JPH02178219A - Titanium oxide-iron oxide multiple sol, cosmetic compounded with the sol and production thereof - Google Patents

Abstract

PURPOSE:To provide a cosmetic having excellent ultraviolet-shielding effect and containing titanium oxide-iron oxide multiple sol having excellent dispersibility in dispersion medium, long-term stability and light-resistance. CONSTITUTION:The objective titanium oxide-iron oxide multiple sol has an Fe2O3/TiO2 weight ratio of 0.05-50 (preferably 0.1-20), is extremely stable over a wide pH range (pH 3-12) and contains uniformly dispersed fine particles having particle diameter of 4-100mmu. Since the sol contains iron oxide, it exhibits excellent shielding effect even to ultraviolet radiation having wavelength of 320-400nm (especially 340-380nm) compared with titanium oxide sol having the same concentration. The multiple sol can be produced by adding hydrogen peroxide to a dispersion of hydrated titanium oxide and hydrated iron oxide to dissolve the hydrated titanium oxide and hydrated iron oxide and heating the obtained solution.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a titanium oxide/iron oxide composite sol that has excellent dispersibility in a dispersion medium, long-term stability, light resistance, etc., and a method for producing the same. the above? The present invention relates to a cosmetic containing a 16-based sol and having an excellent ultraviolet shielding effect, and a method for producing the same.

Technical background of the invention and its problems Titanium oxide is used as a compounding agent or surface coating agent for plastics etc. by utilizing its ultraviolet shielding power or high refractive index, and it is also blended into cosmetic base materials to have an ultraviolet shielding effect. It is used in the production of cosmetics with

The titanium oxide used in these applications is preferably in the form of ultrafine particles, and in particular colloidal titanium oxide (titanium oxide sol) is preferred from the viewpoint of dispersibility in a medium, stability, and the like. As such a titanium oxide sol, the present inventors proposed a titanium oxide sol having various characteristics not found in conventional titanium oxide sols in ``Titanium oxide sol and its manufacturing method'' (Japanese Patent Application No. 252953/1982).

By the way, titanium oxide fine particles that are added to cosmetics to provide an ultraviolet shielding effect are generally in the form of powder. However, the conventionally known titanium oxide powder is
It was difficult to uniformly disperse it in the cosmetic base material, and therefore its ultraviolet shielding effect was poor. Furthermore, when titanium oxide powder as described above is blended into a lotion, there are problems with dispersibility and stability, such as particles gradually settling.

In order to solve these problems, the present applicant proposed a cosmetic composition containing fine particles of a composite of titanium oxide, silicon oxide, and/or zirconium oxide in Japanese Patent Application No. 62-1.
It was proposed in No. 72293.

However, the titanium oxide sol and titanium oxide-filled aggregate fine particles as described above have an ultraviolet ray of 280 to 320nf.
It shows an excellent shielding effect against ultraviolet rays in the fl wavelength range (CUV-13 region), but it shows an excellent shielding effect against ultraviolet rays in the wavelength range of 320 to 400 nm, especially 3
There was a problem in that it did not show a sufficient shielding effect against ultraviolet rays in the wavelength range of 40 to 380 nffl (UV-A range).

Purpose of the Invention The present invention aims to solve the above-mentioned problems with titanium oxide sol, and uses titanium oxide and iron oxide sol, which have excellent shielding ability against ultraviolet rays in the UV-p and 6H regions. The object of the present invention is to provide a composite sol, a method for producing the same, and a cosmetic containing the composite sol and having an excellent ultraviolet shielding effect.

Summary of the invention The titanium oxide/iron oxide composite sol according to the present invention contains Fe2
It is characterized by an O3/Tl02 (weight ratio) of 0.05 to 50.

In addition, the method for producing a titanium oxide/iron oxide composite sol according to the present invention includes adding hydrogen peroxide to a dispersion of hydrated titanium oxide and hydrated iron oxide, and dispersing the hydrated titanium oxide and hydrated iron oxide. It is characterized by dissolving and then heating the resulting solution.

