the pores, that is, the fine pores, is very fine when the oil component is passed through the membrane during emulsification. In some cases, the oil phase is not allowed to pass through the production.

  In JP-A-2003-275573, a polyhydric alcohol ester of a monohydroxycarboxylic acid self-condensate and an anionic surfactant are contained, so that W / O / which has low viscosity and good stability over time. Although a W-type emulsion composition is disclosed, there is a manufacturing problem in providing an appropriate dosage form in a wide range of fields.

  JP-A-60-199833   JP-A-2-95433   JP-A-2-215881   Japanese Patent Laid-Open No. 5-220382   JP 2001-179077 A   JP 2003-275573 A

  The object of the present invention relates to a W / O / W emulsion composition which is excellent in stability over time and can be applied to a wide range of products.

  As a result of intensive studies, the present inventors have prepared in advance a W / O emulsion composition containing an oil component that is liquid at 25 ° C. and a polyhydric alcohol ester of a monohydroxycarboxylic acid self-condensate, and then the composition. The W / O / W type pre-emulsion dispersed in a water phase containing a hydrophilic surfactant is press-fitted into a fluid mixing device having a disk in which a small chamber of a honeycomb structure open to the front is arranged. As a result, it was found that a W / O / W emulsion composition having excellent stability over time could be prepared, and the present invention was completed.

The present invention provides the inventions described in the following items.
Item 1 A W / O emulsion composition containing an oil component that is liquid at 25 ° C. and a polyhydric alcohol ester of a monohydroxycarboxylic acid self-condensate is prepared in advance, and then an aqueous phase containing a hydrophilic surfactant is prepared. A plurality of convection currents obtained by concentrically polymerizing a W / O / W type pre-emulsion in which the composition is dispersed in a disk in which small chambers of a honeycomb structure having an open front surface are arranged so that the honeycomb chambers are offset by half. A W / O / W type emulsion composition produced by press-fitting into a fluid mixing device composed of unit bodies.
Item 2 Polyhydric alcohol ester of monohydroxycarboxylic acid self-condensate is polyglycerin ester of self-condensate of hydroxystearic acid, polyethylene glycol ester of self-condensate of hydroxystearic acid, polyglycerin ester of self-condensate of ricinoleic acid The W / O / W emulsion composition according to claim 1, which is any one of the following.
Item 3. The W / O / W emulsion composition according to any one of claims 1 to 2, wherein the oil component that is liquid at 25 ° C is animal or vegetable oil, fatty acid ester oil, or silicone oil. .

  According to the present invention, it is possible to provide a W / O / W emulsion composition having excellent daily stability, which is used in a wide range of fields such as cosmetics, pharmaceuticals, and foods.

The present invention is described in detail below.
A fluid mixing apparatus having a disk in which small chambers of a honeycomb structure having an open front surface used in the present invention are disclosed in Japanese Patent Publication No. 59-39173. Co., Ltd.) (also known as Lamond mixer or Lamond super mixer).

  The Lamond mixer is composed of a cylindrical casing having an inlet and an outlet at both ends, and two large and small discs in which a large number of polygonal chambers open to the front are arranged in a honeycomb shape on opposite surfaces. The small chambers of the disc and the small-diameter disc are arranged in different positions so that they communicate with other chambers facing each other and concentrically superimpose, and the large-diameter disc matches the inner diameter of the casing. What has a matching diameter and has a through-hole in the center is one flow unit, and two flow units are concentrically polymerized so that small-diameter disks are combined. When one unit is used, the fluid mixing apparatus is configured such that a plurality of units are superposed in a cylindrical casing provided with an inlet and an outlet at both ends so that the flow holes communicate with the inlet and the outlet of the casing. Although the number of units can be set suitably, 3-10 are preferable.

  The oil component that is liquid at 25 ° C. used in the present invention is not particularly limited as long as it is an oil component that is liquid at 25 ° C., such as animal and vegetable oils, fatty acid esters, and silicone oils.

  Specifically, animal and vegetable oils include olive oil, sesame oil, rice bran oil, safflower oil, soybean oil, corn oil, rapeseed oil, palm oil, palm kernel oil, sunflower oil, almond oil, cottonseed oil, palm oil, peanut oil Fish oil, whale oil, squalene, squalane and the like. Examples of hydrocarbon oils include liquid paraffin and light liquid isoparaffin. Examples of fatty acid esters include diisobutyl adipate, diethylhexyl succinate, cetyl 2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, hexyldecyl ethylhexanoate, and triethyl. Hexanoin, neopentyl glycol diethylhexanoate, trimethylolpropane triethylhexanoate, pentaerythrityl tetraethylhexanoate, neopentyl glycol dicaprate, ethylhexyl isononanoate, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, hexyl laurate, Isopropyl myristate, octyldodecyl myristate, isocetyl myristate, isopropyl palmitate, ethyl palmitate Ruhexyl, octyl palmitate, ethyl stearate, octyl stearate, isocetyl stearate, ethyl isostearate, isopropyl isostearate, hexyldecyl isostearate, isostearyl isostearate, glyceryl triisostearate, polyglyceryl triisostearate, triisostearate tris Examples include methylolpropane, pentaerythrityl tetraisostearate, ethyl oleate, glyceryl tri (capryl / caprate), octyldodecyl 12-stearoyl stearate, and the like.

