WO2013047759A1 - Cosmetic preparation - Google Patents

Abstract

A cosmetic preparation that contains at least casein nanoparticles and a thickener which has a viscosity ratio I/II of 10 or less, wherein I is the viscosity (mPa·s) of a liquid prepared by incorporating 0.2 mass% the thickener into water, as measured with a Brookfield viscometer (measuring conditions; 25ºC, 30 s, and 30 rpm) and II is the viscosity (mPa·s) of a liquid prepared by incorporating the thickener into test liquid A in an amount of 0.2 mass% in terms of the content of the thickener in 100 g, adding water thereto to a total amount of 100 g, and adjusting the pH of the mixture to 7.5 with an aqueous sodium hydroxide solution (1 M), as measured with a Brookfield viscometer (measuring conditions; 25ºC, 30 s, and 30 rpm). Test liquid A A liquid prepared by dissolving 1.47 g of sodium citrate, 1 g of sodium casein, and 5 g of 1,3-butylene glycol in water, regulating the total amount to 90 g, and then adjusting the pH of the solution to 7 with an aqueous sodium hydroxide solution (1 M).

Description

Cosmetics

The present invention relates to cosmetics.

Particulate materials are expected for wide use in the biotechnology field. Particularly, nanoparticulate materials produced by the advancement of nanotechnology are actively studied for application to foods, cosmetics, pharmaceuticals, etc., and many research results on nanoparticulate materials have been reported.
For example, in recent years, in the cosmetics field, customer demand for clearer skin effects has increased. For this reason, cosmetic companies are trying to improve the functionality and usability of their own cosmetics and differentiate them from other cosmetics by incorporating various new technologies including nanotechnology.
Generally, the skin has a stratum corneum as a barrier, so that the active ingredient has low permeability to the skin. In order to fully exhibit the effects of cosmetics on the skin, it is essential to improve the skin permeability of the active ingredient. In addition, even if the active ingredient has high effectiveness for the skin, the active ingredient has low storage stability and is likely to cause irritation to the skin. There are many ingredients. In order to solve these problems, various fine particle materials have been developed for the purpose of improving transdermal absorbability, improving storage stability, and reducing skin irritation. Various fine particles such as ultrafine emulsions and liposomes are being developed. Materials have been studied (for example, Mitsuhiro Nishida, Fragrance Journal, November, p.17 (2005)).

It has also been proposed to use protein nanoparticles, which are fine particle materials, for various skin external compositions. For example, casein, a kind of protein, is a natural surfactant molecule and can be used as a water-soluble emulsifier. For this reason, various techniques using casein as a water-soluble emulsifier are known.

Japanese Patent Application Laid-Open No. 2008-179551 discloses casein nanoparticles containing (containing) a fat-soluble antioxidant or the like. Japanese Patent Laid-Open No. 2008-201767 discloses a hair composition containing protein nanoparticles such as casein nanoparticles. It is described that since an active ingredient is encapsulated in casein nanoparticles, a hair composition having high permeability to the hair and scalp can be obtained. In addition, WO 2004/114262 discloses casein nanoparticles and a method for producing the same, and produces casein nanoparticles having an arbitrary particle size without using a surfactant or a synthetic polymer. It is stated that you can.

By the way, since various dosage forms exist in cosmetics, there are many cosmetics that require thickening to compensate for the disadvantages of each dosage form. On the other hand, the thickener that gives viscosity to the cosmetic may remain on the skin when the cosmetic is applied to the skin and dried. In addition, it is not preferable to contain an excessive thickener in the cosmetic because it causes a decrease in feeling of use such as stickiness or film feeling.

In addition, in cosmetics containing protein nanoparticles, the knowledge that it is difficult to adjust the viscosity of cosmetics when blending synthetic thickeners such as carboxyvinyl polymer as a content acceptable as cosmetics. The present inventors obtained. However, cosmetics containing protein nanoparticles and having a desired viscosity have not yet been obtained.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a cosmetic containing casein nanoparticles that are protein nanoparticles and having a desired viscosity.

Means for solving the above problems are as follows.
[1] Viscosity value I (when measuring at least a casein nanoparticle and a liquid containing 0.2% by mass in water using a B-type viscometer (measurement conditions: 25 ° C., 30 s, 30 rpm) mPa · s) and the following test solution A containing 100% by weight so that the content is 0.2% by mass, adjusted to 100 g, and adjusted to pH 7.5 with aqueous sodium hydroxide (1M) The viscosity ratio (I / II) with the viscosity value II (mPa · s) measured using a B-type viscometer (measurement conditions: 25 ° C., 30 s, 30 rpm) is 10 or less. Cosmetics containing an agent.
Test solution A:
A solution prepared by dissolving 1.47 g of sodium citrate, 1 g of sodium caseinate and 5 g of 1,3-butylene glycol in water to make the total amount 90 g, and then adjusting the pH to 7 with an aqueous sodium hydroxide solution (1M).
[2] The cosmetic according to [1], wherein the thickener is a polysaccharide or a derivative thereof.
[3] The cosmetic according to [1] or [2], wherein the casein nanoparticles have a volume average particle diameter of 10 nm to 100 nm.
[4] The cosmetic according to any one of [1] to [3], wherein the thickening agent is at least one selected from xanthan gum, locust bean gum, alkaline-genes-producing polysaccharide, and derivatives thereof. Fee.
[5] The cosmetic according to any one of [1] to [4], wherein the content of the thickener is 2% by mass or less based on the total mass of the cosmetic.
[6] Any one of [1] to [5], wherein the casein nanoparticles contain an active ingredient
Cosmetics according to item.