Furthermore, the cosmetic according to the present invention is characterized in that it contains titanium oxide/iron oxide composite fine particles obtained as described above.

DETAILED DESCRIPTION OF THE INVENTION A method for producing a titanium oxide/iron oxide composite sol according to the present invention will be described.

First, in the present invention, a mixed gel or sol of hydrated titanium oxide and hydrated iron oxide, or a co-precipitated gel or sol of both is prepared.

A mixed gel of hydrated titanium oxide and hydrated iron oxide is, for example, a hydrated titanium oxide gel obtained by neutralizing and hydrolyzing a titanium salt aqueous solution such as titanium chloride or titanyl sulfate, and a hydrated titanium oxide gel obtained by neutralizing iron salts such as iron chloride. It is obtained by mixing with hydrated iron oxide gel obtained by hydrolysis. Alternatively, a mixed gel can be obtained by preparing a hydrated titanium oxide gel or a hydrated iron oxide gel in advance, and adding an aqueous iron salt solution or a titanium salt aqueous solution to neutralize and hydrolyze it.

Further, the mixed sol can be obtained by peptizing the mixed gel prepared by the method described in Section 2 with an acid such as nitric acid or hydrochloric acid.

A coprecipitated gel of hydrated titanium oxide and hydrated iron oxide is obtained by neutralizing and hydrolyzing a mixed aqueous solution of a titanium salt and an iron salt. Furthermore, a sol can be obtained by peptizing this coprecipitated gel with acid. These mixed gels or sols, or coprecipitated gels or sols can be prepared not only by the above-mentioned method but also by conventionally known methods. In this specification, "hydrated titanium oxide" and "hydrated iron oxide" refer to titanium oxide, iron oxide hydrate, titanic acid, titanium hydroxide,
A general term that includes iron hydroxide.

The ratio of titanium oxide and iron oxide in the gel or sol obtained by these methods is determined by the ratio of Fe2O3/Tl in the final product.
02 (weight ratio) is 0.05 to 50, preferably 0.1 to 2
The value should be within the range of 0. Fe 203/Tl 02
If the weight ratio is less than 0.05, the effect of adding iron oxide will not be exhibited. Moreover, if the ratio of iron oxide exceeds 10, the stability of the final product sol will deteriorate. Furthermore, it becomes difficult to dissolve hydrated iron oxide with hydrogen peroxide during sol production.

Next, hydrogen peroxide is added to the gel and/or sol obtained by the above method to dissolve hydrated titanium oxide and hydrated iron oxide to prepare a uniform aqueous solution. At this time, 5
It is preferable to heat to 0° C. or higher. The amount of hydrogen peroxide added is H2O. /(TI O+Fo.03) (weight ratio) of 1.5 or more allows complete dissolution of hydrated titanium oxide and hydrated iron oxide. H2O. /(T
When I O+ Fe 20 a ) is less than 1.5,
This is not preferable because hydrated titanium oxide and hydrated iron oxide are not completely dissolved and remain. Also, H202/(TIO+Fe2
When the weight ratio of 03) is large, the solubility of hydrated titanium oxide and hydrated iron oxide is high, and the reaction is completed in a short time.

However, if too much hydrogen peroxide is used, a large amount of unreacted hydrogen peroxide remains in the system, which is not economical and also affects the next step, which is not preferable. Therefore, H2
The weight ratio of O2/(TIO2+Fe203) is 1.5 to 1
0, preferably in the range of 4 to 7. If hydrogen peroxide in this range is used, hydrated titanium oxide and hydrated iron oxide will be approximately 0.5% depending on the concentration and heating temperature.
Completely dissolves in ~8 hours.

If the concentration of hydrated titanium oxide and hydrated iron oxide is too high,
It takes a long time to dissolve, and undissolved substances may precipitate, and the resulting aqueous solution may become too viscous. Therefore, the concentration in the aqueous solution after dissolution is approximately 6 as (TlO+Fe203).
It is desirable that the amount be less than 4% by weight, preferably less than about 4% by weight.