  Silicone oils include dimethylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methylphenylpolysiloxane, amino-modified silicone oil, epoxy-modified silicone oil, polyether-modified silicone oil, and carboxy-modified. Examples include silicone oils, alcohol-modified silicone oils, alkyl-modified silicone oils, ammonium salt-modified silicone oils, and modified silicone oils such as fluorine-modified silicone oils.

  The blending amount of the oil component that is liquid at 25 ° C. used in the present invention can be appropriately set in the invention that can achieve the desired effect of the present invention, but usually 0.01% relative to the total amount of the composition of the present invention. It is about 45% by weight, preferably about 0.1 to 40% by weight, and more preferably 0.5 to 30% by weight.

  The polyhydric alcohol ester of the monohydroxycarboxylic acid self-condensate used in the present invention is not particularly limited, and the monohydroxycarboxylic acid constituting the ester may have 8 to 24 carbon atoms, and carbon Numbers 12 to 22 are more preferable. Of these, ricinoleic acid having 18 carbon atoms or hydroxystearic acid hydrogenated to ricinoleic acid is most preferable.

  The polyhydric alcohol constituting the ester is not particularly limited, and specifically, glycerins such as glycerin and polyglycerin; ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, polyoxyethylene polyoxypropylene glycol Alkylene glycols such as; methylol compounds such as trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol and dipentaerythritol; alkyl glucosides such as methyl glucoside; sugar alcohols such as sorbitol and mannitol; glucose, saccharose And sugars such as glucamine and the like. In particular, polyglycerin and polyethylene glycol are preferable, and polyglycerin having a polymerization degree of 3 to 8 and polyethylene glycol having a polymerization degree of 20 to 50 are most preferable.

  As suitable examples of the polyhydric alcohol ester of monohydroxycarboxylic acid self-condensate, polyglycerin ester of self-condensate of hydroxystearic acid (DEHYMULS PGPH: Cognis), polyethylene glycol ester of self-condensate of hydroxystearic acid (ARLACEL) P135: Unikema), polyglycerin ester of a self-condensate of ricinoleic acid (Sunsoft NO. 818H: Taiyo Kagaku) and the like.

  In the present invention, the polyhydroxy alcohol ester of the monohydroxycarboxylic acid self-condensate is lipophilic and blended in the oil phase, and the blending amount is 0.001 to 10% by weight, preferably based on the total amount of the composition. 0.01 to 5% by weight.

The outer aqueous phase of the emulsion of the present invention includes water, a hydrophilic surfactant, a polyhydric alcohol, a lower alcohol such as ethanol, a higher alcohol such as cetyl alcohol, a water-soluble polymer, a plant extract, a preservative, and a metal sequestering agent. Components such as an agent, an antioxidant, a colorant, a pH adjuster, and a fragrance can be appropriately blended.
The hydrophilic surfactant to be blended in the outer water phase is not particularly limited as long as it is a hydrophilic surfactant. Nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric It can be suitably selected from surfactants.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene phytosterol, polyoxyethylene Examples thereof include oxyethylene lanolin alcohol, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylphenyl ether, polyglycerin fatty acid ester, sucrose fatty acid ester, and polyoxyalkylene-modified organopolysiloxane.

  Examples of the anionic surfactant include alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, α-olefin sulfonate salt, monoalkyl phosphate ester salt, polyoxyethylene monoalkyl ether phosphate ester salt, monoalkyl sulfosuccinic acid. Ester salt, polyoxyethylene alkyl acetate salt, fatty acid soap, polyoxyethylene alkyl monoethanolamide sulfate ester, N-acyl glutamate, N-acyl-N-alkyl amino acid, acylated peptide, α-sulfo fatty acid methyl ester Examples include salt. Examples of the cationic surfactant include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, and benzalkonium chloride.

  Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaines, alkylamidodimethylaminoacetic acid betaines, and 2-alkyl-N-carboxy-N-hydroxyimidazolinium betaines.

  The W / O / W emulsion composition of the present invention can be used in a wide range of fields such as cosmetics, pharmaceuticals, and foods. In the cosmetics field, lotion, emulsion, skin cream, hair treatment, hair tonic, hair restorer, In the case of pharmaceuticals such as hair dyes, permanents, bathing agents, and antiperspirants, various coating agents, children's syrup-type oral drugs, ship drugs, agricultural chemicals, etc., in the case of foods, dressings, ice creams, health drinks, etc. In addition, it can be used for paints, inks, water-based adhesives, fragrances, repellents and the like.

