TWI503167B - Emulsion compositions - Google Patents

Description

Emulsified composition

The present invention relates to a polymer emulsifier and an emulsified composition which is emulsified by the polymer emulsifier.

The applicant continued to develop a component having low skin irritation (low skin permeability, low irritation, and water-soluble component), and continued development of a cosmetic containing the component.

For example, an invention has been proposed in which a copolymer of an antimicrobial monomer and a water-soluble monomer is contained as an antibacterial compound in a cosmetic material (Patent Document 1: Japanese Patent No. 4174596, Patent Document 2: Japanese Patent No. 4182186) .

A copolymer of methoxypolyethylene glycol methacrylate is known to be used as a hair fixing polymer (Patent Document 3: JP-A-2002-201116), but for methoxypolyethylene glycol methyl group. The acrylate homopolymer has a surface active function, can exert an emulsification and solubilizing function for a specific oil component, has a use as an emulsifier, and can be used for a cosmetic material by emulsifying an emulsified composition emulsified with the emulsifier.

In addition, it is known that an acrylic methacrylate copolymer is commercially available as a polymer emulsifier, and an emulsified composition or a cosmetic which is emulsified by using the same is disclosed (Patent Document 4: Japanese Patent Laid-Open No. Hei 10-194922) .

Polymer emulsifiers have been recognized by consumers as different substances from so-called surfactants such as polyoxyethylene hardened castor oil, and are used to promote the use of surfactants. Acrylic acid alkyl methacrylate copolymer, for example, PEMULEN (manufactured by BF Goodrich Co., Ltd.) is a representative product of a polymer emulsifier for cosmetics, and has a characteristic that it can be emulsified regardless of the type of oil.

PEMULEN TR-2 (manufactured by BF Goodrich Co., Ltd.), which is a product having a low viscosity, is commercially available and has a viscosity of 1,500 to 5,000 mPa ‧ (0.2% aqueous solution). For example, when it is a cosmetic, the suitable range is a cream, an emulsion, or a gel. Therefore, when emulsifying an oil component in a product having almost no viscosity such as a lotion, a method of blending a conventional surfactant such as polyoxyethylene to castor oil is usually used, and it is desired to develop an oily component even if the surfactant is not formulated. Emulsified polymer emulsifier technology.

Patent Document 1 Japanese Patent No. 4174596

Patent Document 2 Japanese Patent No. 4182186

Patent Document 3 Japanese Patent Laid-Open Publication No. 2002-201116

Patent Document 4 Japanese Patent Laid-Open No. Hei 10-194922

When an oil component is emulsified in a product having almost no viscosity such as a lotion, a method of blending a conventional surfactant such as castor oil with polyoxyethylene is usually used. However, the object of the present invention is to develop a surfactant even if it is not formulated. A polymer emulsifier in which an oily component is emulsified.

The present invention has been proposed based on the idea that a methacrylic compound having a polyethylene glycol side chain structure in which a terminal substituent is a methyl group has a emulsification function as a monomer, and a novel polymer emulsifier has been proposed. The present invention is a polymer emulsifier and an emulsified composition emulsified by the polymer emulsifier.

The main components of the present invention are as follows.

(1) A polymer emulsifier comprising methoxypolyethylene glycol polymethacrylate.

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

(3) The polymer emulsifier according to (2), wherein the molecular weight in terms of polystyrene is 1,000 or more and 100,000 or less.

(4) An emulsion composition comprising the polymer emulsifier according to any one of (1) to (3), and an oil component.

(5) The emulsified composition according to (4), wherein the oil component is selected from the group consisting of polysilicon, alkyl glyceryl ether, dimer dilinoleic acid diethylene glycol. One or more of an ester oligomer and an essential oil.

(6) The emulsified composition according to (4), wherein the oil component is selected from the group consisting of cyclopentasiloxane, cyclohexaoxane, dimethicone, and dimerized linoleic acid. One or more of diethylene glycol ester oligomer, ethylhexyl glycerol, rosemary oil, and orange oil.

