JP4577721B2 - Cosmetics - Google Patents

Description

  The present invention relates to cosmetics. More specifically, the present invention relates to a white turbid cosmetic that is excellent in white turbidity and excellent in storage stability and use feeling.

  In recent years, cloudy cosmetics represented by cloudy lotion have a cosmetic effect such as moisturizing, moisturizing, and richness on the skin compared to transparent lotions because of the appearance characteristic of cloudiness. It attracts attention for the reason of giving. For example, it is the same reason that Shirahone hot springs in Nagano Prefecture are popular because they feel the effects of hot springs due to cloudiness.

  Conventional white cloudy cosmetics include cosmetics in which an aqueous phase and an oil phase are emulsified and dispersed with a surfactant, and cosmetics in which a surfactant and an oily substance are dissolved in ethanol and dispersed in an aqueous phase. ing.

  However, there is a problem that it is difficult to select a surfactant to be used in order to obtain a white turbid cosmetic excellent in sufficient turbidity and storage stability. In addition, there is a method of adding a water-soluble thickener in order to improve the storage stability, but there is a problem that it is sticky in terms of usability or is unfamiliar.

  For these problems, it is excellent in stability of turbidity and does not cause coloring or odor over time even under high temperature conditions. A cloudy cosmetic composition in which glycylglycine is blended with a cloudy cosmetic composition using an ionic and / or anionic surfactant as an emulsifier has been developed (Patent Document 1).

  In addition, by dissolving a specific oily substance such as tocopherol or its derivative, oryzanol, and nonionic surfactant in ethanol, and mixing with water, the cloudiness is good and the cloudiness is excellent in storage stability and usability. Cosmetics have been developed (Patent Document 2).

Furthermore, tocopherol or its derivative, parahydroxybenzoic acid alkyl ester, and nonionic surfactant are dissolved in ethanol, and then mixed with water, so that the white turbidity has good turbidity and excellent storage stability and usability. A material has been developed (Patent Document 3).
JP-A-10-59838 JP-A-11-279043 JP-A-11-269055

  The present invention provides cosmetics obtained by means fundamentally different from conventional cloudy cosmetics, and is obtained by polymerizing a specific polyethylene oxide macromonomer, a hydrophobic monomer, and a crosslinkable monomer. Surprisingly, when the obtained copolymer is dispersed in water, it is surprising that the present invention has been completed as a result of finding that a cosmetic having good white turbidity and excellent storage stability and usability can be obtained.

  The present invention is a cosmetic obtained by using a specific copolymer as a clouding agent and dispersing it in water.

（１）
Ｒ₁は炭素原子数１〜３のアルキルを表し、ｎは２０〜２００の数である。ＸはＨまたはＣＨ₃を表す。

（２）
Ｒ₂は炭素原子数１〜３のアルキルを表し、Ｒ₃は炭素原子数１〜８のアルキルを表す。

（３）
Ｒ₄とＲ₅はそれぞれ独立に炭素原子数１〜３のアルキルを表し、ｍは０〜２の数である。 That is, the present invention contains a copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (2), and a crosslinkable monomer of the following formula (3). The present invention provides cosmetics characterized by the following.

(1)
R ₁ represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200. X represents H or CH ₃ .

(2)
R ₂ represents alkyl having 1 to ₃ carbon atoms, and R ₃ represents alkyl having 1 to 8 carbon atoms.

(3)
R ₄ and R ₅ each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.

（１）
Ｒ ₁ は炭素原子数１〜３のアルキルを表し、ｎは２０〜２００の数である。ＸはＨまたはＣＨ ₃ を表す。

（２）
Ｒ ₂ は炭素原子数１〜３のアルキルを表し、Ｒ ₃ は炭素原子数１〜８のアルキルを表す。

（３）
Ｒ ₄ とＲ ₅ はそれぞれ独立に炭素原子数１〜３のアルキルを表し、ｍは０〜２の数である。
Further, the present invention is represented by the following (A), (B), under the conditions of (C), (D), the following monomers (1) to (3) Water - by radical polymerization from ethanol mixed solvent A cosmetic comprising a microgel comprising a copolymer obtained.
(A) The hydrophobic monomer has a composition in which one or more methacrylic acid derivatives having an alkyl having 1 to 8 carbon atoms are mixed. (B) The charged amount of the polyethylene oxide macromonomer and the hydrophobic monomer is polyethylene. Oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio) (C) The charged amount of the crosslinkable monomer is 0.1 to 1.5 with respect to the charged amount of the hydrophobic monomer. (D) The water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (20 ° C. volume ratio).

(1)
R ₁ represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200. X represents H or CH ₃ .

