JP3205249B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic provided with ultraviolet shielding properties.

[0002]

2. Description of the Related Art Metal oxide powders used in cosmetics have specific coloring power and are used as pigments, and also have functions such as ultraviolet shielding property, infrared shielding property and antibacterial property. Some of them are used as functional materials because they have them.

If the particle size of these metal oxide powders is reduced, for example, to 0.1 μm or less, visible light (
(0.4-0.8 μm) is transmitted with very little absorption. As a result, the metal oxide powder becomes transparent. For example, hematite (ferric oxide: Fe ₂ O ₃ ), which is used as a red pigment, if the particle diameter is reduced to 0.1 μm or less, the coloring power is reduced, but instead, a color excellent in transparency is obtained. An even red color can be developed.

[0004] In recent years, there has been a tendency for consumers to weaken the concealing power of the cosmetic and to have a natural finish when the cosmetic is used. In this sense, the cosmetics have excellent transparency. Metal oxide fine powder can be said to be a raw material suitable for producing such cosmetics. In the case of functional materials, the performance often depends on the size of the surface area, and the higher the surface area, the higher the tendency to be. Therefore, if the metal oxide has a particle size of 0.1 μm or less, the surface area is Since the size is remarkably large, higher functions can be obtained.
Generally, in the case of a metal oxide fine particle powder having a function such as an ultraviolet shielding property and an antibacterial property, this is well applied.

Therefore, the particle diameter of the metal oxide is set to 0.1 μm.
If it is less than m, both transparency and functionality can be significantly increased, and the usefulness as a raw material for cosmetics will also increase. In addition to transparent and UV-shielding powder, besides the method using metal oxides described above, benzophenone-based, benzotriazole-based and salicylate-based organic UV absorbers There is also a method using powder.

However, these organic UV absorbers are:
In general, since the solubility in the resin is not so high, it is difficult to produce a resin powder containing an organic UV absorber at a high concentration, and a resin powder containing such a low concentration of an organic UV absorber is difficult. If an attempt is made to produce a cosmetic having a sufficient ultraviolet shielding effect using the body, the amount of the resin powder must be increased, which hinders the product design of the cosmetic.

[0007] In general, organic UV absorbers are
It is easier to bleed out than resin powder and tends to come out on the surface of the resin. It has been pointed out that there is a possibility of causing allergic symptoms at the time of the treatment, and there is a concern about such safety in the case of the organic ultraviolet absorbent which has bleed out on the surface of the resin powder.

In the above-mentioned conventional technology, in the case of a cosmetic using a metal oxide having an ultraviolet shielding property, if the particle diameter of the metal oxide is reduced, the usefulness as a raw material of the cosmetic is increased. Is not always a good thing,
There are also disadvantages. For example, when the particle diameter decreases, the surface area of the particles increases, and the surface energy increases remarkably, so that the particles are easily aggregated. Even if the primary particles are 0.1 μm or less, they become much larger as the secondary particles. It becomes difficult to exhibit transparency.

On the other hand, when the particle diameter is 0.1 μm or less, the surface energy becomes large, so that the particles have a rough feel when coming into contact with the skin, which is a disadvantage as a raw material for cosmetics. Further, when the particle size is such a small value, catalytic activity may occur, and when incorporated into cosmetics, it acts on a vehicle of other components to induce phenomena such as alteration, coloring, and gelling. Sometimes.

[0010] For this reason, there has been a problem that it is considerably technically difficult to use such metal oxide fine particles as a raw material for cosmetics. In addition, cosmetics that use resin powder that contains an organic UV absorber and have ultraviolet shielding properties have to increase the amount of the resin powder compounding material, hindering product design and causing allergic symptoms. There was a problem that it could cause it.

[0011]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in the prior art, and an object of the present invention is to use metal oxide particles contained in a resin powder. It is another object of the present invention to provide a cosmetic that eliminates technical difficulties associated with the use of metal oxide fine particles as a raw material of the cosmetic and the adverse effects of using only an organic ultraviolet absorber.

[0012]

According to the present invention, in order to achieve the above object, the cosmetic according to claim 1 has an average particle diameter of 0.003 to 0.1 μm having ultraviolet shielding ability.
1 to 50% by weight of the metal oxide
Is dispersed in a resin monomer in the presence of a dispersant, and is subjected to suspension polymerization or emulsion polymerization while maintaining the dispersion particle diameter of the metal oxide at 0.003 to 0.1 μm, thereby comprising an encapsulated resin powder. It is characterized in that the resin powder is blended into a cream cosmetic, a milky cosmetic or a liquid foundation cosmetic.

Further, the cosmetic according to claim 2 is characterized in that a metal oxide having an average particle diameter of 0.003 to 0.1 μm having an ultraviolet shielding ability is added in the presence of a dispersant in an amount of 1 to 50% by weight based on the metal oxide. By dispersing in a resin monomer and performing suspension polymerization or emulsion polymerization while maintaining the dispersion particle diameter of the metal oxide at 0.003 to 0.1 μm, the resin powder is composed of an encapsulated resin powder, and the resin powder is used for the cosmetic product. It is characterized by being blended into cosmetics molded into the shape used.

The cosmetic according to claim 3 is characterized in that the molded cosmetic is a solid white powder cosmetic, a foundation cosmetic, a stick cosmetic, a lipstick cosmetic, an eyeline cosmetic or an eye shadow cosmetic.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Cosmetics are prepared by adding a metal oxide having an ultraviolet shielding ability useful as a raw material for cosmetics into fine particles having a particle diameter of 0.003 to 0.1 μm and then adding the metal oxide to a resin powder. 0.1 ~ 30μ of resin powder containing oxide
m, and dispersed and mixed into the substrate.