The mass ratio of the polymer emulsifier and the oil component according to any one of (1) to (3), wherein the mass ratio of the polymer emulsifier according to any one of (1) to (3), It is 1:5 to 100:1.

(8) The emulsified composition as described in (4) to (7), which is characterized in that it does not contain a surfactant.

(9) An emulsified composition characterized in that the polymer emulsifier according to any one of (1) to (3) is formulated in an amount of from 0.02 to 20% by mass.

The present invention can provide a polymeric emulsifier.

Since the emulsified composition emulsified by the polymer emulsifier of the present invention can be emulsified without blending other surfactants, it is possible to promote the absence of a surfactant, so that the commercial value is high.

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

Because cyclopentaoxane, cyclohexaoxane, dimethyl hydrazine oil, diethylene linoleate diethylene glycol ester oligomer, ethylhexyl glycerol, rosemary oil, orange oil can be emulsified, especially for Ethylhexyl glycerin (antibacterial component), essential oil (perfume component), and the like, which are only a small amount of oily component, can be solubilized. Therefore, it is particularly excellent as an emulsifier for cosmetics such as lotion and beauty lotion.

The amount of the compound that functions as an emulsifier does not affect the viscosity of the product, so it is not necessary to select a dosage form.

The polymer emulsifier of the present invention is nonionic, and the type of tackifier which can be optionally contained in the emulsified composition of the present invention is large, and the dosage form is rich in change.

The cosmetic emulsified by the polymer emulsifier of the present invention is characterized in that it is not sticky and has a feeling of use which makes the skin smooth.

The polymer suitable for use in the present invention is a polymer obtained by homopolymerizing methoxypolyethylene glycol methacrylate.

The methoxy polyethylene glycol methacrylate can be obtained, for example, by reacting polyethylene glycol methyl ether with methacrylic acid ruthenium chloride. In addition, some are commercially available as reagents. For example, NK Ester M-90G (chemical name: methoxypolyethylene glycol #400 methacrylate) commercially available from Shin-Nakamura Chemical Co., Ltd. or Blemmer PME (PME) commercially available from Nippon Oil Co., Ltd. -400: n≒9) Used as a monomer. Next, the method for producing the polymer can be obtained by reacting a monomer in a solvent in the presence of a polymerization initiator in accordance with a usual method.

The synthesis examples of the polymer related to the present invention are shown below.

Synthesis Example 1 methoxypolyethylene glycol polymethacrylate (average degree of polymerization of polyoxyethylene chain is 9)

0.0403 g of a polymerization initiator AIBN was weighed in a 100 ml eggplant type flask, and after replacing the inside of the flask with argon gas three times, 30 ml of distilled benzene was added and stirred at room temperature until the AIBN was dissolved. 5 ml of polyethylene glycol methyl ether methacrylate (having an average degree of polymerization of PEG of 9) was added thereto, and the mixture was heated at 60 ° C for 48 hours, followed by heating at 70 ° C for 24 hours to carry out polymerization. Then, the polymerization is stopped and the object is recovered.

The molecular weight of the polymer was determined using GPC. As a result, the molecular weight of Synthesis Example 1 was converted into polystyrene, and the number average molecular weight Mn was 15363, and the mass average molecular weight Mw was 35,680.

The molecular weight of the polymer according to the present invention obtained as described above can be variously adjusted depending on the purpose of use, but in view of emulsifying property, feeling, gelation property, film formation property, etc., it is usually converted into polystyrene. It is 1000 or more and 100000 or less, preferably 2,500 or more and 100,000 or less. In the cosmetic of the present invention, the polymer is usually contained in an amount of from 0.01 to 20% by mass, preferably from 0.02 to 20% by mass based on the total amount of the cosmetic.

When the amount is less than 0.01% by mass, it is difficult to sufficiently emulsify the oil component, and when it is more than 20% by mass, workability is poor, which is not preferable.

In the present invention, methoxypolyethylene glycol polymethacrylate acts as an emulsifier. When the polymer is contained, other surfactants used in combination with the emulsified composition can be reduced, or an excellent emulsified composition can be obtained without containing other surfactants.

