KR20120031879A - Emulsion composition - Google Patents

Abstract

PURPOSE: An emulsion composition containing polymethacrylic acid methoxy polyethylenen glycol, polyglycerin fatty acid ester, and glycerin is provided to suppress moisture evaporation. CONSTITUTION: An emulsion composition contains polymethacrylic acid methoxy polyethyelene glycol, polyglyerine fatty acid ester, glycerine, and oil phase ingredients. The oil phase ingredients include squalene and/or triethyl hexanoin. The emulsion composition additionally contains 1,3-butylene glycol.

Description

Emulsion composition

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

It is known that the copolymer of methoxy polyethyleneglycol methacrylate is used as a hair fixing polymer (Patent Document 1: Japanese Patent Laid-Open No. 2002-201116).

Applicant, when emulsifying the oily component in a product having little viscosity such as a lotion, polymethacrylic acid methoxypolyethylene glycol, polymethacrylic acid glycol and polymethacrylic acid, which is a polymer emulsifier capable of emulsifying the oily component without blending a surfactant A patent application was filed for a polymer emulsifier containing methoxy polyethylene glycol (Patent Document 2: Japanese Patent Application No. 2010-171291).

Since then, intensive research has been conducted on the technical development of the polymer emulsifier.

On the other hand, since the delicate adjustment of HLB is unnecessary and emulsification of polar oil is also easy, the D-phase emulsification method is widely used for preparation of emulsion of cosmetics.

The D phase emulsification method is a method of producing an O / D (Oil-in-Surfactant) emulsion using a surfactant continuous phase and diluting the system to form an O / W emulsion. Emulsification method or drug dispersing method has been developed (Patent Document 3: Japanese Patent Application Laid-Open No. 06-279254, Patent Document 4: Japanese Patent Publication No. 2003-511235, Patent Document 5: Patent Publication No. 2001-510150, Patent Document 6: Japanese Patent Publication No. 58-106532, Patent Document 7: Japanese Patent Publication No. 03-502661, Patent Document 8: Japanese Patent Publication No. 2005- 187355).

Since the emulsified particle diameter of the diluted O / W emulsion is maintained in the emulsified particle diameter of the O / D (Oil-in-Surfactant) emulsion, the finer the emulsified particle diameter of the O / D (Oil-in-Surfactant) emulsion is The stability of the / W emulsion is increased, and as a result, the amount of the thickener to be added can be reduced to compensate for the stability of the diluted O / W emulsion.

There is a need for a technique for further miniaturizing the emulsified particle diameter of an oil-in-surface (O / D) emulsion.

Japanese Patent Publication No. 2002-201116 Japanese Patent Application No. 2010-171291 Japanese Patent Laid-Open No. 06-279254 Japanese Patent Publication No. 2003-511235 Japanese Patent Publication No. 2001-510150 Japanese Patent Laid-Open No. 58-106532 Japanese Patent Publication Hei 03-502661 Japanese Patent Publication No. 2005-187355

In the cosmetic preparation using the D-phase emulsification method gel composition, it is a subject to produce the emulsion composition with the small emulsion particle diameter which improved the emulsion stability and reduced the compounding quantity of a thickener.

The present invention is to prepare a gel composition by a D-phase emulsification method together with a polyglycerol fatty acid ester of a homopolymer having a methacrylic acid compound having a polyethyleneglycol side chain structure having a terminal substituent as a methyl group as a monomer. Based on the finding that the emulsified particle size at the time of dispersion becomes smaller than when emulsified with surfactant (polyglycerin fatty acid ester) alone, the polymethacrylic acid methoxy polyethylene glycol, polyglycerol fatty acid ester, glycerin, and an oily component are included, It is an emulsion composition emulsified by the phase emulsion method.

The main structure of this invention is as follows.

(1) polymethacrylic acid methoxy polyethylene glycol,

Polyglycerin fatty acid esters,

Glycerin,

Oily ingredients

Emulsifying composition comprising a.

(2) The emulsion composition according to (1), wherein the oily component is squalane and / or triethylhexanoin.

(3) The emulsion composition as described in (1) or (2) which added 1, 3- butylene glycol.

(4) The emulsion composition according to any one of (1) to (3), wherein the emulsion is emulsified by the D-phase emulsification method.

(5) Particle diameter is less than 1.25 micrometers, The emulsion composition in any one of (1)-(4) characterized by the above-mentioned.

