KR20120022528A - Polymeric emulsifier and emulsion compositions - Google Patents

Abstract

PURPOSE: A polymer emulsifier and emulsion composition are provided to save cost by emulsifying and solublizing the emulsion composition at room temperature. CONSTITUTION: A polymer emulsifier contains polymethacrylic acid methoxypolyethylene glycol which has an average polymerization degree of polyoxyethylene chain of 9. The molecular weight of the polymer emulsifier is 1000-100000 in conversion of polystyrene. Emulsion composition contains the polymer emulsifier and oily components. The oily components are more than 1type or 2 types which are selected from a group consisting of silicone, alkylglycerylether, dimer dilinoleic acid diethylene glycol oligomer ester, or oil refining.

Description

Polymer emulsifier and emulsion compositions

The present invention relates to a polymer emulsifier and an emulsion composition emulsified with the polymer emulsifier.

Applicants continue to develop components having low skin irritation (components having low skin permeability, hypoallergenic and water-soluble), and are developing cosmetics containing the components.

For example, the invention which included the copolymer of an antimicrobial monomer and a water-soluble monomer as a antimicrobial compound in the cosmetics was proposed (patent document 1: Unexamined-Japanese-Patent No. 441796, patent document 2: Unexamined-Japanese-Patent No.4182186).

It is known that the copolymer of methoxy polyethyleneglycol methacrylate is used as a polymer for hair fixation (Patent Document 3: Japanese Patent Laid-Open No. 2002-201116), but a homopolymer of methoxypolyethylene glycol methacrylate is used. It is not known at all that it has surfactant activity, exhibits functions of emulsification and solubilization with respect to a specific oily component, has a use as an emulsifier, and makes it possible to use an emulsified composition emulsified with the emulsifier as a cosmetic.

On the other hand, an acrylic methacrylate acrylic copolymer is commercially available as a polymer emulsifier, and the emulsion composition and cosmetics which were emulsified using it are known (patent document 4: Unexamined-Japanese-Patent No. 10-194922).

Polymer emulsifiers are recognized by consumers as being different from so-called surfactants such as polyoxyethylene cured castor oil, and are preferably used in products that emphasize the nonuse of surfactants. For example, PEMULEN (manufactured by BFGoodrich), which is an alkyl methacrylate copolymer, is a typical product of a polymer emulsifier used in cosmetics, and is characterized by emulsification regardless of oil.

Although PEMULEN TR-2 (manufactured by BFGoodrich) is commercially available for low viscosity products, the viscosity is 1,500 to 5,000 mPa · s (0.2% aqueous solution). For example, the range of application is cosmetics, creams, emulsions and gels. . Therefore, in the case of emulsifying the oil component in a product having little viscosity such as a lotion, a method of blending common surfactants such as polyoxyethylene hydrogenated castor oil is generally used without adding a surfactant. The technical development of the emulsifier which can emulsify was desired.

[Patent Document 1] Japanese Patent No. 4,4596, Publication

[Patent Document 2] Japanese Unexamined Patent Publication No. 421986

[Patent Document 3] Japanese Patent Publication No. 2002-201116

[Patent Document 4] Japanese Patent Application Laid-Open No. 10-194922

In the present invention, when emulsifying an oily component in a product having little viscosity such as a lotion, a method of blending common surfactants such as polyoxyethylene-cured castor oil is common, but the present invention does not blend surfactants. An object of the present invention is to develop a polymer emulsifier capable of emulsifying oily components without the need.

The present invention proposes a new polymer emulsifier based on the fact that the homopolymer having a methacrylic acid compound having a polyethyleneglycol side chain structure of which the terminal substituent is a methyl group as a monomer has an emulsifying function. The present invention is an emulsion composition emulsified with a polymer emulsifier and the polymer emulsifier.

The main structure of this invention is as follows.

(1) A polymer emulsifier comprising polymethacrylate methoxy polyethylene glycol.

