JP5689322B2 - Emulsified composition - Google Patents

Description

  The present invention relates to the technical field of oil-in-water emulsion compositions.

It is known that a copolymer of methoxypolyethylene glycol methacrylate is used as a hair fixing polymer (Patent Document 1: Japanese Patent Application Laid-Open No. 2002-201116).
The applicant, when emulsifying the oil component in a product such as lotion, which has almost no viscosity, polymethoxy methacrylate polyethylene glycol, which is a polymer emulsifier that can emulsify the oil component without adding a surfactant, and A patent application was filed for a polymer emulsifier characterized by containing methoxypolyethylene glycol polymethacrylate (Patent Document 2: Japanese Patent Application No. 2010-171291).
Since then, he has been continually researching the technical development of polymer emulsifiers.
By the way, since the fine adjustment of HLB is unnecessary and emulsification of polar oil is easy, the D phase emulsification method is widely used for preparation of cosmetic emulsions.
The D phase emulsification method is a method of preparing an O / D (Oil-in-Surfactant) emulsion using a surfactant continuous phase and diluting the system to make an O / W emulsion. However, an emulsification method or a drug dispersion method using this method has been developed (Patent Document 3: JP 06-279254 A, Patent Document 4: JP 2003-511235 A, Patent Document 5: Special Table). 2001-510150, Patent Document 6: Japanese Patent Laid-Open No. 58-106532, Patent Document 7: Japanese Patent Publication No. 03-502661, Patent Document 8: Japanese Patent Laid-Open No. 2005-187355).
The emulsion particle size of the diluted O / W emulsion is the same as that of the O / D (Oil-in-Surfactant) emulsion, so the emulsion particle size of the O / D (Oil-in-Surfactant) emulsion is fine. Thus, the stability of the diluted O / W emulsion is increased, and as a result, the amount of the thickener added to supplement the stability of the diluted O / W emulsion can be reduced.
There is a need for a technique for making the emulsified particle diameter of an O / D (Oil-in-Surfactant) emulsion finer.

JP 2002-201116 A Japanese Patent Application No. 2010-171291 Japanese Patent Laid-Open No. 06-279254 Special table 2003-511235 gazette JP-T-2001-510150 JP 58-106532 A Japanese translation of PCT publication No. 03-502661 JP 2005-187355 A

  It is an object of the present invention to produce an emulsified composition having a small emulsified particle diameter with improved emulsion stability and a reduced blending amount of a thickener in preparation of a cosmetic using a D-phase emulsification method gel composition. .

In the present invention, when a gel composition is prepared by a D-phase emulsification method together with a polyglycerin fatty acid ester, a homopolymer having a methacrylic acid compound having a polyethylene glycol side chain structure whose terminal substituent is a methyl group as a monomer, Based on the knowledge that the emulsified particle size when the gel composition is dispersed in water becomes finer than when emulsified with a surfactant (polyglycerin fatty acid ester) alone, poly (methoxypolyethyleneglycol methacrylate) and polyglycerin It is an emulsified composition emulsified by a D-phase emulsification method containing a fatty acid ester, glycerin and an oil component.
The main configuration of the present invention is as follows.
(1) polymethoxypolyethylene glycol polymethacrylate,
Polyglycerol fatty acid ester,
Glycerin,
An emulsified composition containing an oil component and having an emulsified particle diameter of less than 1.25 μm .
(2) The emulsion composition according to (1), wherein the oil component is squalane or / and triethylhexanoin.
(3) The emulsified composition according to (1) or (2), wherein 1,3-butylene glycol is added.
(4) The emulsified composition according to any one of (1) to (3), which is emulsified by a D-phase emulsification method.

The gel composition prepared by the D-phase emulsification method containing polymethacrylic acid methoxypolyethylene glycol, polyglycerin fatty acid ester, glycerin and oily component of the present invention has a fine emulsion particle size when dispersed in water. When the gel composition obtained in the phase emulsification method is used as cosmetics such as skin lotions and emulsions, the amount of thickener added for the purpose of improving the stability of the cosmetics can be reduced. As a result, it was possible to provide an emulsified composition (cosmetic) having no specific stickiness due to the thickener.
The emulsified composition of the present invention had an effect of suppressing moisture evaporation. Therefore, it is possible to provide an anti-wrinkle cosmetic and an anti-aging cosmetic that require a high moisturizing effect.