According to the present invention, a cosmetic containing casein nanoparticles and having a desired viscosity can be provided.

It is a graph which shows the addition amount dependence of the thickening with respect to the test liquid A about a xanthan gum, locust bean gum, an Arcacylan, and a hydroxypropyl xanthan gum. It is a graph which shows the addition amount dependence of the thickening with respect to water and the test liquid A about a carboxy vinyl polymer.

Hereinafter, the cosmetic of the present invention will be described in detail.
In this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used if the intended purpose of this process is achieved. included.
In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
Further, in the present invention, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, the plurality present in the composition unless otherwise specified. Means the total amount of substances.

The cosmetic of the present invention is a case where at least a casein nanoparticle and a liquid containing 0.2% by mass in water are measured using a B-type viscometer (measurement conditions: 25 ° C., 30 s, 30 rpm). Viscosity value I (mPa · s) and the following test solution A were added so that the content with respect to 100 g was 0.2% by mass and adjusted to 100 g, and the pH was adjusted to 7.5 with an aqueous sodium hydroxide solution (1M). The viscosity ratio (I / II) with the viscosity value II (mPa · s) measured using a B-type viscometer (measurement conditions: 25 ° C., 30 s, 30 rpm) is 10 or less. It is a cosmetic containing a thickener.

Test solution A:
A solution prepared by dissolving 1.47 g of sodium citrate, 1 g of sodium caseinate and 5 g of 1,3-butylene glycol in water to make the total amount 90 g, and then adjusting the pH to 7 with an aqueous sodium hydroxide solution (1M).

More specifically, the test liquid A is a dispersion containing casein nanoparticles as a dispersoid.

The cosmetic of the present invention contains casein nano particles and a thickener having a viscosity ratio (I / II) of 10 or less (hereinafter referred to as “specific thickener” as appropriate). Contains particles and has the desired viscosity.

According to the knowledge of the present inventors, it has been difficult to dissolve or disperse synthetic thickeners such as carboxyvinyl polymer, which are conventionally used in cosmetics, in a prescription system containing protein nanoparticles. Therefore, the desired viscosity cannot be obtained in cosmetics containing protein nanoparticles. In addition, the use of the conventional general-purpose thickener in cosmetics that require transparency has the problem that turbidity occurs and transparency is impaired.
On the other hand, in the present invention, by adding a specific thickener, even cosmetics containing casein nanoparticles, which are protein nanoparticles, are sufficiently dissolved or dispersed in the system. The desired viscosity is achieved. Moreover, even if the specific thickener in this invention is the prescription which reduced content of the thickener, desired viscosity is obtained in cosmetics. In addition, when the cosmetic of the present invention is applied to cosmetics that require transparency, it is possible to achieve excellent transparency in which generation of turbidity and the like is suppressed as well as viscosity.

(Casein nanoparticles)
The cosmetic of the present invention contains casein nanoparticles.
Casein used for casein nanoparticles is not particularly limited in its origin, and may be derived from milk or bean. Examples of casein include α-casein, β-casein, γ-casein, κ-casein, and mixtures of two or more thereof. In the cosmetic of the present invention. Casein may be present alone or in the form of an alkali metal salt. Casein is preferably in the form of an alkali metal salt from the viewpoint of dispersibility, and among them, casein sodium salt (casein Na) having high water solubility is more preferable.

The casein nanoparticles preferably contain an active ingredient. These active ingredients may be used alone or in combination of two or more.
The active ingredient is not particularly limited, and can be selected from those known as active ingredients for cosmetics. Examples of active ingredients include, for example, moisturizers, whitening agents, anti-wrinkle agents, UV absorbers, active oxygen scavengers, antioxidants, anti-inflammatory agents, blood circulation promoters, anti-aging agents, collagen synthesis promoters, vitamins Agents, minerals, amino acids and the like.