(2)
R ₂ represents alkyl having 1 to ₃ carbon atoms , and R ₃ represents alkyl having 1 to 8 carbon atoms.

(3)
R ₄ and R ₅ each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.

  Furthermore, the present invention provides the cosmetic described above, wherein the particle size of the microgel is 50 to 300 nm.

  The present invention further provides a cosmetic comprising an oil and an oil-soluble drug and / or fragrance that dissolves in the oil.

(1) The cosmetics of the present invention are extremely excellent in white turbidity. Good turbidity can be obtained even if the amount of the copolymer is small.
(2) The cosmetic of the present invention is excellent in storage stability. That is, the turbidity is stable even after long-term storage.
(3) The cosmetic of the present invention is excellent in the feeling of use. That is, there is no stickiness and there is a feeling of richness. In addition, it is very familiar and has the effect of suppressing shine when applied to the skin.

  The present invention is described in detail below.

"Copolymer used in the present invention"
As the polyethylene oxide macromonomer of the formula (1), for example, a reagent commercially available from Aldrich or Bremer (registered trademark) marketed by Nippon Oil & Fats can be used. The molecular weight (namely, the value of n) of these commercially available polyethylene oxide moieties of formula (1) is wide and can be used. A preferable size of the molecular weight of the polyethylene oxide portion is n = 50 to 200. For example, Nippon Oil & Fats Blemmer (registered trademark) PME1000 or Blemmer (registered trademark) PME4000 is suitable.

As the hydrophobic monomer of the formula (2), for example, a reagent commercially available from Aldrich or Tokyo Kasei can be used. The alkyl chain of R _{3 in} formula (2) is alkyl having 1 to 8 carbon atoms. Formula (2) is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate. Butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate and the like. In particular, methyl methacrylate, butyl methacrylate, and octyl methacrylate are suitable. These hydrophobic monomers are general-purpose raw materials and can be easily obtained as general industrial raw materials.

  The crosslinkable monomer of the formula (3) can be obtained as a commercially available reagent or an industrial raw material. This crosslinkable monomer is preferably hydrophobic. The value of m in the formula (3) is preferably 1 to 3. Specifically, ethylene glycol dimethacrylate sold by Aldrich, Bremer (registered trademark) PDE-50 manufactured by NOF Corporation is suitable.

The copolymer used in the present invention is obtained by copolymerizing the above monomer by an arbitrary polymerization method, and particularly under the following conditions (A), (B), (C), and (D): It is preferably a copolymer (microgel) obtained by radical polymerization of the monomers (1) to (3) in a water-ethanol mixed solvent.
(A) The charged amount of polyethylene oxide macromonomer and hydrophobic monomer is polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio) (B) The charged amount of crosslinkable monomer is It is 0.1-1.5 mass% with respect to the preparation amount of a hydrophobic monomer. (C) Water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (20 degreeC volume ratio). (D) The water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (20 ° C. volume ratio).

  The charged amount of the polyethylene oxide macromonomer and the hydrophobic monomer (A) is within the range of polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio), and the corona-core type microgel can be polymerized. . When the charged amount of the ethylene oxide macromonomer is less than 1/10 of the hydrophobic monomer by molar ratio, the polymer to be polymerized becomes water-soluble and no corona-core type polymer microgel is formed. Further, when the hydrophobic monomer becomes 250 times or more with respect to the molar amount of the polyethylene oxide macromonomer, the dispersion stabilization by the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer by the insoluble hydrophobic monomer aggregates and precipitates. The charging ratio of the polyethylene oxide macromonomer and the hydrophobic monomer is preferably in the range of 1:10 to 1: 200. More preferably, it is in the range of 1:25 to 1: 100.

  By copolymerizing the crosslinkable monomer (B), a microgel in which the hydrophobic polymer in the core portion is crosslinked can be polymerized. If the charge amount of the crosslinkable monomer is less than 0.1% by weight of the charge amount of the hydrophobic monomer, the crosslink density is low, and the microgel collapses when swollen. On the other hand, when the content exceeds 1.5% by weight, the microgel particles are aggregated and suitable microgel particles having a narrow particle size distribution cannot be polymerized. The amount of the crosslinkable monomer charged is preferably 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5% by weight.

