JP2004339243A - Cosmetic compounded with flaky metal oxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality cosmetic compounded with a gold particulate dispersoid-containing flaky metal oxide, having bright color development, various tones, uniformly coloring ability, excellent stability, good extendability and excellent feeling. <P>SOLUTION: The cosmetic comprises, as a main ingredient, at least one metal oxide selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide and zirconium oxide, contains 0.01-30 mass% dispersed gold particulate having 1-300 nm particle diameter and is compounded with a flaky metal oxide colorant having 0.1-2 μm average thickness and 5-150 aspect ratio. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention incorporates a flaky metal oxide, particularly a flaky metal oxide that is suitable for a colorant that develops various color tones, having excellent coloring properties, stability, excellent safety, and excellent extensibility and tactile sensation. Related to cosmetics.

Until now, attempts have been made to use fine gold particles as a coloring agent for cosmetics. Examples thereof include cosmetics containing an extender such as mica or talc having gold fine particles fixed on the surface (Japanese Patent Application Laid-Open No. 1-215865), and cosmetics containing a protein or silk fibroin powder dyed with colloidal gold ( JP-A-3-90012, JP-A-3-77806), and cosmetics (JP-B-5-87045) in which a metal oxide powder having gold fine particles fixed thereto is blended.
JP-A 1-215865 JP-A-3-90012 JP-A-3-77806 Japanese Patent Publication No. 5-87045

  Powders having these gold fine particles fixed thereon exhibit vivid colors of reddish purple to purple, and are used as cosmetics. However, the color may be dull by touching the oil component of the cosmetic base material or the oil and fat on the skin, and it may cause discoloration or discoloration due to the dropping or agglomeration of the fine gold particles on the carrier surface, or strong pressure when crushing and crushing. In some cases, the gold fine particles were deformed and discolored to cause color unevenness.

  Also, depending on the manufacturing method, it does not become a vivid color and tends to develop a color that is not desirable for cosmetics, such as brown or gray, and vivid color requires strict management and know-how of the manufacturing process. There was also a problem that it took time and effort. Furthermore, in the obtained gold fine particle fixed powder, it is difficult to uniformly disperse it in a medium, and even once dispersed, agglomeration with time may form a so-called "dama" or unevenness. there were. In particular, when a large amount is blended as a cosmetic, the above problem becomes remarkable, and further, there is a problem that slippage is deteriorated and extensibility (expansion) on skin is deteriorated.

  In view of the above prior art, the present invention is a high-quality blended flake containing fine gold particles, which has vivid color development, stability, uniform coloring, good extensibility (expansion), and excellent tactile sensation. It provides a perfect cosmetic.

  In order to solve this problem, the present inventors have added a gold colloid or a gold compound to a solution containing an organometallic compound capable of hydrolysis and polycondensation and water, and added the gold colloid or gold compound to a substrate, preferably a surface. Applying it on a smooth substrate, drying it, and peeling it from the substrate, and then heat-treating it, it is possible to easily and efficiently produce a flake-like metal oxide containing fine gold particles with excellent coloring and stability. We have found the present invention.

  That is, the present invention comprises, as a main component, at least one metal oxide selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide and zirconium oxide, and gold fine particles having a particle diameter of 1 to 300 nm of 0.01 to 30. It is a cosmetic containing a flake-shaped metal oxide colorant dispersed and contained by mass% and having an average thickness of 0.1 to 2 μm and an aspect ratio of 5 to 150.

  The particle size of the fine gold particles in the flaky metal oxide, which is a coloring agent to be incorporated in the cosmetic of the present invention (the length in the case of a rod shape), is 1 nm or more and 300 nm or less. If the particle size is smaller than 1 nm, the coloring effect of the gold fine particles is reduced, and no vivid coloring is observed. On the other hand, when the particle size is larger than 300 nm, the effect of light scattering is increased and the color becomes cloudy. The shape of the gold fine particles is not particularly limited. Any shape such as a spherical shape, an oval shape, a rod shape, and a plate shape may be used. Further, as described later, the gold fine particles in the present invention are derived from a gold colloid solution or gold fine particles precipitated in a metal oxide by heating.

  The gold content in the flaky metal oxide in the present invention is 0.01% by mass or more and 30% by mass or less. A more preferred content is 0.2 to 25% by mass. When the content of gold is less than 0.01% by mass, the coloring effect is not sufficient. Even if the content is more than 30% by mass, the coloring concentration is not so high and the cost is high. Among the cosmetics containing this flaky metal oxide, the gold content in the flaky metal oxide for powder foundations, skin creams, hand creams, and makeup bases that require relatively light coloring is In many cases, the content is relatively small, for example, 0.2 to 3% by mass is preferable. For nail enamels, eye shadows, lipsticks, and the like that require relatively deep coloring, the gold content in the flake-shaped metal oxide is Relatively large, for example, 3 to 25% by mass is often preferred. However, depending on the composition, there may be a case where the ratio deviates from the above-mentioned preferable range in consideration of other colorants.

The matrix of the flaky metal oxide in the present invention is made of at least one selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide, and zirconium oxide.
The flake-like metal oxide matrix in the present invention may be any of amorphous, crystalline, and a mixture of amorphous and crystalline. Whether it becomes amorphous or crystalline depends mainly on the composition of the flake-like metal oxide matrix and the heat treatment conditions, and the metal oxide consisting of titanium oxide, aluminum oxide, or zirconium oxide alone becomes crystalline. In many cases, a flaky metal oxide composed of silicon oxide alone or a mixture thereof with titanium oxide, aluminum oxide, or zirconium oxide is often amorphous or a mixture of amorphous and crystalline. . Preferably, an amorphous state, particularly a glassy state, is desired, since the touch of the flake-like metal oxide powder is particularly good.

  The method for producing the flake-like metal oxide in the present invention is not particularly limited, but as a first production method, a gold colloid is added to a solution containing an organic metal compound capable of hydrolysis and polycondensation and water, and this is added. A method in which the composition is applied to a substrate, preferably a substrate having a smooth surface, dried and separated from the substrate, and then heat-treated to produce a method. In the second production method, a solution containing an organometallic compound capable of hydrolysis and polycondensation and water is added to a solution containing gold, such as chloroauric acid, sodium chloroaurate, gold cyanide, gold potassium cyanide, or diethylamine trichloroaurate. Add the compound, apply it on the substrate, preferably on a substrate with a smooth surface, dry and peel off from the substrate, heat treatment, ultraviolet irradiation, etc. to precipitate gold fine particles in the metal oxide matrix It is a way to make it. These methods are preferable because a flake-like metal oxide containing gold fine particle dispersion having particularly excellent characteristics can be obtained.

