JP5680895B2 - Polymer emulsifier and emulsified composition - Google Patents

Description

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

The applicant has continued to develop components with low skin irritation (components having low skin permeability, low irritation and water solubility), and are developing cosmetics containing the components.
For example, an invention in which a copolymer of an antibacterial monomer and a water-soluble monomer is included in cosmetics as an antibacterial compound has been proposed. (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: Japanese Patent Application Laid-Open No. 2002-201116). It is capable of emulsifying and solubilizing specific oily components, having use as an emulsifier, and being able to make an emulsified composition emulsified with the emulsifier into a cosmetic. unknown.
On the other hand, an alkyl methacrylate copolymer is marketed as a polymer emulsifier, and an emulsified composition and cosmetics emulsified using the copolymer are known (Patent Document 4: JP-A-10-194922).
Polymer emulsifiers are recognized by consumers as being different from so-called surfactants such as polyoxyethylene hydrogenated castor oil, and are favorably used in products that require no surfactant. For example, PEMULEN (manufactured by BF Goodrich), which is an alkyl methacrylate copolymer, is a typical product of a polymer emulsifier used in cosmetics, and is characterized in that it can be emulsified regardless of the type of oil.
PEMULEN TR-2 (manufactured by BF Goodrich) is commercially available for products with low viscosity, but the viscosity is 1,500 to 5,000 mPa · s (0.2% aqueous solution). Or latex, gel. For this reason, when emulsifying oil components in products such as lotions, it is common to use ordinary surfactants such as polyoxyethylene hydrogenated castor oil. There has been a demand for the development of a polymer emulsifier that can emulsify oily components without the need.

Japanese Patent No. 4174596 Japanese Patent No. 4182186 JP 2002-201116 A JP-A-10-194922

  In the present invention, when emulsifying an oil component in a product such as lotion, which is almost free of viscosity, a general method of blending a normal surfactant such as polyoxyethylene hydrogenated castor oil was used. An object of the present invention is to develop a polymer emulsifier that can emulsify an oil component without blending a surfactant.

The present invention provides a new polymer emulsifier based on the knowledge that a homopolymer having a methacrylic acid compound having a polyethylene glycol side chain structure whose terminal substituent is a methyl group as a monomer has an emulsifying function. suggest. The present invention is a polymer emulsifier and an emulsified composition emulsified with the polymer emulsifier.
The main configuration of the present invention is as follows.
(1) A polymeric emulsifier comprising polymethoxymethacrylate polyethylene glycol having an average degree of polymerization of polyoxyethylene chain of polymethacrylic acid polyethylene glycol of 9 and a molecular weight of 1000 or more and 100000 or less in terms of polystyrene. .
(2) (1) Symbol containing polymeric emulsifier and oil component mounting, the oil component is silicone, alkyl glyceryl ether, dimerdilinoleic diethylene glycol oligomer ester, is one or more selected from the group consisting of essential oils The emulsion composition characterized by the above-mentioned.
(3) The emulsion composition according to (2) , wherein the silicone is cyclopentasiloxane, cyclohexasiloxane, dimethicone, the alkyl glyceryl ether is ethylhexyl glycerin , and the essential oil is rosemary oil or orange oil. .
(4) The emulsion composition according to (2) or (3), wherein the mass ratio of the polymer emulsifier and the oil component according to (1) is 1: 5 to 100: 1.
(5) emulsified composition according to any one of the polymeric emulsifier and wherein the blended 0.02 to 20 wt% (2) to (4) described in (1).

A polymer emulsifier could be provided.
The emulsified composition emulsified with the polymer emulsifier of the present invention can be emulsified without blending with other surfactants and has high commercial value because it can be free of surfactants.
The polymer emulsifier of the present invention is economical because it can be emulsified and solubilized at room temperature (5 to 35 degrees) without any particular heating.
Cyclopentasiloxane, cyclohexasiloxane, dimethicone, dimer dilinoleic acid diethylene glycol oligomer ester, ethyl hexyl glycerin, rosemary oil, orange oil can be emulsified, especially in small quantities in products such as ethyl hexyl glycerin (antibacterial component) and essential oil (fragrance component) Since it was solubilized with the oily component that does not, it is particularly excellent as an emulsifier for cosmetics such as lotions and cosmetics.
Since the blending amount that functions as an emulsifier does not affect the viscosity of the product, it can be used regardless of the dosage form.
The polymer emulsifier of the present invention is nonionic, and there are many types of thickeners that can be optionally contained in the emulsified composition of the present invention.
The cosmetic emulsified with the polymer emulsifier of the present invention is not sticky and has a characteristic of feeling that the skin becomes smooth.

