JPH0611685B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improved cosmetics and the like relating to make-up cosmetics, which imparts a good spreadability and a soft touch at the time of application, and has an excellent transparency as a makeup finish. Further, it is intended to provide a new cosmetic composition having a good function of controlling sebum and water and having excellent makeup durability.

Various powders have heretofore been widely used in cosmetics, but from the viewpoint of usability, they are limited to talc, sericite, muscovite and the like. In these natural minerals, the thickness of the particles is not uniform, and the particles are weakly bound to each other, so that air is likely to remain, which causes cracks in the pressed product and various problems.

In powder cosmetics, the desired long-lasting makeup when the cosmetic is applied to the skin depends on the absorption amount and absorption rate of each of the water content and oil content contained in the powder product. That is, an ideal product is achieved by finding a powder having properties that the oil absorption amount and the water absorption amount are both appropriately high, and that the oil absorption rate is fast and the water absorption rate is slow. However, in the current products, there is almost no powder which is a decisive factor in satisfying these conditions.
Of the general powder products, there are few powders that have high oil absorption and water absorption, and even if they are high, whether the oil absorption and water absorption speeds are both high or low. It is only biased. When both oil absorption and water absorption are fast, the skin is easily dried when the cosmetic is applied to the skin, and unevenness occurs during or after the application. Further, when the oil and water absorption rates are both low, the skin oil secreted from the skin causes makeup deterioration, which is extremely difficult to prevent. This tendency is not an exception for synthetic powders such as inorganic hollow powders and porous powders that have been provided recently, and a drastic solution has been required.

Therefore, the present inventors have conducted intensive studies to overcome these drawbacks, and found that the inclusion of a spherical porous resin powder having a specific particle diameter is effective in solving the above problems, This has already been proposed (JP-A-57-9).
8205). However, the spherical porous resin powder has the aspect that it is difficult to control its porosity (porosity). For example, if the porosity becomes too high, the oil absorption
There is a point that the desired effect is difficult to obtain when the amount of water absorption becomes excessive and conversely approaches too non-porous. In addition, in general, spherical spherical resin powders generally have less light scattering on the particle surface and higher transparency than conventional powders, but have completely solved the problem of minute light scattering in the porous part. I couldn't finish it.

Under these circumstances, the present inventors have not obtained a powder having excellent transparency, a small variation in oil absorption / water absorption control function, and a softness rich in elasticity, and a cosmetic containing the same. As a result of further research, it was found that the hollow powder having spherical voids inside the spherical resin powder sufficiently satisfies the above-mentioned object, and the present invention has been completed here.

The present invention has an average particle size of 1 to 50 μ and an apparent specific gravity of 0.
The present invention relates to a cosmetic, which is 8 or less and further contains a hollow spherical organic polymer having one or more spherical vacuoles therein.

The hollow spherical organic polymer applied to the present invention has an average particle size of 1 to 50 μm. If the average particle size is less than 1μ, it is because when used as a cosmetic, the makeup finish becomes whiter and the spreadability deteriorates, and if it exceeds 50μ, the feeling of foreign matter (gritty feeling) during application is strong. This is because Further, the hollow spherical organic polymer and the spherical shape in the spherical vacuoles naturally include not only true spherical shapes but also inertia circles and other similar spherical shapes.

Further, the apparent specific gravity of the hollow spherical organic polymer is 0.8 or less. The size of the apparent specific gravity here is governed by the type of resin applied and the size and number of spherical vesicles present inside the spherical organic polymer, which is, as it is, a transparent feeling,
It is closely related to softness and lightness due to elasticity as well as water absorption and oil absorption characteristics.

The hollow spherical organic polymer has a specific surface area of about 3 to 50 m ² / g
And is preferably 30 m ² / in terms of suppressing minute light scattering.
g (more preferably 20 m ² / g) or less.

Next, the content of the hollow spherical organic polymer according to the present invention in a cosmetic composition varies depending on the intended product type, but 1 to 90% by weight based on the total weight of the cosmetic composition can be said to be a suitable range.