Since the gel composition prepared by the D-phase emulsification method including the polymethacrylic acid methoxypolyethylene glycol, the polyglycerin fatty acid ester, the glycerin, and the oily component of the present invention is small in the emulsified particle size when dispersed in water, the D-phase emulsification When using the gel composition obtained in the method to form a cosmetic such as a lotion or an emulsion, the amount of the thickener to be added for the purpose of improving the stability of the cosmetic can be reduced, and as a result, an emulsified composition having no specific stickiness due to the thickener is obtained. Could provide (cosmetics).

The emulsion composition of the present invention had an effect of suppressing water evaporation. Therefore, it is possible to provide an anti-wrinkle cosmetic or an anti-aging cosmetic that requires a high moisturizing effect.

1 is a particle diameter distribution diagram of Example 1 and Comparative Examples 1 and 3. FIG.
2 is a particle diameter distribution diagram of Examples 2 and 3 and Comparative Example 2. FIG.
3 is a particle diameter distribution diagram of Example 4 and Comparative Example 3. FIG.
4 is a view showing the amount of moisture evaporation of Example 4 and Comparative Example 3. FIG.

Polymethacrylic acid methoxy polyethyleneglycol applied to this invention is obtained by homopolymerizing methacrylic acid methoxy polyethyleneglycol.

Methacrylic acid methoxy polyethyleneglycol can be obtained by making polyethylene glycol methyl ether and methacrylic acid chloride react, for example. In addition, some of them are commercially available as reagents. For example, NK ester M-230G (n ≒ 23) marketed by Shin-Nakamura Chemical Co., Ltd., NK ester M-90G (n ≒ 9), and Blemmer PME-1000 (n ≒ 23) marketed by Nichiyu Co., Ltd. , Blemmer PME-400 (n ≒ 9), Blemmer PME-200 (n ≒ 4) can be used as the monomer. Next, the manufacturing method of a polymer may be followed by a conventional method, and is obtained by making a monomer react in presence of a polymerization initiator in a solvent.

Below, the synthesis example of the polymethacrylic-acid methoxy polyethyleneglycol of this invention is shown.

Synthesis Example 1 Polymethacrylate methoxy polyethylene glycol (average degree of polymerization of polyoxyethylene chain 4.5)

0.0306 g of the polymerization initiator AIBN was weighed into a 100 ml Naus flask, the flask was replaced with argon gas three times, and 30 ml of distilled benzene was added, followed by stirring at room temperature until the AIBN was dissolved. 5 ml of polyethyleneglycol methyl ether methacrylate (the average degree of polymerization of PEG is 4.5) was added to this, and it heated at 60 degreeC for 48 hours, and then heated at 70 degreeC for 24 hours, and superposed | polymerized. Thereafter, the polymerization was stopped to recover the target product.

Synthesis Example 2 Polymethacrylate methoxy polyethylene glycol (average degree of polymerization of polyoxyethylene chain 9)

0.0403 g of the polymerization initiator AIBN was weighed into a 100 ml Naus flask, the flask was replaced with argon gas three times, and 30 ml of distilled benzene was added, followed by stirring at room temperature until the AIBN was dissolved. 5 ml of polyethyleneglycol methyl ether methacrylate (the average degree of polymerization of PEG is 9) was added to this, and it heated for 48 hours at 60 degreeC, and then heated at 70 degreeC for 24 hours, and superposed | polymerized. Thereafter, the polymerization was stopped to recover the target product.

Synthesis Example 3 Polymethacrylate methoxypolyethylene glycol (average degree of polymerization of polyoxyethylene chain 22.7)

0.00753 g of the polymerization initiator AIBN was weighed into a 100 ml Naus flask, the flask was replaced with argon gas three times, and 30 ml of distilled benzene was added, followed by stirring at room temperature until the AIBN was dissolved. 5 ml of polyethyleneglycol methyl ether methacrylate (average degree of polymerization of PEG is 22.7) was added to this, and it heated for 48 hours at 60 degreeC, and then heated at 70 degreeC for 24 hours, and superposed | polymerized. Thereafter, the polymerization was stopped to recover the target product.

The molecular weight of the obtained methacrylic acid methoxy polyethylene glycol was measured using GPC. As a result, the molecular weight of Synthesis Example 1 was number average molecular weight Mn = 13800, and mass average molecular weight Mw = 40400 in polystyrene conversion. The molecular weight of the synthesis example 2 was number average molecular weight Mn = 15363, and mass mean molecular weight Mw = 35680 in polystyrene conversion. The molecular weight of the synthesis example 3 was number average molecular weight Mn = 8300, and mass mean molecular weight Mw = 10000 in polystyrene conversion.