Next, this aqueous solution can be used as is or (T10 +
After adjusting the Fe203) concentration by adding water to the aqueous solution, it is heated to 60° C. or higher, preferably 80° C. or higher for hydrolysis. In this way, a titanium oxide/iron oxide composite sol in which composite particles of titanium oxide and iron oxide are dispersed is obtained.

The titanium oxide/iron oxide composite sol here refers to a mixed sol of titanium oxide particles and iron oxide particles, a sol in which composite oxide particles in which titanium oxide and iron oxide are chemically combined, or a sol in which titanium oxide and iron oxide particles are dispersed. It means a sol in which single particles physically combined with iron oxide are dispersed, or a hybrid sol of these.

The sol obtained by the above method has a particle size of about 4 to 100 mμ.
It is a stable sol with excellent light resistance, in which fine particles with an average particle size of A sol can also be produced by heating and hydrolyzing in the presence of a compound. That is, Zn
Group II of the periodic table such as Afi, Group III such as Afi, TI
After mixing the above aqueous solution with an inorganic compound of one or more elements selected from Group IV such as Zr, SI Sn, Group V such as V, sb, and Group V such as W, The resulting mixture is heated to 60° C. or higher for hydrolysis.

The above-mentioned inorganic compounds are used in the form of salts, oxides, hydroxides, oxyacids, oxyacids, and the like. These inorganic compounds may be used in solid form or as an aqueous solution, but it is preferable to use them in the form of a gel or sol.

When the inorganic compound is used in the form of a sol, the average particle size of the dispersed particles is preferably about 30 mμ or less, preferably about 15 mμ or less. For example, in the case of silicon,
Alkali silicates, silica gels, silica sol or silicic acid liquids are used.

Here, the silicic acid liquid means a low polymer solution of silicic acid obtained by dealkalizing an aqueous alkali silicate solution by an ion exchange method or the like.

Increasing the amount of the inorganic compound mixed improves the long-term stability and light resistance of the resulting sol, and also provides a highly concentrated sol. However, after these effects reach a predetermined level, even if the amount of the inorganic compound mixed is increased any further, the effect of improving long-term stability, light resistance, etc. will not increase, which is not preferable. On the other hand, if the amount of the inorganic compound mixed is small, the effect of mixing the inorganic compound will not be achieved, which is not preferable.

Considering the above, the amount of inorganic compounds to be mixed is determined by adding hydrogen peroxide to a dispersion of hydrated titanium oxide and hydrated iron oxide to dissolve the hydrated titanium oxide and hydrated iron oxide. The ratio of the weight of titanium and iron in the resulting aqueous solution (hereinafter referred to as hydrogen peroxide dissolved aqueous solution) converted to (TIO+Fe203) and the weight of the inorganic compound converted to oxide (MO) (TIO" F 020s) /
It is preferable that MOx (weight ratio) is in the range of 0.25 to 200.

There are no particular restrictions on the method of mixing the aqueous solution of hydrogen peroxide and the inorganic compound, and a predetermined amount of the aqueous solution of hydrogen peroxide and the inorganic compound may be mixed all at once; It is also possible to first mix and heat a portion of each and then add the remainder of both as the reaction progresses. Furthermore, it is also possible to first mix and heat the entire amount of the inorganic compound and a portion of the hydrogen peroxide-dissolved aqueous solution, and then add the remaining aqueous solution.

Furthermore, the timing of mixing the inorganic compounds does not necessarily have to be after the hydrated titanium oxide and hydrated iron oxide have been dissolved in hydrogen peroxide; they can also be mixed in the gel or sol stage before being dissolved in hydrogen peroxide. Furthermore, hydrated titanium oxide and hydrated iron oxide may be mixed together when preparing a gel or sol.

In short, when the aqueous solution dissolved in hydrogen peroxide is heated and hydrolyzed, it is sufficient that the above-mentioned inorganic compound is present in the reaction system.