  The organometallic compound capable of hydrolysis and polycondensation used in the present invention may be basically any compound as long as it undergoes hydrolysis and dehydration condensation, but a metal alkoxide having an alkoxyl group is preferred. Specifically, methoxide such as Si, Ti, Al, and Zr, ethoxide, propoxide, butoxide, and the like are used alone or as a mixture.

  The organic solvent of the solution containing the organometallic compound may be basically any solvent as long as the organometallic compound is substantially dissolved, but alcohols such as methanol, ethanol, propanol and butanol are most preferred. In some cases, no solvent is required.

  Water is required for the hydrolysis of the organometallic compound. This may be acidic, neutral or basic, but it is preferable to use water acidified with hydrochloric acid, nitric acid, sulfuric acid or the like in order to promote hydrolysis. The amount of the acid added is not particularly limited, but is preferably 0.001 to 2 in a molar ratio to the organometallic compound. When the amount of the added acid is less than 0.001 in molar ratio, the promotion of the hydrolysis of the organometallic compound is not sufficient, and when the amount is more than 2, the effect of promoting the hydrolysis is no longer improved. Is excessive, which is not preferable.

  The added water is also necessary for stabilizing the dispersion of the gold colloid in the case of using the first production method. The addition amount of water is preferably 10% by mass or more and 80% by mass or less of the solution. However, the water content here is the sum of the amount of water contained in the colloid and the newly added water. If the amount of water added is less than 10% by mass of the solution, the colloid tends to be unable to exist stably, which is not preferable. On the other hand, if the amount of water added is more than 80% by mass of the solution, the concentration in terms of solid content in the solution becomes too low, and the yield of flakes becomes low.

  In addition, an organic thickener or the like may be added to change the properties of the solution. However, if this addition amount is large, carbonization may occur in the final stage of heating, so the addition amount should be kept to 10% by mass or less.

  Among the above-mentioned production methods, in the first production method in which a gold colloid is added, the colloid can be uniformly dispersed in a solution containing the organometallic compound and water, and a flake-like metal oxide finally obtained is obtained. It is relatively easy to control the shape and size of the gold fine particles therein, and it is possible to easily manufacture fine particles having various characteristics. The gold colloid can be produced by a known method. For example, an aqueous solution of a gold compound such as chloroauric acid, sodium chloroaurate, gold cyanide, gold potassium cyanide, or diethylamine trichloride is prepared by using citric acid, sodium citrate, ascorbic acid, formaldehyde, hydrazine, sodium borohydride, or the like. By using a known reducing agent such as, for example, gold colloid can be obtained. Further, it can also be obtained by irradiating the gold compound aqueous solution with ultraviolet rays instead of using a reducing agent.

  A surfactant or an organic polymer may be added to the gold compound aqueous solution or the gold colloid dispersion before the preparation of the gold colloid for the purpose of improving stability. Any surfactant can be used as long as it is generally used, and is not particularly limited. Examples thereof include cationic surfactants such as stearyltrimethylammonium chloride, didodecyldimethylammonium bromide, and hexadecyltrimethylammonium chloride; Anionic surfactants such as sodium (2-ethylhexyl) sulfosuccinate, sodium cetyl sulfate, sodium N-acyl-L-glutamate, and nonionic surfactants such as polyoxyethylene cetyl ether, polyethylene glycol monolaurate, and sorbitan sesquioleate Surfactants, zwitterionic surfactants such as betaine lauryldimethylaminoacetate, sodium β-laurylaminopropionate, and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine. That. Among them, the above-mentioned cationic surfactant is particularly preferably used because the gold colloid negatively charged in the aqueous solution is more strongly stabilized.

  The addition amount of the surfactant is preferably 0.001 to 10% by mass based on the gold compound aqueous solution or gold colloid. If the amount is less than 0.001% by mass, the stabilizing effect of the gold colloid is too small, and if it is more than 10% by mass, the effect on stabilization is not significantly improved except for the purpose of controlling the shape of the gold colloid particles described later. A more preferable addition amount of the surfactant is 0.1 to 5% by mass.

  The organic polymer is not particularly limited, but gelatin, dextrin, soluble starch, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol and the like are used.

  The amount of the organic polymer to be added is preferably 0.01 to 10% by mass relative to the gold compound aqueous solution or gold colloid. If it is less than 0.01% by mass, the stabilizing effect of the gold colloid is too small, and if it is more than 10% by mass, the effect on stabilization is not so much improved. The more preferable addition amount of the organic polymer is 0.2 to 5% by mass.

  A large amount of a surfactant may be added to the aqueous gold compound solution before the production of the gold colloid in order to control the particle shape of the gold colloid. The surfactant takes various aggregate states depending on the concentration, and the particle shape of the gold colloid becomes various shapes such as an egg shape, a rod shape, and a plate shape in addition to the spherical shape due to this effect. The type of surfactant is not particularly limited, and various surfactants described above can be used. In particular, cationic surfactants such as stearyltrimethylammonium chloride, didodecyldimethylammonium bromide, and hexadecyltrimethylammonium chloride can be used. Since the agent has a strong interaction with the negatively charged gold colloid particles in the aqueous solution, it is easier to control the shape of the gold colloid particles, which is particularly preferable. For example, rod-shaped fine gold particles are generated in a solution of 25% by mass of hexadecyltrimethylammonium chloride, but spherical gold fine particles are obtained when this surfactant is not added.

  The addition amount of the surfactant for controlling the shape of the colloidal gold particles varies depending on the type of the surfactant, but is preferably about 10 to 50% by mass based on the solution before the preparation of the colloidal gold. When the amount is less than 10% by mass, a remarkable effect of controlling the shape of the colloidal gold particles is not recognized, and when the amount is more than 50% by mass, an effect corresponding to the added amount cannot be obtained from the viewpoint of shape control.

  Such a solution containing a large amount of a surfactant and a gold compound is treated by the above-mentioned known method, and the gold compound is reduced to obtain gold colloids having various particle shapes.