Particle size distribution chart of Example 1 and Comparative Examples 1 and 3 Particle size distribution chart of Examples 2 and 3 and Comparative Example 2 Particle size distribution chart of Example 4 and Comparative Example 3 The figure which shows the amount of moisture transpiration of Example 4 and Comparative Example 3

  The polymethoxypolyethylene glycol glycol applied to the present invention is obtained by homopolymerizing methoxypolyethylene glycol methacrylate.

  Methoxypolyethylene glycol methacrylate can be obtained, for example, by reacting polyethylene glycol methyl ether with methacrylic acid chloride. Some are commercially available as reagents. For example, NK ester M-230G (n≈23), NK ester M-90G (n≈9) commercially available from Shin-Nakamura Chemical Co., Ltd., Blemmer PME-1000 (n≈23 commercially available from NOF Corporation) ), Blemmer PME-400 (n≈9), Blemmer PME-200 (n≈4) can be used as monomers. Next, the production method of the polymer may be in accordance with a conventional method, and it is obtained by reacting the monomer in a solvent in the presence of a polymerization initiator.

  Below, the synthesis example of the polymethacrylic acid methoxypolyethyleneglycol which concerns on this invention is shown.

Synthesis Example 1 Polymethoxymethyl glycol polymethacrylate (average polymerization degree of polyoxyethylene chain is 4.5)
In a 100 ml eggplant flask, 0.0306 g of polymerization initiator AIBN was weighed and the inside of the flask was replaced with argon gas three times. Then, 30 ml of distilled benzene was added and stirred at room temperature until AIBN was dissolved. To this was added 5 ml of polyethylene glycol methyl ether methacrylate (average polymerization degree of PEG is 4.5), and the mixture was heated at 60 ° C. for 48 hours and then at 70 ° C. for 24 hours to carry out polymerization. Thereafter, the polymerization was stopped and the desired product was recovered.

Synthesis Example 2 Polymethoxy methacrylate polyethylene glycol (average polyoxyethylene chain polymerization degree is 9)
In a 100 ml eggplant flask, 0.0403 g of polymerization initiator AIBN was weighed, and the inside of the flask was replaced with argon gas three times. Then, 30 ml of distilled benzene was added and stirred at room temperature until AIBN was dissolved. To this was added 5 ml of polyethylene glycol methyl ether methacrylate (average degree of polymerization of PEG 9), and polymerization was carried out by heating at 60 ° C. for 48 hours and subsequently at 70 ° C. for 24 hours. Thereafter, the polymerization was stopped and the desired product was recovered.

Synthesis Example 3 Poly (methoxypolyethyleneglycol methacrylate) (average degree of polymerization of polyoxyethylene chain is 22.7)
In a 100 ml eggplant flask, 0.00753 g of the polymerization initiator AIBN was weighed, and the inside of the flask was replaced with argon gas three times. Then, 30 ml of distilled benzene was added and stirred at room temperature until the AIBN was dissolved. To this was added 5 ml of polyethylene glycol methyl ether methacrylate (average polymerization degree of PEG 22.7), and the mixture was heated at 60 ° C. for 48 hours and then at 70 ° C. for 24 hours for polymerization. Thereafter, the polymerization was stopped and the desired product was recovered.

  The molecular weight of the resulting polymethacrylic acid methoxypolyethylene glycol was measured using GPC. As a result, the molecular weight of Synthesis Example 1 was a number average molecular weight Mn = 13800 and a mass average molecular weight Mw = 40400 in terms of polystyrene. The molecular weight of Synthesis Example 2 was a number average molecular weight Mn = 15363 and a mass average molecular weight Mw = 35680 in terms of polystyrene. The molecular weight of Synthesis Example 3 was a number average molecular weight Mn = 8300 and a mass average molecular weight Mw = 10000 in terms of polystyrene.

The molecular weight of the methoxypolyethylene glycol polymethacrylate according to the present invention obtained as described above can be variously adjusted according to the purpose of use, such as emulsifying performance, touch surface, gel composition forming ability, film forming ability, etc. In view of the above, it is usually 1000 or more and 100000 or less, preferably 2500 or more and 100000 or less in terms of polystyrene. In the cosmetic of the present invention, the polymer is usually contained in the range of 0.05 to 20% by mass with respect to the entire cosmetic.
If the amount is less than 0.05% by mass, the effect of reducing the particle size of the emulsified particles may not be obtained even when used in combination with a surfactant in the D-phase emulsification method. It is not preferable.
In the present invention, methoxypolyethylene glycol polymethacrylate acts as an emulsification aid in the D-phase emulsification method. When the polymer is included, the particle size of the emulsified particles when the gel composition prepared in the D-phase emulsification method is dispersed in water can be reduced.

