JP2011032249A - Oil-in-water type emulsion composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-in-water type emulsion composition which can be formulated with various oil components and has water resistance with even little irritation to skin which is a stable oil-in-water type emulsion composition having a fresh feeling of use when applied to the skin with a safe polymer emulsifier. <P>SOLUTION: The oil-in-water type emulsion composition is emulsified with a polyion complex formed from a cationic polymer and carboxymethylcellulose. In the oil-in-water type emulsion composition, the ratio of cationicity of the cationic polymer to the degree of etherification of the carboxymethylcellulose is within the range of 1/3 to 3/1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an oil-in-water emulsion composition that is stabilized using a polymer emulsifier, has excellent water resistance, and is less irritating to the skin, and a cosmetic using the same.

  Many studies on emulsification techniques have been made not only in the field of cosmetics, and stable emulsions have been obtained in various systems. However, many of the conventional emulsions used in the cosmetics field are nonionic surfactants having polyoxyethylene chains, anionic surfactants typified by fatty acid soaps, or imidazoline-based and betaine-based amphoteric agents. Surfactants are used as emulsifiers, and it is also true that there are general consumers who are worried about the safety of blending these conventional low molecular weight emulsifiers into cosmetics.

  In recent years, cosmetics using water-soluble polymers that are considered to be highly safe as emulsifiers have been proposed, but water-soluble polymers have less emulsifying power than conventional low-molecular emulsifiers, so stable emulsification Some device is necessary to get things.

For example, in Patent Documents 1 and 2, a water-in-oil emulsion composition containing an oil phase containing oil-soluble cellulose and an aqueous phase containing a polyion complex composed of cationic cellulose and anionic hyaluronic acid is emulsified. It describes that it is excellent in stability, safety and usage examples.
Since such a water-in-oil emulsion composition has an oily outer phase, it is used as a conventional sunscreen cosmetic that requires durability against sweat and water and sebum. Originally had problems such as stickiness caused by oil and poor skin care effects such as moisturizing effects.

  Patent Document 3 describes an oil-in-water emulsion composition using a cationic polymer emulsifier such as chitin and a chitosan derivative, and the sunscreen cosmetic containing an ultraviolet ray inhibitor in the oil phase has a water resistance and a feeling of use. In addition, it is described that the moisturizing effect is excellent. Furthermore, there is a description that stability is improved by adding an amphoteric or anionic polymer to form a composite. However, the chitin and chitosan derivatives used have good affinity and adhesion to the skin, and have the property of binding to the skin's keratin etc., so it is considered that they may show irritation to the skin. Moreover, since the emulsifying power is not high, it is difficult to blend a large amount of oil.

  Patent Document 4 describes an oil-in-water emulsion composition in which an oil phase containing a cationic polymer is dispersed in an aqueous phase containing an anionic polymer, and a polyion complex is formed at the interface between the oil phase and the water phase, There is a description that the emulsion stability is excellent even if a conventional low-molecular emulsifier is not included. However, since an oily cationic polymer (modified silicone) is blended, the types of oil that can be used are limited, and a stable emulsion may not be obtained depending on the combination with the oil.

JP-A-8-268834 JP-A-9-301824 JP 2004-307434 A JP 2005-220117 A

  Therefore, the problem in the present invention is a stable oil-in-water emulsion composition having a fresh feeling when applied to the skin using a safe polymer emulsifier, which is water-resistant and irritate the skin. The object is to provide a small oil-in-water emulsion composition.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have achieved stable oil-in-water emulsification by using a polyion complex formed from a specific combination of a cationic polymer and an anionic polymer as an emulsifier. A composition was obtained, and various oils could be blended, and the obtained oil-in-water emulsion showed excellent water resistance, and the present invention was completed.
That is, the present invention is an oil-in-water emulsion composition emulsified by a polyion complex formed from a cationic polymer and an anionic polymer, particularly carboxymethylcellulose, wherein the cationic degree of the cationic polymer and the carboxymethylcellulose Provided is an oil-in-water emulsion composition, wherein the ratio of the degree of etherification is in the range of 1/3 to 3/1.