  The gold colloid that can be produced by the above-mentioned various methods has a gold concentration of 0.001 to 5% by mass, a particle diameter of 1 to 300 nm, and various particle shapes such as an oval shape, a rod shape, and a plate shape in addition to a spherical shape. Have. This gold colloid is added to a solution containing the above-mentioned organometallic compound and water, and after obtaining a uniform solution, this is coated on a substrate, preferably a substrate having a smooth surface, and dried to form a substrate. And then heat-treated to produce a flaky metal oxide containing 0.01 to 30% by mass of fine gold particles of 1 to 300 nm in size.

  Among the above-mentioned production methods, in the second production method in which a gold compound is added to a solution containing an organic metal compound capable of hydrolysis and condensation polymerization and water, gold particles are precipitated in a metal oxide matrix by heat treatment or ultraviolet irradiation. Let it. This method is advantageous in terms of the process because it does not require time and effort to produce a gold colloid, and can easily produce a flake-shaped metal oxide having a high content of fine gold particles.

  In the first and second production methods, the affinity and stability of the fine gold particles in the metal oxide precursor (gel) matrix are increased, and as a result, the content of the fine gold particles in the metal oxide matrix is improved. Examples of the method include 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, An aminosilane such as bis (3-aminopropyl) -1,1,3,3 tetramethyldisiloxane or 3-aminopropyltris (trimethylsiloxy) silane is added to a solution containing the above-mentioned organometallic compound and colloidal gold (or gold compound). You may add and mix.

  The amount of the aminosilane to be added is not particularly limited, but is preferably 0.01 to 1.5 in a molar ratio with respect to the organometallic compound. When the amount of the added acid is less than 0.01 in a molar ratio, the effect of fixing the fine gold particles in the metal oxide matrix is not sufficient, and when the amount is more than 1.5, the solution tends to gel. And flake formation becomes difficult, which is not preferable.

The preferred compounding ratio of the coating solution containing the above-mentioned gold fine particles (or gold compound), an organic metal compound capable of hydrolysis and polycondensation, water and an organic solvent is as follows based on the gold fine particles (or gold compound). It is.
Gold fine particles (or gold compound) 1 part by weight Organometallic compound capable of hydrolysis and condensation polymerization 5 to 40 parts by weight Water 10 to 80 parts by weight Acid 0.00009 to 10 parts by weight Organic solvent 1 to 50 parts by weight

  The coating substrate used in the present invention is made of a material such as metal, glass or plastic and has a smooth surface. A liquid containing the above-mentioned organometallic compound is applied to such a substrate to form a thin film having a thickness of 0.06 to 50 μm. The film shrinks when dried, but the substrate does not shrink, so that the film cracks and becomes flake-like. In order to cause separation between the substrate and the film, it is preferable that the substrate and the film have little interaction such as strong bonding.

  The technique of forming a film on the surface of the substrate may be a known technique, for example, a method of immersing the substrate in a liquid containing the above-mentioned organometallic compound, followed by a method of pulling up or dropping the liquid on the substrate, , A method of spraying the liquid on the substrate, a method using a roll coater, a method using a curtain coater, and the like.

  The flakes applied on the substrate, dried and released from the substrate are then heat treated. There is no particular limitation on the heat treatment method. Regarding the sintering temperature and time, it is preferable to heat at a high temperature for a predetermined time in order to ensure the transition of the matrix from gel to glass or crystal, and to stably exist or precipitate gold fine particles, Usually, heating is performed at 300 to 1200 ° C. for 5 minutes to 5 hours. Depending on the purpose of use, for example, when the mechanical strength of the flake-like powder is not required and the gold fine particles are already dispersed in the flake-like powder, the heat treatment after drying may not be required. .

  Further, among the above-mentioned production methods, in the above-mentioned second production method in which a gold compound is added to a solution containing an organometallic compound capable of hydrolysis and polycondensation and water, the heat treatment or ultraviolet irradiation irradiates the metal oxide matrix with gold. Fine particles are precipitated. There is no particular limitation on the method of ultraviolet irradiation. Irradiation is performed for 1 minute to 100 hours using a generally used mercury lamp or xenon lamp. The irradiation may be performed at any time, such as before or after applying the solution to the substrate, before or after drying, or before or after collecting the flaky gel.

  The thickness of the flake-shaped metal oxide varies depending on the solution or film forming conditions, but is generally between 0.05 μm and 5 μm. When the thickness is more than 5 μm, the difference in drying speed between the free surface after film formation and the vicinity of the substrate becomes too large, and peeling between films in a direction parallel to the substrate occurs. Conversely, if the thickness is less than 0.05 μm, the adhesion between the substrate and the film becomes too large, and the film does not peel off from the substrate. The thickness of the flaky metal oxide coloring agent to be incorporated in the cosmetic of the present invention is 0.1 to 2 μm. Flake powder having a thickness in this range has a good touch. More preferably, it is 0.1 to 1 μm. Flake powders in this range have particularly good tactile sensation and very good elongation.

  The aspect ratio of the flaky metal oxide in the present invention is from 5 to 150. The flake-like powder having an aspect ratio in this range has no unevenness and can obtain a smooth touch and extensibility (spreadability). A more preferred aspect ratio is 10 to 100.

  The particle size of the flake-shaped metal oxide in the present invention is preferably from 2 to 150 μm, and the flake-shaped powder having the particle size in this range has no unevenness and can obtain a smooth touch and extensibility (spreadability). Can be A more preferred particle size is 5 to 80 μm.

  The flaky metal oxide in the present invention has a different color tone depending on the size and shape of the gold fine particles, the type of the metal oxide, and the like, and exhibits various colors such as red, magenta, purple, blue-violet, and blue. For example, when the fine gold particles have a size of 100 nm or more, they tend to have a blue color, depending on the matrix, and when the dielectric constant of the matrix is high, even if the fine gold particles have a size of several tens of nanometers, they may have a purple color. The color becomes blue. If the size of the normal gold colloid (several tens of nm or less) is in a low dielectric constant matrix, the color tends to be reddish. Also, as the aspect ratio of the fine gold particles increases, the color tends to gradually change from red to blue.

  The cosmetic of the present invention containing the flaky metal oxide coloring agent has no change with time such as agglomeration or falling off of the fine gold particles, and there is no direct contact between the fine gold particles and the oils and fats or oil components. It has coloring, stability and uniform coloring. Further, depending on the heat treatment temperature, the hardness of the metal oxide is sufficiently high, so that the gold fine particles are not deformed by external pressure or external force, and there is no color unevenness or discoloration. Furthermore, since the flake-like metal oxides containing dispersed fine gold particles do not agglomerate with each other, and have a smooth surface and a good sliding property, they have good extensibility (spreadability) and are excellent in use feel. It becomes.