The resin powder containing the metal oxide is 0.1 to
Make the particle size 30 μm. If the particle size of the resin powder is less than 0.1 μm, the dehydration treatment becomes difficult and the resin powder easily aggregates.
The cohesiveness of the resin powders becomes stronger and the dispersibility worsens, making it difficult to produce resin powder containing an ultraviolet shielding agent.
If it exceeds m, the particle size is too large to adversely affect slippage or elongation, touch, and the like, and it is difficult to uniformly impart ultraviolet shielding properties of the cosmetic. When this resin powder has a spherical shape, it has an effect of further improving elongation and slippage of the compounded cosmetic. Furthermore, since the surface of the metal oxide particles is covered with the resin, the catalytic activity is suppressed, and there is no adverse effect on other vehicles in the cosmetic. Therefore, if metal oxide fine particles are dispersed in a resin matrix, while utilizing the advantages of transparency or high functionality due to the fine particles, the disadvantages of the fine particles such as cohesiveness, poor elongation and slippage, and catalytic activity are eliminated. Be able to improve.

The particle size of the metal oxide dispersed in the resin matrix of the resin powder (hereinafter referred to as the dispersed particle size)
Is 0.003 to 0.1 μm, the fine particles of the metal oxide are
Since it is fixed in the resin, it naturally does not re-aggregate and does not grow. For this reason, if a resin with sufficiently high transparency is selected, the fine particle diameter in the resin is 0.1 μm or less and the visible light transmittance is high, so the resin powder containing such a metal oxide is totally transparent. It will be excellent in property. If the metal oxide used at this time is a functional material, its performance will be further enhanced.

As the metal oxide, those having an ultraviolet shielding function, such as zinc oxide, titanium oxide, and cerium oxide, can be used.
The resin powder having a content of 0.003 to 0.1 μm has transparency and an ultraviolet shielding function. For this reason,
If resin powder is manufactured using a metal oxide having an ultraviolet shielding function so as to have a dispersed particle diameter of 0.003 to 0.1 μm, in addition to transparency and ultraviolet shielding properties, in terms of long-term stability and safety, etc. Excellent materials can be made.

As described above, the dispersed particle diameter of the metal oxide in the resin powder is set to 0.003 to 0.1 μm. More preferably, the thickness is 0.01 to 0.05 μm. This dispersed particle size
If it is less than 0.003 μm, the degree of crystallinity is reduced and the ultraviolet shielding function is not exhibited, and if it exceeds 0.1 μm, the scattering coefficient of the particles for visible light increases, the transparency is significantly impaired, and the light transmittance decreases. And transparency becomes worse. On the other hand, if the dispersed particle diameter is 0.1 μm or less, and if it is 0.003 μm or more, which is an industrially mass-producible range, no problem occurs in the production of the resin powder.

The dispersion particle diameter in the resin is 0.003 to 0.1 μm
In order to achieve this, the particle size of the starting metal oxide must also be 0.003-0.1 μm. If the particle size of the metal oxide is less than 0.003 μm, the degree of crystallinity will decrease and the UV shielding function will not be exhibited, so there is no point in reducing the size. If it exceeds 0.1 μm, the light transmittance will decrease and the transparency will decrease. Gets worse.

Such metal oxide fine particles can be produced, for example, by the method described in JP-A-2-311314. That is, hydrogen sulfide was passed through a mixed solution of an acidic salt of zinc and ammonium acetate to remove soluble salts from the obtained precipitate, and then the precipitate was dispersed in a non-aqueous solvent. Heat at ~ 400 ° C to remove gaseous matter, then dry the obtained powder to 500 ~
Heat treatment at 800 ° C. yields zinc oxide fine particles.

For many of the other metal oxide fine particles,
As described above, first, a precipitate is obtained by a neutralization reaction between the acid salt of the metal and the alkali, and then the precipitate is subjected to a high-temperature and high-pressure treatment using an autoclave, thereby producing the precipitate in the same manner as in the case of zinc oxide. can do.

However, simply mixing a powder having a primary particle diameter of 0.003 to 0.1 μm with a resin and mixing the powder with the resin will reduce the dispersed particle diameter.
It cannot be 0.003-0.1 μm, and the shape of the resin powder cannot be 0.1-30 μm spherical. It is preferable that the dispersion particle diameter is 0.003 to 0.1 μm, the particle diameter of the resin powder is 0.1 to 30 μm and the shape is spherical.

Next, the content of the metal oxide in the resin powder is preferably 1 to 80% by weight. If the content is 1% by weight or less, the content is too small. For example, this metal oxide is a functional material, and a resin powder containing the metal oxide is blended into a cosmetic to make the function of the metal oxide cosmetic. Even if it is desired to provide the cosmetic, the resin powder must be blended in a large amount in order to sufficiently exhibit the performance, and it is extremely difficult to design the blend of the cosmetic.

On the other hand, if the content is 80% by weight or more, the amount of the metal oxide relative to the resin monomer is too large at the stage of preparing the dispersion before polymerization, so that the viscosity of the dispersion becomes extremely high, Since the dispersion energy cannot be effectively given to the oxide fine particles, it is difficult to make the metal oxide fine particles highly dispersed. For this reason, it is impossible to produce a dispersion in which the dispersed particle diameter of the metal oxide is 0.003 to 0.1 μm. In this case, it becomes impossible to produce a resin powder containing a metal oxide with a dispersed particle diameter of 0.003 to 0.1 μm.

In this case, there is also a method of dispersing the metal oxide powder in a mixture of a resin monomer and a solvent, but the solvent must be considerably increased relative to the resin monomer. After polymerization, since a large amount of solvent remains in the resin powder, if the resin powder is used as a raw material for cosmetics, the solvent must be removed for safety. Remains.