Casein is known to behave as an acid at a pH higher than the isoelectric point and as a base at a pH lower than the isoelectric point. For this reason, casein nanoparticles are mixed by mixing casein with a basic aqueous medium solution and lowering the pH of the resulting mixture while stirring to a pH higher than 0.5 by an isoelectric point of the casein used. Can be produced. Alternatively, it can be prepared by mixing casein with an acidic aqueous medium solution and raising the pH of the obtained mixed solution with stirring to a pH 0.5 or more lower than the isoelectric point of the casein used.
Examples of the method for producing casein nanoparticles according to the present invention include a method in which casein is mixed in a basic aqueous medium solution, and the resulting mixed solution is injected into an acidic aqueous medium. Casein is mixed in a basic aqueous medium solution. And a method of lowering the pH of the obtained mixed solution while stirring, and a method of mixing casein with an acidic aqueous medium and raising the pH of the obtained mixed solution while stirring. .
Moreover, the casein nanoparticle containing an active ingredient can be produced by adding an active ingredient to the basic aqueous medium or the acidic medium, for example.
In addition, it is preferable to adjust pH of the dispersion liquid containing the obtained casein nanoparticle to neutrality from a viewpoint of suppressing decomposition | disassembly of casein in the obtained casein nanoparticle.

As a method of mixing casein into a basic aqueous medium liquid and injecting the obtained mixed liquid into an acidic aqueous medium, it is convenient and preferable to use a syringe, but the injection speed, solubility, temperature, stirring state If it is the method of satisfying, it will not specifically limit. In general, the injection rate can be 1 mL / min to 100 mL / min.
The temperature of the basic aqueous medium can be appropriately set, but can be normally 0 ° C. to 80 ° C., and preferably 25 ° C. to 70 ° C. The temperature of the acidic aqueous medium can be appropriately set, but can be normally 0 ° C. to 80 ° C., preferably 25 ° C. to 60 ° C.
The stirring speed can be appropriately set, but it can be normally set to 100 rpm to 3000 rpm, and preferably 200 rpm to 2000 rpm.

As a method of mixing casein with a basic aqueous medium liquid and lowering the pH of the obtained mixed liquid while stirring, it is convenient and preferable to add an acidic aqueous medium dropwise, but the solubility, temperature, and stirring state are changed. There is no particular limitation as long as it is a satisfactory method.

As a method of mixing casein with an acidic aqueous medium and raising the pH of the obtained mixed liquid with stirring, it is convenient and preferable to add a basic aqueous medium dropwise, but the solubility, temperature, and stirring state are adjusted. There is no particular limitation as long as it is a satisfactory method.

The temperature of the basic or acidic aqueous medium can be appropriately set. The temperature of the basic or acidic aqueous medium can typically be 0 ° C. to 80 ° C., preferably 25 ° C. to 70 ° C. The stirring speed can be set as appropriate, but it can be normally set to 100 rpm to 3000 rpm, preferably 200 rpm to 2000 rpm.

Examples of aqueous media used to make casein nanoparticles include organic acid or organic base aqueous solutions, inorganic acid or inorganic base aqueous solutions, and buffers. Specifically, citric acid, ascorbic acid, gluconic acid, carboxylic acid, tartaric acid, succinic acid, acetic acid, phthalic acid, trifluoroacetic acid, morpholinoethanesulfonic acid, 2- [4- (2-hydroxyethyl) -1- Piperazinyl] organic acids such as ethanesulfonic acid; organic bases such as tris (hydroxymethyl) aminomethane, ammonia; inorganic acids such as hydrochloric acid, perchloric acid, carbonic acid; sodium phosphate, potassium phosphate, calcium hydroxide, water Examples include, but are not limited to, an aqueous solution using an inorganic base such as sodium oxide, potassium hydroxide, and magnesium hydroxide.
In the present invention, an aqueous solution of an organic acid or an organic base is preferably used from the viewpoint of stability in the preparation.
The concentration of the aqueous medium described above is preferably about 10 mM to about 1M. More preferably, it is about 20 mM to about 200 mM.

The pH of the basic aqueous medium is preferably 7 or more, and preferably 8-12. More preferably, the pH is 8.5 to 10. If the pH is too high, there is concern about hydrolysis and danger in handling, so the above range is preferable.

The pH of the acidic aqueous medium is preferably 4 or less, preferably 3.5 or less, and it is desirable not to exceed the isoelectric point in order to obtain positively charged casein nanoparticles.

In the present invention, the temperature at which casein is mixed with the aqueous medium is preferably 0 ° C. to 80 ° C., more preferably 10 ° C. to 70 ° C. More preferably, it is 30 ° C to 70 ° C.

The pH of the aqueous medium used for producing the casein nanoparticles is preferably a pH that is separated by 0.5 or more from the isoelectric point of casein or a salt thereof. Outside the above range, the particle size tends to increase.

For example, since the isoelectric point of casein is generally about pH 4.6, the casein nanoparticles are preferably mixed with an aqueous medium having a pH lower than pH 4.1 or an aqueous medium having a pH higher than pH 5.1.