  The mixing ratio of water / ethanol which is the polymerization solvent of (C) is such that the water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (volume ratio at 20 ° C.). The polymerization solvent needs to add ethanol in order to uniformly dissolve the hydrophobic monomer. The mixing ratio of ethanol is 10-60 volume ratio. When the mixing ratio of ethanol is lower than 10 volume ratio, it becomes difficult to solubilize the hydrophobic monomer, and the particle size distribution of the microgel particles to be polymerized becomes wide. When the mixing ratio of ethanol exceeds 60 volume ratio, the polymer to be polymerized is dissolved in the polymerization solvent, and microgel particles cannot be obtained. A preferable water / ethanol mixing ratio is such that the water-ethanol mixed solvent is water: ethanol = 90 to 60:10 to 40 (volume ratio of 20 ° C.). More preferably, it is water: ethanol = 80-70: 20-30 (20 degreeC volume ratio).

As the polymerization initiator used in this polymerization system, a commercially available polymerization initiator used for usual water-soluble thermal radical polymerization can be used.
In this polymerization system, it is possible to obtain a very narrow particle size distribution of the polymerized microgel particles even when the polymerization is performed without strictly controlling the stirring conditions.

  By the above production method, a microgel composed of monodisperse particles having a particle diameter of 50 to 300 nm and a dispersity of less than 0.01 is obtained. In addition, this microgel has the characteristic that it swells in an organic solvent.

但し、Ｄは拡散係数、ｋはボルツマン定数、Ｔは絶対温度（Ｋ）、ηは溶媒の粘度、およびｒは粒子の半径である。
この測定は市販の測定装置で簡便に測定可能である。たとえば大塚電子製 DLS7000、マーベルン製 ゼータサイザー４７００、ブルックヘーブン製 ゼータプラスなどで測定が可能である。
上述の市販の測定装置にはデータ解析ソフトが搭載されており、測定データを自動的に解析することが出来る。この解析ソフトを用いることで平均粒子径、分散度の値を得ることが出来る。ここで分散度とは粒子径の平均値からのばらつきを示す値であり、キュムラント解析における二次キュムラントの値、即ち、分散値を規格化した値である。一般的にこの分散度が０．０１以下であればそのサンプルの粒子径分布はほぼ単分散とみなすことが出来る。 In general, the particle diameter of so-called colloidal particles such as emulsified particles or polymer emulsions can be measured by a method called dynamic light scattering method or photon correlation method. This measurement method measures the translational diffusion coefficient (average value) of sample particles by irradiating a sample dispersion prepared to a sufficiently dilute concentration with laser light and measuring the intensity of scattered light scattered from the sample particles. It is a method to do. The sample particles are always moving in Brownian motion in the dispersion. The moving speed of the particles by the Brownian motion, that is, the translational diffusion coefficient (average value) can be analyzed from the result of the temporal change in the scattered light intensity. The hydrodynamic size of the sample particles can be calculated from the translation diffusion coefficient (average value) thus obtained according to the Stokes-Einstein equation (Equation 1).

Where D is the diffusion coefficient, k is the Boltzmann constant, T is the absolute temperature (K), η is the viscosity of the solvent, and r is the radius of the particles.
This measurement can be easily performed with a commercially available measuring apparatus. For example, measurement is possible with Otsuka Electronics DLS7000, Marveln Zetasizer 4700, Brookhaven Zeta Plus.
The above-mentioned commercially available measuring apparatus is equipped with data analysis software, and can automatically analyze measurement data. By using this analysis software, values of average particle diameter and degree of dispersion can be obtained. Here, the degree of dispersion is a value indicating a variation from the average value of the particle diameter, and is a value of the secondary cumulant in the cumulant analysis, that is, a value obtained by normalizing the dispersion value. In general, if the degree of dispersion is 0.01 or less, the particle size distribution of the sample can be regarded as almost monodisperse.

Further, the particle diameter of the copolymer particles when the microgel polymerized by the above-described production method is dispersed in water is d ₀ , and the mixed solvent is mixed with benzene that swells and saturates the copolymer particles, until the swelling and saturation is reached. An organic solvent swellable microgel having a swelling ratio (d / d ₀ ) ³ of 20 to 450 is obtained, where d is the particle diameter of the copolymer particles when stirred.