For example, in Japanese Patent Publication No. 62-51931,
In that example, there is a description that a spherical porous resin powder is obtained by polymerization in a mixed system of titanium oxide fine powder, vinyl acetate, and hexane, but in this publication, in order to make the resin powder porous, Since a large amount of solvent hexane is used for vinyl acetate which is a resin monomer, after obtaining resin powder,
Repeated washing with isopropyl alcohol to remove residual hexane.

[Production of Spherical Resin Powder] When a suspension polymerization method is used, the resin powder is produced through the following steps. First Step: A metal oxide having a particle size of 0.003 to 0.1 μm is dispersed in a highly dispersed state in a resin monomer or a mixture of a resin monomer and a solvent. Second stage The dispersion obtained in the first stage is mixed with an aqueous phase to which a suspension protective agent has been added in the presence of a polymerization initiator, and after stirring, the temperature is raised to a temperature higher than necessary for the initiation of polymerization. , Hold for a certain time. After completion of the polymerization, the resultant is filtered, washed, and dried to obtain a resin powder as an object of the present invention.

Hereinafter, the process of each stage will be described in detail. [Process of the first step] As the resin monomer used in the first step, acrylic acid ester, methacrylic acid ester, acrylic styrene copolymer, vinyl acetate, polyamide, epoxy resin, urethane, polyester, silicone resin, etc. Use the selected one. That is, any polymer can be used as long as it has high transparency and can be used as a raw material for cosmetics.

The weight ratio between the metal oxide and the resin monomer is:
(Metal oxide) / (resin monomer) = 70/30 or less is preferable. If the ratio is higher than this ratio, the viscosity of the liquid increases, and it is difficult to make the metal oxide into a good dispersion state. The metal oxide particles are dispersed in these resin monomers. At this time, an organic solvent may be used as necessary to promote the dispersion. The organic solvent used here is, for example, alcohols such as isopropyl alcohol, ketones such as methyl ethyl ketone, esters such as ethyl acetate, etc., as long as they can be easily removed by drying in the final step of the second stage. However, the present invention is not limited to this.

The amount of the organic solvent to be added to the resin monomer is within a range where a good dispersion state of the metal oxide can be ensured.
The less is better. The smaller the amount added, the better
This is because the removal of the organic solvent is facilitated by evaporation in the drying step. The technical point of the first stage is 0.0
When a metal oxide having a particle size of 03 to 0.1 μm is dispersed in a resin monomer or a mixture of a resin monomer and a solvent, it is how to select an appropriate dispersant.

As the dispersing agent to be used, a dispersing agent having high affinity with the resin monomer and having high hydrophobicity in consideration of the production in the second step as described later is preferable. That is,
The dispersant promotes dispersion of the resin monomer by coating the metal oxide, and at the same time, the metal oxide particles become almost monodispersed in a relatively short time, and the dispersed particle diameter becomes 0.003 to 0.1 μm. .

Further, since the dispersant imparts hydrophobicity to the metal oxide particles, when the resin monomer is polymerized in the second step,
The metal oxide particles do not escape from the polymer and help to be incorporated into the resin without moving into the aqueous phase. Such dispersants include carboxylic acids or salts thereof (eg, sodium carboxymethylcellulose), sulfonic acids or salts thereof (eg, sodium alkanesulfonate), sulfates or salts thereof (eg, polyoxyethylene nonyl phenyl ether sulfate) Sodium), phosphate esters or salts thereof (eg, polyoxyethylene oleyl ether diethanolamine phosphate), and phosphonic acid or salts thereof (sodium lauryl phosphate).
These dispersants must at the same time be recognized as raw materials for cosmetics.

The addition ratio of the dispersant to the metal oxide is 1 to
50% by weight is preferred. If the addition rate is less than 1% by weight, it is too small to cover the surface of the metal oxide and a sufficient dispersion state of the metal oxide cannot be obtained, while if it is more than 50% by weight, the addition rate is further increased. However, the dispersibility cannot be further improved, and the dispersant is wasted.

Examples of the dispersing device include a ball mill, a sand mill, an ultrasonic dispersing machine, and a homogenizer. However, the dispersing device is not limited thereto as long as it can give a sufficient dispersion energy to the dispersion system. In general, the dispersion time is preferably about 30 minutes to 2 hours, but an appropriate time may be selected in consideration of the dispersion state and the production cost. Under the above conditions, it is possible to obtain a dispersion in which the dispersed particle diameter of the metal oxide particles is 0.003 to 0.1 μm.

[Process of the Second Step] First, a polymerization initiator is added to the dispersion obtained in the first step, and this is used as a resin monomer phase. The rate of addition of the polymerization initiator to the resin monomer is usually 0.1 to 0.5% by weight. In this case, the polymerization initiator may be dissolved in the resin monomer and then added to the dispersion.

As the polymerization initiator, benzoyl peroxide,
Lauroyl peroxide, tert. Peroxide such as -butylperoxy 2-ethylhexanoate, 2,2 azobis 2,
Examples include azo compounds such as 4-dimethylvaleronitrile and 2,2 azobisisobutyronitrile. A suspending agent for stabilizing the resin monomer in the aqueous phase is added to the aqueous phase in advance. The suspension protectant includes an organic type and an inorganic type. Examples of the organic suspension protectant include partially saponified polyvinyl alcohol, polyvinylpyrrolidone, gelatin, starch, and the like. Also,
Examples of the inorganic suspension protective agent include phosphates such as magnesium and calcium, and anionic surfactants are often used in combination with these.