Casein may be cross-linked. The crosslinking treatment can be performed during and / or after the formation of casein nanoparticles. The crosslinking treatment may be any of chemical crosslinking, physical crosslinking, and biological crosslinking.
A crosslinking agent may be used for the crosslinking treatment. Examples of the crosslinking agent include enzymes such as transglutaminase and compounds such as glutaraldehyde. The amount of the crosslinking agent used for the crosslinking treatment can be appropriately set. The addition amount of the cross-linking agent is not limited as long as the nanoparticles are constituted, but it is preferable to add in an amount of 0.1 to 100% by mass with respect to the mass of casein.

The volume average particle size of the casein nanoparticles used in the present invention is usually 1 nm to 1000 nm, preferably 10 nm to 1000 nm, more preferably 10 nm to 200 nm, still more preferably 10 nm to 100 nm, and particularly preferably. Is 20 nm to 50 nm. By setting it as such a volume average particle diameter, the outstanding skin penetration effect can be exhibited.

The average particle size of the casein nanoparticles can be measured with various commercially available particle size distribution analyzers, etc., but from the particle size range and ease of measurement, the dynamic light scattering method is applied in the present invention. To do. Commercially available measuring devices using dynamic light scattering include Nanotrac UPA (Nikkiso Co., Ltd.), dynamic light scattering type particle size distribution measuring device LB-550 (Horiba, Ltd.), and a concentrated particle size analyzer. Examples thereof include FPAR-1000 (Otsuka Electronics Co., Ltd.), Nano-ZS (Malvern Co., Ltd.), and the like.

The particle size of the casein nanoparticles in the present invention is a value measured using “Nano-ZS” manufactured by Malvern Co., Ltd., and specifically, the value measured as follows is adopted. That is, the particle diameter is measured by using a quartz cell after diluting with pure water so that the concentration of casein contained in the sample is 0.1% by mass. The particle diameter can be determined as a volume average particle diameter when 1.333 (pure water) is set as the refractive index of the dispersion medium and the viscosity of pure water is set as the viscosity of the dispersion medium.

(Specific thickener)
The cosmetic of the present invention has a viscosity value I (mPa · s) when a liquid containing 0.2% by mass in water is measured using a B-type viscometer (measurement conditions: 25 ° C., 30 s, 30 rpm). Then, the following test solution A was added so that the content with respect to 100 g was 0.2% by mass, adjusted to 100 g, and adjusted to pH 7.5 with an aqueous sodium hydroxide solution (1M). Thickener (specific increase) whose viscosity ratio (I / II) is 10 or less when measured with a viscometer (measurement conditions: 25 ° C., 30 s, 30 rpm) (Viscous).

~ Test solution A ~
Test solution A was prepared by dissolving 1.47 g of sodium citrate, 1 g of sodium caseinate, and 5 g of 1,3-butylene glycol in water to make a total amount of 90 g, and then adjusting the pH to 7 with an aqueous sodium hydroxide solution (1M). It is the adjusted liquid.

As the water used for measuring the viscosity value I and the viscosity value II, MilliQ water is preferably used.

Viscosity value I was prepared by preparing a liquid containing 0.2% by mass of a thickener in water, and measuring the viscosity of the liquid using a B-type viscometer (25 ° C., 30 s, 30 rpm). It is the measured value obtained by measuring. The viscosity value II was adjusted to 100 g by adding a thickener to the test solution A so that the content with respect to 100 g was 0.2% by mass, and the pH was adjusted to 7.5 with an aqueous sodium hydroxide solution (1M). It is the measured value obtained by preparing the liquid adjusted to 1 and measuring the viscosity of this liquid on a measurement condition (25 degreeC, 30 s, 30 rpm) using a B-type viscometer.

As the B-type viscometer in the present invention, a viscometer (product name: TVB-10M, manufactured by Toki Sangyo Co., Ltd.) is used.

The viscosity ratio (I / II) in the specific thickener is a value obtained by dividing the viscosity value I obtained above from the viscosity value II. As the specific thickener in the present invention, the viscosity ratio (I / II) Is 10 or less. The viscosity ratio (I / II) of the specific thickener is preferably 5 or less from the viewpoint of stability of cosmetics and prevention of deterioration of the feeling of use.

Specified thickeners can be used alone or in combination of two or more.

The specific thickener is not particularly limited as long as it satisfies the viscosity ratio (I / II) in the present invention. However, since it can exhibit more excellent thickening, it may be a sugar or a nonionic group. It is preferably a polymer, polysaccharide or derivative thereof modified with

The polysaccharide or derivative thereof applicable as the specific thickener may be derived from natural products or obtained by chemical synthesis.

The specific thickener that is a polysaccharide derived from a natural product or a derivative thereof is roughly classified into a polysaccharide derived from an animal system, a plant system, and a microbial system, or a derivative thereof, and any of them may be used.

