JPS63270620A - Cosmetic and production thereof - Google Patents

Abstract

PURPOSE:To obtain a cosmetic, transmitting visible rays, having excellent ultraviolet ray cutoff effects and improved dispersibility, stability, light fastness and usability, by blending complex fine particles of titanium oxide with silicon oxide and/or zirconium oxide. CONSTITUTION:Hydrogen peroxide in an amount so as to provide 1-6, preferably 2-6 ratio (H2O2/TiO2) is added to a hydrous titanic acid sol or gel or a mixture thereof to dissolve the hydrous titanic acid and prepare a homogeneous aqueous solution, which is then heated in the presence of a silicon compound, such as silicic acid solution or silica sol, or zirconium compound, such as gel or sol of hydrous zirconium oxide, or a mixture thereof at >=60 deg.C, preferably >=80 deg.C to afford a stable colloidal solution containing dispersed complex fine particles having >=4mum, preferably 5-28mum average particle diameter. The resultant colloidal solution is directly blended in a cosmetic or the solvent is replaced with an organic solvent and blended therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cosmetic containing composite fine particles of titanium oxide, silicon oxide, and/or zirconium oxide, and a method for producing the same. More specifically, it is obtained by blending fine particles of a composite of titanium oxide, silicon oxide, and/or zirconium oxide with a specific particle size into cosmetics, which transmits visible light but does not transmit ultraviolet rays. The present invention relates to a novel cosmetic that has excellent shielding effects, good dispersibility, stability, light resistance, and ease of use, and a method for producing the same.

Techniques, Background and Problems Cosmetics commonly contain titanium oxide in order to impart concealing power to the product or to obtain an ultraviolet shielding effect. In particular, there are examples of titanium oxide fine particles being added to prevent sunburn (Special Publications Publication No. 47).
-42502, JP-A-61-229809, JP-A-62
-84017>.

In addition, cosmetics containing titanium oxide fine particles surface-treated with metal soap have also been proposed (Japanese Patent Laid-Open No. 58-493).
07, Japanese Unexamined Patent Publication No. 59-172415).

When these titanium oxide fine particles are incorporated into cosmetics, they are all in powder form, and the manufacturing method is as follows:
A method of thermally decomposing titanium chloride, titanium alkoxide, etc., or a method of adding a basic aqueous solution to a titanium salt aqueous solution and hydrolyzing it, followed by dehydration, drying, and baking, are used.

However, conventional titanium oxide fine particles have poor UV-shielding effects because they are difficult to disperse as primary particles.Furthermore, when they are incorporated into lotions, for example, and the cosmetics are stored for a long period of time, the particles tend to settle and disperse. There was a major problem in that it was inferior in performance and stability. Cosmetics containing titanium oxide as described above also have a problem in that they are not necessarily fully satisfactory in terms of light resistance.

If a conventionally known titanium oxide sol with relatively good dispersibility is used instead of such fine particulate titanium oxide powder, this titanium oxide sol will become unstable if mixed with an organic solvent such as alcohol or if solvent replacement is performed. There are problems such as the particles becoming stable and gelling, and the particles settling out.Also, the conventionally known titanium oxide sol, which has relatively good dispersibility, is strongly acidic with a discharge value of 1 to 2, so it cannot be used in cosmetics. There was a problem in that it was difficult to blend.

As described above, there has not been a cosmetic containing a titanium oxide-based colloidal solution that is highly effective in preventing sunburn, has excellent transparency, and has good dispersibility.

The present inventors used composite fine particles of titanium oxide, silicon oxide, and/or zirconium oxide, which are different from conventionally known titanium oxide fine particles, and mixed them with water, alcohol, or polyhydric alcohol such as glycol or glycerin. It has been found that each of the above-mentioned performances can be satisfied by blending it into cosmetics in the form of a colloidal solution dispersed in a colloidal solution.

The present invention aims to solve the problems associated with the conventional technology as described above.The present invention is intended to solve the problems associated with the conventional technology as described above. The purpose of the present invention is to provide a cosmetic with good dispersibility, light resistance, and stability, and a method for producing the same.