The addition ratio of the suspension protective agent to the resin monomer is 0.5 to 10% by weight, and when a surfactant is used, 0.01 to 0.2% by weight based on water. Next, after mixing the resin monomer phase and the aqueous phase, the temperature is increased while stirring to initiate polymerization.
The temperature is preferably 50 to 80 ° C. In general, the polymerization time while maintaining the temperature is preferably about 1 to 5 hours.

The metal oxide is dispersed in the resin by the suspension polymerization process, and the dispersion particle diameter of the dispersion in the first stage is 0.003.
A resin powder taken in with a thickness of about 0.1 μm is obtained. During the suspension polymerization, the resin monomer becomes spherical in order to have the minimum surface energy in water, so that the resin powder produced after the polymerization is also spherical. At this time, the particle size of the resin powder can be determined by controlling the stirring conditions and controlling the shearing state of the spherical resin monomer.

The particle size of the resin powder is preferably 0.1 to 30 μm. Generally, when applying cosmetics to the skin, the applied thickness is
If the particle size of the resin powder is 30 μm or more, the particle size is too large as compared with the coating thickness, and lacks smoothness when applied. Also,
When the thickness is 0.1 μm or less, the dehydration treatment becomes difficult, so that the resin powder is easily aggregated. Therefore, the cohesiveness between the resin powders is increased, the dispersibility is deteriorated, and the production of fine particles becomes difficult. Continued
After filtration, the resin powder is separated from the aqueous phase, further washed, and dried at room temperature to obtain a resin powder containing metal oxide fine particles.

When compounding resin powder with cosmetics,
The amount is preferably 1 to 50% by weight. When the amount is less than 1% by weight, the amount of the resin powder is too small, so that the effect of adding the resin powder such as coloring and imparting functionality is not clearly recognized. Even if it is increased, a remarkable effect is not enhanced, so that the resin powder is wasted.

In general, fine metal oxide powders are fine as primary particles, but have a high tendency to agglomerate due to their high surface energy. In the present invention, the fine particles of the primary particles can be maintained as they are by including the metal oxide fine particles in the resin powder, and the advantages of the metal oxide fine particles can be utilized. In addition, if the particle diameter of the metal oxide included in the resin powder is 0.003 to 0.1 μm, the metal oxide has high transparency, and when the metal oxide is a functional material, the conventional metal oxide is used. It has higher functionality than when it is used, and if it is used, the resulting cosmetic can be of higher added value.

Further, a metal oxide dispersant having a particle diameter of 0.003 to 0.1 μm was prepared, and the dispersion was subjected to suspension polymerization or emulsion polymerization, so that the dispersion particle diameter of the metal oxide was 0.003 to 0.1 μm. By making a spherical resin powder of ~ 0.1 μm, the resin powder keeps the fine particles of the primary particles of the metal oxide as it is, and enhances the functional properties of the metal oxide such as transparency and ultraviolet shielding. Because it is possible to maintain and obtain a fine spherical powder, such a resin powder can be used for cream cosmetics, emulsion cosmetics, liquid foundation cosmetics, or compression molding or casting into the shape used by the cosmetics. By blending into cosmetics such as solid white powder cosmetics, foundation cosmetics, stick cosmetics, eyeline cosmetics, eye shadow cosmetics, etc. Excellent cosmetic sliding and elongation it is possible to bring out the functional properties of the oxide sufficiently obtained.

As an alternative to such an embodiment, a small amount of an organic ultraviolet absorber is added within a range that does not cause a problem due to the use of the organic ultraviolet absorber, and inorganic and organic ultraviolet absorbers are added. By using an absorbent together, both advantages may be used. In this case, as the organic UV absorber, salicylic acid UV absorber,
Examples thereof include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber. Examples of the salicylic acid-based ultraviolet absorber include pt-butylphenyl salicylate and p-octylphenyl salicylate. Benzophenone ultraviolet absorbers include 2,4-droxy-4-methoxy-
5-sulfobenzophenone and the like. Benzotriazole-based ultraviolet absorbers include 2- (2-hydroxy-5)
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3-5-di-tert-butylphenyl) -5-chlorobenzotriazole Etc. Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate, and the like.

[0045]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but it goes without saying that the present invention is not limited to the scope of these examples.

(1) Example of Dispersion as First Stage [Preparation Example 1] The following materials were mixed and dispersed for 2 hours using a ball mill to obtain a dispersion of fine zinc oxide particles. Zinc oxide (Sumitomo Osaka Cement, average particle size 0.02 μm) 40 parts by weight Methyl methacrylate (resin monomer) 50 parts by weight Dioctyl sodium sulfosuccinate (dispersant) 10 parts by weight

[Adjustment Example 2] The following materials were mixed and subjected to a dispersion treatment for 3 hours using a sand mill to obtain a dispersion liquid of fine cerium oxide. Fine particle cerium oxide (average particle size 0.02 μm) 37 parts by weight Methyl methacrylate (resin monomer) 26 parts by weight Toluene (solvent) 29 parts by weight Polyoxyethylene alkyl ether phosphoric acid (dispersant) 8 parts by weight

[Adjustment Example 3] The following materials were mixed and subjected to a dispersion treatment for 2 hours using an ultrasonic disperser to obtain a dispersion liquid of fine particle titanium oxide. Fine particle titanium oxide (average particle size 0.04 μm) 40 parts by weight Vinyl acetate (resin monomer) 50 parts by weight Disodium lauryl sulfosuccinate (dispersant) 10 parts by weight Particle size distribution of dispersed particles of metal oxide in a dispersion of not less than 10 parts by weight Was measured using an electrophoretic light scattering photometer (manufactured by Otsuka Electronics Co., Ltd.). The measurement results are shown in FIGS.