The preferred oily component when the emulsified composition is produced by the above polymer emulsifier is polysiloxane, alkyl glyceryl ether, diethylene linoleate diethylene glycol oligomer, essential oil or the like.

Examples of the polyoxyalkylene oxide include cyclopentaoxane, cyclohexaoxane, and dimethylhydrazine. The alkyl glyceryl ether may, for example, be ethylhexyl glycerol. As the essential oil, rosemary oil, orange oil, or the like can be exemplified.

The cyclopentaoxane is a cyclic polyoxane, and is commercially available as KF-995 of Shin-Etsu Chemical Co., Ltd., and the like.

The cyclohexaoxane is a cyclic polyoxane, and is commercially available as a polyoxyalkylene DC246 of Toray Dow Corning Co., Ltd., and the like.

The dimethyl hydrazine oil is a chain polysiloxane, and it is commercially available, and it can be used for KF-96A-6cs of Shin-Etsu Chemical Co., Ltd., etc..

The dimerized linoleic acid diethylene glycol ester oligomer is a product obtained by esterifying dimer linoleic acid with diethylene glycol, and is exemplified by Example 1 as described in Japanese Patent No. 4288306. Oil agent (DEG-DA5).

Ethylhexyl glycerol is an ether of glycerin and 2-ethylhexanol, and is commercially available as SENSIVA SC50 manufactured by Schulke & Mayr GmbH.

Rosemary oil is an essential oil obtained from rosemary (plant), and is commercially available as a rosemary oil of PAYAN & BERTRAND.

Orange oil is an essential oil extracted from the peel of orange orange, and it is commercially available as a Japanese Pharmacy of the Ogawa Spice Co., Ltd., and is used.

Among them, ethylhexyl glycerol which is prepared for the purpose of antibacterial action of the product, and essential oil components such as rosemary oil and orange oil which are formulated for the purpose of imparting aroma to the product, can impart a purpose to the cosmetic in a small amount (antibacterial, The oily component which imparts a scent effect can be exemplified by the emulsifier of the present invention, so that it can be exemplified as a particularly preferred oil component. Further, since the emulsified state of the polyoxyalkylene is particularly excellent, it can be exemplified as a particularly preferred oil agent.

The polymer emulsifier of the present invention tends to be difficult to emulsify oil having a low polarity. For example, in squalane, since the emulsification agent of the present invention is poor in compatibility when emulsified, the emulsified state is also poor, which is not preferable.

When the surfactant is emulsified only by the polymer emulsifier of the present invention, the amount of the oil component is preferably 20% by mass or less.

When the polymer emulsifier of the present invention is contained in an amount of 1/5 times the amount of the oil component in the formulation, it is preferably emulsified or solubilized. When the composition is an emulsion composition such as a lotion, an emulsion or a cosmetic liquid, the mass ratio of the polymer emulsifier to the oil component of the present invention is preferably from 1:5 to 100:1. When the polymer emulsifier of the present invention is less than 1/5 times the amount of the oil component, the emulsification may be incomplete, which is not preferable.

The polymer emulsifier of the present invention may be a homopolymer of methoxypolyethylene glycol methacrylate which itself is an emulsifier, and may be optionally mixed with a water-soluble component such as water, polyol or ethanol to form an emulsifier. By adjusting the viscosity by mixing the emulsifier of the present invention with a water-soluble component, an emulsifier having good handleability can be formed.

When a polyol is contained, since compatibility with an oil component is improved, it is preferable. The polyhydric alcohol may, for example, be glycerin, 1,3-butanediol, dipropylene glycol, propylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol or polyethylene glycol. Wait. Particularly preferred are 1,3-butanediol, dipropylene glycol, and propylene glycol.

The emulsified composition of the present invention is suitable for use in external skin medicine, quasi drug for external use, and cosmetics.

In the polymer emulsifier, the emulsified composition, and the external preparation for skin (medicine, quasi-drug, and cosmetic) of the present invention, a component which is usually used as a cosmetic component can be blended as an optional component within a range that does not impair the effects of the invention. For example, antioxidants, UV absorbers, humectants, perfumes, perfumes, preservatives, tackifiers, pH adjusters, blood flow enhancers, cold feelers, antiperspirants, fungicides, skin activators and others. Beauty ingredients, medicinal ingredients, etc.