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

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

  Below, the synthesis example of the polymer which concerns on this invention is shown.

Synthesis Example 1 Polymethoxy methacrylate polyethylene glycol (average polyoxyethylene chain polymerization degree: 9)
In a 100 ml eggplant flask, 0.0403 g of polymerization initiator AIBN was weighed, and the inside of the flask was replaced with argon gas three times. Then, 30 ml of distilled benzene was added and stirred at room temperature until AIBN was dissolved. 5 ml of polyethylene glycol methyl ether methacrylate (average polymerization degree of PEG is 9) was added thereto, and the mixture was heated at 60 ° C. for 48 hours and then at 70 ° C. for 24 hours for polymerization. Thereafter, the polymerization was stopped and the desired product was recovered.

  The molecular weight of the 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 according to the present invention obtained as described above can be variously adjusted depending on the purpose of use, but when considering emulsifying performance, touch surface, gelling ability, film forming ability, etc. Usually, it is 1000 or more and 100000 or less, preferably 2500 or more and 100000 or less in terms of polystyrene. In the cosmetic of the present invention, the polymer is contained in an amount of usually 0.01 to 20% by mass, preferably 0.02 to 20% by mass, based on the entire cosmetic.
If it is less than 0.01% by mass, it is difficult to sufficiently emulsify the oily component, and if it exceeds 20% by mass, handling is poor and this is not preferred.
In the present invention, methoxypolyethylene glycol polymethacrylate acts as an emulsifier. When this polymer is included, other surfactants used in the emulsion composition can be reduced, or an excellent emulsion composition can be obtained even if other surfactants are not included.

Preferred oily components for producing an emulsified composition with the polymer emulsifier are silicone, alkyl glyceryl ether, dimer dilinoleic acid diethylene glycol oligomer ester, essential oil and the like.
Examples of silicone include cyclopentasiloxane, cyclohexasiloxane, and dimethicone. An example of the alkyl glyceryl ether is ethylhexyl glycerin. Examples of essential oils include rosemary oil and orange oil.
Cyclopentasiloxane is a cyclic silicone, and commercially available products such as KF-995 from Shin-Etsu Chemical Co., Ltd. can be obtained and used.
Cyclohexasiloxane is a cyclic silicone, and commercially available products such as silicon DC246 from Toray Dow Corning Co., Ltd. can be obtained and used.
Dimethicone is a chain silicone, and commercially available products such as KF-96A-6cs from Shin-Etsu Chemical Co., Ltd. can be obtained and used.
Dimerlinoleic acid diethylene glycol oligomer ester is obtained by esterifying dimerlinoleic acid and diethylene glycol, and can be exemplified by the oil agent (DEG-DA5) of Example 1 described in Japanese Patent No. 4288306.
Ethylhexylglycerin is an ether of glycerin and 2-ethylhexyl alcohol. As a commercial product, SENSIVA SC50 manufactured by Schulke & Mayr GmbH can be obtained and used.
Rosemary oil is an essential oil obtained from Mannen wax (plant), and commercially available products such as rosemary oil from PAYAN & BERTRAND can be used.
Orange oil is an essential oil extracted from the peel of orange, and as a commercial product, Japanese Pharmacopoeia orange oil of Ogawa Fragrance Co., Ltd. can be obtained and used.
Among them, essential oil components such as ethyl hexyl glycerin formulated for the purpose of antibacterial effects on products and rosemary oil and orange oil formulated for the purpose of flavoring products are used in small amounts (antibacterial and flavoring). It is an oily component that can impart an effect to the cosmetic, but it can be solubilized with the emulsifier of the present invention, and can be exemplified as a particularly preferred oily component. Moreover, since the emulsified state of silicone was 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 with low polarity. For example, when squalane is emulsified only with the emulsifier of the present invention, since the compatibility is not good, the emulsified state becomes unfavorable.

When emulsifying only with the polymer emulsifier of the present invention without containing any other surfactant, the blending amount of the oil component is preferably 20% by mass or less.
It is preferable for emulsification and solubilization to contain the polymer emulsifier of the present invention in an amount of 1/5 times the oil component. In the case of an emulsified composition such as a lotion, milky lotion, or cosmetic liquid, the mass ratio of the polymer emulsifier of the present invention to the oil component is preferably 1: 5 to 100: 1. If the polymer emulsifier of the present invention is less than 1/5 times the oil component, emulsification may be incomplete, which is not preferable.