  In the cosmetics of the present invention, other than the above-mentioned flake-like metal oxide colorant containing fine gold particles dispersed therein, if necessary, a commonly used pigment or the like may be used in combination. For example, titanium oxide, zinc oxide, zirconium oxide, yellow iron oxide, black iron oxide, red iron oxide, ultramarine, navy blue, chromium oxide, inorganic pigments such as chromium hydroxide, titanium mica, pearlescent pigments such as bismuth oxychloride, tar Pigments, natural pigments, powders such as silica beads, plastic beads such as nylon and acrylic, talc, kaolin, mica, sericite, other mica, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, clay, etc. Illustrated.

  The amount of the flake-shaped metal oxide colorant containing the fine gold particles dispersed therein varies depending on the type of the intended cosmetic, but is used in the range of 1 to 80% by mass based on the solid component such as a pigment. The range of 2 to 50% by mass is preferred. If the content is less than this, there is a problem that the coloring effect is not remarkably exhibited, the coloring is not good, and the like. Conversely, even if more flake-like metal oxides are added than the upper limit, the coloring effect does not increase, and Pigment component decreases, making it difficult to adjust the color tone and increase the adhesion to the skin.

  Further, to improve the dispersibility of the gold fine particle dispersion-containing flaky metal oxide colorant used in the present invention in cosmetics, or to improve the feel, the flaky metal oxide is subjected to a surface treatment, There is no problem with reforming. For example, in addition to methyl hydrogen polysiloxane, reactive alkyl polysiloxane, metal soap, hydrogenated lecithin, acylamino acid, metal salt selected from aluminum, magnesium, calcium, titanium, zinc, zirconium, iron of acylated collagen, etc. When the surface treatment is carried out with a so-called hydrophobizing agent, the surface of the flake-like metal oxide changes from hydrophilic to hydrophobic, so that the familiarity with the oil agent added at the time of preparation of the cosmetic is improved, and the cosmetic with a good feel It becomes.

  Examples of the cosmetics referred to in the present invention include makeup cosmetics such as lipstick, eye shadow, powder foundation, nail enamel, eyebrow ink, eyeliner, soap, cleansing cream, cold cream, skin cream, skin milk, skin lotion, and milky milk. Lotion, T-zone essence, essence powder, pack, hand cream, makeup base, shaving foam, shaving cream, baby oil, etc., cleaning cosmetics, basic cosmetics, hair tonic, hair liquid, hair treatment, hair cream, hair oil, It can also be used for cosmetics for hair such as shampoo, rinse and hair spray.

  The cosmetics of the present invention have no change over time such as agglomeration or falling off of fine gold particles and no direct contact between the fine gold particles and oils or fats, so that vivid color development and color tone stability, uniform coloring property are obtained. Have. In addition, the gold fine particles are not deformed by external pressure or external force, there is no color unevenness or discoloration, the transparency, the glossiness is good, and the gold fine particle dispersion-containing flake-shaped metal oxide coloring agent may aggregate with each other. In addition, since the surface is smooth and shows good sliding properties, various cosmetic products having good extensibility (spreading), good adhesion (sticking), and excellent feeling in use can be obtained.

Examples will be described below.
[Production Example 1]
Water 1300ml and 1 wt% of chloroauric acid (HAuCl ₄ · 4H ₂ O) aqueous solution of 200ml were mixed and heated to boiling. After adding 500 ml of a 1% by mass aqueous citric acid solution, 12 g of polyvinyl alcohol (degree of polymerization: 50) was immediately added, and the mixture was heated and boiled for a while to obtain a reddish purple colloid (0.125% by mass of gold). . When the particle size of the gold colloid was measured by the dynamic light scattering method, the average particle size was about 10 nm.

1600 ml of this gold colloid, 100 ml of 0.8N nitric acid, 980 ml of silicon tetramethoxide, 600 ml of ethanol and 600 ml of 2-propanol were mixed and cured at 50 ° C. for about 15 hours to obtain a coating solution.
A 0.5 mm thick stainless steel plate whose surface was polished and smoothed was immersed in this liquid, pulled up at a speed of 30 cm / min, and the liquid was applied to the surface. This was dried at 150 ° C., and the applied gel film was peeled off to form flakes, which were sintered at 1000 ° C. for 1 hour. This sintered flake was pulverized and classified by a jet mill to obtain a pink flake silica powder having an average particle size of about 10 μm.

  As a result of examining the flake powder by X-ray diffraction, the matrix was silica in a glassy state. As a result of chemical analysis of the flakes after sintering, the content of gold was about 0.5% by mass. Observation of the flakes with a transmission electron microscope revealed that spherical gold fine particles having a diameter of about 10 nm were dispersed in the silica glass matrix without being aggregated. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 μm.

  When the flaky powder was picked up by hand and the feel was examined, it was very smooth. Further, even when the flake powder was ground using a mortar, no discoloration was observed. Separately, a small amount of castor oil was added to the flake powder and the mixture was stirred, but again no significant color change was observed.

[Comparative Production Example 1]
1600 ml of water, 100 ml of 0.8N nitric acid, 980 ml of silicon tetramethoxide, 600 ml of ethanol and 600 ml of 2-propanol were mixed and cured at 50 ° C. for about 15 hours to obtain a coating solution.
A 0.5 mm thick stainless steel plate whose surface was polished and smoothed was immersed in this liquid, pulled up at a speed of 30 cm / min, and the liquid was applied to the surface. This was dried at 150 ° C., and the applied gel film was peeled off to form flakes, which were sintered at 1000 ° C. for 1 hour. This sintered flake was pulverized and classified by a jet mill to obtain a flaky silica glass powder having an average particle size of about 10 μm.

100 g of the flaky silica glass powder was dispersed in 3000 ml of water, and the pH was adjusted to about 11 by adding sodium carbonate. While stirring the suspension, it was added dropwise slowly 0.1 wt% of chloroauric acid (HAuCl ₄ · 4H ₂ O) aqueous solution of 1000 ml. After the dropwise addition, the mixture was stirred for several hours, the flakes were filtered, washed with water, dried at 150 ° C., and then heat-treated at 300 ° C. for 1 hour to obtain pink flake powder.