The material applied to the hollow spherical organic polymer of the present invention is preferably amorphous and transparent (light transmissive) per se, and examples thereof include vinyl chloride, acrylonitrile, methacrylonitrile, vinyl acetate and methyl vinyl ether. Such as vinyl-based monomers, acrylic acid, acrylic acid-based monomers such as acrylic acid esters (methyl, ethyl), methacrylic acid-based monomers such as methacrylic acid, methacrylic acid esters (methyl, ethyl), styrene, α-methylstyrene, etc. Styrene monomers, and further homopolymers or copolymers of one or more hydrophobic monomers selected from vinylidene chloride, divinylbenzene, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and the like satisfy the above conditions. However, the material is not necessarily limited to these materials as long as the above conditions are satisfied.

Further, the method itself for producing a hollow spherical organic polymer having spherical vacuoles in the present invention is, that is, the above-mentioned hydrophobic organic monomer having a polymer unsaturated bond such as acrylic acid or styrene, and a nonionic surfactant. Agents such as sorbitan monooleate, sorbitan trioleate, polyoxyethylene cetyl ether, polyoxyethylene sorbitan monooleate, polyoxyethylene hydrogenated castor oil, and benzoyl peroxide soluble in the hydrophobic organic monomer. A polymerization initiator is mixed, and this is dispersed as a monomer phase in an aqueous phase containing an ionic surfactant such as sodium lauryl sulfate, sodium lauroyl-L-glutamate, sodium dioctylsulfosuccinate, and sodium oleate. Water phase / monomer phase / water phase (hereinafter W / / W abbreviated) emulsion to form the can be obtained by further polymerization. And, in such a polymerization process, by appropriately combining the types of nonionic surfactant and ionic surfactant, or by adjusting the emulsifier concentration, not only the average particle diameter is adjusted but also the internal of the spherical organic polymer is adjusted. It is also possible to control the size and number of spherical vacuoles contained in.

In the following, in order to further describe in detail the method for producing a hollow spherical organic polymer having spherical vacuoles, a production example will be shown. The mixing ratio is such that the organic monomer is by volume (m) and the other components are by weight (g).

Synthesis example 1 (Method) A was charged and dissolved in a reactor equipped with a cooler, a stirrer, a thermometer, and a nitrogen inlet. After dissolving B at room temperature, A
Was gradually added to the mixture while stirring. The temperature was kept at 65 ° C., being careful to always fill the inside of the reactor with nitrogen, and the polymerization reaction was carried out for 4 hours and then stopped. After the contents were decompressed, they were thoroughly washed with water, replaced with isopropyl alcohol and hexane sequentially and dried.

The resulting hollow spherical organic polymer had an average particle size of 19 μ, an apparent specific gravity of 0.58 and had one spherical vacuole inside.

The methods for measuring the average particle diameter and the apparent specific gravity are as follows.

<Measurement method of average particle size> Measuring instrument: Coulter Counter Measuring method: Disperse 1 g of the sample in 50 ml of a 0.5% aqueous solution of sodium dioctylsulfosuccinate to obtain a stock solution for measurement. 1 ml of this stock solution is put into a sample beaker filled with an electrolyte solution ISOTON-II (manufactured by Conlter), and measurement is carried out.

Measured value: 50% particle size is obtained from the cumulative number histogram and used as the average particle size.

<Measuring method of apparent specific gravity> Measuring device: Tapping machine Measuring method: 20 g of the sample is put in a 90 ml test tube for tapping and tapped 200 times at a head of 15 mm and a rotation speed of 30 rpm.

Measured value: The volume of the sample after tapping is read, and the apparent specific gravity is calculated from the following formula.

Hereinafter, the average particle diameter and the apparent specific gravity were measured in the same manner as above.

Synthesis example 2 (Method) It was manufactured in the same manner as in Synthesis Example 1.