In the polymer emulsifier of the present invention, a homopolymer of methoxypolyethylene glycol methacrylate itself becomes an emulsifier, but can be arbitrarily mixed with a water-soluble component such as water, a polyhydric alcohol, or ethanol to make an emulsifier. By mixing the emulsifier of the present invention with a water-soluble component and adjusting the viscosity, it becomes an emulsifier with good handling.
The inclusion of a polyhydric alcohol is preferable because the compatibility with the oil component is improved. Examples of the polyhydric alcohol 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 emulsified composition of the present invention is suitable for a skin external medicine, a skin external quasi-drug, and a cosmetic.
In the polymer emulsifier, emulsified composition, skin external preparation (medicine, quasi-drug, cosmetics) of the present invention, components that are usually used in cosmetics as long as they do not impair the effects of the invention as optional components, For example, antioxidants, ultraviolet absorbers, moisturizers, fragrances, fragrances, preservatives, thickeners, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators and other Cosmetic ingredients and medicinal ingredients can be blended.
When a thickener is included, the stability of the emulsion composition may be further improved. Moreover, the variation of the dosage form of an emulsion composition can be increased.
As the thickener, a water-soluble polymer is preferable. The water-soluble polymer may be any of natural polymer, semi-synthetic polymer, and synthetic polymer. For example, examples of the natural polymer include tragacanth gum, karaya gum, xanthan gum, guar gum, cationized guar gum, anionized guar gum, tara gum, gum arabic, tamarind gum, juran gum, locust bean gum, carrageenan, quince seed, dextran, and the like. Examples of the semisynthetic polymer include hydroxypropylmethylcellulose, sodium carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, hydroxypropylmethylcellulose, cationized cellulose, propylene glycol alginate, sodium alginate, bentonite and the like. Examples of the synthetic polymer include carboxyvinyl polymer, polyvinyl pyrrolidone, polyvinyl alcohol, dialkyl polyethylene glycol, polyoxyethylene dioleic acid methyl glucoside, polyethylene glycol, polyethylene glycol distearate, synthetic smectite, and the like. These compounding amounts are preferably 0.01 to 3%, more preferably 0.1 to 2%. If the blending amount is less than 0.01%, the thickening effect is not sufficient, and if it exceeds 3%, it is not preferable because it becomes sticky or sticky.

  The emulsified composition of the present invention can be made into cosmetics such as skin lotion, cosmetic liquid, milky lotion, cream and pack. In particular, it is preferably used for lotion. Thickeners can be included to make serums, emulsions, creams, packs, and the like.

  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.

(Method for preparing emulsified composition)
A solution prepared by mixing the aqueous solution (A) containing Synthesis Example 1 and the oil component (B) is emulsified using a homomixer (9000 rpm, 2 minutes, room temperature) while being added to purified water (C). An emulsion composition was prepared by mixing (D).

[Evaluation of emulsified state]
(Compatibility evaluation)
The dissolved state when the aqueous solution (A) containing Synthesis Example 1 and the oil component (B) were mixed was visually evaluated according to the following criteria. This evaluation is an evaluation for predicting the result of the main emulsification by evaluating the compatibility between the polymer emulsifier of the present invention and the oil component before proceeding to the main emulsification.
○: Transparent △; Translucent ×: Not mixed

(Evaluation of emulsified state of emulsified composition)
The emulsified states of the emulsified compositions of Examples 1 to 18 and Comparative Examples 1 to 6 were visually evaluated according to the following criteria. The emulsified particle size (volume average) was measured with a laser diffraction particle size distribution meter.
○: Emulsified well △: Oily component bleeds on the surface or oil droplets are slightly floating
×: Complete separation or obvious oil droplets

[Usage evaluation]
The emulsified compositions of Examples and Comparative Examples were applied to the entire face of 10 female subjects (23 to 55 years old), and the feeling after use was evaluated.
(Evaluation criteria)
○: Sticky, smooth feel ×: Sticky (judgment)
○: 8 to 10 people evaluated as ○ based on evaluation criteria Δ; 7 to 5 people evaluated as ○ based on evaluation criteria ×; 4 to 1 people evaluated as ○ based on evaluation criteria