(2) The polymer emulsifier according to (1), wherein the average degree of polymerization of the polyoxyethylene chain of methoxypolyethylene glycol polymethacrylate is 9.

(3) Molecular weight is 1000 or more and 100000 or less in polystyrene conversion, The polymeric emulsifier as described in (2) characterized by the above-mentioned.

(4) The emulsion composition characterized by containing the polymer emulsifier and an oil-based component in any one of (1)-(3).

(5) The emulsion composition according to (4), wherein the oily component is one or two or more selected from the group consisting of silicone, alkyl glyceryl ether, dimer dilinoleic acid diethylene glycol oligomer ester, and essential oils.

(6) The oily component is one or two or more selected from the group consisting of cyclopentasiloxane, cyclohexasiloxane, dimethicone, dimer dilinoleic acid diethylene glycol oligomer ester, ethylhexylglycerine, rose marioyl and orange oil. The emulsion composition according to (4).

(7) The mass ratio of the polymer emulsifier in any one of (1)-(3) and an oil-based component is 1: 5-100: 1, The emulsion composition in any one of (4)-(6) characterized by the above-mentioned. .

(8) The emulsion composition as described in (4)-(7) characterized by not containing surfactant.

(9) 0.02-20 mass% of the polymeric emulsifiers in any one of (1)-(3) were mix | blended. The emulsion composition characterized by the above-mentioned.

A polymer emulsifier could be provided.

The emulsified composition emulsified with the polymer emulsifier of the present invention can be emulsified without blending other surfactants, and since the surfactant-free can be emphasized, the merchandise value is high.

The polymer emulsifier of the present invention is economical because it can be emulsified and solubilized at normal temperature (5 degrees to 35 degrees) without heating.

Cyclopentasiloxane, cyclohexasiloxane, dimethicone, dimer dilinoleic acid diethylene glycol oligomer ester, ethyl hexyl glycerine, rose marioyl, orange oil can be emulsified, especially ethylhexyl glycerine (antibacterial component), essential oil (fragrance component), etc. Since it could be solubilized about the oil-based component which mix | blends only a small quantity with a product of, it is especially excellent as an emulsifier of cosmetics, such as a lotion and a beauty liquid.

Since the compounding quantity which functions as an emulsifier does not affect the viscosity of a product, it can be used without selecting a formulation.

The polymer emulsifier of the present invention is nonionic, and there are many kinds of thickeners that can be optionally included in the emulsion composition of the present invention, and the formulation is rich in modification.

The cosmetics emulsified with the polymer emulsifier of the present invention have a feature of feeling that the skin becomes smooth without being sticky.

The polymer 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-90G (chemical name: methoxy polyethylene glycol # 400 methacrylate) sold by Shin-Nakamura Chemical Co., Ltd. or Bremmer PME (PME-400: n ≒ 9) sold by Nichi Oil Co., Ltd. It can be used as a 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 polymer of this invention is shown.

Synthesis Example 1 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.

The molecular weight of the polymer was measured using GPC. As a result, the molecular weight of Synthesis Example 1 was number average molecular weight Mn = 15363 and mass average molecular weight Mw = 35680 in terms of polystyrene.

The molecular weight of the polymer of the present invention obtained as described above can be adjusted in various ways depending on the purpose of use, but in view of emulsifying performance, texture, gelling ability, film formation ability, etc., it is usually 1000 or more and 100000 or less in terms of polystyrene. It is preferably 2500 or more and 100000 or less. In the cosmetics of this invention, the said polymer is contained in 0.01-20 mass% normally with respect to the whole cosmetics, Preferably it is contained in 0.02-20 mass%.

If it is less than 0.01 mass%, it is difficult to fully emulsify the oily component, and if it exceeds 20 mass%, handling is bad, which is not preferable.

In the present invention, methacrylic acid methoxypolyethylene glycol acts as an emulsifier. Inclusion of this polymer can reduce other surfactants used in the emulsion composition, or can provide an excellent emulsion composition without including other surfactants.