(2) Example of suspension polymerization in the second stage [Preparation Example 4] Each phase was prepared with the following composition. Resin monomer phase dispersion (according to Examples 1 to 3 and Comparative Example 1) 30 parts by weight Methyl methacrylate (resin monomer) 70 parts by weight Ethylene glycol dimethacrylate (resin monomer) 20 parts by weight 2,2 azobis 2,4 dimethylvaleronitrile (Polymerization initiator) 0.2 parts by weight Aqueous phase water 500 parts by weight Polyvinyl alcohol (degree of saponification 87%) 10 parts by weight

The resin monomer phase and the aqueous phase were mixed, and the mixture was stirred at 2,000 rpm in a homomixer to adjust the monomer droplets to about 7 μm. Next, this dispersion was transferred to a reactor equipped with a stirrer and a thermometer, and the temperature was raised to 55 ° C. to initiate polymerization. After further polymerization at this temperature for 5 hours, the mixture was cooled to room temperature, and the obtained resin powder was separated by suction filtration. After washing with an appropriate amount of warm water and methanol, it was dried at room temperature.

Each of the resin powders obtained in Preparation Example 4 was embedded in an acrylic resin, and the thickness was set to 0.1 μm using a microtom.
Cut out. This thin section is taken with a transmission electron microscope (TEM).
And the dispersion particle diameter of the metal oxide in the resin was measured. Table 1 shows the results.

[0052]

[Table 1]

Next, (resin powder) / (liquid paraffin)
= 30/70 weight ratio resin powder was sufficiently dispersed in liquid paraffin using a stirrer,
Wet with an applicator on film 25
It was applied to a thickness of μm, and its spectral transmittance was measured. The result is shown in FIG.

First, in the dispersions of Preparation Examples 1 to 3 prepared in the first stage from FIGS. 1 to 3, the dispersed particle diameters of the metal oxides are almost the same as those of the primary particles. And it is less than 0.1μm,
It can be seen that according to the method of the present invention, dispersion progresses efficiently and the state is very close to monodispersion.

Next, from the result of TEM observation (see Table 1) of the resin powder produced in the second stage, Preparation Example 4,
When the dispersion particle diameter in the dispersion is 0.1 μm or less, the dispersion particle diameter in the resin powder is also maintained at 0.1 μm or less. That is, according to the method of the present invention, the dispersed particle diameter in the dispersion liquid produced in the first stage is almost kept as it is in the resin powder after polymerization in the second stage. I understand. In addition, in order to make the dispersed particle diameter of the metal oxide in the resin powder 0.003 to 0.1 μm, it is necessary to prepare a dispersion of the metal oxide having a dispersed particle diameter of 0.003 to 0.1 μm as a pre-polymerization stage. That is.

FIG. 5 shows the results obtained by dispersing the resin powder prepared in Preparation Example 4 in liquid paraffin, applying the dispersion to a PET film, and measuring the spectral transmittance thereof. Resin powder made using the dispersion liquid, i.e., the dispersed particle size of the metal oxide in the resin powder is 0.003 to 0.1 μm
When a resin powder of m is applied, it is excellent in transparency of visible light and high in transparency, while on the other hand, in the ultraviolet part having a wavelength of 400 nm or less, absorption is rapidly started and the ultraviolet ray shielding effect is excellent. You can see that. This is because when the dispersed particle diameter of the metal oxide is 0.003 to 0.1 μm, it is less than one-fourth of the wavelength of visible light, so that visible light is transmitted with little scattering, and the surface area is remarkably large. This is because it becomes larger and absorbs ultraviolet rays efficiently. By the method as described above, the dispersed particle diameter of the metal oxide is 0.003 to 0.
If a resin powder having a thickness of 1 μm is made, the resin powder will be excellent in transparency and ultraviolet shielding.

(3) Example of Emulsion Polymerization in Second Stage The case where suspension polymerization is used as the polymerization method has been described above, but as a pre-stage prior to the polymerization, the dispersed particle diameter of the metal compound is 0.1 μm or less. Is not limited to suspension polymerization, and an emulsion polymerization method may be used.

The process in the case of emulsion polymerization is as follows. That is, the metal oxide particles are highly dispersed in a resin monomer or a mixture of a resin monomer and a solvent by exactly the same method as described above to prepare a dispersion. Further, a predetermined amount of an emulsifier or a dispersant is added to this dispersion. On the other hand, a polymerization catalyst is added to and dissolved in water. These two liquids are mixed and heated with stirring to start the polymerization reaction. Next, when the polymerization is completed, the mixture is filtered, washed, and dried to obtain a resin powder. In the case of emulsion polymerization, a resin powder having a smaller particle size is generally obtained than in the case of suspension polymerization.

Also in this case, when the resin monomer and the aqueous phase are mixed, the effect of minimizing the surface energy works, and the resin monomer becomes spherical, and the resin powder obtained after emulsion polymerization also becomes spherical. Further, in the previous examples, metal oxides having an ultraviolet shielding effect were selected and described in detail. However, as described above, the present invention is not limited to these metal oxides, and other Metal oxides, metal nitrides, and metal carbides may be used.

An important point of the present invention is that the dispersed particle diameter of these metal compounds is adjusted to 0.003 to 0.1 μm so as to be contained in the resin powder so that the various functions of the metal compounds can be further improved while maintaining the transparency. It is to make it show effectively. And
Since the particle size of the resin powder is spherical, when used for cosmetics and the like, elongation and slippage are improved. In addition, the catalytic activity of many fine particles against other vehicles in the cosmetic, which acts due to the large surface energy, can be significantly suppressed.