In addition, the specific thickener is obtained by binding a part of the sugar in the polysaccharide to a polymer having an alkyl group, a polyethylene oxide group, a polypropylene oxide group, glucose, lactose or sucrose as a single unit or a sugar as a constituent unit. It may be.

The specific thickener may be a compound in which a sugar or a nonionic group is bonded to the main chain of a polymer compound such as an acrylic polymer or a carboxyvinyl polymer. Examples of such compounds include, for example, polyethylene oxide groups, polypropylene oxide groups, glucose, lactose, sucrose alone or polymers having these sugars as structural units, and polymer compounds such as acrylic polymers and carboxyvinyl polymers. The thing connected to the chain | strand is mentioned.

Specific examples of the thickening agent that can be applied as the specific thickening agent include, for example, xanthan gum, arabic gum, alkaline-genes-producing polysaccharide (also referred to as Alcacilan), tragacanth gum, caraya gum, tamarind gum, guar gum, hydroxypropyl guar gum, Locust bean gum, quince seed, gellan gum, native gellan gum, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, alginic acid, carrageenan, hyaluronic acid, chondroitin sulfate, dermatan sulfate, collagen, chitin derivatives, pectin, gelatin, and these Salts or derivatives.

In the present invention, it is preferable that the thickener is a cosmetic which is a polysaccharide or a derivative thereof.

The specific thickener is preferably at least one selected from xanthan gum, locust bean gum, alkali-genes-producing polysaccharide, and derivatives thereof from the viewpoint of preventing deterioration of the feeling of use.

As content of the specific thickener in the cosmetics of this invention, it is preferable that it is 2 mass% or less with respect to the total mass of cosmetics from a viewpoint of coexistence of a viscosity and a feeling of use, More preferably, it is 0.8. 01 to 2% by mass, and more preferably 0.05 to 1.5% by mass.

(Other ingredients)
The cosmetic of the present invention has various functional oil components (for example, fats and oils, fatty acids, higher alcohols, oil-soluble pigments, minerals, etc. within the range not impairing the effects of the present invention, in addition to the above-described components. Oil, polysilicon compound, etc.), surfactant (eg, glycerin fatty acid ester, behentrimonium chloride, fatty acid amidopropyl betaine), polyhydric alcohol (eg, glycerin, 1,3-butylene glycol, pentylene glycol, ethylhexyl) Coglycerin, etc.), water-soluble polymer compounds (for example, methacrylic polymers, etc. Note that specific thickeners are not included in the water-soluble polymer compound), alcohols, inorganic substances (for example, titanium oxide, mica, silica, etc. ), And other ingredients such as fragrances.

In addition, various known ingredients used as cosmetic ingredients or pharmaceutical ingredients can be blended in the cosmetic of the present invention. Cosmetic ingredients include, for example, emollients, treatment agents, lubricants, moisturizers, hair restorers, hair nourishing agents, hair growth agents, anti-whitening agents, anti-aging agents, antioxidants, collagen synthesis promoters, vitamins, and fragrances. , Pigments, antiperspirants, cooling agents, cooling agents, warming agents, and the like. Examples of the pharmaceutical ingredient include a hair restorer, a hair nourishing agent, a hair growth agent, an antibiotic, a bactericidal agent, an anti-inflammatory agent, and an antiallergic agent.
These other components may be used alone or in combination of two or more.

(water)
The cosmetic of the present invention is preferably an aqueous cosmetic containing water.
The amount of water in the cosmetic is the remaining amount of components other than water, and is 60% by mass to 90% by mass.

The pH of the cosmetic composition of the present invention is preferably pH 5.0 to 8.5, more preferably pH 5.5 to pH 8.0, and more preferably pH 5.8 to pH 7 from the viewpoint of stability, particularly prevention of coloring. .5 is particularly preferred.

The cosmetic of the present invention can be prepared by mixing the above-described components by a conventional method, and the production method is not particularly limited.

Examples of the dosage form of the cosmetic of the present invention include lotions, essences, gels, and the like. The cosmetic of the present invention can be applied in the form of an ointment, cream or the like as it is or with a suspending agent or stabilizer added.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[Test Example 1]
In Test Example 1, the viscosity, viscosity ratio, solubility or dispersibility, and casein when added to water or a casein nanoparticle-containing dispersion for each of the specific thickener and the comparative thickener The dependence of thickening on the amount of thickener added to the nanoparticle-containing dispersion was confirmed. Details are as follows.

(1) Preparation of Casein Nanoparticle-Containing Dispersion (Test Solution A) After dissolving 1.47 g of sodium citrate, 1 g of sodium caseinate, and 5 g of 1,3-butylene glycol in water at 60 ° C. to make the total amount 90 g By adjusting the pH to 7 with an aqueous sodium hydroxide solution (1M), a casein nanoparticle-containing dispersion (Test Solution A) was obtained.