Preferable oil-based components in the case of producing an emulsion composition by the above-mentioned polymer emulsifier are silicone, alkyl glyceryl ether, dimer dilinoleic acid diethylene glycol oligomer ester, essential oil and the like.

As silicone, cyclopentasiloxane, cyclohexasiloxane, dimethicone, etc. can be illustrated. Ethylhexyl glycerine can be illustrated as alkyl glyceryl ether. Examples of essential oils include rosemary oil and orange oil.

Cyclopentasiloxane is cyclic silicone, and KF-995 etc. of Shin-Etsu Chemical Co., Ltd. can be obtained and used as a commercial item.

Cyclohexasiloxane is cyclic silicone, As a commercial item, Toray Dow Corning Co., Ltd. silicon DC246 etc. can be obtained and used.

Dimethicone is a chain silicone, and KF-96A-6cs of Shin-Etsu Chemical Co., Ltd. can be obtained and used as a commercial item.

The dimer dilinoleic acid diethylene glycol oligomer ester is obtained by esterifying dimer dilinoleic acid and diethylene glycol, and the emulsion of Example 1 (DEG-DA5) described in Japanese Patent No. 4288306 can be exemplified.

Ethyl hexyl glycerine is an ether of glycerin and 2-ethylhexyl alcohol, SENSIVA SC50 etc. by Schulke & Mayr GmbH can be obtained and used as a commercial item.

Rosemary oil is an essential oil obtained from microflora (plant), and it can obtain and use Rosemary oil etc. of PAYAN & BERTRAND as a commercial item.

Orange oil is an essential oil extracted from the skin of an orange, and it can obtain and use Ogawa Flavor Co., Ltd. Japanese pharmacy orange oil etc. as a commercial item.

Among these, essential oil components such as ethylhexylglycerin formulated for the purpose of antibacterial action and rosemary oil and orange oil formulated for the purpose of fragrance into the product are used for the purpose (antibacterial, fragrance) in small amounts. Although it is an oil-based component which can give the effect to cosmetics, since it can be solubilized with the emulsifier of this invention, it can be illustrated as especially preferable oil-based component. Moreover, since the emulsification state of silicone was especially excellent, it can be illustrated as an especially preferable oil agent.

The polymer emulsifier of the present invention tends to be difficult to emulsify oil having low polarity. For example, in the case of emulsifying only squalane with the emulsifier of the present invention, since the compatibility is poor, the emulsified state is poor, which is not preferable.

When emulsifying only with the polymer emulsifier of this invention, without including another surfactant, 20 mass% or less is preferable for the compounding quantity of an oil-based component.

It is preferable for emulsification and solubilization if the polymer emulsifier of the present invention in a 1 / 5-fold amount of the oily ingredient is included in the formulation. In the case of an emulsion composition such as a lotion, an emulsion or a cosmetic liquid, the mass ratio of the polymer emulsifier of the present invention to an oily component is preferably 1: 5 to 100: 1. If the polymer emulsifier of the present invention is less than 1/5 times of the oil component, the emulsification may be incomplete, which is not preferable.

Although the homopolymer of methacrylic acid methoxy polyethyleneglycol itself becomes an emulsifier, the polymeric emulsifier of this invention can be mixed with water-soluble components, such as water, a polyhydric alcohol, and ethanol, and can be used as an emulsifier. The emulsifier of the present invention is mixed with a water-soluble component to adjust the viscosity to obtain a good handling emulsifier.

It is preferable to include polyhydric alcohol because the compatibility with oily components is improved. Examples of the polyhydric alcohols include glycerin, 1,3-butylene glycol, dipropylene glycol, propylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, polyethylene glycol, and the like. . In particular, 1, 3- butylene glycol, dipropylene glycol, and propylene glycol are preferable.

The emulsion composition of this invention is suitable for a skin external medicine, a skin external quasi drug, and cosmetics.