Summary of the Invention The cosmetic according to the present invention is characterized by containing composite fine particles of titanium oxide, silicon oxide, and/or zirconium oxide having a specific particle size.

Furthermore, the method for producing cosmetics according to the present invention includes heat-treating an aqueous titanic acid solution obtained by adding hydrogen peroxide to a hydrous titanic acid gel or sol in the presence of a silicon compound and/or a zirconium compound. The resulting colloidal solution of fine composite particles of titanium oxide, silicon oxide, and/or zirconium oxide is blended into a cosmetic base material.

Since the cosmetic according to the present invention contains composite fine particles of titanium oxide, silicon oxide, and/or zirconium oxide, it has an excellent ultraviolet shielding effect and high sunburn prevention effect, and has transparency. It has excellent dispersibility, light resistance, and stability.

Hereinafter, regarding the cosmetics and the manufacturing method thereof according to the present invention,
I will explain in detail.

Titanium oxide used in the present invention, silicon oxide and (
or) Composite particles with zirconium oxide are not simply a mixture of titanium oxide and silicon oxide, titanium oxide and zirconium oxide, or titanium oxide, silicon oxide, and zirconium oxide, but are chemically bonded to form a composite. It has a groove. The silicon oxide and zirconium oxide mentioned herein include not only oxides but also hydrated oxides or hydrated oxides to which water is added.

The average particle size of the composite fine particles used in the present invention is 4 mμ
It is less than 30 mμ, preferably 5 to 28 mμ. If the average particle size is less than 4 mμ, long-term stability is lacking when incorporated into cosmetics, while if it is 30 mμ or more, long-term stability increases but transparency is undesirable.

In the present invention, the particle size of the composite fine particles is determined by plotting the projected area of the particles in a transmission electron microscope photograph, assuming a circle with the same area, and determining the diameter of the circle as the particle size of the composite fine particles according to the present invention. And so.

Next, a method for producing a colloidal solution of composite fine particles used in the present invention will be explained.

First, a hydrous titanic acid gel or sol is prepared by a conventionally known method. Hydrous titanic acid gel is obtained by neutralizing an aqueous solution of a titanium salt such as titanium chloride or titanium sulfate by adding an alkali to it. Further, a hydrous titanate sol can be obtained by passing an aqueous solution of a titanium salt through an ion exchange resin to remove anions. In order to prepare such a gel or sol, not only the above-mentioned method but also a wide variety of conventionally known methods can be used.

Next, hydrogen peroxide is added to the gel or sol of hydrous titanic acid obtained as described above, or a mixture thereof to dissolve the hydrous titanic acid to prepare a homogeneous aqueous solution. At this time, it is preferable to heat or stir as necessary. At this time, if the concentration of titanium oxide is too high, it will take a long time to dissolve the hydrous titanic acid, and undissolved gel will precipitate, or the resulting aqueous solution will become too viscous, so this is not preferable. do not have. For this reason, hydrated titanium! The i concentration is preferably about 10 Iffi% or less, preferably about 5 mono% or less, as TiO2.

The amount of hydrogen peroxide that should be added is 1202/T! If the weight ratio of titanic acid is 1 or more, hydrous titanic acid can be completely dissolved. ]-]202/T! If the 02 ratio is less than 1, the hydrous titanic acid will not be completely dissolved and unreacted gel or sol will remain, which is not preferable. Also H2O2/T
! The larger the 02 ratio, the faster the dissolution rate of hydrous titanic acid is and the reaction will complete in a shorter time. However, if too much hydrogen peroxide is used, a large amount of unreacted hydrogen peroxide will remain in the system. This is not preferable because it has a negative effect on the next process. Therefore, if the 1-12 o2/Tie2 ratio is 1
It is desirable to use hydrogen peroxide in an amount such that the amount is preferably about 2 to 6. If hydrogen peroxide is used at such times, the hydrous titanic acid will be completely dissolved in about 2 to 20 hours. The reaction temperature at this time is desirably 50'C or higher, preferably 70C or higher.