The volume average particle diameter of the casein nanoparticles contained in the test solution A was measured using a light scattering photometer, “Nano-ZS” manufactured by Malvern Co., and found to be 21 nm.

(2) Addition of thickener (2-1) Preparation of evaluation sample with thickener added to water Evaluation sample (viscosity value I evaluation sample) with thickener added to water is as follows: Prepared.
Specifics shown in Table 1 below so that the content of the thickener in the sample for evaluation of viscosity value I is 0.05 mass%, 0.1 mass%, 0.2 mass%, or 0.4 mass% A thickener or a comparative thickener was mixed with water to make a total amount of 100 g, and the pH was adjusted to 7.5 with an aqueous sodium hydroxide solution (1M) to obtain samples for evaluation.

(2-2) Preparation of Evaluation Sample with Thickener Added to Test Solution A An evaluation sample (viscosity value II evaluation sample) with a thickener added to Test Solution A was prepared as follows.
Table 1 below shows that the content of the thickener in the sample for evaluation of viscosity value II is 0.05% by weight, 0.1% by weight, 0.2% by weight, or 0.4% by weight as the final concentration. The specific thickener or comparative thickener shown in FIG. 5 is mixed with 90 g of the test liquid A obtained above, and adjusted with water so that the total amount becomes 100 g, and an aqueous sodium hydroxide solution (1M ) To adjust the pH to 7.5 to obtain samples for evaluation.

 

Details of each thickener shown in Table 1 are as follows.

<Specific thickener>
~ Polysaccharides ~
・ Xanthan gum (manufactured by Sankisha, product name: Celtrol CG-T)
・ Locust bean gum (manufactured by Sanki Co., Ltd., product name: GENUGAMU RL-200J)
・ Arcasilan (Hakuto Chemical Co., polysaccharide)
-Polysaccharide derivatives-
・ Hydroxypropylxanthan (Dainippon Pharmaceutical Co., Ltd., product name: Labor gum EX, polysaccharide derivative)

<Thickener for comparison>
-Synthetic polymer-
・ (Methyl vinyl ether / maleic acid) cross polymer (manufactured by Sankisha, product name: Stabilise QM)
・ Acryloyldimethyltaurine / VP (manufactured by Clariant Japan, product name: Aristoflex AVC)
・ Acrylic acid methacrylate copolymer (manufactured by Nikko Chemicals, product name: Carbopol Ultrez 20)
・ Carboxyvinyl polymer (manufactured by Nikko Chemicals, product name: Carbopol 981)

(3) Viscosity value I, viscosity value II, viscosity ratio (I / II)
Among each sample for evaluation containing 0.2% by mass of a thickener in water, xanthan gum, alkathylan or hydroxypropyl xanthan gum as a specific thickener, and carboxyvinyl polymer as a comparative thickener are contained. About each sample, the viscosity value I was measured on measurement conditions (25 degreeC, 30 s, 30 rpm) using the viscometer (product name: TVB-10M, Toki Sangyo Co., Ltd. product). The results are shown in Table 2 below.

Among each sample for evaluation containing 0.2% by mass of a thickener in Test Solution A, xanthan gum, alkathylan, hydroxypropylxanthan gum as a specific thickener, and carboxyvinyl polymer as a comparative thickener are contained. About each sample, viscosity value II was measured on measurement conditions (25 degreeC, 30 s, 30 rpm) using the viscometer (product name: TVB-10M, Toki Sangyo Co., Ltd. product). The results are shown in Table 2 below.

Furthermore, the viscosity ratio (I / II) of each thickener was calculated based on the measurement results of the obtained viscosity value I and viscosity value II. The results are shown in Table 2 below.

 

Of the thickeners for comparison shown in Table 1, (methyl vinyl ether / maleic acid) crosspolymer, acryloyldimethyltaurine / VP, and alkyl methacrylate copolymer were dispersed in test solution A. Therefore, the viscosity ratio (I / II) could not be calculated.

(4) Solubility or dispersibility of thickener (4-1) Solubility in water By visually observing each evaluation sample with a thickener added to water, a specific thickener or a comparative thickener The solubility of the adhesive was confirmed and evaluated according to the following evaluation criteria. Table 3 shows the results.
OK: soluble (transparent).
NG: Insoluble (the thickener is separated without dissolving in the sample).

(4-2) Dispersibility in test solution A By visually observing each evaluation sample in which a thickener was added to test solution A, the specific thickener or comparative thickener was added to test solution A. Dispersibility was evaluated according to the following evaluation criteria. The results are shown in Table 3 below.
-Evaluation criteria-
A: Transparent.
B: Cloudiness is generated.
C: It is opaque or the thickener is separated without being dispersed in the sample.