  As a result of examining the flake powder by X-ray diffraction, the matrix was in a glassy state. As a result of chemical analysis, the content of gold was about 0.5% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 20 nm adhered to the silica glass surface. When the flakes were observed with a scanning electron microscope, the thickness was about 0.6 μm.

  The flaky powder was picked up and examined for a feeling of touch. As a result, a slight resistance was felt, but a smooth feel was felt. When this flaky powder was ground using a mortar, it turned partially reddish brown or grayish blue. Separately, a small amount of castor oil was added to the flake powder, and the mixture was stirred.

[Example 1 and Comparative Example 1]
Powder foundations were prepared with the formulations shown in Tables 1 to 3 below.

[Table 1]
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-1 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Flake of the present invention produced in Production Example 1 15.8
Talc 73.5
Titanium oxide (primary particle size 200 to 250 nm) 3.8
Fine particle titanium oxide (primary particle size 30 to 50 nm) 1.9
2.9 magnesium stearate
Yellow iron oxide 0.8
Black iron oxide 0.1
Silk powder 0.5
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 2]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-2 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Squalane 0.5
Sorbitan sesquioleate 0.1
−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 3]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-3 blending amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Fragrance 0.1
−−−−−−−−−−−−−−−−−−−−−−−−−−−

  Component-1 was stirred with a Henschel mixer for 5 minutes. This was stirred and mixed while dropping the component-2 uniformly melted at 70 ° C. Further, after adding the component-3, the mixture was stirred and mixed for 1 minute, and pulverized by an atomizer to obtain a product-1 (Example 1).

  In place of the flake silica glass (thickness: 0.6 μm, particle size: 10 μm, gold content: 0.5% by mass) containing fine gold particles prepared in Production Example 1 in Component-1, gold prepared in Comparative Production Example 1 Product-2 (Comparative Example 1) was obtained in exactly the same manner as described above, except that flake silica glass (thickness 0.6 μm, particle size 10 μm, gold content 0.5% by mass) was added.

  Table 4 shows the results of a sensory test in which 20 panelists were used for 10 days and evaluated by a 5-point scale of 1 to 5 points with the highest point being 5 points.

[Table 4]
==================================
Item Powder of the present invention (product-1) Comparative powder (product-2)
(Example 1) (Comparative example 1)
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Nobi 4.8 4.0
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
With 4.4 3.5
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Transparency 4.7 2.4
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Gloss 4.5 2.8
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Color 4.8 2.2
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Performance sustainability 4.1 3.2
==================================

  Thus, it was confirmed that the cosmetic of the present invention had good spreadability (adhesiveness), good transparency and glossiness, was excellent in color development, and did not easily fade.

[Production Example 2]
Water 500ml dissolved chloroauric acid _{(HAuCl 4 · 4H 2 O)} 209g, this silicon tetramethoxide 490 ml, 1N hydrochloric acid 100 ml, ethanol 600 ml, was added and mixed 3-aminopropyltriethoxysilane 368 g. Separately, a solution prepared by dissolving 356 g of titanium isopropoxide in 1,000 ml of 2-propanol was prepared, and the solution was slowly added to the previously prepared solution containing chloroauric acid and silicon tetramethoxide and mixed. This mixture was cured at 60 ° C. for about 20 hours to obtain a coating solution.

  A polyimide film plate (made by Ube Industries, trade name: Upilex) was immersed in this solution, pulled up at a speed of 30 cm / min, and the surface was coated with the solution. This was dried at 150 ° C., and then the coated substrate was put in a large amount of water, and the gel film on the substrate surface was peeled off in water to form a flake. The flakes in water were collected by filtration and dried at 120 ° C. to obtain a flaky gel. Thereafter, the flake gel was sintered at 850 ° C. for 3 hours, pulverized and classified by a jet mill to obtain a blue-violet flake powder having an average particle diameter of about 10 μm and having an ultraviolet absorbing ability.

  As a result of examining the flake-like powder by X-ray diffraction or the like, it was confirmed that the matrix was mainly composed of silica-titania two components in a glassy state and that crystals of anatase-type titanium oxide were mixed. As a result of chemical analysis of the flakes after sintering, the content of gold was approximately 20% by mass, the content of titanium oxide was approximately 20% by mass, and the content of silicon oxide was approximately 60% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 30 nm were dispersed in the flakes without aggregation. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.7 μm.

  The flaky powder was picked up by hand and the feel was examined. As a result, the feel was very smooth. Further, even when the flake powder was ground using a mortar, no discoloration was observed. Separately, a small amount of castor oil was added to the flake powder and the mixture was stirred, but again no significant color change was observed.

[Comparative Production Example 2]
1600 ml of water, 200 ml of 6N hydrochloric acid, 490 ml of silicon tetramethoxide, 600 ml of ethanol and 368 g of 3-aminopropyltriethoxysilane were added and mixed. Separately, a solution prepared by dissolving 356 g of titanium isopropoxide in 500 ml of 2-propanol was prepared, and this was slowly added to the previously prepared solution and mixed. This mixture was cured at 60 ° C. for about 20 hours to obtain a coating solution.

  A polyimide film plate (made by Ube Industries, trade name: Upilex) was immersed in this liquid, pulled up at a speed of 30 cm / min, and the surface was coated with the liquid. This was dried at 150 ° C., and then put into a large amount of water together with the substrate, and the gel film was peeled off in water to form flakes. The flakes in water were collected by filtration and dried at 120 ° C. to obtain a flaky gel powder.

100 g of the flaky gel powder was dispersed in 3000 ml of water, and the pH was adjusted to about 12 by adding ammonia. While stirring the suspension, it was added dropwise slowly 3 wt% of chloroauric acid (HAuCl ₄ · 4H ₂ O) aqueous solution 1743Ml. After the dropwise addition, the mixture was stirred for several hours, the flakes were filtered, washed with water, dried at 150 ° C., and then heat-treated at 850 ° C. for 3 hours to obtain a gray-blue flake-like powder.

  As a result of examining the flake powder by X-ray diffraction or the like, it was confirmed that the matrix was mainly composed of silica-titania two components in a glassy state, and that crystals of anatase type titanium oxide were mixed. As a result of chemical analysis of the flakes after sintering, the content of gold was approximately 14% by mass, the content of titanium oxide was approximately 21% by mass, and the content of silicon oxide was approximately 65% by mass. Observation of the flakes with a transmission electron microscope revealed that spherical gold fine particles having a primary particle size of about 50 nm were attached to the silica glass surface. When the flakes were observed with a scanning electron microscope, the thickness was about 0.7 μm.