(4) Examples of Cosmetic Examples Next, examples in which the resin powder thus obtained is applied to various cosmetics will be described. [Example 1] A cream cosmetic having a sunscreen effect was prepared by the following composition. Resin powder 20 parts by weight Kaolin 2 parts by weight Cetyl alcohol 1 part by weight Vaseline 9 parts by weight Liquid paraffin 1 part by weight Silicone oil 1 part by weight Glyceryl monostearate 1 part by weight Cetyl alcohol ether 1 part by weight Propylene glycol 4 parts by weight Purified water 60 parts by weight Pigment suitable amount Here, the resin powder used in Preparation Example 4 was used.

First, a resin powder, kaolin, and a pigment were mixed by a blender to prepare a powder portion. Next, propylene glycol was added to the purified water and heated to 65 ° C. The powder portion described above was added, dispersed by a homomixer, and dissolved by heating to maintain an aqueous phase at 65 ° C. The other components in the above mixture were mixed, dissolved by heating, and maintained at 65 ° C. to obtain an oil phase. afterwards,
The oil phase was added to the aqueous phase, uniformly emulsified and dispersed with a homomixer, and stirred while cooling to obtain a sunscreen cream cosmetic.

Comparative Example 1 In place of the resin powder used in Example 1, 2 parts by weight of fine zinc oxide (manufactured by Sumitomo Osaka Cement, average particle size 0.02 μm) was used. Sunscreen cream cosmetics were prepared in exactly the same manner as in Example 5.

Example 2 An emulsion cosmetic having a sunscreen effect was prepared by the following formulation. Resin powder 10.0 parts by weight Stearic acid 2.5 parts by weight Cetyl alcohol 1.5 parts by weight Vaseline 5.0 parts by weight Liquid paraffin 10.0 parts by weight Polyethylene (10 mol) monooleate 2.0 parts by weight Polyethylene Glycol 1500 3.0 parts by weight Triethanolamine 1.0 part by weight Purified water 64.5 parts by weight Fragrance 0.5 part by weight Preservatives suitable amount Here, the resin powder used was the one prepared in Preparation Example 4.

First, stearic acid, cetyl alcohol,
Vaseline, liquid paraffin, and polyethylene monooleate are heated and dissolved, resin powder is added, mixed with a kneader, and kept at 70 ° C (oil phase). In addition, polyethylene glycol and triethanolamine are added to purified water, dissolved by heating, and kept at 70 ° C (aqueous phase). The oil phase was added to the aqueous phase, preliminarily emulsified, and then uniformly emulsified with a homomixer. After emulsification, the emulsion was cooled to 30 ° C. with stirring to obtain an emulsion cosmetic.

Comparative Example 2 1 part by weight of fine zinc oxide (manufactured by Sumitomo Osaka Cement, average particle size 0.02 μm) was used in place of the resin powder of Example 2, and the other components were the same as those of Example 2. , And the manufacturing process was exactly the same as in Example 6 to obtain an emulsion cosmetic.

Example 3 A solid white powder cosmetic product having a sunscreen effect was prepared by the following formulation. Resin powder 40.0 parts by weight Titanium dioxide 5.5 parts by weight Talc 40.0 parts by weight Stearic acid 1.5 parts by weight Lanolin 5.0 parts by weight Squalane 5.0 parts by weight Sorbitan sesquioleate 2.0 parts by weight Triethanolamine 1.0 part by weight Pigment appropriate amount Perfume appropriate amount Here, the resin powder used in Preparation Example 4 was used.

First, a resin powder, talc, and a pigment are thoroughly mixed with a kneader (powder part). Triethanolamine
Add 50 parts by weight of purified water and keep at 70 ° C (aqueous phase).
Mix the other ingredients except the fragrance, heat and dissolve and keep at 70 ° C (oil phase). The oil phase is added to the water phase, uniformly emulsified by a homomixer, added to the powder portion, kneaded with a kneader, evaporated to remove water, and processed by a crusher. Further, while stirring this well, the fragrance was sprayed uniformly and compression molded to obtain a solid white powder cosmetic.

Comparative Example 3 In place of the resin powder in Example 3, 4 parts by weight of fine zinc oxide (manufactured by Sumitomo Osaka Cement, average particle size 0.02 μm) was used. And the manufacturing process was exactly the same as in Example 3 to obtain a solid white powder cosmetic.

Example 4 A foundation cosmetic having a sunscreen effect was prepared by the following composition. Resin powder 20.0 parts by weight Talc 6.0 parts by weight Titanium dioxide 3.0 parts by weight Stearic acid 2.0 parts by weight Cetyl alcohol 0.3 parts by weight Liquid paraffin 20.0 parts by weight Polyethylene (10 mol) monooleic acid Ester 1.0 part by weight Sorbitan trioleate 1.0 part by weight Propylene glycol 5.0 parts by weight Polyethylene glycol 4000 5.0 parts by weight Triethanolamine 1.0 part by weight Pea gum 0.5 part by weight Purified water 50.2 Part by weight Pigment appropriate amount Perfume appropriate amount Preservative appropriate amount Here, the resin powder used in Preparation Example 4 was used.

First, resin powder and talc, titanium dioxide,
The pigment is mixed with a kneader (powder part). Polyethylene glycol, triethanolamine, propylene glycol, and pea gum are added to purified water and dissolved by heating. Add the powder part to the mixture, homogenously disperse the powder with a homomixer
(Water phase). The other components are mixed, dissolved by heating and kept at 70 ° C. (oil phase). The aqueous phase was added to the oil phase to carry out a reaction emulsification, uniformly emulsified and dispersed by a homomixer, and then cooled while stirring to obtain a foundation cosmetic.