  The composition according to the present invention is a stable oil-in-water emulsion emulsified by a polyion complex formed from a cationic polymer and carboxymethylcellulose, and can provide a fresh and good use feeling when applied to the skin. it can. Moreover, it is superior in water resistance and less irritating to the skin as compared with an oil-in-water emulsion composition using a conventional surfactant.

  The oil-in-water emulsified composition of the present invention is emulsified by a polyion complex formed from a cationic polymer and carboxymethyl cellulose, and the ratio of the degree of cationization of the cationic polymer to the degree of etherification of carboxymethyl cellulose is 1/3. It is in the range of 3/1, preferably 1/2 to 2/1. If the ratio between the degree of cationization and the degree of etherification is out of the above range, the stability of the emulsion becomes insufficient, the spread when applied to the skin tends to be poor, and stickiness tends to occur.

The “degree of cationization” in the present specification means an average value of the number of cationic dissociation groups present per monomer constituting each polymer. For example, when a cationic polymer having a polymerization degree n has m cationic dissociation groups in one molecule, the cationization degree of the cationic polymer is represented by m / n.
On the other hand, “degree of etherification” in the present specification means an average value of the number of anionic dissociation groups (carboxymethyl groups) present in a unit sugar skeleton (anhydroglucose unit) constituting cellulose.

The oil-in-water emulsion composition of the present invention can be prepared generally according to the following steps.
(1) One ionic (cationic or anionic) polymer is dissolved in a part of water.
(2) An oil component is added to (1) and dispersed and emulsified.
(3) The other ionic (anionic or cationic) polymer is dissolved in another part of water, added to (2), and further emulsified with stirring force.
(4) Add the remaining aqueous component and stir to obtain the desired oil-in-water emulsion composition.

  That is, both the cationic polymer and the anionic polymer used in the present invention must be water-soluble. One (preferably anionic polymer) is used as an emulsifier, and a dispersed phase (oil phase) is dispersed in a continuous phase (aqueous phase), and the other (preferably cationic polymer) added thereto is an aqueous phase and an oil phase. It is thought that the emulsion is stabilized by forming an ion complex at the interface.

The cationic polymer used in the present invention is not particularly limited as long as it is a water-soluble polymer having a cationic group in the molecule. For example, a chlorinated O- [2-hydroxy-3- (trimethylammonio) propyl] group is used. Hydroxyethyl cellulose (polyquaternium-10) is preferably used.
For example, Kachinal HC-100 (molecular weight: 350,000; cationization degree: 0.30 to 0.40) manufactured by Toho Chemical Industry, Katchinal HC-200 (molecular weight: 1,600,000; cationization degree: 0.30 to 0.00). 40), kachinal LC-100 (molecular weight 350,000; cationization degree 0.15-0.25), kachinal LC-200 (molecular weight 2,000,000; cationization degree 0.15-0.25), kachinal PC-100 (molecular weight 1,200,000; degree of cationization 0.20 to 0.35), kachinal HC-35 (molecular weight 120,000; degree of cationization 0.30 to 0.40), and polymer from Amerchol Commercial products such as JR can be used. Among them, those having a molecular weight of 2,000,000 or less are preferable.

  Other cationic polymers include the HC polymer series (vinyl pyrrolidone-dimethylaminomethylethyl methacrylate copolymer diethyl sulfate (polyquaternium-11), molecular weight 140,000 to 200,000, manufactured by Osaka Organic Chemical Co., Ltd .; Degree of conversion 0.5), rubicut FC370 (molecular weight 40,000; cationization degree 0.2), which is a methyl vinyl imidazolium chloride / vinylpyrrolidone copolymer manufactured by BASF, ruby cut FC550 (molecular weight 80,000; cationization) Degree 0.5), Rubycut FC905 (molecular weight 100,000; cationization degree 0.95), Rubycut HM552 (molecular weight 400,000; cationization degree 0.5) and the like.