The molecular weight of the polymethacrylic methoxy polyethylene glycol of the present invention obtained as described above can be variously adjusted according to the purpose of use, but in view of emulsifying performance, texture, gelling ability, film forming ability, etc., polystyrene is usually It is 1000 or more and 100000 or less in conversion, Preferably it is 2500 or more and 100000 or less. In the cosmetics of this invention, the said polymer is contained in 0.05-20 mass% with respect to the whole cosmetics normally.

If it is less than 0.05 mass%, even if it uses together with surfactant in a D-phase emulsification method, the effect of reducing emulsified particle diameter may not be acquired, and when it exceeds 20 mass%, since a usability will worsen, it is unpreferable.

In the present invention, the polymethacrylic acid methoxy polyethylene glycol acts as an emulsifying aid in the D phase emulsification method. When the polymer is included, the emulsified particle diameter when the gel composition prepared in the D-phase emulsification method is dispersed in water can be made small.

In the present invention, polyglycerol fatty acid ester is an essential component.

As the polyglycerol fatty acid ester, those obtained by esterification of 1 to 5 fatty acids having 8 to 22 carbon atoms to a polyglycerol polymerized with 2 to 20 glycerin can be used. Specifically, monostearate decaglyceryl and monolaurate deca Glyceryl, Decaglyceryl Monostearate, Decaglyceryl Monostearate, Decaglyceryl Monooleate, Decaglycerol Monooleoleic Acid, Decaglyceryl Distearate, Decaglyceryl Diteastearate, Deca of Tristearic Acid Glyceryl, tricaic acid decaglyceryl, pentastearic acid decaglyceryl, pentahydroxystearate decaglyceryl, pentaisostearic acid decaglyceryl, pentaoleate decaglyceryl, monostearate tetraglyceryl, monooleic acid tetraglycerol Reel, Tristearate Tetraglyceryl, Monolauric Hexaglyceryl, Monomyritic Acid Hexane And the like glyceryl, monostearate hexadecyl glyceryl mono oleate hexadecyl glyceryl such as polyglycerol fatty acid esters.

As for the HLB of polyglycerol fatty acid ester, 6.0 or more and 15.0 or less are preferable, and when HLB is less than 6.0 and 15.0 or more, stability of an emulsion composition is bad.

As for the compounding quantity of polyglycerol fatty acid ester, 0.05 mass% or more and 10.0 mass% or less are preferable. If it is less than 0.05 mass%, emulsion stability is bad, and when it exceeds 10.0 mass%, a skin irritation may arise and a problem may arise in safety.

In the present invention, glycerin is an essential ingredient. As for the compounding quantity of glycerin, 0.5 mass% or more and 30.0 mass% or less are preferable. If it is less than 0.5 mass%, D phase emulsification may not be performed well. If it exceeds 30.0 mass%, stickiness may be generated, which is not preferable.

Examples of the oil agent 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 and rapeseed oil. Oils such as corn oil, sesame oil, germ oil, wheat germ oil, glycerin trioctanoate, stearic acid, cacao butter, palm oil, hardened palm oil, palm oil, palm kernel oil, beeswax, waxy kernel oil, hardened oil, hardened castor oil And waxes such as solid fats, beeswax, carnauba wax, candelilla wax, cotton wax, rice bran wax, lanolin, lanolin acetate, liquid lanolin, sugar cane wax, and jojoba oil.

As for the compounding quantity of an oil agent, 0.1 mass% or more and 40.0 or less are preferable. When it exceeds 40.0 mass%, stickiness, smearing, etc. may arise, and it may be unpreferably feel.

In addition to polyglycerol fatty acid ester, nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, surfactant derived from nature, etc. can be mix | blended with this invention.

As a nonionic surfactant, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hardened castor oil, sucrose fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, etc. are mentioned, for example. have.

As anionic surfactant, For example, fatty acid salts, such as sodium laurate, higher alkyl sulfate ester salts, such as sodium lauryl sulfate, alkylether sulfate ester salts, such as POE lauryl sulfate triethanolamine, N-acyl sarcosinic acid, and sulfo Succinate, N-acylamino acid salt, etc. are mentioned.

As a cationic surfactant, alkyltrimethylammonium salts, such as stearyl trimethylammonium chloride, benzalkonium chloride, benzetonium chloride, etc. are mentioned, for example.

As amphoteric surfactant, betaine-type surfactant, such as alkylbetaine and an amide betaine, etc. are mentioned, for example.