When a tackifier is contained, the stability of the emulsified composition is sometimes further improved. In addition, variations in the dosage form of the emulsified composition can also be increased.

As the tackifier, a water-soluble polymer is preferred. The water-soluble polymer may be any of a natural polymer, a semi-synthetic polymer, and a synthetic polymer. For example, as the natural polymer, tragacanth gum, karaya gum, xanthan gum, guar gum, cationized guar gum, anionization can be exemplified. Guar gum, tara gum, gum arabic, tamarind gum, gellan gum, Locust bean gum, carrageenan, hazelnut ( Quince seed), dextran, etc. The semisynthetic polymer may, for example, be hydroxypropylmethylcellulose, sodium carboxymethylcellulose, methylcellulose, cationized cellulose, propylene glycol alginate, sodium alginate or bentonite. The synthetic polymer may, for example, be a carboxy vinyl polymer, polyvinylpyrrolidone, polyvinyl alcohol, dialkyl polyethylene glycol, polyoxyethylene methyl glucoside dioleate or polyethylene glycol. , polyethylene glycol distearate, synthetic smectite and the like. The amount of these substances is preferably from 0.01 to 3%, more preferably from 0.1 to 2%. When the blending amount is less than 0.01%, the tackifying effect is insufficient, and when it is more than 3%, slipping or stickiness may occur, which is not preferable.

The emulsified composition of the present invention can be applied to cosmetics such as lotions, cosmetic liquids, lotions, creams, masks and the like. Especially suitable for lotions. The emulsified composition contains a tackifier which can be applied to a cosmetic liquid, an emulsion, a face cream, a mask, and the like.

Example

The emulsified compositions of Examples 1 to 18 and Comparative Examples 1 to 6 were prepared using the polymer emulsifier of the present invention, and the emulsified state was evaluated.

(Preparation method of emulsified composition)

The solution containing the aqueous solution (A) of Synthesis Example 1 and the oil component (B) was placed in purified water (C), and emulsified using a homo-mixer (9000 rpm, 2 minutes, room temperature). Further, the aqueous component (D) is mixed to prepare an emulsified composition.

[Evaluation of emulsification status] (evaluation of compatibility)

The dissolution state when the aqueous solution (A) containing the synthesis example 1 and the oil component (B) were mixed was visually evaluated by the following criteria. This evaluation was evaluated as follows: The results of the present emulsification were predicted by evaluating the compatibility of the polymer emulsifier of the present invention with the oil component before the emulsification.

○; transparent

△; translucent

×; not mixed

(Evaluation of emulsified state of emulsified composition)

The emulsified state of the emulsified compositions of Examples 1 to 18 and Comparative Examples 1 to 6 was visually evaluated by the following criteria. The emulsified particle size (volume average) was measured using a laser diffraction type particle size distribution measuring instrument.

○; good emulsifying

△; oily components ooze out on the surface or a small amount of oil droplets float out

×; completely separated or with clear oil droplets

[use evaluation]

The emulsified composition of the examples and the comparative examples was applied to the entire face by 10 female subjects (23 to 55 years old), and the feeling of use after application was evaluated.

(evaluation standard)

○; not sticky, smooth to the touch

×; sticky

(determination)

○; According to the evaluation criteria, 8 to 10 are evaluated as ○

△; According to the evaluation criteria, 7 to 5 are evaluated as ○

×; According to the evaluation criteria, 4 to 1 are evaluated as ○

The results of evaluation of the emulsified state and the feeling of use of the emulsified composition of Synthesis Example 1 are shown in Tables 1 to 4.