  In addition, the inner aqueous phase of the W / O / W emulsion composition of the present invention is composed of components such as water, as in the case of the outer aqueous phase, and can particularly contain a water-soluble active ingredient. The active ingredient may be water-soluble and is not particularly limited. For example, anti-inflammatory agents such as dipotassium glycyrrhizinate, β-glycyrrhetinic acid and mugwort extract; antioxidants such as glucosylrutin; , Blood circulation promoters such as benzyl nicotinate; moisturizers such as sodium hyaluronate, sodium pyrrolidone carboxylate, mugwort extract, eucalyptus extract, urgonum extract, birch extract; hormonal agents such as ethinyl estradiol; vitamins such as vitamin C; Examples include nutrients such as amino acids, peptides, nucleic acids and derivatives thereof; bioactive peptides, various water-soluble anticancer agents, enzymes, repellents, and the like.

  The amount of the inner aqueous phase of the W / O / W type emulsion is usually 0.01 to 45% by weight, preferably about 0.1 to 40% by weight, more preferably 0.5 to 0.5% with respect to the total amount of the composition. 30% by weight.

  Moreover, the particle diameter of the W / O / W emulsion in the present invention is appropriately set according to the use of the emulsion, and is usually 0.3 to 30 μm.

  In the emulsion composition of the present invention, in addition to the above-described components, components that can be used in cosmetics, pharmaceuticals, foods, etc. within the range not impairing the effects of the present invention are appropriately blended according to the use, form, etc. of the composition. be able to.

Below, the manufacturing method of this invention W / O / W type | mold emulsion composition is demonstrated. In the present invention, first, a W / O type emulsion is prepared, and after it is uniformly dispersed in the outer aqueous phase, it is refined using a Lamond mixer.
i) Preparation of W / O type emulsion The preparation of the W / O type emulsion can be performed according to a conventional method, and the method is not particularly limited. For example, a homogenizer, a high-speed stirrer, a high-pressure homogenizer, an ultrasonic wave An emulsifier or the like can be used.

ii) Preparation of W / O / W type emulsion Next, the W / O type emulsion was pre-dispersed in an aqueous phase containing a hydrophilic surfactant to form a W / O / W type pre-emulsion. Using a Lamond mixer (manufactured by Environmental Science Industrial Co., Ltd.), a W / O / W emulsion is prepared by passing and refining at a flow rate of 1 to 20 L / min while heating at room temperature or as necessary.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to these. Unless otherwise specified, [%] indicates [% by weight].

Preparation of Examples 1 to 5 and Comparative Examples 1 to 5 (1) Preparation of W / O type emulsion According to Table 1, the inner aqueous phase was dissolved at room temperature, and the oil phase was appropriately heated and dissolved. In Examples 1 to 5 and Comparative Examples 1 to 4, the oil phase and the inner aqueous phase were at room temperature, and in Comparative Example 5 after heating the oil phase and the inner aqueous phase, respectively, Stirring was performed using a high-speed stirrer [TK homomixer HV-M, manufactured by Tokki Kika Kogyo Co., Ltd.] to obtain a W / O type emulsion.

(2) Preparation of W / O / W type emulsion The above W / O type emulsion is put into a uniformly dissolved outer water phase, and S is used with a propeller stirrer [trade name: MAZELAZ-1200, manufactured by Tokyo Rika Machinery Co., Ltd.]. Pre-disperse using a character paddle. This preliminary dispersion is performed at normal temperature in Examples 1 to 5 and Comparative Examples 1 to 4, and in Comparative Example 5 by heating. After preliminary dispersion, the fine particles were refined as follows according to the W / O / W preparation method shown in Table 1.

  In Examples 1 to 5 and Comparative Examples 3 to 5, the W / O / W type preliminary emulsion is passed through the casing of the Lamond mixer and refined.

Production of Comparative Examples 1 and 2 The W / O / W type preliminary emulsion is refined using a high-speed stirrer [trade name: TK Homomixer HV-M, manufactured by Tokushu Kika Kogyo Co., Ltd.].

Evaluation of W / O / W type emulsions of Examples 1 to 5 and Comparative Examples 1 to 5 The W / O / W type emulsions of Examples 1 to 5 and Comparative Examples 1 to 5 were used as samples, and their temporal stability was evaluated. As an evaluation, the W / O / W emulsion state after 3 months at 40 ° C. and the leakage rate of the inner aqueous phase component were evaluated. Each evaluation method and evaluation criteria are shown.