Next, to the titanic acid aqueous solution obtained as above,
A silicon compound such as a silicic acid solution or a silica sol, a zirconium compound such as a hydrous zirconium oxide gel or sol, or the above-mentioned silicon compound and zirconium compound are mixed and heated to 60'C or higher, preferably 80C or higher.

In this way, a stable colloidal solution in which fine particles of a composite of titanium oxide, silicon oxide, and/or zirconium oxide are dispersed can be obtained. The silicic acid liquid referred to herein is a solution of a low polymer of silicic acid obtained by dealkalizing an aqueous solution of an alkali silicate such as water glass by an ion exchange method or the like.

The larger the amount of silicon compound or zirconium compound to be mixed with the titanic acid aqueous solution, the higher the long-term stability of the resulting colloidal solution, the higher the concentration of the colloidal solution, and the higher the light resistance. However, as the number of mixing ports increases, no increase in stability or light resistance is observed. Therefore, the mixing ratio of silicon compounds or zirconium compounds to achieve the object of the present invention is Ti 02 /M
Ox (weight ratio) selected from the range of 0.25 to 200 (MOx: Sf 02 and/or Zr
02>.

The timing of mixing the silicon compound and zirconium compound does not necessarily have to be after the hydrated titanic acid has been dissolved in hydrogen peroxide; instead, it is possible to mix the hydrated titanic acid at the gel or sol stage before it is dissolved in hydrogen peroxide. Alternatively, they may be mixed when preparing a gel or sol.

Generally, as a mixing method, a predetermined titanic acid aqueous solution and a silicon compound and/or a zirconium compound may be mixed at the same time.
Another method is to mix all or part of the zirconium compound and a part of the titanic acid aqueous solution, heat it, and then add the remaining titanic acid aqueous solution and the remaining silicon compound and/or zirconium compound as the reaction progresses. In short, it is necessary that the silicon compound and the zirconium compound coexist when the titanic acid aqueous solution is heat-treated.

According to the above manufacturing method, it is possible to produce 1 q of a colloidal solution in which fine particles having an average particle diameter of 4 TrLμ or more and less than 30 mμ, preferably 5 to 28 mμ are dispersed in water. Furthermore, when the average particle diameter of fine particles is DA, (1±0.3
A colloidal solution in which fine particles of extremely uniform particle size are dispersed, with 60% or more of the total particles existing in the range >DA, can be obtained.

The concentration of the composite fine particles at this time is usually about 30% by weight or less, but it can be concentrated or diluted depending on the purpose of use.

Next, after adjusting the concentration of the colloidal solution thus obtained, it is blended with other cosmetic base materials by a well-known method to obtain the desired cosmetic.

As can be seen from the above-mentioned production method, the colloi solution obtained by the present invention uses water as a dispersion medium, and its l) H
is 3 or more, usually 5 to 9.

Therefore, it will not cause any difference if it is blended into cosmetics as it is.

Further, a mixture of this water-dispersed colloidal solution with an organic solvent such as alcohol, glycol, or glycerin, or a solvent-substituted solution is also very stable even without adding a surfactant or the like. Therefore, depending on the type of cosmetics blended,
A colloidal solution of composite fine particles according to the present invention is an organic colloidal solution using the above organic solvent as a dispersion medium,
It can also be added to makeup.

In addition, titanium oxide as mentioned above, silicon oxide and (
or) Regarding the manufacturing method of composite fine particles with silconium oxide, the present applicant has previously applied for "Titania sol and its manufacturing method" (Japanese Patent Application No. 12367/1982).
and ``Titanium Oxide Sol and Method for Producing the Same'' (Japanese Patent Application No. 61-257950).

In the cosmetic according to the present invention, the blending ratio of the colloidal solution of composite fine particles varies greatly depending on the type of cosmetic, but the proportion of oxides contained in the colloidal solution (TiO2 + MOx > conversion) with respect to the total weight of the cosmetic from 0.005
A weight range of 90% by weight is preferred. If the blending vj ratio is less than 0.001% by weight, the resulting cosmetic will not have a sufficient ultraviolet shielding effect, which is not preferable.