“When mixed benzene is mixed with this mixed solvent so that the copolymer particles swell and saturate, and is stirred until the swell is saturated”, even if the amount of benzene and the stirring time are increased, the swollen microgel This means that the amount of benzene and the stirring time are required so that the particle size swelling ratio (d / d ₀ ) ^{3 of the} slag does not increase further.
For example, if the microgel is dispersed in water and benzene having the same volume as the mixed solvent is added and stirred for 5 hours, it is sufficient to swell and saturate.
When the polymerization solvent is a mixed solvent of water: ethanol = 8: 2 (20 ° C. volume ratio), the polymerization dispersion is sufficiently dialyzed against pure water after polymerization, and the dispersion is exchanged with pure water. It is sufficient to dilute this microgel aqueous dispersion with water to an appropriate concentration, add benzene of the same volume as the measurement sample to a sample prepared so that the concentration of the microgel is constant, and mix and stir for 5 hours. .
The particle diameters d and d ₀ can be measured by a dynamic light scattering method. The measurement conditions are as follows.
First, the particle size in water of the microgel before adding the organic solvent is measured as a control value, that is, a value of d ₀ . This measurement can be easily performed using a commercially available dynamic light scattering measurement apparatus. For example, measurement is possible with Otsuka Electronics DLS7000, Marbern Autosizer 4700, Brookhaven Zeta Pulse. These commercially available measuring apparatuses are equipped with data analysis software, and can automatically obtain the average particle diameter and the degree of dispersion. On the other hand, the particle diameter d after swelling with an organic solvent is processed by the following method. That is, an organic solvent such as benzene of the same volume is added to a microgel aqueous dispersion having a constant concentration, preferably about 0.01% by weight, and sealed in a covered sample tube. The sample tube is stirred for a certain time while gently stirring at room temperature. A stirring time of about 5 hours is sufficient. After stirring, the sample tube is lightly centrifuged at about 1000 × g to float the organic solvent, and the aqueous phase portion in which the microgel is dispersed is carefully collected with a syringe. The average particle diameter and the degree of dispersion of this collected sample are similarly measured using the above-mentioned commercially available dynamic light scattering measuring device.
The value of swelling ratio (d / d ₀ ) ³ can be calculated from the values of d and d ₀ thus obtained.

In addition, all the conventional microgels made of synthetic polymers are those using a polymer electrolyte such as polyacrylic acid, and have no acid resistance or salt resistance in water dispersibility. However, when considering application as a compounding ingredient of pharmaceuticals and cosmetics, acid resistance and salt resistance are very important performances in adaptation under physiological conditions. The microgel of the present invention is a microgel stabilized with a polyethylene oxide chain, which is a nonionic polymer, and its dispersion stability in water can be expected to have acid resistance and salt resistance.
Also known is a polymer microparticle polymerization method using a macromonomer method that applies a macromonomer containing a water-soluble polymer structure, but this method is applied to produce a microgel by crosslinking the core with a crosslinkable monomer. There is no known way to do it.
The microgel used in the present invention has a core-corona in which a hydrophilic macromonomer and a hydrophobic monomer are ordered in a solvent as shown in FIG. 1, the particle diameter is substantially constant, and the core portion is crosslinked. Type polymer microgel is considered to be formed.
The core-corona type polymer microgel is considered to function as an excellent turbidity agent.

  The above is the description of the copolymer used in the present invention. The cosmetic of the present invention is produced by mixing and dispersing this copolymer in water (or an aqueous phase in which water-soluble cosmetic ingredients are dissolved) by a conventional method. That is, the cosmetic of the present invention is a cosmetic having an excellent commercial value that can be produced by a very simple manufacturing process.

  As the microgel used in the present invention, it is desirable to use a microgel having a particle size in the range of 50 to 250 nm when dispersed in ion-exchanged water. If the particle size of the microgel is less than 50 nm, it is difficult to obtain a stable cloudy cosmetic. If the particle size exceeds 250 nm, it is not preferable as a cosmetic from the viewpoint of stability in long-term storage under high temperature conditions, or the feeling of use is favorable. It may not be rare.

  The microgel used in the present invention is preferably blended in a range of usually 0.01 to 5% by mass (hereinafter simply indicated by%) with respect to the total amount of the cosmetic. When the blending amount of the microgel is less than 0.01%, it is difficult to obtain a stable cloudy cosmetic. When the blending amount exceeds 5%, it is not preferable as a cosmetic from the viewpoint of stability in long-term storage under high temperature conditions, or when it is used. May not be preferred.

  The microgel used in the present invention can be visually confirmed to be clouded only by adding 0.01% to water. The L value measured with a Macbeth color difference meter with a compounding amount of 0.01% to 0.1% ( When a white turbidity of 1 to 80 is obtained, it functions as an excellent clouding agent. The conventional cloudy lotion technology using emulsification has a large amount of surfactant and oil, and it is difficult to balance stability and feeling of use.

In the present invention, the white turbid cosmetic means a cosmetic that can be visually recognized as having a white turbid appearance. The turbidity with the L value of 1 to 90 is preferred. More preferably, the turbidity is 1 to 60. Within this range, the significance of the present invention is high. This is because the white cloudy cosmetic having an L value of 1 to 60 is very difficult to adjust the balance between the surfactant and the oil, depending on the conventional technology, and it is difficult to produce a stable cloudy cosmetic.
A translucent lotion prepared by the microemulsion method or the like is also a cloudy cosmetic of the present invention, and its L value is around 90.