As surfactant derived naturally, saponin, a bile acid, a sugar ceramide, etc. are mentioned, for example.

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, diglycerol, polyglycerol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, etc. are mentioned.

The emulsion composition of the present invention is suitable for external skin medicines, external skin quasi drugs, and cosmetics.

In the polymer emulsifier, emulsifying composition, and external preparation for skin (medicine, quasi-drug, cosmetic) of the present invention, components commonly used in cosmetics, such as antioxidants and ultraviolet absorbers, as long as they do not impair the effects of the invention as arbitrary components. , Moisturizers, fragrances, flavoring agents, preservatives, thickeners, pH adjusters, blood circulation accelerators, cooling agents, limiting agents, fungicides, skin rejuvenating agents, other cosmetic ingredients, active ingredients and the like can be blended.

Inclusion of a thickener improves the stability of the emulsion composition.

As the thickener, a water-soluble polymer is preferable. As the water-soluble polymer, any of a natural polymer, a semisynthetic polymer, and a synthetic polymer may be used. For example, natural polymers include tragacanth gum, karaya gum, xanthan gum, guar gum, cationic guar gum, anionized guar gum, tara gum, gum arabic, tamarind gum, gellan gum, locust bean gum, carrageenan, Queen's seed, dextran, etc. can be illustrated. Examples of the semisynthetic polymer include hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, methyl cellulose, cationic cellulose, propylene glycol ester alginate, sodium alginate and bentonite. Examples of the synthetic polymer include carboxyvinyl polymer, polyvinylpyrrolidone, polyvinyl alcohol, dialkyl polyethylene glycol, polyoxyethylene dioleate methyl glucoside, polyethylene glycol, distearate polyethylene glycol, synthetic smectite and the like. Preferably these compounding quantities are 0.01-0.5 mass%, More preferably, they are 0.01-0.2 mass%. If the blending amount is less than 0.01% by mass, it is not preferable because the effect of thickening to increase stability is not sufficient, and if it exceeds 0.5% by mass, Nurutsky is generated or sticky and impairs the effect of the present invention.

The emulsion composition of this invention can be made into cosmetics, such as a lotion, a beauty liquid, an emulsion, cream, and a pack.

The emulsion compositions of Examples 1 to 4 and Comparative Examples 1 to 3 having the constitution of the present invention were prepared to evaluate the emulsified state and usability.

[How to prepare]

The emulsion composition of the present invention does not require a special apparatus called a microfluidizer because it is prepared using the D-phase emulsification method. First, a gel composition is prepared and an emulsion composition is prepared using it.

(Preparation of gel composition by D phase emulsification method)

Polymethacrylic acid methoxypolyethylene glycol and polyglycerol fatty acid ester were dissolved in glycerine, purified water and 1,3-butylene glycol were also added and dissolved in stirring. The oil component was slowly added little by little to this to prepare a gel composition. Here, purified water and 1,3-butylene glycol are added before the addition of the oily component. However, this slightly disintegrates the liquid crystal produced by polymethacrylic acid methoxypolyethylene glycol, polyglycerin fatty acid ester, and glycerin, resulting in an oily component. It was formulated for the purpose of making it easy to absorb. When stirring using a mechanical force with a disper etc., it is not essential, Purified water and 1, 3- butylene glycol are not an essential component in this invention.

(Preparation of emulsion composition)

0.5 mass% of the obtained gel composition was disperse | distributed to 99.5 mass% purified water, and the emulsion composition was prepared.

[Evaluation of Emulsification State of Emulsifying Composition]

The emulsion stability of the emulsion composition which disperse | distributed the gel composition of Examples 1-3 and Comparative Examples 1-3 was visually evaluated based on the following reference | standard. The emulsified particle diameter (volume average) was measured by the laser diffraction particle size distribution meter.

(Circle): Creaming does not generate | occur | produce more than 7 days in 40 degreeC preservation.

(Triangle | delta): Creaming generate | occur | produced before 7 days after 1 day in the storage of 40 degreeC.

X: The creaming generate | occur | produced more than 1 day in the storage of 40 degreeC.

[Evaluation]

Ten female subjects (23-55 years old) were apply | coated the emulsion composition which disperse | distributed the gel composition of an Example and a comparative example to purified water to the whole face, and the usability after application was evaluated.

(Evaluation standard)

○: smooth texture

×: Not a smooth texture

(Judgment)

(Circle): 8-10 people evaluated by the evaluation criteria as ○.

(Triangle | delta): Seven to five people evaluated as ○ by the evaluation criteria.