The cosmetics according to the present invention can be in the form of powder, cake, pencil, snack, soft cream, liquid, etc., and specifically include lotion, foundation, cream, milky lotion, eye shadow, and makeup. Includes base, nail enamel, eyeliner, mascara-1 lipstick, pack, shampoo, conditioner, hair cosmetics, etc.

Effects of the invention In the present invention, the average particle size is 47 nμ or more and 30 mμ
By blending fine particles of a composite of titanium oxide, silicon oxide, and/or zirconium oxide into cosmetics, it is possible to achieve excellent transparency and UV protection, which could not be achieved by just blending conventional titanium oxide fine particles. It is now possible to produce 1 q of cosmetics with excellent anti-burning effect and light resistance, as well as good dispersibility and finish.

For example, in the past, it was difficult to incorporate titanium oxide fine particles into transparent cosmetics such as lotions, but the colloidal solution of composite fine particles used in the present invention has excellent transparency and light resistance, and is easily dispersed. Because it has good properties and long-term stability, it can be incorporated into transparent cosmetics such as lotions, and the resulting cosmetics also have excellent sunburn prevention effects.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Daijinkoshiyu (Preparation of titanium oxide-silicon oxide composite colloidal solution) Titanium sulfate was dissolved in pure water, and 1 q of an aqueous solution containing 0.4% by weight of TiO2 was prepared. While stirring this aqueous solution, 15% aqueous ammonia was gradually added.
A white slurry liquid of No. 5 was obtained. This slurry was filtered and washed to obtain a cake of hydrous titanic acid having a solid content concentration of 9% by weight.

555g of this cake, 33% hydrogen peroxide solution 600!7
and 1,340y of water at 80'C.
Heating for 2.5 hours, a solution of 2.0% by weight as TiO2
I got 00y. This titanic acid solution is yellowish-brown and transparent.
)H was 8.1.

Next, the average particle size is 7 mμ and the 5i02IN degree is 1
5% by weight silica sol 49. After mixing i, the above titanic acid solution 9009, and water 19.10 (1),
Heated at 80°C for 192 hours.

The solution was initially a yellowish brown liquid, but after 192 hours it became a pale milky white transparent colloidal liquid.

pH of this titanium oxide-silicon oxide complex colloidal solution
was 7.1, and the average particle size of the particles was 11.5TrLμ.

Next, glycerin was added to this colloidal solution, and water was distilled off by heating to obtain a glycerin-dispersed colloidal solution having a T I 02 + S I 02 concentration of 10% by weight.

(Manufacture of lotion) A lotion having the following composition was manufactured according to the following procedure.

Glycerin-dispersed colloidal solution 5.0 thousand 96 propylene glycol 4, O oiler alcohol 0,1//polyoxyethylene lauryl ether Q, 5 rt ethanol
11.5 u fragrance
0.1 Pure water
78.5! Nozome
Mix the glycerin-dispersed colloidal solution obtained as above and propylene glycol into the base water. Separately, a mixed solution of ethanol, euryl alcohol, polyoxyethylene lauryl ether, and fragrance is prepared, and the above-mentioned pure water mixed solution is added thereto.

After adding dye to adjust the color, it is filtered and used as a product.

Take a portion of this lotion, put it in a 1 m thick quartz cell, and measure the absorbance in the ultraviolet region (400 nm or less) using a spectrophotometer (Hitachi Model 330).
The above visible light transmittance was measured. The results are shown in Figure 1 (to the curve, A').

In addition, in order to evaluate light resistance, this lotion was sealed in a quartz cell, and the degree of discoloration of the lotion after being left exposed to sunlight for 30 days was observed. Similarly, the degree of discoloration was also examined after irradiation with carbon arc light for 300 hours and after irradiation with xenon lamp for 300 hours.

The results are shown in Table 1 (sample A).

Comparative Example 1 In place of the glycerin-dispersed titanium oxide-silicon oxide composite colloid 1 solution of Example 1, fine titanium oxide powder obtained by vapor phase oxidation of titanium chloride (Aerosil, P manufactured by Degutsusa) was used.
-25) glycerin dispersion (Ti 0210mFfi
The absorbance, light transmittance, and light resistance of the lotion were evaluated in the same manner as in Example 1, except that the same composition and the same method as in Example 1 were used, except that %) was used.