  The cosmetic of the present invention is particularly preferably used as a cloudy cosmetic such as a cloudy lotion or a cloudy cosmetic liquid.

  The cosmetics of the present invention further include medicinal agents, moisturizing ingredients, anti-inflammatory agents, antibacterial agents, antiseptics, ultraviolet absorbers, antioxidants, organic and inorganic powders, and fragrances that are commonly used in cosmetics, pharmaceuticals, etc. , Pigments and the like can be blended as necessary.

  ADVANTAGE OF THE INVENTION According to this invention, even in the cosmetics which mix | blended the oil component and the oil-soluble chemical | medical agent and / or fragrance | flavor which melt | dissolve in this oil component, it can provide the cosmetics excellent in white turbidity and excellent in storage stability. Also in this case, as described above, the turbidity with the L value of 1 to 90 is preferable, and the turbidity with 1 to 60 is more preferable.

  The oil component to be blended in the system may be any of a liquid oil, a solid oil, a semi-solid oil, or a substance hardly soluble in water. For example, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, flaxseed oil, safflower oil, Cottonseed oil, evening primrose oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagari oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, trioctanoic acid glycerin, triisopalmitic acid glycerin, etc. Liquid oil, cacao oil, coconut oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cow leg fat, Solid oils and fats such as mole, hardened castor oil, beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nukarou, Norin, cabbage wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, jojoballow, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated Waxes such as lanolin alcohol ether, liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalane, petrolatum, microcrystalline wax and other hydrocarbons, isopropyl myristate, octyl octoate, octyldodecyl myristate, isopropyl palmitate, Butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, dimethylo Hexyldecyl tanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl monoisostearate Glycol, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexylate, tri Glycerin-2-ethylhexylate, trimethylolpropane triisostearate, cetyl-2-ethylhexanoate, 2-ethylhexylpa Lumitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisopropyl adipate, N-lauroyl- L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, 2-cyanohexyl-2-cyano-3,3-diphenyl-2-propenoate, ethyl laurate, di-2-ethylhexyl sepatate, Such as 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, etc. Synthetic ester, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid (behenyl) acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tolic acid, lanolin fatty acid, isostearic acid, linoleic acid, linolenic acid, ester Higher fatty acids such as icosapentaenoic acid, lauric alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerene ether (batyl alcohol), 2-decyltetradecinol, lanolin alcohol, cholesterol, Linear, branched higher alcohols such as hexyl decanol, isostearyl alcohol, octyl dodecanol, dimethylpolysiloxane, methylphenylpolysiloxane Silicone oil such as sun, perfluorocarbon or perfluoropolyether such as perfluorodecalin, perfluorohexane, triperfluoro-n-butylamine, vitamin A and derivatives thereof, vitamin D and derivatives thereof, vitamin E and derivatives thereof, vitamins Vitamins such as K and its derivatives, sterols, natural and synthetic fragrances, etc. are mentioned, and among them, a melting point of a normal temperature or lower is distinguished from a liquid oil, and a melting point of a normal temperature or higher is distinguished from a solid or semi-solid oil. Among these, it is most preferable to add a liquid polar oil.