  The results of evaluating the emulsified state and feeling of use of the emulsified composition containing 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 emulsifies cyclopentasiloxane, cyclohexasiloxane, dimethicone, dimerlinoleic acid diethylene glycol oligomer ester, ethylhexyl glycerin, rosemary oil, orange oil. We were able to. The emulsified compositions of Examples 1 to 7 were not sticky and had a smooth feel and excellent usability. In the emulsion compositions of Examples 5 and 6, the emulsion composition is so transparent that the particle size cannot be measured by a laser diffraction particle size distribution meter that measures the particle size from the light scattering behavior, and the oily component is solubilized. Met. Here, the term “transparent” refers to a level at which the emulsified composition placed in a transparent glass cylindrical container having a diameter of 4 cm is hardly discernable visually when compared with the case where purified water is placed in a similar container. The viscosities of the emulsified compositions of Examples 1 to 7 were not more than a limit value of 10 mPa · s that could be measured with a B-type viscometer.

As shown in Table 2, also in Examples 8 to 11 in which the amount of cyclopentasiloxane that is an oil component is 0.2, 1.0, 2.0, and 5.0, the polymer of Synthesis Example 1 is 1 It was emulsified by blending the mass%. As shown in Example 11 and Example 13, silicone (cyclopentasiloxane, dimethicone) corresponding to 5 times the amount of the polymer of Synthesis Example 1 could be emulsified. The emulsified state of each of the emulsified compositions of Examples 12 to 15 in which the oil component was any of cyclopentasiloxane, dimethicone, and rosemary oil, and the blending amount of the polymer of Synthesis Example 1 was increased or decreased. It was.
The emulsified compositions of Examples 8 to 15 had a smooth feel without stickiness and an excellent feeling of use. The viscosities of the emulsified compositions of Examples 8 to 11, 13, and 15 were not more than a limit value of 10 mPa · s that could be measured with a B-type viscometer.

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

乳化組成物に多価アルコール(１，３−ブチレングリコール)を含ませると、油性成分との相溶性がよくなり、乳化状態も良好であった。

When polyhydric alcohol (1,3-butylene glycol) was included in the emulsified composition, the compatibility with the oil component was improved and the emulsified state was also good.

Formulation Example 1 Lotion (Formulation ingredients) (mass%)
1. 1. Purified water balance Glycerin 10
3. Methylparaben 0.1
4). Citric acid 0.01
5. Sodium citrate 0.05
6.1,3-Butylene glycol 5.0
7). Rosemary oil 0.003
8). Polymer obtained in Synthesis Example 1 0.3

(Manufacturing method)
Ingredients 1-5 are heated and dissolved at 70 ° C., cooled to 30 ° C., 6-8 mixed in advance are added, and stirred and mixed uniformly.

  The lotion of Formulation Example 1 was transparent. It was non-sticky and the skin was smooth and comfortable to use. The storage stability was also good.

Formulation Example 2 Gel serum (formulation component) (mass%)
(A)
1. 1. Purified water balance 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

(Manufacturing method)
(A) 1 to 5 are heated and dissolved at 70 ° C., 6 is added, and the mixture is cooled to 30 ° C. (B) Add 8 to 11 after mixing and emulsify using a homomixer. (A) and (B) are stirred and mixed uniformly.

  The gel cosmetic liquid of Formulation Example 2 had a cloudy appearance and was excellent in storage stability. It was non-sticky and the skin was smooth and comfortable to use.

Claims (5)

A polymer emulsifier characterized by containing poly (methacrylic acid) methoxypolyethylene glycol having a polyoxyethylene chain average polymerization degree of 9 and a molecular weight of 1000 or more and 100000 or less in terms of polystyrene . Containing polymeric emulsifier and oil component of claim 1 Symbol mounting, characterized in that the oil component is silicone, alkyl glyceryl ether is dimerdilinoleic diethylene glycol oligomer ester, one selected from the group consisting of essential oils, or two or more An emulsified composition. The emulsion composition according to claim 2 , wherein the silicone is cyclopentasiloxane, cyclohexasiloxane, dimethicone, the alkyl glyceryl ether is ethylhexyl glycerin , and the essential oil is rosemary oil or orange oil. The emulsified composition according to claim 2 or 3, wherein the mass ratio of the polymer emulsifier according to claim 1 to the oil component is 1: 5 to 100: 1. The emulsified composition according to any one of claims 2 to 4 , wherein 0.02 to 20% by mass of the polymer emulsifier according to claim 1 is blended.