  As the carboxymethyl cellulose used in the present invention, those conventionally used in cosmetics and the like can be used. For example, Serogen F-SH (degree of etherification 0.60 to 0.70), Serogen-F (degree of etherification 0.60 to 0.70), Serogen-3H (degree of etherification 0. 0) manufactured by Daiichi Kogyo Seiyaku. 55-0.65), Serogen F-5A (degree of etherification 0.70 to 0.80), Serogen-7A (degree of etherification 0.70 to 0.80), Serogen-F907A (degree of etherification 0.90) -0.95), Serogen F-SL (Degree of etherification 0.80 to 0.95), Serogen-8A (Degree of etherification 0.70 to 0.80), Serogen-810A (Degree of etherification 0.75 0.85), Serogen 815A (degree of etherification 0.80 to 0.90), Serogen-PR (degree of etherification 0.60 to 0.70), Serogen-F-SB (degree of etherification 0.85 to 0) .95), Serogen F-930A ( -Tellation degree 0.85 to 0.95), serogen-SA (degree of etherification 0.70 to 0.80), serogen-AG (degree of etherification 0.85 to 0.95), serogen AGS (degree of etherification) 0.90 to 0.95), Serogen-820B (Degree of etherification 0.80 to 0.95), Serogen-4H (Degree of etherification 0.55 to 0.65), Serogen BSH (Degree of etherification 0.70) -0.80), Serogen-BSH-3 (Degree of etherification 0.65-0.75), Serogen-BSH-4 (Degree of etherification 0.65-0.75), Serogen-BSH-5 (Etherification) Degree 0.65-0.75), Serogen-BSH-6 (etherification degree 0.65-0.75), Serogen-BSH-12 (etherification degree 0.65-0.75), Serogen-815C ( Degree of etherification 0.80-0. 0) can be used commercially available products such as Celogen -6HS9 (etherification degree 0.80 to 0.90). Among them, those having a molecular weight of 2,000,000 or less are preferable.

The amount of the cationic polymer used in the present invention is usually 0.05 to 20% by mass, preferably 0.1 to 10% by mass, and the amount of carboxymethyl cellulose is also usually 0.05 to 20% by mass. 20% by mass, preferably 0.1 to 10% by mass.
In the present invention, a stable emulsion can be obtained by appropriately selecting a combination of a cationic polymer having a cationization degree / etherification ratio in the above range and a carboxymethyl cellulose, and blending within the above range, preferably In the polyion complex to be formed, it is preferable to adjust the anion charge to be excessive, since the emulsion stability and usability such as freshness are further improved only when applied to the skin. The charge in the polyion complex can be adjusted by varying the blending ratio of each polymer based on the degree of cationization and etherification of the selected polymer.

  Further, the total amount of the cationic polymer and carboxymethyl cellulose to be blended is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass. When the total amount is less than 0.05% by mass, the stability of the emulsion may be deteriorated. When the total amount exceeds 20% by mass, the feeling of use such as good spread may be deteriorated.

  The oil-in-water emulsion composition of the present invention has characteristics derived from being an oil-in-water emulsion, that is, has a property of giving a fresh feeling when applied to the skin and not causing stickiness during and after application. is doing. Furthermore, since an ion complex composed of a specific combination of a cationic polymer and carboxymethyl cellulose is used as an emulsifier, it is extremely stable even if a conventional low molecular emulsifier is not blended. Therefore, the composition of the present invention may not contain a conventional low molecular weight emulsifier containing a hydrophilic surfactant, and the amount may be a small amount, for example, 0.1% by mass or less. .

Moreover, the oil-in-water emulsion composition of the present invention is excellent in water resistance when applied to the skin or the like. Therefore, it is particularly suitable for skin care cosmetics, such as sunscreen cosmetics, which have conventionally used water-in-oil emulsions to ensure water resistance.
Therefore, the present invention provides skin care cosmetics such as sunscreen cosmetics comprising the oil-in-water emulsion composition of the present invention.

  The cosmetic of the present invention may contain various components usually blended in skin care products. For example, in the case of a sunscreen cosmetic, an ultraviolet absorber or the like is appropriately blended.

Hereinafter, the present invention will be described in more detail with specific examples, but the present invention is not limited to the following examples. Moreover, the compounding quantity in a following example etc. shows the mass% unless there is particular notice.
The oil-in-water emulsion compositions (Examples) and comparative compositions of the present invention were prepared and evaluated for the stability, spreadability, non-stickiness, and water resistance of each composition. Each item was evaluated as follows.