The drug component may be any of oil-soluble, water-soluble, and amphiphilic. Specific examples include agents such as whitening agents, moisturizers, anti-inflammatory agents, antibacterial agents, hormone agents, vitamins, various amino acids and their derivatives, enzymes, antioxidants, and hair restorers.
Examples of whitening agents include hydroquinone derivatives such as arbutin, kojic acid, L-ascorbic acid (vitamin C) and derivatives thereof, pantotenyl ethyl ether, tranexamic acid and derivatives thereof, placenta extract and plant extract (eg chamomile extract), etc. Examples of these extracts are exemplified.
Examples of L-ascorbic acid derivatives include L-ascorbic acid monostearate, L-ascorbic acid monopalmitate, L-ascorbic acid monoalkyl esters such as L-ascorbic acid monooleate, L-ascorbic acid monophosphate, L L-ascorbic acid monoesters such as ascorbic acid-2-sulfate; L-ascorbic acid dialkyl esters such as L-ascorbic acid distearate, L-ascorbic acid dipalmitate, L-ascorbic acid dioleate; L-ascorbic acid dilin L-ascorbic acid diesters such as acid esters; L-ascorbic acid trialkyl esters such as L-ascorbic acid tristearate, L-ascorbic acid tripalmitate, L-ascorbic acid trioleate; - ascorbic acid triesters such as ascorbic acid triphosphate ester; and L- ascorbic acid glucosides such as L- ascorbic acid 2-glucoside and the like. Examples of L-ascorbic acid and derivatives thereof include L-ascorbic acid, L-ascorbic acid phosphate, L-ascorbic acid-2-sulfate, L-ascorbic acid 2-glucoside, or salts thereof.
Examples of the tranexamic acid derivatives include dimers of tranexamic acid (for example, trans-4- (trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid, etc.), and esters of tranexamic acid and hydroquinone (for example, trans-4 -Aminomethylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester, etc.), ester form of tranexamic acid and gentisic acid (for example, 2- (trans-4-aminomethylcyclohexylcarbonyloxy) -5-hydroxybenzoic acid and its salt, ), Amides of tranexamic acid (for example, trans-4-aminomethylcyclohexanecarboxylic acid methylamide and salts thereof, trans-4- (P-methoxybenzoyl) aminomethylcyclohexanecarboxylic acid and And salts of trans-4-guanidinomethylcyclohexanecarboxylic acid and salts thereof, and the like.
Examples of the anti-inflammatory agent include glycyrrhizin, glycyrrhizinate (eg, dipotassium glycyrrhizinate, ammonium glycyrrhizinate, etc.), allantoin and the like.
Examples of the humectant include urea.
Examples of the antibacterial agent include resorcin, sulfur, salicylic acid and the like.
Examples of the hormone agent include oxytocin, corticotropin, vasopressin, secretin, gastrin, calcitonin, hinokitiol, ethinyl estradiol and the like.
Examples of vitamins include vitamin A and its derivatives (for example, retinol, vitamin A palmitate, etc.), vitamin B6, vitamin B6 derivatives such as vitamin B6 hydrochloride, nicotinic acid derivatives such as nicotinic acid and nicotinamide, vitamin E And derivatives thereof, β-carotene and the like.
Examples of various amino acids and their derivatives and enzymes include L-glutamic acid, urocanic acid, trypsin, lysozyme chloride, chymotrypsin, semi-alkaline proteinase, serrapeptase, lipase, and hyaluronidase.
Examples of the antioxidant include thiotaurine, glutathione, catechin, albumin, ferritin, metallothionein and the like.
Examples of the hair restoring agent include β-glycyrrhetinic acid, pantothenyl ethyl ether, minoxidil and the like.
Also, a refreshing agent such as camphor or menthol can be used.

  Next, an Example is given and this invention is demonstrated. The present invention is not limited to these examples. Initially, the manufacture example of the copolymer (microgel) used for the Example is shown. Unless otherwise specified, the amount is expressed in mass%.

"Examples of microgel production"
The polymerization of the microgel was carried out by the following method. In a 200 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 50 mL of a water-ethanol mixed solvent (water: ethanol = 40: 60 volume ratio) was added to PME-4000, methyl methacrylate (MMA), butyl methacrylate (nBMA), 2- Dissolve ethylhexyl methacrylate (EHMA) and ethylene glycol dimethacrylate (EGDMA). After sufficiently dissolving, 2,2 ′ azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total monomer amount and further dissolved. The completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours in an oil bath at 65 to 70 ° C. while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water.
The amount (g) of the monomer used is shown in “Table 1”.

"Measurement method of particle size and degree of dispersion"
The particle size of the microgel was measured using a Zetasizer manufactured by Malvern. The microgel concentration of the microgel dispersion is adjusted to about 0.1%, a measurement sample is prepared, dust is removed with a 0.45 micrometer filter, the scattering intensity at 25 ° C. is measured at a scattering angle of 90 °, The average particle size and the degree of dispersion were calculated with analysis software installed in the measuring device. The particle diameter is analyzed by a cumulant analysis method, and the degree of dispersion is a numerical value obtained by standardizing the value of the secondary cumulant obtained by the cumulant analysis. This degree of dispersion is a commonly used parameter and can be automatically analyzed by using a commercially available dynamic light scattering measurement device. As the viscosity of the solvent necessary for the particle size analysis, the viscosity of pure water at 25 ° C., that is, 0.89 mPas was used.
The measurement was performed 10 times for each sample, and the average value was taken.

"Microgel particle size and dispersity"
The particle diameter and dispersity of the obtained microgel are shown in “Table 2”.

"Method of measuring white turbidity"
The turbidity was evaluated by measuring the L-containing lotion with a Macbeth color difference meter and obtaining the L value (brightness).