The results are shown in FIG. 1 (curves B and B') and Table 1 (sample B).

Table 1 The light resistance in Table 1 was evaluated by visually observing the presence or absence of blackening of the lotion after standing or irradiation, and those that did not darken were designated as Q1, and those that blackened were designated as X.

As can be seen from FIG. 1 and Table 1, the lotion of the present invention is significantly superior in ultraviolet shielding effect, transparency, and light resistance.

Example 2 Using the water-dispersed titanium oxide-silicon oxide complex colloidal solution prepared in Example 1, a cream was manufactured according to the following procedure.

(Manufacture of cream) Water-dispersed colloid solution 58.0% by weight (
TiO+SiO2: 10wt%) stearyl alcohol 5.0wt% stearic acid
8. O〃Squalane
9,5〃Propylene glycol monostearate 3. O〃 Polyoxyethylene cetyl ether 1. O Propylene glycol 830 Glycerin
4, O〃Triethanolamine
1. O Beeswax 2
．． O〃Fragrance Q,
5 u Preservative Add propylene glycol, glycerin, and triethanolamine to a suitable water-dispersed colloid solution and heat to 70°C (aqueous phase).

Separately, components other than the above are mixed and heated and melted to 70°C. This oil phase was added to the aqueous phase and uniformly emulsified using a homogenizer, and then cooled to 30°C to obtain a cream.

The obtained cream was applied to a thickness of 5 μm on a quartz plate.
Dry for 15 minutes, spectrophotometer (Hitachi Model 330)
The absorbance in the ultraviolet region was measured.

The results are shown in Figure 2 (curve C).

In addition, this cream was applied to a thickness of 35 mm (7) on a quartz plate, dried for 30 minutes, and the light transmittance at a wavelength of 500111 m in the visible light region was measured using the same spectrophotometer.
Sample C> to obtain the result.

Comparative Example 2 Instead of the water-dispersed titanium oxide-silicon oxide composite colloidal solution of Example 2, an aqueous dispersion (Ti 0210) of commercially available fine titanium oxide powder (Aerosil, P-25 manufactured by Degutsusa) was used.
Absorbance and light transmittance were measured using a cream manufactured by the same method and composition as in Example 2, except that 58.0% by weight of 58.0% (wt%) was used, and the results shown in Figure 2 and Table 2 were obtained. .

(Curved, sample D).

As is clear from FIG. 1, FIG. 2, and Table 2, the cosmetic composition containing the titanium oxide-silicon oxide composite particles according to the present invention has a It shows significantly high values in ultraviolet absorbance and visible light transmittance, and has excellent ultraviolet shielding effect and transparency. In particular, the wavelength in the region around 300nll1 almost corresponds to the UV-B region that causes sunburn, and it can be seen that the cosmetic of the present invention is excellent in preventing sunburn.

Table 2 (Preparation of titanium oxide-zirconium oxide composite colloidal solution) Zirconyl chloride was dissolved in pure water, and ZrO2 was 1.0
A %wt aqueous solution was obtained. While stirring this aqueous solution,
% ammonia water was gradually added to give a white slurry of pt-19.0). This slurry is filtered, washed,
A cake of hydrous zirconium oxide having a solid content concentration of 15.0% by weight was obtained.

13 g of this cake and 9 of the titanic acid solution obtained in Example 1
After mixing 009 and 19,100g of pure water,
It was heated at ℃ for 96 hours. The solution was initially yellowish brown, but
After 96 hours, it became a deep white transparent colloidal solution.

The l)H of the titanium oxide-zirconium oxide composite colloidal solution thus obtained was 7.6, and the average particle size of the particles was 13.1 mμ. Next, glycerin was added to this colloidal solution, water was distilled off by heating and steaming, and Ti 0
2 + Zr 028 degrees to obtain a 10Wff1% glycerin-dispersed colloidal solution.

(Production of Lotion) A lotion was produced with the same composition and method as in Example 1, except that a titanium oxide-zirconium oxide complex colloidal solution was used instead of the titanium oxide-silicon oxide complex colloidal solution.