In the present invention, polyglycerol fatty acid ester is an essential component.
As the polyglycerin fatty acid ester, a polyglycerin obtained by polymerizing 2 to 20 glycerin and an ester bond of 1 to 5 fatty acids having 8 to 22 carbon atoms can be used, specifically, decaglyceryl monostearate, Decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monoisostearate, decaglyceryl monooleate, decaglyceryl monolinoleate, decaglyceryl distearate, decaglyceryl diisostearate, decaglyceryl tristearate, decaglyceryl trioleate , Decaglyceryl pentastearate, decaglyceryl pentahydroxystearate, decaglyceryl pentaisostearate, decaglyceryl pentaoleate, tetraglyceryl monostearate, Tetraglyceryl oleate, tristearate tetraglyceryl monolaurate hexaglyceryl, monomyristate hexaglyceryl monostearate hexaglyceryl, polyglycerol fatty acid esters such as hexaglyceryl monooleate and the like.

The HLB of the polyglycerol fatty acid ester is preferably 6.0 or more and 15.0 or less, and if the HLB is less than 6.0 or 15.0 or more, the stability of the emulsion composition is poor.
The blending amount of the polyglycerol fatty acid ester is preferably 0.05% by mass or more and 10.0% by mass or less. If it is less than 0.05% by mass, the emulsification stability is poor, and if it exceeds 10.0% by mass, the skin may be irritated and safety may be problematic.

  In the present invention, glycerin is an essential component. The blending amount of glycerin is preferably 0.5% by mass or more and 30.0% by mass or less. If it is less than 0.5% by mass, D-phase emulsification may not be performed well, and if it exceeds 30.0% by mass, stickiness may occur, which is not preferable.

Examples of the oil used in the present invention include squalane, silicone, liquid paraffin, glyceryl tri-2-ethylhexanoate, isostearic acid, camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, germ oil , Liquid oils such as wheat germ oil, glycerin trioctanoate, stearic acid, cocoa butter, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, owl, owl kernel oil, hydrogenated oil, hydrogenated castor oil And waxes such as beeswax, carnauba wax, candelilla wax, cotton wax, nuka wax, lanolin, lanolin acetate, liquid lanolin, sugarcane wax, jojoba oil and the like.
The blending amount of the oil is preferably 0.1% by mass or more and 40.0 or less. When it exceeds 40.0 mass%, stickiness, glare, etc. will arise and it may be unpreferable in touch.

  In the present invention, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a naturally derived surfactant, and the like can be blended as a surfactant in addition to the polyglycerol fatty acid ester. .

Examples of the nonionic surfactant include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, sucrose fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, and the like. .
Examples of the anionic surfactant include fatty acid salts such as sodium laurate, higher alkyl sulfates such as sodium lauryl sulfate, alkyl ether sulfates such as POE lauryl sulfate triethanolamine, N-acyl sarcosine acid and sulfosuccinic acid. Salts, N-acylamino acid salts and the like.
Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, benzalkonium chloride, and benzethonium chloride.
Examples of amphoteric surfactants include betaine surfactants such as alkyl betaines and amide betaines.
Examples of naturally occurring surfactants include saponins, bile acids, sugar ceramides, and the like.

  In the present invention, a polyhydric alcohol can be blended in addition to glycerin. Examples of the polyhydric alcohol include erythritol, pentaerythritol, sorbitol, maltitol, polyethylene glycol, diglycerin, polyglycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1 , 2-hexanediol, 1,2-octanediol and the like.

The emulsified composition of the present invention is suitable for a skin external medicine, a skin external quasi-drug, and a cosmetic.
In the polymer emulsifier, emulsified composition, skin external preparation (medicine, quasi-drug, cosmetics) of the present invention, components that are usually used in cosmetics as long as they do not impair the effects of the invention as optional components, For example, antioxidants, ultraviolet absorbers, moisturizers, fragrances, fragrances, preservatives, thickeners, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators and other Cosmetic ingredients and medicinal ingredients can be blended.
Inclusion of a thickener improves the stability of the emulsion composition.
As the thickener, a water-soluble polymer is preferable. The water-soluble polymer may be any of natural polymer, semi-synthetic polymer, and synthetic polymer. For example, examples of the natural polymer include tragacanth gum, karaya gum, xanthan gum, guar gum, cationized guar gum, anionized guar gum, tara gum, gum arabic, tamarind gum, juran gum, locust bean gum, carrageenan, quince seed, dextran, and the like. Examples of the semisynthetic polymer include hydroxypropylmethylcellulose, sodium carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, hydroxypropylmethylcellulose, cationized cellulose, propylene glycol alginate, sodium alginate, bentonite and the like. Examples of the synthetic polymer include carboxyvinyl polymer, polyvinyl pyrrolidone, polyvinyl alcohol, dialkyl polyethylene glycol, polyoxyethylene dioleic acid methyl glucoside, polyethylene glycol, polyethylene glycol distearate, synthetic smectite, and the like. These compounding amounts are preferably 0.01 to 0.5% by mass, and more preferably 0.01 to 0.2% by mass. If the blending amount is less than 0.01% by mass, the effect of increasing the viscosity and improving the stability is not sufficient, and if it exceeds 0.5% by mass, the effect of the present invention is impaired due to sliminess or stickiness. Therefore, it is not preferable.