The titanium oxide/iron oxide composite sol obtained in this way has particles with an average particle size of 4 to 100 mμ dispersed in an aqueous dispersion medium, and has excellent dispersibility, long-term stability, and light resistance, and has a wide pH range. It is a stable sol in the region (3-12).

The titanium oxide/iron oxide composite sol obtained by the production method according to the present invention can be used as is for various purposes, but it can be concentrated to an appropriate concentration using known methods such as vacuum evaporation and ultrafiltration. It can also be used as Further, depending on the application, it may be mixed with or substituted with an organic solvent such as alcohol or glycol to form an organic solvent-dispersed sol.

Further, the sol of the present invention exhibits a color ranging from yellow to reddish brown depending on the proportion of iron oxide. Therefore, it can also be used as a stable liquid colored pigment.

Next, the cosmetic and the method for producing the same according to the present invention will be described. In the present invention, after adjusting the concentration of titanium oxide/iron oxide composite fine particles in the composite sol obtained as described above, this composite sol is mixed with other cosmetic base materials by a well-known method. By doing so, cosmetics can be obtained. As can be seen from the above-mentioned production method, the composite sol obtained in the present invention has a pH of 4 or higher, usually 5 to 9, and can therefore be incorporated into cosmetics as is.

In addition, even if the titanium oxide/iron oxide composite sol of the present invention using water as a dispersion medium is mixed with an organic solvent such as alcohol, glycol, or glycerin, or even if the solvent is replaced, the composite sol will not be affected by surfactants, etc. It is very stable even without the addition of Therefore, depending on the type of cosmetic, the composite sol according to the present invention can be blended into the cosmetic as an organic sol using the above-mentioned organic solvent as a dispersion medium.

In the cosmetic according to the present invention, the titanium oxide/iron oxide composite sol is expressed as (F (3203+Tl02)) based on the total weight of the cosmetic, although it varies depending on the type of cosmetic.
It is blended in an amount of 0.1% by weight or more, preferably 0.5% by weight or more. If the amount of the composite sol is less than 0.1% by weight, it is not preferable because the resulting cosmetic will not have a sufficient ultraviolet shielding effect.

In addition, when used as a pigment for toning makeup cosmetics, eye shadows, eyeliners, etc., it is easy to adjust the color during production, and the product has excellent sun protection effects, and the appearance color and applied color are consistent. Cosmetics with excellent effects such as no inconsistency and no change in color after application can be obtained.

The cosmetics according to the present invention can be in the form of powder, cake, pencil, snack, ointment, liquid, etc., and specifically include lotions, foundations, creams, milky lotions, eye shadows, and makeup bases. This includes nail enamel, eyeliner, mascara, lipstick, bags, shampoo conditioner, hair cosmetics, etc.

Effects of the Invention The titanium oxide/iron oxide composite sol according to the present invention has a pH of 3.
The sol is extremely stable over a wide range of particle diameters from 4 to 100 mμ, and has excellent dispersibility, long-term stability, and light resistance. In addition, since iron oxide is included, 320-400 nl11. Especially 340-3
It also has a superior shielding effect against ultraviolet rays in the 80 r+m range compared to titanium oxide sol of the same concentration.

The titanium oxide/iron oxide composite sol according to the present invention can be used in various ways by utilizing the above characteristics.

If you mix a water-dispersed sol with an organic solvent or replace the solvent to make an organic solvent-dispersed sol and use it as a compounding agent for plastics and paints, it can be used to prevent deterioration of plastics due to ultraviolet rays and discoloration of pigments in paints. You can expect good results. Furthermore, if it is incorporated into plastic film for food packaging, it can be stored for a longer period of time compared to conventional packaging materials.

Raw material plastics for eyeglass lenses (e.g. IIEM
When dispersed in ^), it becomes an eyeglass lens that has the effect of protecting the retina from ultraviolet rays.

Further, by applying a coating solution prepared by mixing and dispersing the organic solvent-dispersed sol in a coating solution for forming a transparent film onto glass and applying a transparent thin film to the glass surface, an ultraviolet-shielding glass can be obtained. In addition, by utilizing the high refractive index of titanium oxide and iron oxide in the composite sol according to the present invention, it can also be applied to positive and tic lenses to produce high refractive index lenses.