The absorbance and light transmittance of this lotion were measured in the same manner as in Example 1, and the results were almost the same as in Example 1. Also, regarding light resistance, none of them changed color.

Example 4 (Preparation of titanium oxide-silicon oxide composite colloidal solution) A commercially available No. 3 sodium silicate solution was diluted with pure water to obtain St.
After adjusting the concentration of 02 to 5.2% by weight, dealkalization was performed with a cation exchange resin to obtain S! 1N of silicic acid solution with 02 concentration of 5.1 wt ω%. Titanic acid solution obtained in Example 1 2.5009
After mixing 146.2 g of the above silicic acid solution and 19,000 g of water, the mixture was heated at 180'C for 192 hours. 192
After an hour, a deep-pore white transparent colloidal liquid was obtained.

Discharge 1 of this titanium oxide-silicon oxide complex colloidal solution
was 7.6, and the average particle size of the particles was 11.6 mμ.

This is then concentrated and T! 02 +S! 02
An aqueous colloidal solution having a concentration of 10% by weight was obtained.

(Manufacturing method of (emulsion) 1 foundation) A foundation having the following composition was manufactured according to the following procedure.

Aqueous dispersion colloidal solution 68.1% by weight Triethanolamine 1.1 Methyl paraoxybenzoate suitable Reinforcing Lupoxymethylcellulose 0.2g % bentonite
0.5 Stearic acid
2,4〃Propylene glycol monostearate 2. Ott Cetostearyl alcohol 0.2 u Liquid paraffin 3. O Liquid lanolin 2. O Isopropyl myristate 8.5 Propyl paraoxybenzoate Appropriate amount Titanium oxide pigment
1.0% by weight
11.0 /Fragrance Appropriate amount After dispersing carboxymethylcellulose in a water-dispersed colloidal solution, bentonite is added and heated to 70'C with thorough stirring to swell the bentonite well.

Next, 1-liethanolamine and methyl p-oxybenzoate are added to this solution. Add a mixed powder of pigment and talc to this, disperse well with a colloid mill, and heat to 75°C.

Separately, a mixture of stearic acid, propylene glycol monostearate, cetostearyl alcohol, liquid paraffin, isopropyl myridate, and propyl paraoxybenzoate is prepared, heated to 80°C, mixed with the above dispersion mixture, and thoroughly stirred. Thereafter, the mixture is cooled, and a fragrance is added at 45°C, followed by stepwise cooling to room temperature.

The obtained milky lotion foundation was used by a female panelist and the finish was evaluated.

The results are shown in Table 3 (Sample E).

Comparative Example 3 Commercially available titanium oxide fine powder (manufactured by Degussa, P
-25> water dispersion (TiO2 concentration 10% by weight) at 68%
．． A milky lotion foundation was produced using the same composition and method as in Example 4, except that 1% of type was used, and the finish was evaluated in the same manner as in Example 4.

The results are shown in Table 2 (Sample F).

Table 3 Example 5 (Preparation of titanium oxide-silicon oxide composite colloidal solution) 900 g of the titanic acid solution obtained in Example 1, 13 g of silica sol with an average particle size of 7 mμ and a 5in2 concentration of 15% by weight,
and pure water1. After mixing ioog, heat at 95°C for 6
Heated for 24 hours. The mixture was initially yellowish brown, but after 6
After 24 hours, it became a milky-white and transparent colloidal solution.

The titanium oxide-silicon oxide composite colloidal solution thus obtained had a pH of 5.6 and an average particle size of 27.
It was 1 mμ.

Next, propylene glycol was added to this colloidal solution, and water was distilled off by heating and distillation to obtain a propylene glycol-dispersed colloidal solution having a TiO2+SiO2 concentration of 10% by weight.

(Manufacture of milky lotion foundation) A foundation having the following composition was manufactured according to the following procedure.