Comparative Example 4 In place of the resin powder used in Example 4, 2 parts by weight of fine zinc oxide (manufactured by Sumitomo Osaka Cement, average particle size 0.02 μm) was used. And the manufacturing process was exactly the same as in Example 4 to obtain a foundation cosmetic.

Example 5 A stick cosmetic having a sunscreen effect was prepared by the following composition. Resin powder 20.0 parts by weight Kaolin 10.0 parts by weight Titanium dioxide 10.0 parts by weight Mica powder 5.0 parts by weight Iron oxide (red) 1.4 parts by weight Iron oxide (yellow) 4.0 parts by weight Iron oxide (Black) 0.1 parts by weight Solid paraffin 5.0 parts by weight Carbanalow 3.0 parts by weight Liquid paraffin 33.5 parts by weight Isopropyl myristate 5.0 parts by weight Isobitan sesquioleate 3.0 parts by weight Fragrance Appropriate amount Here, the resin powder used in Preparation Example 4 was used.

First, the resin powder, titanium dioxide, kaolin, mica powder and each iron oxide are mixed well with a blender (powder part). A part of liquid paraffin and sorbitan sesquioleate are added to the powder part, and the mixture is uniformly dispersed with a homomixer. The other ingredients are dissolved by heating, and the mixture is stirred well. This was poured into a container and cooled to obtain a stick cosmetic.

Comparative Example 5 In place of the resin powder of Example 5, 2 parts by weight of fine zinc oxide (manufactured by Sumitomo Osaka Cement, average particle size 0.02 μm) was used. A stick cosmetic was obtained in exactly the same manner as in Example 1 and the manufacturing process was exactly the same as in Example 5.

Example 6 A lipstick cosmetic having a sunscreen effect was prepared by the following composition. Resin powder 10.0 parts by weight Titanium dioxide 3.0 parts by weight Red 202 No. 0.5 parts by weight Red No. 204 2.0 parts by weight Red 223 0.05 part by weight Ceresin 12.0 parts by weight Beeswax 8.0 parts by weight Part Cetyl alcohol 5.0 parts by weight Whale wax 4.0 parts by weight Carbana wax 1.0 part by weight Liquid paraffin 21.0 parts by weight Liquid lanolin 20.0 parts by weight Butyl stearate 11.45 parts by weight Sorbitan sesquioleate 2 0.0 parts by weight Perfume Appropriate amount Antioxidant Appropriate amount Here, the resin powder used in Preparation Example 4 was used.

First, resin powder and titanium dioxide, red 20
No. 2 and Red No. 204 are added to a part of liquid paraffin and mixed well with a caller (pigment part). Red No. 223 is dissolved in brill stearic acid ester (dye part). After the other components are mixed and dissolved by heating, the pigment part and the dye part are added, and the mixture is uniformly dispersed with a homomixer. After dispersion, the mixture was poured into a mold and rapidly cooled to obtain a sticky lipstick cosmetic.

Comparative Example 6 In place of the resin powder in Example 6, 2 parts by weight of fine zinc oxide (manufactured by Sumitomo Osaka Cement, average particle size 0.02 μm) was used. A lipstick cosmetic product was obtained in exactly the same manner as in Example 1 and the manufacturing process was exactly the same as in Example 6.

Example 7 An eye shadow cosmetic product having an effect of sunscreen and light resistance was prepared by the following composition. Resin powder 20.0 parts by weight Titanium dioxide 3.0 parts by weight Kaolin 27.5 parts by weight Iron oxide (red) 6.0 parts by weight Iron oxide (yellow) 8.0 parts by weight Iron oxide (black) 6.0 parts by weight Part Pearl pigment 20.0 parts by weight Beeswax 2.0 parts by weight Hexadecyl palmitate 5.0 parts by weight Glyceryl quinostearate 0.5 parts by weight Perfume Appropriate amount Here, the resin powder was prepared in Preparation Example 4. Was used.

First, the resin powder and titanium dioxide, kaolin, each iron oxide, and pearl pigment are mixed well with a blender (powder part). After mixing other ingredients and heating and melting,
Eye shadow cosmetics were obtained by uniformly adding to the powder, treating with a crusher, and compression molding.

Comparative Example 7 In place of the resin powder used in Example 7, 2 parts by weight of fine zinc oxide (manufactured by Sumitomo Osaka Cement, average particle size 0.02 μm) was used. And the manufacturing process was exactly the same as in Example 7, to obtain an eye shadow cosmetic.

A sensory test was conducted by 20 panelists on the sunscreen cream cosmetics, milky lotion cosmetics, white powder cosmetics, foundation cosmetics, stick cosmetics, lipstick cosmetics, and eye shadow cosmetics thus prepared.
Transparency, slippage, and elongation were selected as evaluation items in this test, and each item was evaluated on a 5-point scale based on the following criteria. 1 ... bad 2 ... somewhat bad 3 ... normal 4 ... somewhat good 5 ... good The results of this sensory test are shown in Tables 2-8. In addition, the numerical value in a table | surface is an average value of the evaluation stage of 20 persons.

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

[Table 8]

From this table, a dispersion liquid was prepared using metal oxide fine particles according to Preparation Examples 1 to 3, and a resin powder having a dispersion particle diameter of 0.003 to 0.1 μm was prepared according to Preparation Example 4. For example, when making a milky lotion cosmetic, a white powder cosmetic, a foundation cosmetic, a stick cosmetic, a lipstick cosmetic, and an eye shadow cosmetic, it can be understood that these cosmetics are excellent in transparency and also excellent in sliding and elongation.

If a dispersion is prepared using a zinc oxide powder having a large particle size as in the prior art and a resin powder is prepared, the dispersed particle diameter of zinc oxide in the resin powder also increases. As a result, emulsion cosmetics, white powder cosmetics, foundation cosmetics, stick cosmetics, lipstick cosmetics, and eye shadow cosmetics have poor transparency and have a white, cloudy feel.