"Method for evaluating storage stability"
Storing microgel-containing lotion in a constant temperature bath of -5 ° C, 0 ° C, RT, 37 ° C, 50 ° C and M1Cy (changed from 5 to 45 ° C and staying at 5 ° C and 45 ° C for 2 hours, 2 cycles a day) Then, the L value after one month was measured.
The following evaluation was performed based on the difference in the L value from the initial value.
<Evaluation>
○: Change from the initial value is less than ± 5 ×: Change from the initial value is ± 5 or more

"Evaluation of use"
The quality of the feeling of use (“no stickiness”, “feeling of feeling”, “fastness of familiarity”, “feeling of suppressing shine”)) was evaluated by 10 professional panels according to the following criteria.
A: More than 7 out of 10 answered “good” or “can feel”.
○: 5 or more out of 10 answered “good” or “real”.
Δ: 3 or more out of 10 answered “good” or “real”.
X: 2 or less of 10 respondents answered “Good” or “I can feel it”.

“Production of Examples 1 to 11 and Comparative Example 1”
The following cloudy lotion (moisturizing lotion) was prepared by the following production method. In addition, the lotion of the comparative example 1 does not mix | blend the polymer of a manufacture example, but is a transparent lotion.
<Production method>
(A) Each component is uniformly mixed and dissolved. The components (B) in “Table 3” and “Table 4” are uniformly mixed and dissolved. Add (B) to (A) with stirring to obtain each cloudy moisturizing lotion. This was used as a sample and evaluated according to the above evaluation method.

(A) 73.5% by mass of ion exchange water
Ethyl alcohol 10
Glycerin 0.5
Dipropylene glycol 5.0
Polyethylene glycol 1000 1.0
Polyoxyethylene polyoxypropylene 2-decyltetradecyl ether
8.5
Button extract 0.01
Raspberry extract 0.01
Yukinoshita extract 0.01
l-Menthol JP 0.002
Citric acid (food) 0.02
Sodium citrate 0.08
Sodium hexametaphosphate 0.03
Phenoxyethanol 0.3
New fragrance 0.05

(B) Dispersed aqueous solution of copolymer

"Evaluation of storage stability"
As shown in the following “Table 5” and “Table 6”, the cloudy lotion was excellent in long-term stability.

"Evaluation of use"
As shown in the following "Table 7" and "Table 8", the white cloudy lotion of each example is particularly improved in the stickiness derived from the surfactant of the conventional white cloudy lotion, and has a rich feeling and a quick familiarity. It is a lotion that can also be used to control shine.

The other cloudy cosmetics of the present invention are listed below.
The present invention can provide an excellent cloudy cosmetic even in a cosmetic containing a cosmetic raw material oil and further containing an oil-soluble drug and / or a fragrance.

"Example 12 whitening lotion"
Copolymer of Production Example 4 0.3
Ethanol 10
Dipropylene glycol 1
Polyethylene glycol 1000 1
Polyoxyethylene methyl glucoside 1
Glyceryl tri-2-ethylhexanoate 0.1
Polyoxyethylene hydrogenated castor oil 0.2
Polyglyceryl diisostearate 0.15
N-stearoyl-sodium L-glutamate 0.1
Citric acid 0.05
Sodium citrate 0.2
Potassium hydroxide 0.4
Dipotassium glycyrrhizinate 0.1
Arginine hydrochloride 0.1
Nettle extract 0.1
Tranexamic acid 2
Potassium 4-methoxysalicylate 1
Edetate trisodium 0.05
2-Ethylhexyl paramethoxycinnamate 0.01
Dibutylhydroxytoluene Suitable amount Paraben Suitable amount Deep sea water 3
Purified water Residual fragrance

"Example 13 whitening moisturizing lotion"
Copolymer of Production Example 6 0.5
Glycerin 1
Dipropylene glycol 12
Ethanol 8
POE methyl glucoside 3
POE (24) POP (13) Decyl tetradecyl ether 0.5
Citric acid 0.02
Sodium citrate 0.08
Hydroxypropyl-β-cyclodextrin 0.5
Thiotaurine 0.1
Adenosine triphosphate-2sodium 0.1
Sodium hyaluronate 0.01
EDTA 3 sodium 0.01
Hydroxyethyl cellulose 0.1
L-ascorbic acid 2-glucoside 2
Arbutin 0.05
Paraben Appropriate amount Purified water Residual perfume Appropriate amount

"Example 14 moisturizing lotion"
Copolymer of Production Example 11 0.2
Ethanol 5.0
POE oleyl alcohol ether 2.0
Diethoxyethyl succinate 3.0
2-Ethylhexyl-P-dimethylaminobenzoate 0.18
1,3 butylene glycol 9.5
Sodium pyrrolidonecarboxylate 0.5
Nicotinamide 0.3
Glycerin 5.0
Fragrance 0.05
Purified water residue