The resulting hollow spherical organic polymer had an average particle diameter of 22 μ, an apparent specific gravity of 0.69, and had several tens of spherical vacuoles inside.

1 and 2 are micrographs of the hollow spherical organic polymer obtained according to the method of Synthesis Example 1. For comparison, micrographs of commercially available spherical particles and commercially available porous particles are shown in FIGS. 3 and 4, respectively. According to FIGS. 1 to 4, it can be seen that the hollow spherical organic polymer in the present invention has voids (black portion inside the particles).

In addition, the hollow spherical organic polymer (vacuum number 1
The reference photograph is an electron micrograph (about 15,000 times) of the broken pieces.

The features of the hollow spherical organic polymer applied to the present invention will be described in detail below. First, the hollow spherical organic polymer used in the present invention is a spherical porous resin powder that has been conventionally used. Compared to all other powders including, the light scattering on the particle surface and inside the particle is small and the transparency is large, so when applied on the skin, even if the particles become finer, it is much more than other powders. It is transparent and does not have a white appearance.

Secondly, the hollow spherical organic polymer of the present invention has one or more spherical vacuoles inside unlike the conventional porous resin powder having continuous mesh-like voids. Therefore, in combination with the spherical outer shape, it has elasticity different from that of the porous resin powder like a rubber mull, and a softer, softer and tactile feel can be obtained in terms of usability. Further, unlike the conventional various powders, there is no irregular shape and uneven thickness, and the rolling effect provides good spreadability, gives a feeling of light elongation, and does not give a feeling of thickness.

Thirdly, various powders have been conventionally used in cosmetics, but most of them do not have high oil absorption and water absorption, and they are not well-adapted to oil and have a low oil absorption rate. Most things. For this reason, many of them secrete sebum and lose their makeup in a short time. In addition, some synthetic inorganic powders have high oil absorption and high water absorption, but these have extremely high oil absorption and water absorption speeds, and the skin becomes tight.
The skin became dry, and the makeup was liable to be uneven, which impaired the makeup effect. The hollow spherical organic polymer of the present invention has a large oil absorption amount like the spherical porous resin powder, a large water absorption amount, has a property that the oil absorption rate is fairly fast and the water absorption rate is relatively fast, and the water absorption rate is relatively slow. It has the property of evaporating, makes it possible to apply the makeup effect for a long time and evenly apply it to the skin, and does not make the skin feel uncomfortable. Further, if the difference between the conventional spherical porous powder and the hollow spherical polymer of the present invention is additionally mentioned, the hollow spherical organic polymer of the present invention has a control of the degree of vacuole as shown in the above-mentioned production method. Is easy,
It overcomes the variations in lipophilicity / hydrophilicity due to the type of organic monomer, and always obtains the desired oil / water absorption characteristics, and is highly uniform.

Fourthly, conventional inorganic powders have irregular particle sizes and irregular shapes, and their thicknesses are also irregular.Therefore, air tends to remain in the pressed product of the powder, which causes cracking. However, the use of the hollow spherical organic polymer of the present invention makes it easier to form a close-packed structure, so that these drawbacks can be prevented.

Next, in order to prove that the hollow spherical organic polymer of the present invention has an excellent light-transmitting property, the hollow spherical organic polymer of the present invention (MMA / EDMA system, average particle diameter) obtained in Synthesis Example 1 above is used. 19μ,
Spherical vacuole number 1) and conventional commercially available spherical particles (manufactured by Nippon Chemical Co., MMA / EDMA system, average particle size of about 10μ, non-porous) and porous particles (manufactured by Nippon Chemical Co., MMA / EDMA system,
A comparative test of the specific surface area and the light transmittance in the visible light region was carried out by using the average particle diameter of 10 μm and the pores. The results are shown in Table 1 and Table 2. (In the table, the spherical polymer refers to the hollow spherical organic polymer of the present invention.) <Method for measuring specific surface area> The adsorption amount of nitrogen gas is measured to determine the specific surface area.