(5) Viscosity to test solution A (depending on the amount of thickener added)
Using each evaluation sample having a thickener addition amount of 0.05% by mass, 0.1% by mass, 0.2% by mass, or 0.4% by mass with respect to the test solution A, the viscosity of each evaluation sample was increased. Was evaluated according to the following evaluation criteria based on the addition amount dependency of the thickener. The results are shown in Table 3 below.
-Evaluation criteria-
A: The addition amount dependence of the thickener is large.
B: The addition amount dependency of the thickener is small.
C: The thickener is insoluble or not dependent.
It should be noted that the thickener addition amount dependency is large because the thickening in the system containing casein nanoparticles is proportional to the thickener addition amount, and the desired viscosity can be easily adjusted by adjusting the thickener addition amount. It shows that it is obtained.

FIG. 1 shows the dependence of the thickener on the test solution A for xanthan gum, locust bean gum, alkathylan, and hydroxypropyl xanthan gum, which are specific thickeners.
FIG. 2 shows the addition of thickeners to water and test solution A for the carboxyvinyl polymer that was not thickened to test solution A although it was thickened to water among the comparative thickeners. The amount dependency is shown.

As is apparent from Tables 2 to 3 and FIG. 1, the specific thickener satisfying the viscosity ratio (I / II) in the present invention is excellent in both solubility in water and dispersibility in test solution A. Moreover, it turns out that it is excellent also in the thickening.
In addition, the combination of the specific thickener and the test liquid A used in Test Example 1 can be used as a cosmetic.

[Test Example 2]
Test solution A was prepared in the same manner as in Test Example 1.
An evaluation sample was prepared in the same manner as in Test Example 1 except that a thickener was added to water or the test solution A so as to have the content shown in Table 4 below. About each obtained sample for evaluation, the viscosity was measured on measurement conditions (25 degreeC, 30 s, 30 rpm) using the viscometer (Product name: TVB-10M, Toki Sangyo Co., Ltd. product). The results are shown in Table 4 below.

The details of each thickener not shown in Table 1 shown in Table 4 are as follows.

<Specific thickener>
・ Hydroxyethyl cellulose A (Daicel Chemical Industries, product name: SE-900)
・ Hydroxyethylcellulose B (manufactured by Daicel Chemical Industries, product name: SE-800)
・ Carboxymethylcellulose (manufactured by Shin-Etsu Silicone, product name: Metroles SM-4000)
・ Xanthan gum (Dainippon Pharmaceutical Co., Ltd., product name: Keldent)

<Thickener for comparison>
・ Carboxyvinyl polymer (manufactured by Nikko Chemicals, product name: Carbopol 981)

As shown in Table 4, when the specific thickener satisfying the viscosity ratio (I / II) in the present invention is added to either water or the test liquid A, the same viscosity can be obtained with the same addition amount. I understand that.
On the other hand, the carboxyvinyl polymer, which is a comparative thickener, showed a large thickening when added to water, but it does not show any thickening with respect to the test solution A.
In addition, the combination of the specific thickener and test liquid A used in Test Example 2 can be used as a cosmetic.

[Examples 1 to 6]
A cosmetic having the composition shown in Table 5 below was prepared by a conventional method. The composition of each example is 100% by mass in total. The cosmetics of Examples 1 to 3 and 5 can be applied as cosmetic liquids, and the cosmetics of Examples 4 and 6 can be applied as skin lotions.
The casein sodium in the composition is present in cosmetics as casein nanoparticles of 10 nm to 50 nm. Casein nanoparticles contain astaxanthin and tocopherol acetate as active ingredients. In addition, the sucrose fatty acid ester of Table 5 is sucrose stearate ester.

 

[Example 7]
A whitening emulsion having the following composition was prepared by a conventional method (total amount: 100% by mass).

[Composition] [Content (% by mass)]
・ Squalane 8.0
Jojoba oil 7.0
-Glyceryl paraaminobenzoate 1.0
・ Ascorbyl magnesium phosphate 0.5
・ Arbutin 0.3
・ Cetyl alcohol 1.5
・ Glycerin monostearate 2.0
・ Polyoxyethylene cetyl ether 3.0
・ Polyoxyethylene sorbitan monooleate 2.0
・ 1,3-Butylene glycol 1.0
・ Glycerin 2.0
1,2-pentanediol 3.0
・ Collagen 1.0
・ Casein 0.3
・ Xanthan gum 0.05
Hydroxyethyl cellulose A 0.05
・ Sodium citrate 1.0
・ Fragrance appropriate amount ・ Purified water remaining