Furthermore, the composite sol according to the present invention is also useful as a stable liquid pigment of yellow to reddish brown color.

Next, the cosmetic of the present invention has an excellent ultraviolet shielding effect, and is particularly suitable for 340-300, which is easy to cause melanin pigmentation on the skin.
It very well blocks ultraviolet rays around 80 nm (UV-A region), providing excellent protection for the skin from ultraviolet rays, and has excellent dispersibility even when added to cosmetic base +4 in large quantities. It has excellent light resistance, usability, and finish. In addition, cosmetics containing titanium oxide/iron oxide composite particles with an average particle size of approximately 80 mμ or less do not lose their transparency even when added in relatively large amounts, so they are required to have a transparent feel. Suitable as a cosmetic compounding agent.

The composite sol of the present invention can be mixed with various sols including the aforementioned titanium oxide sol or the titanium oxide/cerium oxide composite sol (Japanese Patent Application No. 134161/1983) previously filed by the present inventors. Of course, it can be used.

Example 1 5 g of ferric chloride as a Fe2O3 source and 5 g of titanium tetrachloride as a TIO□ source were dissolved in pure water,
0 g of mixed aqueous solution was prepared.

15% ammonia water was gradually added to this mixed aqueous solution until the pH reached 9.0, to obtain a coprecipitated gel of hydrated titanium oxide and hydrated iron oxide.

After dehydrating and washing the coprecipitated gel thus obtained, 115 g of 35% hydrogen peroxide and 25 g of pure water were added to 110 g of the coprecipitated gel, and then heated to 80°C.
250 g of a reddish brown aqueous hydrogen peroxide solution was obtained. The pH of this aqueous hydrogen peroxide solution was 7.8. This aqueous solution was diluted with pure water to give an oxide (TiO+Fe203) of 1.0% by weight, and then heated at 95° C. for 96 hours. After 96 hours, the mixture was cooled, and a titanium oxide/iron oxide composite sol as shown in Table 1 was obtained. Further, this sol was stable even when ia reduced to a (TIO+Fe203) concentration of 20% by weight using a vacuum evaporation method.

In addition, a part of the sol obtained above was added to an oxide (TIO
e203) to a concentration of 0.05% by weight, placed in a quartz cell with a thickness of 10 mm, and the light transmittance of 260 to 600 nIl was measured using a spectrophotometer (Model 330, manufactured by Hitachi, Ltd.).

The results are shown in FIG. 1 (curve A).

Example 2 9 g of ferric chloride as a Fe203 source and 1 g of titanium tetrachloride as a TlO2 source were dissolved in pure water, and 100
0 g of mixed aqueous solution was prepared.

Thereafter, the same procedure as in Example 1 was carried out, and a transparent titanium oxide/iron oxide composite sol as shown in Table 1 was obtained.

Further, the light transmittance was measured in the same manner as in Example 1.

The results are shown in Figure 1 (curve B).

Example 3 1 g of iron sulfate as a Fe203 source and 9 g of titanium sulfate as a TlO2 source were dissolved in pure water to prepare 1000 g of a mixed aqueous solution. Thereafter, the same procedure as in Example 1 was carried out, and a transparent titanium oxide/iron oxide composite sol as shown in Table 1 was obtained.

Further, the light transmittance was determined to 71111 in the same manner as in Example 1.

The results are shown in Figure 1 (curve C).

Example 4 Hydrogen peroxide dissolved aqueous solution 2 obtained in the same manner as Example 1
After mixing 15 g of silica gel with an average particle diameter of 7 mμ, 10% by weight of 5IO21 degrees, and 9.7 kg of pure water, the mixture was heated at 150° C. for 10 hours. After cooling for 10 hours, a transparent titanium oxide/iron oxide composite sol as shown in Table 1 was obtained.