<Stability>
The composition was visually and microscopically observed.
○: No change △: Slight separation of oil phase or water phase is observed ×: Oil phase or water phase is considerably separated

<Mizumizushi>
Freshness was judged by 8 specialist panels.
Judgment criteria:
◎: 7 to 8 out of 8 responded that it was fresh and good in use ○: 5 to 6 out of 8 responded that it was fresh and in good use Δ: 3 to 4 in 8 , Reply as fresh and good usability x: 2 or more of 8 respondents answered that the usability was not good without feeling fresh

<Good quality>
Eight expert panel members judged whether or not to stretch.
Judgment criteria:
○: 7 to 8 out of 8 responded that the spread was good and the usability was good Δ: 5 to 6 out of 8 answered that the spread was good and the usability was good ×: 4 out of 8 More than one person answered that the spread was poor and usability was not good

<No stickiness>
The stickiness at the time of use and after application | coating was judged by 8 expert panels.
Judgment criteria:
◎: 7-8 people out of 8 responded that they were not sticky during use and after application ○: 5-6 out of 8 respondents said that they were not sticky during use and after application △: 3-4 out of 8 respondents , Reply that it is not sticky at the time of use and after application ×: Two or more of eight responded that it was sticky at the time of use and after application

<Water resistance>
The water resistance after coating was determined by 8 specialist panels.
Judgment criteria:
◎: 7 to 8 out of 8 responded that water resistance after application was excellent ○: 5 to 6 out of 8 responded that water resistance after application was excellent Δ: 3 out of 8 ~ 4 respondents said that water resistance after application is excellent x: 2 or more of 8 persons answered that water resistance after application was inferior

Example 1
Samples having the compositions listed in Table 1 below were prepared and evaluated for each item.

  Example 1-1 using a combination of polymers having a ratio of degree of cationization / degree of etherification of about 0.54 has good stability, usability such as freshness, good spread and no stickiness and water resistance. Was very good. On the other hand, the sample which is an emulsion obtained with an acrylic polymer (Comparative Example 1-2) or a nonionic surfactant (Comparative Example 1-2) was particularly inferior in usability and water resistance.

(Example 2)
Samples having the compositions listed in Table 2 below were prepared and evaluated for each item.

  In a combination of a cationic polymer having a cationization degree of 0.30 to 0.40 and a carboxymethyl cellulose having an etherification degree of 0.60 to 0.70, the blending ratio (cationization degree / etherification degree) of the two is about In the case of 7/3, the cation charge and the anion charge are calculated to be equal. When this point is called an isoelectric point, the samples of Examples 2-2 to 2-4 in which the anionic charge is excessive from the isoelectric point were extremely excellent in stability and usability. In Example 2-1, in which the cation was excessive from the isoelectric point, the stability was slightly inferior compared to the case where the anion was excessive. Comparative Examples 2-1 and 2-2 containing only either a cationic or anionic polymer showed insufficient results for all items.

(Example 3)
Samples having the compositions listed in Table 3 below were prepared and evaluated for each item.

  Example 3-1 using a combination of polymers having a ratio of cationization degree / etherification degree of about 0.4 was excellent in stability and usability, but the ratio of cationization degree / etherification degree was high. Comparative Example 3-1 using a combination of about 0.2 showed results inferior to the Examples in all items.

Example 4
Samples having the compositions listed in Table 4 below were prepared and evaluated for each item.

  When the combination of the cationic polymer and carboxymethylcellulose (ratio of cationization degree / etherification degree: about 0.54) and the blending ratio thereof are made constant and the total blending amount of both polymers is changed, the total amount is 0.00. Example 4-1 which was 05 mass% was slightly inferior in stability compared to the other examples. Moreover, Example 4-7 which made the total amount 20 mass% was a little inferior in the usability | use_condition.