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

When a thickener is included, the stability of an emulsion composition may further improve. It is also possible to increase the deformation of the formulation 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, as a natural polymer, tragant 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, hydroxypropyl methyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, cationic cellulose, alginate propylene glycol ester, sodium alginate and bentonite. Examples of the synthetic polymer include carboxyvinyl polymer, polyvinylpyrrolidone, polyvinyl alcohol, dialkyl polyethylene glycol, polyoxyethylenedioleate methylglycoside, polyethylene glycol, polyethylene glycol distearate, synthetic smectite and the like. These compounding quantity becomes like this. Preferably it is 0.01 to 3%, More preferably, it is 0.1 to 2%. If the amount of pears is less than 0.01%, the thickening effect is not sufficient, and if the amount of pears exceeds 3%, it is not preferable because slippage occurs or is sticky.

The emulsion composition of this invention can be made into cosmetics, such as a lotion, a beauty liquid, an emulsion, cream, and a pack. In particular, it is used suitably for lotion. A thickener can be included and used as a cosmetic liquid, an emulsion, a cream, a pack, etc.

Example

The emulsion composition of Examples 1-18 and Comparative Examples 1-6 was prepared using the polymeric emulsifier of this invention, and the emulsion state was evaluated.

(Method of Preparing Emulsifying Composition)

A solution obtained by mixing the aqueous solution (A) and the oil component (B) containing Synthesis Example 1 was emulsified using a homomixer (9000 rpm, 2 minutes, room temperature) while being poured into purified water (C), and additionally, an aqueous component ( D) was mixed to prepare an emulsion composition.

[Evaluation of Oil Painting State]

(Evaluation of compatibility)

The dissolution state when mixing the aqueous solution (A) and oil component (B) containing Synthesis Example 1 was visually evaluated by the following criteria. This evaluation is an evaluation which predicts the result of this emulsification by evaluating the compatibility of the polymeric emulsifier of this invention and an oily component before progressing to this emulsification.

○; Transparency

?; Translucent

×; Not mixed

(Evaluation of Emulsification State of Emulsifying Composition)

The emulsion state of the emulsion composition of Examples 1-18 and Comparative Examples 1-6 was visually evaluated by the following reference | standard. The emulsified particle diameter (volume average) was measured by the laser diffraction particle size distribution analyzer.

○; Well emulsified

?; Oily component bleeds or remains slightly floating on surface

×; There is complete separation or obvious remains

[Evaluation]

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

(Evaluation standard)

○; Non sticky, smooth texture

×; Stickiness

(Judgment)

○; 8 to 10 people rated as ○

?; 7 to 5 people rated as ○

×; As a standard of evaluation, 4 to 1 people rated as ○

Table 1-Table 4 show the results of evaluating the emulsified state and usability of the emulsion composition containing Synthesis Example 1.

As shown in Table 1 (Examples 1-7), the polymer of the synthesis example 1 is cyclopentasiloxane, cyclohexasiloxane, dimethicone, dimer dilinoleic acid diethylene glycol oligomer ester, ethylhexylglycerol, rose marioyl, orange oil. Could be emulsified. The emulsified composition of Examples 1-7 was the outstanding usability with a smooth feeling, without stickiness. In the emulsion compositions of Examples 5 and 6, the emulsion composition was transparent to the extent that the particle diameter could not be measured by a laser diffraction particle size distribution meter that measured the particle size from the light scattering behavior, and the oily component was solubilized. Here, transparency is a level which is hardly discernible with the naked eye, when the emulsion composition put into the transparent glass cylindrical container of diameter 4cm is compared with what put purified water in the same container. The viscosity of the emulsion composition of Examples 1-7 was 10 mPa * s or less of the limit which can be measured with a Brookfield viscometer.