X: 4-1 person evaluated as ○ by the evaluation criteria.

Table 1 shows the results of evaluating the emulsified state and usability of the emulsified composition obtained by dispersing the emulsified composition of Examples 1 to 3 and the gel composition of Comparative Examples 1 to 3 containing polymethacrylic acid methoxypolyethylene glycol in purified water.

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 oily component is dispersed in water. It was found that the emulsified particle diameter of was smaller than that of Comparative Examples 1 and 2 of the polyglycerol fatty acid ester alone. Even when the polyglycerol fatty acid ester was used in the amount of batch (Comparative Example 3), not only the emulsified particle size was reduced but also stickiness due to the surfactant was generated, resulting in unsatisfactory feeling.

It was found that Examples 2 and 3 had a particle diameter of about half than that of Comparative Example 2.

The occlusion property at the time of apply | coating the emulsion composition which disperse | distributed the gel composition of Example 4 and the comparative example 3 to purified water was evaluated by the IN VITRO moisture evaporation measurement test.

[IN VITRO moisture evaporation test using filter paper]

The IN VITRO moisture evaporation measurement test using filter paper was performed using the emulsion composition which disperse | distributed 0.5 mass% of gel compositions of Example 4 to 95.5 mass% of purified water. As a comparison, the emulsion composition which contained 0.5 mass% of the gel composition of the comparative example 3 which did not contain polymethacrylic-acid methoxy polyethyleneglycol, and doubled the polyglycerol fatty acid ester in 95.5 mass% of purified water was used.

A filter paper (No. 2) was placed on the cream bottle, and 0.5 g of the sample was placed and dried overnight with a dryer (set at 60 ° C). Further, 0.5 g of the sample was added dropwise and dried at 60 ° C. for at least 2 hours to prepare a filter paper for use in the experiment. Five sheets of filter paper were prepared for each sample.

Next, 10 g of purified water was put into a cream bottle, covered with each filter paper, stored in a constant temperature room (about 23 ° C., 37 to 40%), and the evaporation amount of purified water was confirmed by periodically measuring the weight.

While the water evaporation amount of the emulsion composition of Comparative Example 3, which doubled the polyglycerol fatty acid ester, was 0.51 g, the water evaporation amount of the emulsion composition combining the polyglycerol fatty acid ester and polymethacrylic acid methoxypolyethylene glycol was 0.23 g. From this, it can be seen that the emulsion composition of Example 4 has suppressed water doubling about twice as much as the emulsion composition of Comparative Example 3. Therefore, the emulsion composition of this invention can be made into the cosmetics for which the moisturizing effect is high, for example, anti wrinkle cosmetics, and anti aging cosmetics.

Prescription 1 emollient lotion

(Compound component) (mass%)

1.Polymethacrylate methoxypolyethylene glycol 0.5

2. Glycerin 0.5

3. Distearic Acid Polyglyceryl-10 0.2

4. Stearic Acid Polyglyceryl-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

(quite)

To component 14, component 8 dispersed in component 7 is added, and components 9 to 13 are also added and stirred to dissolve (aqueous phase). While dissolving components 1-5, component 6 was slowly added to prepare a D-phase gel, and was added to the previously prepared water phase to prepare an emulsified composition (emollient lotion).

The emollient lotion of Formulation example 1 was not sticky, the skin was smooth, and it was comfortable, and it was excellent in the moisturizing effect. The storage stability was also good.

Prescription Example 2 Anti-aging Serum

(Compound component) (mass%)

1.Polymethacrylate methoxypolyethylene glycol 2

2. Glycerin 2

3. Distearic Acid Polyglyceryl-10 0.6

4. Stearic Acid Polyglyceryl-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

(quite)

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

The emulsion composition (anti-aging cosmetic liquid) of Formulation Example 2 was excellent in storage stability. It was not sticky, and skin became smooth, and it was comfortable feeling. Moisturizing persisted.

Claims (5)

Polymethacrylic acid methoxy polyethylene glycol,
Polyglycerin fatty acid esters,
Glycerin,
Oily ingredients
Emulsifying composition comprising a. The method of claim 1,
Emulsion composition characterized in that the oily component is squalane and / or triethylhexanoin. The method according to claim 1 or 2,
1,3-butylene glycol was added, The emulsion composition characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
Emulsification composition emulsified by the D-phase emulsification method. 5. The method according to any one of claims 1 to 4,
Emulsion composition, characterized in that the particle size is less than 1.25 ㎛.

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