"Example 15 daytime serum"
Polymer of Production Example 5 1.0
Ethanol 4.0
Glycerin 1.0
1,3-butylene glycol 5.0
Octyl methoxycinnamate 0.2
Liquid paraffin 0.02
Sodium hexametaphosphate 0.03
Trimethylglycine 1.0
Sodium polyaspartate 0.1
α-Tocopherol 2-L-ascorbic acid phosphate diester potassium
0.1
Thiotaurine 0.1
Green tea extract 0.1
Western mint extract 0.1
Iris root extract 0.1
HEDTA 3 sodium 0.1
Carboxyvinyl polymer 0.05
Potassium hydroxide 0.02
Phenoxyethanol Appropriate amount Purified water Residual perfume Appropriate amount

"Example 17 non-alcohol lotion"
Copolymer of Production Example 1 0.3
Glycerin 2.0
1,3-butylene glycol 4.0
Erythritol 1.0
Polyoxyethylene methyl glucoside 1.0
Polyoxyethylene hydrogenated castor oil 0.5
Citric acid 0.02
Sodium citrate 0.08
Phenoxyethanol appropriate amount methylpolysiloxane 0.02
N-coconut oil fatty acid acyl L-arginine ethyl DL-pyrrolidone carboxylic acid
0.1
Purified water residue

"Example 18 Thorough lotion"
Copolymer of Production Example 3 0.1
Ethanol 5.0
Glycerin 0.5
Dipropylene glycol 2.0
1,3-butylene glycol 6
Rosemary oil 0.01
Sage oil 0.01
Citric acid 0.02
Sodium citrate 0.08
Sodium hexametaphosphate 0.03
Hydroxypropyl-β-cyclodextrin 0.1
Mukuroji extract 0.1
Ages Extract 0.1
Lily extract 0.1
Oat extract 0.1
Togenashi extract 0.1
Kiso Extract 0.1
Lavender oil 0.1
Tounin extract 0.1
Retinol 0.02
Sodium alginate 0.001
Purified water residue

"Example 19 whitening cosmetic liquid"
Copolymer of Production Example 9 0.3
Dimethylpolysiloxane 5
Glycerin 2
1,3-butylene glycol 5
Polyethylene glycol 1500 3
Polyethylene glycol 20000 3
Cetyl octanoate 3
Citric acid 0.01
Sodium citrate 0.1
Sodium hexametaphosphate 0.1
Dipotassium glycyrrhizinate 0.1
Ascorbic acid glucoside 2
Tocopherol acetate 0.1
Ogon Extract 0.1
Yukinoshita extract 0.1
Edetate trisodium 0.1
Xanthan gum 0.05
Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-2)
0.05
Agar powder 1.5
Phenoxyethanol Appropriate amount Dibutylhydroxytoluene Appropriate amount of purified water Residue

ADVANTAGE OF THE INVENTION According to this invention, the cosmetics which are excellent in white turbidity, and excellent in storage stability and a feeling of use can be provided.
The cosmetic of the present invention is a useful white turbid cosmetic that can effectively appeal the impression of the cosmetic effect to consumers because of its excellent turbidity.

It is a schematic diagram which shows the core-corona type polymer nanosphere production | generation mechanism of the microgel used for this invention.

Claims (4)

It contains a copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (2), and a crosslinkable monomer of the following formula (3). Cosmetics.

(1)
R ₁ represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200. X represents H or CH ₃ .

(2)
R ₂ represents alkyl having 1 to ₃ carbon atoms, and R ₃ represents alkyl having 1 to 8 carbon atoms.

(3)
R ₄ and R ₅ each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2. Following (A), under the conditions of (B), (C), (D), the following monomers (1) to (3) Water - a copolymer obtained by radical polymerization from ethanol mixed solvent A cosmetic characterized by comprising a microgel.
(A) The hydrophobic monomer has a composition in which one or more methacrylic acid derivatives having an alkyl having 1 to 8 carbon atoms are mixed. (B) The charged amount of the polyethylene oxide macromonomer and the hydrophobic monomer is polyethylene. Oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio) (C) The charged amount of the crosslinkable monomer is 0.1 to 1.5 with respect to the charged amount of the hydrophobic monomer. (D) The water-ethanol mixed solvent is water: ethanol = 90-30: 10-70 (20 ° C. volume ratio).

(1)
R ₁ represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200. X represents H or CH ₃ .

(2)
R ₂ represents alkyl having 1 to ₃ carbon atoms , and R ₃ represents alkyl having 1 to 8 carbon atoms.

(3)
R ₄ and R ₅ each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.   The cosmetic according to claim 2, wherein the microgel has a particle size of 50 to 300 nm.   The cosmetic according to claim 1, 2, or 3, further comprising an oil and an oil-soluble drug and / or fragrance that dissolves in the oil.

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