  When the flaky powder was picked up by hand and the feel was examined, it was not very good. When the flake powder was ground using a mortar, a part of the powder turned brown or black. Separately, a small amount of castor oil was added to the flake powder, and the mixture was stirred.

[Example 2 and Comparative Example 2]
Nail enamels were prepared according to the formulations shown in Tables 5 to 7 below.

[Table 5]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-4 Amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Nitrocellulose 15.0
Phthalic acid alkyd resin 12.0
Dibutyl phthalate 4.0
−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 6]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-5 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Butyl acetate 25.0
Ethyl acetate 7.0
Toluene 24.0
2-propanol 6.0
Ethanol 2.0
1-butanol 2.0
−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 7]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-6 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Flake of the present invention produced in Production Example 2 3.0
−−−−−−−−−−−−−−−−−−−−−−−−−−−

Component-4 and Component-5 were mixed and dissolved. Ingredient -6 was added thereto, and the mixture was stirred and mixed to obtain product-3 (Example 2).
Product-4 (Comparative Example 2) was obtained in the same manner as described above, except that the flakes produced in Comparative Production Example 2 were used instead of the flakes produced in Production Example 2 as Component-6. .
Table 8 shows the results of a sensory test in which the above product was used by 20 panelists for 10 days, and evaluated according to a five-point method in which the lowest score was 1 point and the highest score was 5 points.

[Table 8]
==================================
Item Cosmetics of the present invention (Product-3) Comparative cosmetics (Product-4)
(Example 2) (Comparative example 2)
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Nobi 4.8 3.5
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
With 4.4 2.8
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Applicability 4.2 2.9
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Glossiness 4.9 3.1
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
4.7 finish
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
4.6 Color
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Uniformity 4.5 1.8
==================================

  As described above, the cosmetic of the present invention is excellent in spreadability (extensibility) and stickiness (adhesiveness), easy to apply uniformly, good in transparency and gloss, good in color development, and excellent in finish. confirmed.

[Production Example 3]
500 g of aluminum sec-butoxide and 3600 ml of 0.03N hydrochloric acid were mixed and heated at 85 ° C. for 8 hours to obtain a sol. After cooling this sol to room temperature, 24 g of chloroauric acid was added and dissolved to obtain a coating solution. A polyetheretherketone film plate (manufactured by Sumitomo Chemical Co., Ltd., Espex-KC) was immersed in this solution, pulled up at a speed of 40 cm / min, and the surface was coated with the solution. This was dried at 150 ° C., and irradiated with light from a 500 W high-pressure mercury lamp for 30 minutes to precipitate gold fine particles in the matrix.

  Thereafter, the coated substrate was placed in a 3% by mass hydrazine aqueous solution, and the film on the substrate surface was peeled off in the liquid to form a flake. The flakes in the liquid are collected by filtration, dried at 200 ° C., then sintered at 1200 ° C. for 1 hour, pulverized and classified by a jet mill to obtain a purple flaky powder having an average particle size of about 10 μm. Was.

  As a result of examining the flake powder by X-ray diffraction or the like, it was found that the matrix was α-alumina crystals. As a result of chemical analysis, the gold content was about 10% by mass. Observation of the flakes with a transmission electron microscope revealed that egg-shaped gold fine particles having a size of about 20 nm were dispersed in the flakes without aggregation. When the flakes were observed with a scanning electron microscope, the surface was smooth and the thickness was about 0.7 μm.

  When the flaky powder was picked up by hand and the feel was examined, the feel was smooth. Further, even when the flake powder was ground using a mortar, no discoloration was observed. Separately, a small amount of castor oil was added to the flake powder and the mixture was stirred, but again no significant color change was observed.

[Comparative Production Example 3]
500 g of aluminum sec-butoxide and 3600 ml of 0.03N hydrochloric acid were mixed and heated at 85 ° C. for 8 hours to obtain a sol. This sol was cooled to room temperature to obtain a coating solution. A polyetheretherketone film plate (manufactured by Sumitomo Chemical Co., Ltd., Espex-KC) was immersed in the solution, pulled up at a speed of 30 cm / min, and the surface was coated with the solution. This was dried at 150 ° C., and then the gel film was peeled off in a 3% by mass hydrazine aqueous solution to form a flake. The flakes in the liquid were collected by filtration and dried at 120 ° C. to obtain a flake-like powder.

100 g of the flake powder was dispersed in 3000 ml of water, and the pH was adjusted to about 10 by adding hydrazine. While stirring the suspension, it was added dropwise 1% by mass of chloroauric acid (HAuCl ₄ · 4H ₂ O) aqueous solution of 2100ml slowly. After the dropwise addition, the mixture was stirred for several hours, the flakes were filtered, washed with water, dried at 200 ° C., and then heat-treated at 1200 ° C. for 1 hour to obtain a purple flaky powder.

  As a result of examining the flake powder by X-ray diffraction or the like, it was found that the matrix was α-alumina crystals. As a result of chemical analysis, the gold content was about 10% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 20 nm were attached to the flake surface. When the flakes were observed with a scanning electron microscope, the thickness was about 0.7 μm.

  When the flaky powder was picked up by hand and the feel was examined, it was not very good. When the flake powder was ground using a mortar, a part of the powder turned brown or black. Separately, a small amount of castor oil was added to the flake powder, and the mixture was stirred.

[Example 3 and Comparative Example 3]
Next, eye shadows were prepared according to the formulations shown in Tables 9 to 11 below.

[Table 9]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component -7 blending amount (mass%)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Flake of the present invention produced in Production Example 3 13.5
Talc 40.0
Mica 21.0
Mica titanium 10.3
8.6 zinc stearate
−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 10]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-8 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Squalane 1.0
Sorbitan sesquioleate 1.0
Liquid paraffin 3.0
Vaseline 1.5
−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 11]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-9 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Fragrance 0.1
−−−−−−−−−−−−−−−−−−−−−−−−−−−

  Component-7 was stirred using a Henschel mixer for 5 minutes. The mixture was stirred and mixed while dropping the component-8 uniformly mixed at 70 ° C. Furthermore, after adding the component-9, the mixture was stirred and mixed for 1 minute, and the pulverized product was compression-molded to obtain a product-5 (Example 3).