[Example 8]
A cream having the following composition was prepared by a conventional method (total amount: 100% by mass).
[Composition] [Content (% by mass)]
・ Cetostearyl alcohol 3.0
・ Glycerin fatty acid ester 2.0
-Polyoxyethylene monooleate (20) sorbitan 1.0
・ Sorbitan monostearate 1.0
N-stearoyl-N-methyltaurine sodium 0.5
・ Vaseline 5.0
・ Dimethylpolysiloxane (100 mPa · s) 3.0
・ Glyceryl tri-2-ethylhexanoate 20.0
・ Astaxanthin 0.05
・ Lactic acid 1.0
・ Dipropylene glycol 10.0
・ Sodium casein 1.0
・ Hydroxypropylxanthane 0.05
・ Sodium citrate 0.5
・ Ascorbyl magnesium phosphate 0.1
・ Titanium oxide 0.1
・ Perfume appropriate amount ・ Edetic acid disodium 0.03
・ Ethyl paraoxybenzoate 0.05
・ Purified water remaining

[Example 9]
A jelly-like serum having the following composition was prepared (100% by mass in total).
[Composition] [Content (% by mass)]
-Butylene glycol 5.0
・ Glycerin 7.0
(PEG-240 / decyltetradeceth-20 / HDI) copolymer 1.0
・ Astaxanthin (Hematococcus alga extract) 0.05
・ Ceramide 1.0
・ Collagen 0.5
・ Water-soluble collagen 0.5
-Ascorbyl palmitate trisodium 0.01
・ Damask rose flower oil appropriate amount ・ PEG60 hydrogenated castor oil appropriate amount ・ Vitamin E 0.01
Tri (caprylic acid / capric acid) glyceryl 0.1
・ Sodium casein 0.1
・ Na phosphate 0.8
・ Xanthan gum 0.01
・ Arcasiran 0.01
・ Sodium hydroxide appropriate amount ・ Phenoxyethanol 0.1
・ Purified water remaining

The entire disclosure of Japanese Patent Application No. 2011-217315 is incorporated herein by reference. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference. The foregoing descriptions of exemplary embodiments of the present invention have been presented for purposes of illustration and description, and are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in this art. The embodiments described above best illustrate the principles and practical applications of the invention, so that others skilled in the art can understand the invention along with various embodiments and various modifications suitable for the particular application envisaged. Selected and described. It is intended that the scope of the invention be defined by the following claims and their equivalents.

Claims (11)

1. at least,
   Casein nanoparticles, and
   Viscosity value I (mPa · s) when a liquid containing 0.2% by mass in water was measured using a B-type viscometer (measurement conditions: 25 ° C., 30 s, 30 rpm),
   A B-type viscometer was prepared by adding the following test solution A so that the content with respect to 100 g was 0.2% by mass and adjusting the water to 100 g and adjusting the pH to 7.5 with an aqueous sodium hydroxide solution (1M). (Viscosity ratio (I / II) with viscosity value II (mPa · s) when measured using (measurement conditions: 25 ° C., 30 s, 30 rpm) is 10 or less,
   Containing cosmetics.
   Test solution A:
   A solution prepared by dissolving 1.47 g of sodium citrate, 1 g of sodium caseinate and 5 g of 1,3-butylene glycol in water to make the total amount 90 g, and then adjusting the pH to 7 with an aqueous sodium hydroxide solution (1M).
2. The cosmetic according to claim 1, wherein the thickener is a polysaccharide or a derivative thereof.
3. The cosmetic according to claim 1 or 2, wherein the casein nanoparticles have a volume average particle size of 10 nm to 100 nm.
4. The thickener is xanthan gum, arabic gum, alkaline genus producing polysaccharide, tragacanth gum, caraya gum, tamarind gum, guar gum, hydroxypropyl guar gum, locust bean gum, quince seed, gellan gum, native gellan gum, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxy Claims 1 to Claims which are at least one selected from the group consisting of methylcellulose, alginic acid, carrageenan, hyaluronic acid, chondroitin sulfate, dermatan sulfate, collagen, chitin derivatives, pectin, gelatin, and salts or derivatives thereof. 4. The cosmetic according to any one of 3 above.
5. The cosmetic according to any one of claims 1 to 4, wherein the thickener is at least one selected from xanthan gum, locust bean gum, alkaline-genes-producing polysaccharide, and derivatives thereof.
6. The cosmetic according to any one of claims 1 to 5, wherein a content of the thickener is 2% by mass or less with respect to a total mass of the cosmetic.
7. The cosmetic according to any one of claims 1 to 6, wherein the casein nanoparticles contain an active ingredient.
8. The active ingredient is a moisturizer, whitening agent, anti-wrinkle agent, ultraviolet absorber, active oxygen scavenger, antioxidant, anti-inflammatory agent, blood circulation promoter, anti-aging agent, collagen synthesis promoter, vitamin agent, mineral, Or the cosmetics of Claim 7 which are any one or more selected from the group which consists of amino acids.
9. The cosmetic according to any one of claims 1 to 8, wherein the casein nanoparticles include an alkali metal salt of casein.
10. The cosmetic according to any one of claims 1 to 8, wherein the casein nanoparticles are made of an alkali metal salt of casein.
11. The cosmetic according to any one of claims 1 to 10, wherein the thickener has a viscosity ratio (I / II) of 5 or less.

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