Example 5 Hydrogen peroxide dissolved aqueous solution 2 obtained in the same manner as Example 2
After mixing 250 g of a silicic acid solution (SIO 25% by weight) obtained by dealkalizing a water glass aqueous solution with a cationic resin and heating it at 170°C for 10 hours, Table 1
A titanium oxide/iron oxide composite sol was obtained as shown in .

Example 6 10 g of ferric chloride as a Fe203 source was dissolved in pure water to prepare 500 g of ferric chloride aqueous solution, which was
% of ammonia water, 80 g of hydrated iron oxide gel was obtained.

Separately, 10 g of titanium tetrachloride as a TlO2 source was dissolved in pure water to prepare 1000 g of titanium tetrachloride aqueous solution, and this was neutralized with 15% aqueous ammonia to obtain hydrated titanium oxide gel 120FC. It was done.

40 g of the above hydrated iron oxide was mixed with pure water to make 100 g, and 60 g of hydrated titanium oxide was mixed with pure water to make 100 g, and 150 g of 35% hydrogen peroxide and 5 g of pure water were mixed.
When 0 g of the solution was added and then heated to 80° C., 400 g of a reddish-brown aqueous hydrogen peroxide solution was obtained. This aqueous hydrogen peroxide solution was diluted with pure water to an oxide concentration of 1% by weight, and then heated at 95° C. for 96 hours.

After 96 hours, the mixture was cooled, and a titanium oxide/iron oxide composite sol as shown in Table 1 was obtained.

Comparative Example 1 Titanium sulfate was dissolved in pure water to obtain an aqueous solution containing 0.4% by weight of TlO2. While stirring this aqueous solution,
15% ammonia water was gradually added to obtain a white slurry liquid with pH of 8.5. This slurry is filtered and washed,
A cake of hydrated titanium oxide gel having a solid content concentration of 9% by weight was obtained.

After adding 610 g of 33% hydrogen peroxide solution and 1300 g of pure water to 550 g of this cake, the mixture was heated at 80°C for 5 hours.
2.5 kg of a 2.0% by weight solution as TlO2 was obtained.

This aqueous solution was yellow-brown and transparent, and had a pH of 8.1.

Next, 13 g of silica sol with a particle size of 7 mμ and a concentration of 15% by weight, 900 g of the above aqueous solution, and 10 g of pure water were added.
00g and then heated at 95°C for 624 hours.

The solution was initially a yellow-brown liquid, but after 624 hours, Table 1
A transparent titanium oxide sol as shown in is obtained.

A part of the obtained titanium oxide sol was diluted with pure water and TIO
□The light transmittance was measured in the same manner as in Example 1, with the concentration being 0.05% by weight.

The results are shown in Figure 1 (curve D).

As is clear from the comparison of curves A-D, the titanium oxide/iron oxide composite sol of the present invention has an excellent shielding effect against ultraviolet rays, especially in the UV-A region, compared to a titanium oxide sol that does not contain iron oxide. I understand that.

Table oleyl alcohol 0.1% by weight Example 7 The titanium oxide/iron oxide composite sol obtained in Example 1 was
A lotion was prepared by blending the following ingredients in the following manner.

・Titanium oxide/iron oxide composite sol (TIO2+ve203-20% by weight) to, o
Weight%・Propylene glycol 4.0% by weight・Polyoxyethylene lauryl ether 0.5% by weight・Ethanol 11.5% by weight・
The titanium oxide/iron oxide composite sol obtained in Example 1 and propylene glycol were mixed with 0.1% by weight of fragrance, 73.8% by weight of pure water, and an appropriate amount of dyestuff in pure water. Separately, a mixture of ethanol, oleyl alcohol, polyoxyethylene lauryl ether, and fragrance was prepared, and the pure water mixture was added thereto. After adding dye and adjusting the color, the mixture was filtered and made into a product.

Take a portion of this lotion and put it into a 1 inch thick quartz cell.
Light transmittance from the visible region to the ultraviolet region was measured using a spectrophotometer. (Curve A in Figure 2). 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 40 days was observed. Similarly, the degree of discoloration was 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 2.