Pretreatment: 5 g, 100 ° C, 24 hours vacuum drying TCD = 70 ° C current = 75mA CoL = 55 ° C range = 64mV Inj. DET = 55 ℃ PN ₂ = 0.257 Chart speed: 10mm / min Measuring temperature (RT): 15-18 ℃ Measuring instrument: Flow soap Measured value: Desorption peak area <Measuring method of light transmittance> Measuring instrument: Hitachi 323 type self-recording spectrophotometer Preparation of sample: Liquid paraffin 8 to 20 parts of square sample
Add 0 parts to make a paste, and apply this to a glass cell (however, reference is only liquid paraffin).

Measurement wavelength: 470 nm (blue area), 530 nm (green area) 660 nm (red area) Measurement value: transmittance (%) As is clear from the results of Table 1 and Table 2, the hollow spherical organic polymer of the present invention has a hollow inside and has a conventional powder (by suppressing the fine scattering in the porous portion as much as possible). It will be understood that the light transmission is superior to that of non-porous and porous).

Furthermore, in order to show how the hollow spherical organic polymer applied to the present invention is ideal for obtaining cosmetics having good makeup lasting, the synthesis examples 1 and 2 and the examples described below are shown. The results of measuring the oil absorption / water absorption amount and the oil absorption / water absorption rate using the hollow spherical organic polymers of the present invention 4 and 5 and conventional powders as samples are shown in Table 3 below. (In the table, the spherical polymer means the hollow spherical organic polymer of the present invention.) (Measurement method) 1 to 5 g of a sample is precisely weighed and taken on a glass plate, and oleic acid (ion-exchanged water) is dropped from the buret to the center of the sample once every 3 to 7 seconds, and each time with a spatula, suffice. Knead into. Repeating the operation of dropping and kneading, the whole becomes the first solid putty-like mass that is rolled up in the spiral shape by the steel spatula, and the end point is reached, and the oleic acid (ion exchanged water) used up to that point Find the quantity,
The oil absorption and the water absorption were calculated by the following formulas. However, the one in which no putty-like lump was rolled up suddenly became soft with one drop of oleic acid (ion-exchanged water) and was set as the end point immediately before sticking to the glass plate.

H: Amount of oleic acid (ml) or amount of ion-exchanged water (ml) S; Weight of sample collected G; Oil absorption or water absorption The oil absorption rate and water absorption rate were measured by press-filling a fixed amount in a cell. Then, a certain amount of water droplets or oil droplets was dropped on the surface, the rate of absorption was measured, and they were classified and displayed.

As is clear from Table 2 above, the conventionally used talc, sericite, and kaolin groups have low oil absorption and water absorption, and talcs have a very low water absorption rate. Since the speed is also quite slow, it tends to be damaged by makeup, and sericite and kaolin have the extremely low oil absorption rate and the very high water absorption rate, and thus they are the most difficult in terms of makeup sustainability. Furthermore, in the case of conventional powders excluding these and spherical porous resin powders, oil absorption,
The water absorption is extremely high, and the oil absorption and water absorption speeds are both high, so that a feeling of dryness is not accompanied by makeup application, and unevenness during application or immediately after application is remarkably exposed. On the other hand, the hollow spherical organic polymer of the present invention has a higher oil absorption / absorption amount than talc which is a practical powder like the spherical porous resin powder, and has a high oil absorption rate and a desired water absorption rate. It satisfies the ideal characteristic of being slow. Further comparing the spherical porous resin powder and the hollow spherical organic polymer of the present invention, the hollow spherical organic polymer of the present invention can control the variation in oil absorption / water absorption between the resins to be small. As a result, even in the case of a cosmetic amount, it is easy for a technician to produce a uniform product regardless of the type of polymer.

Finally, in order to confirm the usability of the hollow-sphere organic polymer of the present invention as a cosmetic, the present inventors conducted a comparative evaluation by a use test of the cosmetic of the present invention and commercial products of Examples 1 to 3 below. Carried out. The results are shown in Table 4 below.