1. W / O / W type emulsion state After 3 months at 40 ° C. in each Example and Comparative Example, each W / O / W type emulsion particle was observed and evaluated with a microscope. The evaluation criteria are shown.
Evaluation Criteria A: W / O / W emulsion is in good condition ○: W / O / W emulsion is partially disintegrated Δ: W / O / W emulsion is more than half disintegrated ×: W / O / W emulsion Is almost collapsed or completely oil-water separated

2. Leakage rate of internal water phase components (40 ° C, 3 months later)
Each Example and Comparative Example was allowed to stand at 40 ° C. for 3 months, then centrifuged (1,000 rpm, 5 minutes), the outer aqueous phase was separated, and its absorbance at 480 nm was measured with a spectrophotometer. The leakage rate was obtained from the equation. The leakage rate was expressed as an average value obtained by repeating the test three times.

Formula 1

  The products of the present invention (Examples 1 to 5) are those of Comparative Examples 1 and 2, monohydroxycarboxylic acid self-condensate obtained by refining a W / O / W type pre-emulsion with a homomixer which is an ordinary stirring type dispersion device. Compared with Comparative Example 3 using a surfactant other than a polyhydric alcohol ester, Comparative Example 5 using an oil component exhibiting a solid at 25 ° C., the stability was remarkably superior.

Example 6 (Cosmetic liquid)
Ingredient Formulation% (wt%)
Internal water phase Glucosylrutin 0.5
Vitamin C 0.5
Sodium chloride 0.03
Paraben 0.03
1,3-butylene glycol 1.5
Purified water 12.44
Oil phase Olive oil 6.0
Isostearyl isostearate 7.0
ARLACEL P135 2.0
External water phase POE (20 mol) oleyl ether 0.8
Sodium chloride 0.07
Carboxyvinyl polymer 0.3
Paraben 0.2
Glycerin 5.0
1,3-butylene glycol 5.0
Triethanolamine appropriate amount (pH 6.5)
Fragrance 0.1
Purified water balance Total 100.0
(Production method)
After the inner aqueous phase and the oil phase are dissolved by heating, the inner aqueous phase is added to the oil phase and stirred using a high-speed stirrer to obtain a W / O emulsion. Next, the outer aqueous phase is dissolved, and a W / O type emulsion is added thereto, followed by stirring with a propeller stirrer and preliminary dispersion. After pre-dispersion, the pre-dispersion W / O / W emulsion was passed through a Lamond mixer (5 units) at a flow rate of 10 L / min and refined to prepare a cosmetic liquid. This cosmetic liquid was excellent in stability over time.

Example 7 (hair treatment)
Ingredient Formulation% (wt%)
Inner water phase Sodium polyaspartate 0.5
Paraben 0.03
1,3-butylene glycol 1.0
Purified water 8.47
Oil phase Highly polymerized methylpolysiloxane 0.2
Methylpolysiloxane 3.0
Cetyl octanoate 3.0
Olive oil 2.0
Sunsoft No. 818H 0.8
External water phase stearyltrimethylammonium chloride 2.0
Distearyldimethylammonium chloride 0.5
Cetanol 4.0
Paraben 0.3
Propylene glycol 5.0
Hydroxyethyl cellulose 0.3
Fragrance 0.3
Purified water balance Total 100.0
(Production method)
After the inner aqueous phase and the oil phase are dissolved by heating, the inner aqueous phase is added to the oil phase and stirred using a high-speed stirrer to obtain a W / O emulsion. Next, the outer aqueous phase is dissolved by heating, and a W / O type emulsion is added thereto, followed by stirring with a propeller stirrer and preliminary dispersion. After pre-dispersion, the pre-dispersion W / O / W emulsion was passed through a Lamond mixer (5 units) at a flow rate of 10 L / min to make a hair treatment. This hair treatment was excellent in stability over time.

Claims (3)

  A W / O emulsion composition containing an oil component that is liquid at 25 ° C. and a polyhydric alcohol esterified product of monohydroxycarboxylic acid self-condensate is prepared in advance, and then the aqueous phase containing a hydrophilic surfactant is added to the aqueous phase. A plurality of current-conducting units formed by concentrically polymerizing a W / O / W type pre-emulsified in which the composition is dispersed and a disk in which a small chamber of a honeycomb structure having an open front surface is disposed so that the honeycomb chamber is half-shifted A W / O / W type emulsion composition produced by press-fitting into a fluid mixing device comprising a body and making it fine.   Polyhydroxyl ester of monohydroxycarboxylic acid self-condensate is polyglycerin ester of hydroxystearic acid self-condensate, polyethylene glycol ester of hydroxystearic acid self-condensate, polyglycerin ester of ricinoleic acid self-condensate The W / O / W emulsion composition according to claim 1, which is any one of them.   The W / O / W emulsion composition according to any one of claims 1 to 2, wherein the oil component that is liquid at 25 ° C is animal or vegetable oil, fatty acid ester oil, or silicone oil.