As shown in Table 2, in Examples 8-11 in which the compounding quantity of cyclopentasiloxane which is an oil-based component was 0.2, 1.0, 2.0, and 5.0, it was emulsified by mix | blending 1 mass% of polymers of the synthesis example 1. As shown in Example 11 and Example 13, the silicone (cyclopentasiloxane, dimethicone) corresponding to 5 times the compounding quantity of the polymer of the synthesis example 1 was emulsified. Emulsification state of all the emulsion compositions of Examples 12-15 which made the oil component any one of cyclopentasiloxane, dimethicone, and rose marioyl increase and decrease the compounding quantity of the polymer of the synthesis example 1 was good.

The emulsified composition of Examples 8-15 was excellent in a non-sticky, smooth texture. The viscosity of the emulsion compositions of Examples 8-11, 13, and 15 was 10 mPa * s or less of the limit which can be measured with a Brookfield viscometer.

Next, the effect of the polyhydric alcohol at the time of preparing an emulsion composition was evaluated. The results are shown in Table 4.

When polyhydric alcohol (1, 3- butylene glycol) was included in an emulsion composition, compatibility with an oily component improved and the emulsion state was also favorable.

Prescription 1 lotion

(Compound Component) (Mass%)

1. Balance of purified water

2. Glycerin 10

3. Methylparaben 0.1

4. Citric Acid 0.01

5. Sodium Citrate 0.05

6. 1,3-butylene glycol 5.0

Rosemary Oil 0.003

8. Polymer 0.3 obtained in synthesis example 1

(quite)

The components 1-5 are heated and dissolved at 70 ° C, and after cooling to 30 ° C, 6-8 mixed in advance are added, and the mixture is stirred and mixed uniformly.

The lotion of Formulation example 1 was transparent. It was not sticky, and skin became smooth, and it was refreshing usability. The storage stability was also good.

Prescription example 2 gel essence

(Compound Component) (Mass%)

(A)

1. Balance of purified water

2. Carboxyvinyl Polymer 0.3

3. Xanthan Gum 0.1

4. Glycerin 10

5. Phenoxyethanol 0.3

6. Potassium Hydroxide 0.09

(B)

7. Purified water 30

8. Cyclopentasiloxane 1

9. Polymer 1 obtained in Synthesis Example 1

10. 1, 3- butylene glycol 1.5

11.purified water 2.5

(quite)

(A) 1-5 are heated and melt | dissolved at 70 degreeC, 6 is added, and it cools to 30 degreeC. (B) 8-11 are added to 7 after mixing and emulsified using a homomixer. (A) and (B) are stirred and mixed uniformly.

The gel cosmetic liquid of the prescription example 2 had a cloudy appearance, and was excellent in storage stability. It was not sticky, and skin became smooth, and it was refreshing usability.

Claims (9)

A polymer emulsifier containing polymethacrylic acid methoxypolyethylene glycol. The method of claim 1,
A polymer emulsifier, characterized in that the average degree of polymerization of the polyoxyethylene chain of polymethacrylic acid methoxypolyethylene glycol is 9. The method of claim 2,
The molecular weight is 1000 or more and 100000 or less in polystyrene conversion, The polymeric emulsifier characterized by the above-mentioned. An emulsion composition comprising the polymer emulsifier of claim 1 and an oily component. The method of claim 4, wherein
An oil-based component is an emulsion composition characterized in that one or two or more selected from the group consisting of silicone, alkyl glyceryl ether, dimer dilinoleic acid diethylene glycol oligomer ester, and essential oils. The method of claim 4, wherein
Emulsion composition characterized in that the oily component is one or more selected from the group consisting of cyclopentasiloxane, cyclohexasiloxane, dimethicone, dimer dilinoleic acid diethylene glycol oligomer ester, ethylhexylglycerine, rose marioyl, orange oil . The method according to any one of claims 4 to 6,
Emulsion composition according to any one of claims 1 to 3, wherein the mass ratio of the polymer emulsifier to the oil component is 1: 5 to 100: 1. 8. The method according to any one of claims 4 to 7,
An emulsified composition comprising no surfactant. 0.02-20 mass% of the polymeric emulsifiers in any one of Claims 1-3 were mix | blended.