(Evaluation items) A: Soft and smooth feeling of use B: Uniformity of sticking to the skin C: Transparency D: Lifting of whiteness E: Adhesion F: Makeup lasting G: Overall evaluation (Evaluation result) X: Quite good Y: Good Z: Normal Next, examples of the present invention will be shown. The mixing ratio is% by weight. The spherical polymer means the hollow spherical organic polymer of the present invention.

Example 1. Face powder A was mixed with a Hesoshell mixer and then pulverized with a pulverizer. While stirring this again with a Henschel mixer, B was added to this and the mixture was stirred and mixed for 10 minutes, C was further added and the mixture was stirred and mixed for 3 minutes. The product was homogenized with a blow shifter and filled in a container to obtain a product.

Example 2. Pressed powder After stirring and mixing A with a ribbon blender for 30 minutes, it was pulverized with a pulverizer. While stirring the pulverized product with a Henschel mixer, B was added thereto and the mixture was stirred and mixed for 12 minutes. Further C
Was added and mixed with stirring for 4 minutes. The product was homogenized with a blow shifter and filled in a medium plate with a filling machine to obtain a product.

Example 3. Emulsion type foundation A is dissolved by heating at 75 ° C. with stirring, uniformly decomposed and kept warm.

Keep B warmed to 80 ° C. The warmed B is gradually added to the A to emulsify the mixture, and the temperature at the time of emulsification is maintained for 10 minutes with stirring, followed by stirring and cooling to 45 ° C.

At this time, C is added, stirring and cooling are continued up to 35 ° C., taken out, and filled in a container to obtain a product.

Example 4. Oily Stick Foundation After heating A to 70 ° C. and uniformly dispersing it with stirring, B is added and the mixture is directly charged into a container while maintaining 70 ° C. Then, it is left to cool to obtain a product.

While the mixture of A is dissolved by heating at 70 ° C., dispersed while being stirred and kept warm, B which is dissolved by heating at 80 ° C. is gradually added to emulsify and hold at 75 ° C. for 5 minutes. afterwards,
When cooled to 40 ° C, C is added and cooled to 30 ° C. It was filled in a container to obtain the cosmetic cream of the present invention.

[Brief description of drawings]

FIG. 1 shows the hollow spherical organic polymer (MMA / E in the present invention.
Micrograph of DMA system, average particle size of about 17μ, number of spherical vacuoles 1). FIG. 2 shows the hollow spherical organic polymer (MMA / E in the present invention.
Micrograph of DMA system, average particle diameter of about 28μ, and many spherical vacuoles). FIG. 3 shows commercially available spherical particles (manufactured by Nippon Chemical Co., Ltd., MMA / E).
Micrograph of DMA system, average particle size of about 10μ, non-porous). FIG. 4 shows commercially available porous particles (manufactured by Nippon Chemical Co., Ltd., MMA /
EDMA system, average particle size about 10μ, porous) micrograph. The magnifying power is x100. Further, in the micrograph, the black portion that can be seen inside the particle indicates a vacuole or pore in which air exists.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masayoshi Nagai 27-1 Takashimadai, Kanagawa-ku, Yokohama, Kanagawa Pola Chemical Industry Co., Ltd. Yokohama Research Laboratory (56) Reference JP-A-57-98205 (JP, A) Kosho 57-50741 (JP, B2)

Claims (3)

[Claims] 1. A hollow spherical organic polymer having an average particle diameter of 1 to 50 μm and an apparent specific gravity of 0.8 or less, and further having one or more spherical vesicles therein. And cosmetics. 2. The hollow spherical organic polymer is selected from vinyl acetate, methyl vinyl ether, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, styrene, α-methylstyrene, divinylbenzene, ethylene glycol dimethacrylate and the like. The cosmetic according to claim 1, which is a homopolymer or a copolymer composed of one or more kinds of hydrophobic monomers. 3. The cosmetic composition according to claim 1, which is a makeup cosmetic composition.