(Example 5)
Sunscreen cosmetics ingredients Ingredients (mass%)
O- [2-Hydroxy-3- (trimethylammonio) propyl] chloride
Hydroxyethyl cellulose (Catinal PC-100) 0.12
Carboxymethylcellulose (Serogen F-SH) 0.18
Decamethylcyclopentasiloxane 3
Methylphenylpolysiloxane 3
1,3-butylene glycol 5
Dipotassium glycyrrhizinate 0.05
Trimethylglycine 1
L-ascorbic acid 2-glucoside 2
Edetate trisodium 0.1
2-methoxyhexyl paramethoxycinnamate 7
Xanthan gum 0.1
Carboxyvinyl polymer 0.3
Phenoxyethanol Appropriate amount Purified water Residual perfume Appropriate amount

Production method:
(1) Dissolve carboxymethyl cellulose in a part of water.
(2) Add an oil containing an ultraviolet absorber to (1), and disperse and emulsify with a homomixer.
(3) Add O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose aqueous solution dissolved in another part of water to (2) and stir with a homomixer for more than 1 minute. Force was applied to emulsify.
(4) An xanthan gum aqueous solution, a carboxyvinyl polymer aqueous solution and other components were added and stirred to obtain the intended oil-in-water composition.

(Example 6)
Sunscreen cosmetics ingredients Ingredients (mass%)
O- [2-Hydroxy-3- (trimethylammonio) propyl] chloride
Hydroxyethylcellulose (Catinal HC-100) 0.1
Carboxymethylcellulose (Serogen F-BSH-12) 0.1
Vaseline 1
Dimethylpolysiloxane 3
Methylphenylpolysiloxane 3
Stearyl alcohol 0.5
Glycerin 7
Dipropylene glycol 3
1,3-butylene glycol 7
Xylitol 3
Squalane 1
Isostearic acid 0.5
Stearic acid 0.5
L-ascorbyl magnesium phosphate 0.1
Tocopherol acetate 0.1
EDTA trisodium 0.05
4-t-butyl-4′-methoxybenzoylmethane 2
2-methoxyhexyl paramethoxycinnamate 5
Carboxyvinyl polymer 0.1
Potassium hydroxide 0.05
Phenoxyethanol Appropriate amount Purified water Residual perfume Appropriate amount

Production method:
(1) Dissolve O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride in a part of water.
(2) Add an oil containing an ultraviolet absorber to (1), and disperse and emulsify with a homomixer.
(3) Another carboxymethyl cellulose aqueous solution dissolved in a part of water was added to (2), and the mixture was further emulsified by applying stirring force for 1 minute or more with a homomixer.
(4) Aqueous carboxyvinyl polymer solution Other components were added and stirred to obtain the desired oil-in-water composition.

(Example 7)
Latex blending ingredients Blending amount (% by mass)
O- [2-Hydroxy-3- (trimethylammonio) propyl] chloride
Hydroxyethyl cellulose (Catinal HC-35) 0.2
Carboxymethylcellulose (Serogen F) 0.3
Dimethylpolysiloxane 3
Decamethylcyclopentasiloxane 4
Ethanol 5
Glycerin 6
1,3-butylene glycol 5
Polyoxyethylene glucoside 3
Sunflower oil 1
Squalane 2
Potassium hydroxide 0.1
Sodium hexametaphosphate 0.05
Hydroxypropyl-β-cyclodextrin 0.1
Dipotassium glycyrrhizinate 0.05
Loquat leaf extract 0.1
Sodium L-glutamate 0.05
Fennel extract 0.1
Yeast extract 0.1
Lavender oil 0.1
Giant extract 0.1
Dimorpholinopyridazinone 0.1
Xanthan gum 0.1
Carboxyvinyl polymer 0.1
Bengala Appropriate amount Yellow iron oxide Appropriate amount Paraben Appropriate amount Purified water Residual

Production method:
(1) Dissolve carboxymethyl cellulose in a part of water.
(2) Add an oil containing an ultraviolet absorber to (1), and disperse and emulsify with a homomixer.
(3) Add O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose aqueous solution dissolved in another part of water to (2) and stir with a homomixer for more than 1 minute. Force was applied to emulsify.
(4) An xanthan gum aqueous solution, a carboxyvinyl polymer aqueous solution and other components were added and stirred to obtain the intended oil-in-water composition.