  Product-6 (Comparative Example 3) was obtained in the same manner as described above, except that the flakes produced in Comparative Production Example 3 were used instead of the flakes produced in Production Example 3 in Component-7. Was.

  Table 12 shows the results of a sensory test in which the above product was used by 20 panelists for 10 days, and evaluated by a five-point method in which the lowest score was 1 and the highest score was 5.

[Table 12]
==================================
Item Cosmetics of the present invention (Product-5) Comparative cosmetics (Product-6)
(Example 3) (Comparative example 3)
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Nobi 4.5 3.8
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
With 4.3 3.7
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Easiness of blur 4.2 3.2
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Gloss 4.0 3.9
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Finish feeling 4.5 3.4
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
4.6 2.8
==================================

  Thus, it was confirmed that the cosmetic of the present invention is excellent in spreading (extensibility) and sticking (adhesiveness), easily blurred, has good color development, and is excellent in finished feeling.

[Production Example 4]
Water 500ml hydroxyethylcellulose 5g, dissolved chloroauric acid _{(HAuCl 4 · 4H 2 O)} 31g, which silicon tetramethoxide 490 ml, 1N hydrochloric acid 100 ml, ethanol 600 ml, was added 3-aminopropyl triethoxysilane 184g mixed did. Separately, a solution prepared by dissolving 55 g of zirconium isopropoxide in 500 ml of 2-propanol was prepared, and this was slowly added to the previously prepared solution containing chloroauric acid and silicon tetramethoxide and mixed. This mixture was cured at 60 ° C. for about 15 hours.

  This liquid was irradiated with light from a 500 W high-pressure mercury lamp for 5 hours to generate fine gold particles in the liquid, and further cured at 50 ° C. for 5 hours to obtain a coating liquid. A polyimide film plate (made by Ube Industries, trade name: Upilex) was immersed in this liquid, pulled up at a speed of 30 cm / min, and the surface was coated with the liquid. This was dried at 150 ° C., and then put into a large amount of water together with the substrate, and the gel film was peeled off in water to form flakes. The flakes in water were collected by filtration and dried at 120 ° C. to obtain a flaky gel. Thereafter, this flaky gel was sintered at 500 ° C. for 3 hours, pulverized and classified by a jet mill to obtain a glossy red-purple flaky powder having an average particle size of about 15 μm.

  As a result of examining the flake-like powder by X-ray diffraction or the like, it was confirmed that the matrix was in a glass state of silica-zirconia binary. As a result of chemical analysis, the content of gold was about 5% by mass, the content of zirconium oxide was about 7% by mass, and the content of silicon oxide was about 88% by mass. Observation of the flakes with a transmission electron microscope revealed that spherical gold fine particles having a diameter of about 5 nm were monodispersed in the flakes. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 μm.

  The flaky powder was picked up by hand and the feel was examined. As a result, the feel was very smooth. Further, even when the flake powder was ground using a mortar, no discoloration was observed. Separately, a small amount of castor oil was added to the flake powder and the mixture was stirred. As a result, it was recognized that the color changed more vividly. This is presumably because the fine holes present in the flakes are impregnated with castor oil and light scattering by the fine holes is reduced.

[Comparative Production Example 4]
500 ml of water, 200 ml of 6N hydrochloric acid, 613 ml of silicon tetramethoxide, and 600 ml of ethanol were added and mixed. Separately, a solution prepared by dissolving 55 g of zirconium isopropoxide in 500 ml of 2-propanol was prepared, and this was slowly added to the previously prepared solution and mixed. This mixture was cured at 60 ° C. for about 20 hours to obtain a coating solution.

  A polyimide film plate (made by Ube Industries, trade name: Upilex) was immersed in this liquid, pulled up at a speed of 30 cm / min, and the surface was coated with the liquid. This was dried at 150 ° C., and then put into a large amount of water together with the substrate, and the gel film was peeled off in water to form flakes. The flakes in water were collected by filtration and dried at 120 ° C. to obtain a flaky gel. Thereafter, the flaky gel was sintered at 500 ° C. for 3 hours, pulverized and classified by a jet mill to obtain an average particle size of about 15 μm.

100 g of the flake powder was dispersed in 3000 ml of water, and the pH was adjusted to about 10 by adding hydrazine. While stirring the suspension, it was added dropwise 1% by mass of chloroauric acid (HAuCl ₄ · 4H ₂ O) aqueous solution of 1150ml slowly. After the dropwise addition, the mixture was stirred for several hours, the flakes were filtered, washed with water, dried at 200 ° C., and then heat-treated at 500 ° C. for 3 hours to obtain a violet flaky powder.

  As a result of examining the flake-like powder by X-ray diffraction or the like, it was confirmed that the matrix was in a glass state of silica-zirconia binary. As a result of chemical analysis, the content of gold was about 5% by mass, the content of zirconium oxide was about 7% by mass, and the content of silicon oxide was about 88% by mass. When the flakes were observed with a transmission electron microscope, it was observed that spherical gold fine particles having a diameter of about 5 nm were attached to the flake surface. When the flakes were observed with a scanning electron microscope, the thickness was about 0.6 μm.

  When the flaky powder was picked up and examined for a feeling of touch, a slight resistance was felt but a good feeling. When the flake powder was ground using a mortar, the powder was divided into dark and light portions, resulting in color unevenness. Separately, a small amount of castor oil was added to the flake powder, and the mixture was stirred. As a result, the color tone became dark, but the whole was slightly darkened.

[Example 4 and Comparative Example 4]
Lipsticks were prepared with the formulations shown in Tables 13 to 15 below.

[Table 13]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-10 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Castor oil 35.0
Octyldodecyl myristate 19.0
Isopropyl myristate 5.4
Lanolin 5.5
Beeswax 2.7
6.6 Candelilla wax
Carnauba wax 0.9
Selesin 7.2
−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 14]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-11 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Flake of the present invention produced in Production Example 4 12.1
5.5 titanium dioxide
−−−−−−−−−−−−−−−−−−−−−−−−−−−

[Table 15]
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Component-12 Compounding amount (% by mass)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
Fragrance 0.1
−−−−−−−−−−−−−−−−−−−−−−−−−−−

Component -10 was mixed and heated and melted at 85 ° C. Ingredient-11 was added to this melt, and stirred and mixed. Further, component-12 was added, mixed with stirring, poured into a mold, cooled, and formed into a rod to obtain product-7 (Example 4).
Product-8 (Comparative Example 4) was obtained in the same manner as described above, except that the flakes produced in Comparative Production Example 4 were used instead of the flakes produced in Production Example 4 in Component-11. Was.
Table 16 shows the results of a sensory test in which the above products were used by 20 panelists for 10 days, and evaluated according to a 5-point method in which the lowest score was 1 point and the highest score was 5 points.