Propylene glycol dispersion colloidal solution 4.0% by weight Triethanolamine i, i% by weight Methyl paraoxybenzoate appropriate amount Carboxymethyl cellulose 0.2% by weight bentonite
0.5 Stearic acid
2,4〃Propylene glycol monostearate 2. O Cetostearyl alcohol 0.2 Liquid paraffin 3. O Liquid lanolin
2. O Isopropyl myristate 8.5 Propyl roseoxybenzoate
Suitable titane oxide pigment 8
．． O〃talli
4. O〃Fragrance
Suitable purest water
64.1% by weight pure water is heated to 70'C, bentonite is added and the mixture is swelled well. To this is added a solution in which carpoxymethylcellulose is previously dispersed in a colloidal solution dispersed in propylene glycol. Next, triethanolamine and methyl p-oxybenzoate are added to this solution. Add a pulverized mixture of pigment and talc to this, disperse well with a colloid mill, and heat to 75°C.

Separately, a mixture of stearic acid, propylene glycol monostearate, cetostearyl alcohol, liquid paraffin, isopropyl myristate, and propyl paraoxybenzoate is prepared, heated to 80'C, mixed with the above dispersion mixture, and thoroughly stirred. Thereafter, the mixture is cooled, a fragrance is added at 45° C., and the mixture is stirred and cooled to room temperature.

The obtained foundation had an excellent finish as in Example 4, and was also excellent in ultraviolet shielding effect and light resistance.

Example 6 (Evaluation of dispersion stability) The water-dispersed titanium oxide-silicon oxide complex colloidal solution obtained in Example 1 was diluted with water to obtain TiO20S+02.
Sample E with a concentration of 10 ppm and titanium oxide fine powder (manufactured by Degussa, P-25) with a concentration of 10 ppm as TiO2.
Sample F was prepared by dispersing it in water so that the amount of After these were sufficiently dispersed in water by ultrasonication for 30 minutes, the absorbance and light transmittance were measured immediately after the dispersion and after being left for one day. The measurement was carried out using a spectrophotometer (Hitachi Model 1330) with the sample placed in a 1 cm thick quartz cell.

The results are shown in Figure 3.

As can be seen from FIG. 3, both the absorbance and the light transmittance of the titanium oxide-silicon oxide composite fine particle dispersion used in the present invention show almost the same values as those immediately after dispersion even after being left for one day.

On the other hand, in a commercially available titanium oxide fine powder dispersion, most of the particles settle after being left for one day, and the absorbance and light transmittance are almost the same as the standard sample of pure water. This result shows that the titanium oxide-silicon oxide composite fine particles used in the present invention have extremely excellent dispersibility.

X dust Lu (Preparation of titanium oxide-silicon oxide composite colloidal solution) 2,500 g of the titanic acid solution obtained in Example 1 and 419.6 g of the silicic acid solution obtained in Example 4 (J, 200,000 g of water)
After mixing, the mixture was heated at 200°C for 72 hours. 72
After an hour, a deep-pore white transparent colloidal liquid was obtained.

pH of this titanium oxide-silicon oxide complex colloidal solution
was 7.3, and the average particle size of the particles was 7.2 mμ.

Next (1' F KotL 'Fr m curl, Ti O2+
A water-dispersed colloidal solution containing 30% Si02m was obtained.

(Lipstick manufacturing method) A lipstick having the following composition was manufactured by the following procedure.

Base: Water-dispersed colloid liquid 9.8 monoffi
% castor oil 40.8
# Hekylidecyl alcohol 22.5 r
/ Lanolin 3.6 / I Beeswax 4゜5 /1 Osikerite 3.61 Nokiyandelilla wax 6.3 Il Carnauba wax i, 3 7 / Antioxidant, preservative Appropriate amount Coloring material: M titanium pigment 1.8 weight %Red 202M
0.5% by weight Red No. 205
2.3 Red 227 @ A Ruki
2.3 Orange No. 201 0
After heating and melting all of the base materials except for the water-dispersed colloid and mixing them uniformly, the water-dispersed colloid is added and thoroughly stirred. Thoroughly disperse through a colloid mill. Add the coloring material, knead it with a roll mill, disperse it evenly, re-melt it, add the fragrance, re-disperse it with a colloid mill, degas it, pour it into a mold, and quickly cool it to harden it. . Remove the solidified material from the mold and load it into a container.