As shown in Table 1 (Examples 1 to 7), the polymer of Synthesis Example 1 may be a cyclopentaoxane, a cyclohexaoxane, a dimethyl hydrazine oil, or a dimerized linoleic acid diethylene glycol ester oligomer. Ethylhexyl glycerol, rosemary oil, orange oil emulsified. The emulsified compositions of Examples 1 to 7 were not sticky, and had a smooth touch and an excellent feeling of use. The emulsified compositions of Examples 5 and 6 were transparent to the extent that the particle size could not be measured by a laser diffraction type particle size distribution measuring instrument which measures the particle size according to the light scattering behavior, and the oily component was in a solubilized state. Here, the term "transparent" means that the emulsified composition contained in a transparent glass cylindrical container having a diameter of 4 cm is hardly recognized by visual inspection when it is filled with purified water in the same container. The viscosity of the emulsified compositions of Examples 1 to 7 was a critical value of 10 mPa·s or less which can be measured by a B-type viscometer.

As shown in Table 2, in Examples 8 to 11 in which the blending amount of the cyclopentaoxane as the oil component was set to 0.2, 1.0, 2.0, and 5.0, the polymer of Synthesis Example 1 was 1% by mass. It can be emulsified by blending. As shown in Example 11 and Example 13, a polypyridoxane (cyclopentaoxane or dimethyl hydrazine oil) equivalent to 5 times the amount of the polymer of Synthesis Example 1 was emulsified. Any of the emulsified compositions of Examples 12 to 15 in which the oil component is any of cyclopentaoxane, dimethyl hydrazine oil, and rosemary oil, and the amount of the polymer of Synthesis Example 1 is increased or decreased, either emulsified The emulsified state of the composition was good.

The emulsified compositions of Examples 8 to 15 were not sticky, and had a smooth touch and an excellent feeling of use. The viscosity of the emulsified compositions of Examples 8 to 11, 13, and 15 was a critical value of 10 mPa·s or less which can be measured by a B-type viscometer.

Then, the effect of the polyol in the preparation of the emulsified composition was evaluated. The results are shown in Table 4.

When the polyol (1,3-butanediol) is contained in the emulsified composition, the compatibility with the oil component is improved, and the emulsified state is also good.

Prescription example 1 lotion

(method of law)

The components of 1 to 5 were dissolved by heating at 70 ° C, and after cooling to 30 ° C, 6 to 8 premixed were added, and the mixture was uniformly stirred and mixed.

The lotion of Formulation Example 1 was transparent. It does not stick, makes skin smooth, and has a comfortable feeling of use. The storage stability is also good.

Formulation Example 2 Gelatinous Beauty Solution

(method of law)

(A) 1 to 5 was dissolved at 70 ° C, and 6 was added to cool to 30 ° C. (B) After mixing 8 to 11, it was added to 7, and emulsified using an emulsifier. (A) and (B) were uniformly stirred and mixed.

The gel-like cosmetic liquid of Formulation Example 2 was white turbid and was excellent in storage stability. It does not stick, makes skin smooth, and has a comfortable feeling of use.

Claims (7)

An emulsified composition comprising a polymer emulsifier and an oil component; the polymer emulsifier comprising methoxypolyethylene glycol polymethacrylate, wherein the oil component is selected from the group consisting of polysilicone, alkane One or more of glyceryl ether, diethylene linoleate diethylene glycol oligomer, and essential oil. The emulsified composition according to claim 1, wherein the polyoxyethylene chain of the methoxypolyethylene glycol polymethacrylate has an average degree of polymerization of 9. The emulsified composition according to the second aspect of the invention, wherein the polymer emulsifier has a molecular weight in terms of polystyrene of 1,000 or more and 100,000 or less. The emulsified composition according to claim 1, wherein the oil component is selected from the group consisting of cyclopentasiloxane, cyclohexaoxane, dimethicone, and dimerized linoleic acid. One or more of ethylene glycol ester oligomer, ethylhexyl glycerol, rosemary oil, and orange oil. The emulsified composition according to any one of claims 1 to 4, wherein the mass ratio of the polymer emulsifier to the oil component is from 1:5 to 100:1. The emulsified composition according to any one of claims 1 to 4, wherein the surfactant is not contained. The emulsified combination according to any one of claims 1 to 4 And 0.02 to 20% by mass of the above polymer emulsifier is formulated.