[Table 16]
==================================
Item Cosmetics of the present invention (Product-7) Comparative cosmetics (Product-8)
(Example 4) (Comparative example 4)
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Noby 4.5 4.0
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
With 4.5 3.8
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Glossy 4.3 4.0
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Finish feeling 4.6 3.5
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Color 4.7 4.7 2.7
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
Makeup sticky 3.9 3.3
==================================

  Thus, it was confirmed that the cosmetic of the present invention is excellent in spreadability (extensibility) and sticking (adhesiveness), good in gloss, good in color development, good in finish and good in makeup.

[Example 5]
2 wt% of chloroauric acid (HAuCl ₄ · 4H ₂ O) aqueous solution of 2000ml polyvinyl alcohol (polymerization degree: 300) 80 g was added and dissolved, which was heated and boiled by adding 5 wt% aqueous citric acid 500 ml, The mixture was heated and boiled for a while to obtain a brown gold colloid (0.74% by mass of gold). When the particle size of the gold colloid was measured by the dynamic light scattering method, the average particle size was about 110 nm.

  A mixture of 1100 ml of this gold colloid, 200 ml of 6N nitric acid, 858 ml of silicon tetramethoxide, 185 g of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 600 ml of ethanol and 600 ml of 2-propanol was mixed at 40 ° C. for about 5 hours. After curing, a coating solution was obtained.

  A 0.5 mm thick stainless steel plate whose surface was chromium-plated was immersed in this liquid, pulled up at a speed of 30 cm / min, and the surface was coated with the liquid. This was dried at 200 ° C., and the applied gel film was peeled off to form flakes, which were sintered at 1000 ° C. for 1 hour. This sintered flake was pulverized and classified by a jet mill to obtain a reddish-brown flake powder having an average particle size of about 20 μm.

  As a result of examining the flake powder by X-ray diffraction, the matrix was silica in a glassy state. As a result of chemical analysis of the flakes after sintering, the content of gold was about 2% by mass. Observation of the flakes with a transmission electron microscope showed that spherical gold fine particles having a diameter of about 100 nm were dispersed in the silica glass matrix without agglomeration. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 μm.

  The flaky powder was picked up by hand and the feel was examined. As a result, the feel was very smooth. Further, even when the flake powder was ground using a mortar, no discoloration was observed. Separately, a small amount of castor oil was added to the flake powder and the mixture was stirred, but again no significant color change was observed.

  Using this flake, a powdery foundation was prepared by the method shown in Example 1, and a cosmetic with good spreadability (adhesiveness), a unique color tone, excellent color development, and less discoloration was obtained. Was.

[Example 6]
12 g of chloroauric acid was added to and dissolved in 2000 ml of a 30% by mass aqueous solution of hexadecyltrimethylammonium chloride. This solution was irradiated with light from a high-pressure mercury lamp of 200 W for 50 hours to generate gold fine particles, thereby obtaining red-purple gold colloid (0.29% by mass of gold). According to transmission electron microscope observation, the gold colloid contains spherical gold fine particles having a diameter of about 20 to 30 nm and rod-shaped gold fine particles having a width of about 20 to 30 nm and a length of about 100 to 200 nm. Was.

  In 1742 ml of this gold colloid, 52 g of polyethylene glycol monolaurate was dissolved, and 100 ml of 0.8 N nitric acid, 980 ml of silicon tetramethoxide, 600 ml of ethanol and 600 ml of 2-propanol were mixed, and the mixture was cured at 50 ° C. for about 15 hours and applied. And

  A 0.5 mm thick stainless steel plate whose surface was polished and smoothed was immersed in this liquid, pulled up at a speed of 30 cm / min, and the liquid was applied to the surface. This was dried at 150 ° C., and the applied gel film was peeled off to form flakes, which were sintered at 1000 ° C. for 1 hour. The sintered flakes were pulverized and classified by a jet mill to obtain a light red-purple flaky powder having an average particle size of about 30 μm.

  As a result of examining the flake powder by X-ray diffraction, the matrix was silica in a glassy state. As a result of chemical analysis of the flakes after sintering, the content of gold was about 1.2% by mass. Observation of the flakes with a transmission electron microscope revealed that spherical gold particles with a diameter of about 20 nm and rod-shaped gold particles with a width of about 20 to 30 nm and a length of about 100 to 200 nm were mixed and aggregated in the silica glass matrix. It was observed that they were dispersed without being dispersed. When the flakes were observed with a scanning electron microscope, the surface was very smooth and the thickness was about 0.6 μm.

  The flaky powder was picked up by hand and the feel was examined. As a result, the feel was very smooth. Further, even when the flake powder was ground using a mortar, no discoloration was observed. Separately, a small amount of castor oil was added to the flake powder and the mixture was stirred, but again no significant color change was observed.

  Using this flake, a powdery foundation was prepared by the method shown in Example 1, and a cosmetic with good spreadability (adhesiveness), a unique color tone, excellent color development, and less discoloration was obtained. Was.

Claims (5)

  It contains at least one kind of metal oxide selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide and zirconium oxide as a main component, and contains 0.01 to 30% by mass of gold fine particles having a particle size of 1 to 300 nm dispersed therein. And a flaky metal oxide coloring agent having an average thickness of 0.1 to 2 μm and an aspect ratio of 5 to 150.   The cosmetic according to claim 1, wherein the flake-shaped metal oxide coloring agent is blended in an amount of 1 to 80% by mass based on all solid components of the cosmetic.   2. The cosmetic according to claim 1, wherein the cosmetic is a powder foundation, a skin cream, a hand cream or a make-up base, and the flaky metal oxide colorant is incorporated in an amount of 0.2 to 3% by mass based on all solid components of the cosmetic. Cosmetics.   The cosmetic according to claim 1, wherein the cosmetic is a nail enamel, an eye shadow, or a lipstick, and the flake metal oxide coloring agent is blended in an amount of 3 to 25% by mass based on all solid components of the cosmetic.   The cosmetic according to any one of claims 1 to 3, wherein the flaky metal oxide colorant is amorphous or glassy.