The obtained lipstick had an excellent finish, ultraviolet shielding effect, and light resistance.

A pack was manufactured using the 30 weight m3 water-dispersed titanium oxide-silicon oxide composite colloidal solution prepared in Example 7 according to the following procedure.

(Jelly-like peel-off type) Water-dispersed colloidal solution 15.0% polyvinyl alcohol 15.0 Carboxymethylcellulose ammonium propylene glycol 3.0 Ethanol 10. Ott Jun
Wednesday 51.5
Fragrance 0
, 5. Preservatives, antioxidants. Mix appropriate amounts of water-dispersed colloidal solution, pure water, and propylene glycol. Polyvinyl alcohol moistened with a portion of ethanol and carboxymethyl cellulose ammonium are added thereto and dissolved while heating to 70°C and stirring. A solution of fragrance, preservative, and antioxidant in the remaining ethanol was added to this mixture, mixed, and then cooled to obtain a jelly-like peel-off type pack.

The obtained pack had excellent ultraviolet shielding effect, transparency, and light resistance.

Example 9 Using the water-dispersed titanium oxide-silicon oxide complex colloidal solution prepared in Example 1, gel hair styling 11 was performed in the following procedure.
was manufactured.

(Transparent gel hair conditioner) Add carboxyvinyl polymer one by one to a mixture of water-dispersed colloid solution and pure water while stirring at room temperature to make it uniform.

Then add triethanolamine with stirring. A separately prepared ethanol phase was added to this aqueous phase and stirred to obtain a uniform transparent gel hair styling product.

The transparent gel conditioner prepared by 1q had an excellent ultraviolet shielding effect and light resistance, and was also excellent in feel when used.

Example 10 Using the water-dispersed titanium oxide-silicon oxide composite colloidal solution prepared in Example 1, a rinse was manufactured according to the following procedure.

Bear Rinse) Water-dispersed colloid liquid 40.0% by weight (
Ti 02 + Si 02 : 10%) Stearyltrimethylammonium chloride2. O Propylene glycol 5. O〃Methyl roseoxybenzoate 0.1〃Pure water
52.9 After mixing the II water-dispersed colloidal solution, pure water and propylene glycol, add stearylmethylammonium chloride, heat to 80°C with stirring to dissolve, and add methyl paraoxybenzoate to this until completely dissolved. After dissolving it in water, cool it to room temperature and use 1q of hair rinse.

The obtained hair rinse had excellent ultraviolet shielding effect and light resistance.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 are curves showing the absorbance and light transmittance of the cosmetic according to the present invention and the known cosmetic. In the figures, curve A is the curve of the cosmetic according to the present invention, and curve B is the curve of the known cosmetic. Curves A' and C are the curves of the cosmetic according to the present invention, and Bo is a curve showing the light transmittance of the cosmetic. D is a curve showing the absorbance of a known cosmetic. FIG. 3 is a curve showing the absorbance and light transmittance of the titanium oxide-silicon oxide complex colloidal solution used in the present invention and a known dispersion of titanium oxide fine powder.
．． Elo and F2°F2' represent the light transmittance and absorbance of the colloidal solution of the invention, and Fl, Flo and F2°F2' represent the light transmittance and absorbance of the known titanium oxide dispersion. Also, El, F2. Fl. F2 is a dispersion rectification curve, E1', F2', Fl. F2' shows the curve after being left for one day.

Claims (3)

[Claims] (1) A cosmetic comprising fine composite particles of titanium oxide, silicon oxide, and/or zirconium oxide. (2) The average particle size of the composite fine particles is 4 mμ or more, 30 m
The cosmetic according to claim 1, which has a particle diameter of less than μ. (3) A titanic acid aqueous solution obtained by adding hydrogen peroxide to a hydrous titanic acid gel or sol is mixed with a silicon compound and (
or) Production of a cosmetic, which comprises heat-treating in the presence of a zirconium compound and blending the resulting colloidal solution of fine composite particles of titanium oxide, silicon oxide, and/or zirconium oxide into a cosmetic base material. Method.