Also, in the case where a fine powder of zinc oxide is suddenly added to a resin monomer at the time of suspension polymerization without preparing a dispersion liquid as in the prior art to form a resin powder, and a resin powder is prepared using the same,
Again, the dispersed particle size of zinc oxide in the resin powder becomes large, and the transparency is not good.

Also, if each cosmetic is made directly from zinc oxide fine powder having a particle size of 0.1 μm or less as a raw material without producing a resin powder as in the prior art, transparency is not so good.
Also, slip and elongation are poor. Further, FIG.
Considering the measurement results of the spectral transmittance of each resin powder shown in the above, an emulsion made using a resin powder containing a metal oxide having an ultraviolet shielding function with a dispersion particle diameter of 0.003 to 0.1 μm Cosmetics, white powder cosmetics, foundation cosmetics,
Stick cosmetics, lipstick cosmetics, eye shadow cosmetics,
It can be seen that the ultraviolet shielding effect is also excellent.

[0094]

As described above, the first aspect of the present invention is as follows.
In the cosmetic according to the above, the average particle diameter having ultraviolet shielding ability
0.003 to 0.1 μm of the metal oxide is dispersed in the resin monomer in the presence of 1 to 50% by weight of the metal oxide with respect to the metal oxide, and the dispersion diameter of the metal oxide is maintained at 0.003 to 0.1 μm. By carrying out suspension polymerization or emulsion polymerization, it is composed of encapsulated resin powder, and by blending the resin powder with cream cosmetics, emulsion cosmetics or liquid foundation cosmetics, the ultraviolet-shielding metal oxide is uniformly dispersed. Dispersed emulsion cosmetics, cream cosmetics,
Alternatively, it is possible to obtain a liquid foundation cosmetic or the like, eliminating the need for an organic UV absorber, and the technical difficulties involved in using metal oxide fine particles, and by using only an organic UV absorber. The disadvantages can be eliminated together, and the ultraviolet ray shielding property can be effectively imparted to the emulsion cosmetic, and the slip and elongation of the metal oxide-containing cosmetic can be improved.

In the cosmetic according to the present invention, a metal oxide having an average particle diameter of 0.003 to 0.1 μm having ultraviolet shielding ability is added in the presence of a dispersant in an amount of 1 to 50% by weight based on the metal oxide. By dispersing in a resin monomer and performing suspension polymerization or emulsion polymerization while maintaining the dispersion particle diameter of the metal oxide at 0.003 to 0.1 μm, the resin powder is composed of an encapsulated resin powder, and the resin powder is used for the cosmetic product. By blending into cosmetics molded into the shape used, it is possible to obtain cosmetics molded with UV-shielding metal oxides uniformly dispersed, eliminating the need for organic UV absorbers and reducing metal oxides. The technical difficulties associated with the use of fine particles of the product and the harm caused by using only organic UV absorbers can be eliminated, and UV shielding properties can be effectively imparted to molded cosmetics. It is possible to improve the sliding and elongation of the metal oxide-containing cosmetics is possible.

In the cosmetic according to the third aspect,
Since the molded cosmetic is a solid white powder cosmetic, a foundation cosmetic, a stick cosmetic, a lipstick cosmetic, an eyeline cosmetic or an eye shadow cosmetic, even if it contains a metal oxide, it has a good ultraviolet shielding function of sliding and elongation. A shaped cosmetic can be obtained.

[Brief description of the drawings]

FIG. 1 is a bar graph showing the particle size distribution of Preparation Example 1 of the present invention.

FIG. 2 is a bar graph showing a particle size distribution of Preparation Example 2 in the present invention.

FIG. 3 is a bar graph showing the particle size distribution of Preparation Example 3 in the present invention.

FIG. 4 is a graph showing a spectral curve of each resin powder in the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI A61K 7/032 A61K 7/032 (72) Inventor Kenzo Teramoto 1259 Izumi, Miguchiguchi-machi, Koka-gun, Shiga Prefecture Sekisui Plastics Co., Ltd. (56 References JP-A-57-120514 (JP, A) JP-A-9-194343 (JP, A) JP-A-6-239728 (JP, A) JP-A-2-212414 (JP, A) 63-122615 (JP, A) JP-A-47-28157 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K ^7/ 00-7/50 CA (STN)

Claims (3)

(57) [Claims] (1) an average particle diameter having ultraviolet shielding ability of 0.003 to
0.1 μm metal oxide is added to the metal oxide
Dispersed in the resin monomer in the presence of 0% by weight of a dispersant,
Keep the dispersed particle diameter of the metal oxide within 0.003 to 0.1 μm.
By performing reluctant suspension or emulsion polymerization, consist was contained resin powder, cream makeup該樹Shifun body
A cosmetic, characterized in that it is incorporated into a cosmetic , emulsion cosmetic or liquid foundation cosmetic . 2. An average particle diameter having an ultraviolet shielding ability of from 0.003 to 0.003.
0.1 μm metal oxide is added to the metal oxide
Dispersed in the resin monomer in the presence of 0% by weight of a dispersant,
Keep the dispersed particle diameter of the metal oxide within 0.003 to 0.1 μm.
By performing reluctant suspension or emulsion polymerization, consist was contained resin powder, a該樹Shifun of the cosmetic
Cosmetic characterized by being blended in cosmetics that is molded into the shape to be used. Wherein the molded cosmetics, solid face powder cosmetics, foundations cosmetics, stick cosmetics, lipstick cosmetic, the cosmetic according to claim 2, wherein it is a A Irain cosmetic or eye shadow cosmetics.