(Example 8)
Sunscreen emulsion blending ingredients Blending amount (mass%)
O- [2-Hydroxy-3- (trimethylammonio) propyl] chloride
Hydroxyethyl cellulose (Catinal HC-100) 0.09
Carboxymethyl cellulose (cellogen F-SH) 0.24
Succinoglycan 0.2
Dipropylene glycol 5
Stearic acid 1
Glyceryl tri-2-ethylhexanoate 3
Cetyl 2-ethylhexanoate 2
Polyoxyethylene glyceryl isostearate 1
Glycerol monostearate 1
Fine particle titanium oxide (30 nm) 2
Sodium hexametaphosphate 0.1
Phenoxyethanol appropriate amount edetate trisodium appropriate amount 4-t-butyl-4'-methoxybenzoylmethane 1
2-methoxyhexyl paramethoxycinnamate 7
Bentonite 1
Purified water Residual fragrance Appropriate amount

Production method:
(1) Dissolve carboxymethyl cellulose in a part of water.
(2) Add an oil containing an ultraviolet absorber to (1), and disperse and emulsify with a homomixer.
(3) Add O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose aqueous solution dissolved in another part of water to (2) and stir with a homomixer for more than 1 minute. Force was applied to emulsify.
(4) Succinoglycan aqueous solution The other components were added and stirred to obtain the desired oil-in-water composition.

Example 9
Latex blending ingredients Blending amount (% by mass)
Methylvinylimidazolium chloride / vinylpyrrolidone copolymer * 10.2.
Carboxymethylcellulose (Serogen F) 0.3
Dimethylpolysiloxane 3
Decamethylcyclopentasiloxane 4
Ethanol 5
Glycerin 6
1,3-butylene glycol 5
Polyoxyethylene glucoside 3
Squalane 2
Potassium hydroxide 0.1
Sodium hexametaphosphate 0.05
Hydroxypropyl-β-cyclodextrin 0.1
Dipotassium glycyrrhizinate 0.05
Sodium L-glutamate 0.05
Lavender oil 0.1
Dimorpholinopyridazinone 0.1
Xanthan gum 0.1
Carboxyvinyl polymer 0.1
Paraben Appropriate amount of purified water Residue * 1 Ruby cut FC905 (manufactured by BASF), degree of cationization per unit sugar skeleton: 0.95

Production method:
(1) Dissolve carboxymethyl cellulose in a part of water.
(2) Add an oil containing an ultraviolet absorber to (1), and disperse and emulsify with a homomixer.
(3) Another aqueous methylvinylimidazolium chloride / vinylpyrrolidone copolymer solution dissolved in a part of water was added to (2), and the mixture was further emulsified by applying stirring force for 1 minute or more with a homomixer.
(4) An xanthan gum aqueous solution, a carboxyvinyl polymer aqueous solution and other components were added and stirred to obtain the intended oil-in-water composition.

Claims (5)

An oil-in-water emulsion composition emulsified with a polyion complex formed from a cationic polymer and carboxymethylcellulose, wherein the ratio of the cationic degree of the cationic polymer to the degree of etherification of the carboxymethylcellulose is 1/3 An oil-in-water emulsion composition characterized by being in the range of 3/1. The composition according to claim 1, characterized in that the cationic polymer is O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride.
The composition according to claim 1 or 2, wherein the polyion complex has an anionic charge excess. 4. The composition according to claim 1, wherein the total amount of the cationic polymer and carboxymethyl cellulose is 0.05 to 20% by mass. 5. (1) a step of dissolving either the cationic polymer or carboxymethyl cellulose in a part of water;
(2) A step of adding and dispersing and emulsifying an oily component to (1),
(3) a step of dissolving a cationic polymer or the other polymer of carboxymethyl cellulose in another part of water, adding it to (2), and further emulsifying with stirring force; and
(4) The manufacturing method of the oil-in-water type emulsion composition of Claim 1 including the process of adding the remaining aqueous component and obtaining the target oil-in-water type emulsion composition by stirring.