  The emulsified composition of the present invention can be made into cosmetics such as skin lotion, cosmetic liquid, milky lotion, cream and pack.

  The emulsified compositions of Examples 1 to 4 and Comparative Examples 1 to 3 having the configuration of the present invention were prepared, and the emulsified state and the feeling of use were evaluated.

[Preparation method]
Since the emulsified composition of the present invention is prepared using the D phase emulsification method, a special apparatus such as a microfluidizer is not required. First, a gel composition is prepared, and an emulsified composition is prepared using the gel composition.
(Preparation of gel composition by D phase emulsification method)
Polymethacrylic acid methoxypolyethylene glycol and polyglycerin fatty acid ester were dissolved by heating in glycerin, and purified water and 1,3-butylene glycol were also added and dissolved and stirred. To this, an oily component was slowly added little by little to prepare a gel composition. Here, purified water and 1,3-butylene glycol are added before the addition of the oil component, but this slightly breaks the liquid crystal made of methoxypolyethylene glycol polymethacrylate, polyglycerin fatty acid ester, and glycerin. Formulated for the purpose of facilitating incorporation of ingredients. It is not essential when stirring using mechanical force with a disper or the like, and purified water and 1,3-butylene glycol are not essential components in the present invention.
(Preparation of emulsion composition)
An emulsion composition was prepared by dispersing 0.5% by mass of the obtained gel composition in 99.5% by mass of purified water.

[Evaluation of emulsified state of emulsified composition]
The emulsification stability of the emulsion compositions in which the gel compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were dispersed in purified water was visually evaluated according to the following criteria. The emulsified particle size (volume average) was measured with a laser diffraction particle size distribution meter.
○: Creaming does not occur for more than 7 days after storage at 40 ° C. Δ: Creaming occurs after 1 day and before 7 days after storage at 40 ° C. ×: Creaming occurs before 1 day after storage at 40 ° C.

[Usage evaluation]
An emulsified composition in which the gel compositions of Examples and Comparative Examples were dispersed in purified water was applied to 10 female subjects (23 to 55 years old) over the entire face, and the feeling after use was evaluated.
(Evaluation criteria)
○: Smooth feel ×; Smooth feel (judgment)
○: 8 to 10 people evaluated as ○ based on evaluation criteria Δ; 7 to 5 people evaluated as ○ based on evaluation criteria ×; 4 to 1 people evaluated as ○ based on evaluation criteria

  Table 1 shows the results of evaluating the emulsified state and feeling of use of the emulsified compositions obtained by dispersing the emulsified compositions of Examples 1 to 3 containing poly (methoxypolyethylene glycol) methacrylate and the gel compositions of Comparative Examples 1 to 3 in purified water. Show.

As shown in Table 1 (Examples 1 to 4), the gel composition prepared by the D-phase emulsification method containing polymethacrylic acid methoxypolyethylene glycol, polyglycerin fatty acid ester, glycerin and an oil component was dispersed in water. It was found that the emulsified particle size was smaller than those of Comparative Examples 1 and 2 in which the polyglycerol fatty acid ester alone was used. Even when the polyglycerin fatty acid ester was doubled (Comparative Example 3), the emulsified particle size was not reduced, and stickiness due to the surfactant was generated, and the feeling in use was not preferable.
It can be seen that the particle diameters of Examples 2 and 3 are about half that of Comparative Example 2.

The blocking property when an emulsion composition in which the gel composition of Example 4 and Comparative Example 3 was dispersed in purified water was applied was evaluated by an IN VITRO moisture transpiration measurement test.
[IN VITRO moisture transpiration measurement test using filter paper]
An IN VITRO moisture transpiration measurement test using filter paper was performed using an emulsion composition in which 0.5% by mass of the gel composition of Example 4 was dispersed in 95.5% by mass of purified water. As a comparison, emulsification in which 0.5% by mass of the gel composition of Comparative Example 3 in which polyglycerin fatty acid ester was doubled was dispersed in 95.5% by mass of purified water without containing poly (methoxypolyethylene glycol) methacrylate. The composition was used.
A filter paper (No. 2) was placed on the cream bottle, and 0.5 g of the sample was placed thereon and dried overnight in a dryer (60 ° C. setting). Further, 0.5 g of a sample was dropped and dried at 60 ° C. for 2 hours or more to prepare a filter paper used in the experiment. Five filter papers were prepared for each sample.
Next, put 10 g of purified water in the cream bottle, cover with each filter paper, store in a constant temperature room (about 23 ° C, 37-40%), and measure the weight regularly by measuring the weight. The amount of evaporation was confirmed.

  The amount of water transpiration of the emulsion composition of Comparative Example 3 in which the polyglycerin fatty acid ester is doubled is 0.51 g, whereas the water content of the emulsion composition in which the polyglycerol fatty acid ester and polymethoxymethacrylate glycol are combined. Since the amount of transpiration is 0.23 g, it can be seen that the emulsion composition of Example 4 suppresses moisture transpiration about twice as much as the emulsion composition of Comparative Example 3. Therefore, the emulsified composition of the present invention can be made into a cosmetic that is required to have a high moisturizing effect, for example, an anti-wrinkle cosmetic or an anti-aging cosmetic.

Formulation Example 1 Emollient lotion
(Compounding ingredients) (mass%)
1. Polymethacrylic acid methoxypolyethylene glycol 0.5
2. Glycerin 0.5
3. Polyglyceryl-10 distearate-10 0.2
4). Polyglyceryl stearate-10 0.4
5. Purified water 0.05
6). Olive oil 3
7). Sorbitol 4
8). Xanthan gum 0.1
9. Glycerin 5
10.1,2-pentanediol 1
11. Trisodium citrate 0.04
12 Citric acid 0.01
13. Phenoxyethanol 0.2
14 Purified water 85

(Manufacturing method)
Component 8 dispersed in component 7 is added to component 14, and components 9 to 13 are also added and dissolved by stirring (aqueous phase). Ingredients 1 to 5 were dissolved and ingredient 6 was slowly added to prepare a D-phase gel. In addition to the previously prepared aqueous phase, an emulsified composition (emollient lotion) was prepared.

  The emollient lotion of Formulation Example 1 was not sticky, had a smooth feeling and a comfortable feeling to use, and had an excellent moisturizing effect. The storage stability was also good.

Formulation Example 2 Anti-aging serum
(Compounding ingredients) (mass%)
1. Polymethacrylic acid methoxy polyethylene glycol 2
2. Glycerin 2
3. Polyglyceryl-10 distearate 0.6 0.6
4). Polyglyceryl stearate-10 1.4
5. Purified water 0.2
6). Olive oil 4
7). Jojoba oil 4
8). Dipropylene glycol 4
9. Carboxyvinyl polymer 0.1
10. Glycerin 8
11. 1,2-Pentanediol 1
12 Elastin 0.1
13. Hyaluronic acid 0.1
14 Collagen 0.1
15. Potassium hydroxide 0.03
16. Purified water 72.37

(Manufacturing method)
Component 9 dispersed in component 8 is added to component 16, and components 10 to 15 are also added and dissolved by stirring (aqueous phase). While dissolving components 1 to 5, slowly add separately mixed components 6 and 7 to prepare a D-phase gel, and add an emulsion composition (anti-aging cosmetic liquid) to the previously prepared aqueous phase. Prepared.

The emulsified composition of Formulation Example 2 (anti-aging serum) was excellent in storage stability. It was non-sticky and the skin was smooth and comfortable to use. The moisturizing feeling lasted.

Claims (4)

Polymethoxypolyethylene glycol glycol,
Polyglycerol fatty acid ester,
Glycerin,
An emulsified composition containing an oil component and having an emulsified particle diameter of less than 1.25 μm .   The emulsified composition according to claim 1, wherein the oil component is squalane or / and triethylhexanoin.   The emulsified composition according to claim 1 or 2, wherein 1,3-butylene glycol is added.   The emulsified composition according to any one of claims 1 to 3, which is emulsified by a D-phase emulsification method.