Example 8 The titanium oxide/iron oxide composite sol obtained in Example 4 was
An emulsion foundation was prepared by blending the following ingredients in the following manner.

・Titanium oxide/iron oxide composite sol (T102+Fe2O3-20% by weight) 30.0
Weight%/Pure water
38.1 ffl amount% triethanolamine
1.1% by weight・Methyl paraoxybenzoate
Appropriate amount/carboxymethylcellulose 0.2
Weight%・Bentonite 0.5% by weight・Stearic acid 2.4% by weight
・Propylene glycol monostearate 2.0% by weight 0.2% by weight 3.0rfI amount% 2.0% by weight 8.5% by weight eCetostearyl alcohol・Liquid paraffin・Liquid lanolin・Isopropyl myristate・Titanium oxide pigment 1 .0% by weight・Tall 1■
,0% by weight・Fragrance
After dispersing an appropriate amount of titanium oxide/iron oxide composite sol in pure water, carboxymethylcellulose was dispersed therein. Bentonite was added to this, and the mixture was heated to 70° C. with thorough stirring to cause the bentonite to swell well. Next, triethanolamine and methyl hydroxybenzoate were added to this solution. A mixed pulverized mixture of pigment and talc was added to this, well dispersed with a colloid mill, and heated to 75°C.

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

The thus obtained foundation had an excellent effect of shielding ultraviolet rays including the UV-A region, and was also excellent in feel upon use.

Example 9 The titanium oxide/iron oxide composite sol obtained in Example 2 was
A liquid eyeliner was prepared by blending the following ingredients and the following manner.

・Titanium oxide/iron oxide composite sol (TiO2+Pe203-:lo weight%) 40.
0% by weight ・Polyacrylic acid emulsion resin (50% liquid) 30.0% by weight ・3% bentonite dispersion 20.0% by weight ψ Butylene glycol 5.0% by weight ・Precipitated calcium carbonate 5.0% by weight 96 ・Preservation Agent Appropriate amount/pure water
Appropriate amount/Fragrance
Add appropriate amount of bentonite 3% dispersion, titanium oxide/iron oxide composite sol, precipitated calcium carbonate, preservative,
Add flavoring ingredients one by one and pass through a homogenizer. Add polyacrylic acid emulsion resin to this and stir to make it uniform. The color of the thus obtained liquid eyeliner after application to the skin was the same as the appearance color, and was stable without pigmentation even after application.

Comparative Example 2 A lotion was produced in the same manner as in Example 7, except that the titanium oxide sol (T102: 20 mm%) of Comparative Example 1 was used instead of the titanium oxide/iron oxide composite sol of Example 7. did. The light transmittance of this lotion is shown in FIG. 2 (curve B). Furthermore, the light resistance was evaluated in the same manner as in Example 7, and the results are shown in Table 2.

As can be seen from FIG. 2 and Table 2, the lotion of the present invention is superior to the lotion containing titanium oxide sol in the ultraviolet shielding effect including the UV-A region and the light resistance.

Table 2 T=1 figure

[Brief explanation of the drawing]

In FIG. 1, curve A1, curve B, and curve C are curves showing the light transmittance of the titanium oxide/iron oxide composite sol according to the present invention, and the curved line is a curve showing the light transmittance of the titanium oxide sol. In FIG. 2, curve A is F e 20 according to the present invention.
/TiO2-1 (weight/weight) is a curve showing the light transmittance of a lotion containing a titanium oxide/iron oxide composite sol,
Similarly, curve B is a curve showing the light transmittance of the lotion containing the titanium oxide/iron oxide composite sol of FO□03/Tl07-4. Wavelength (71m) Figure 3 Procedural Amendment March 1, 1989 1, Indication of Case 1988 Patent Application No. 335,246 2, Title of Invention Titanium oxide/iron oxide composite sol and its sol Compounded cosmetics, their manufacturing methods 3, and their relationship with the amended case Patent applicant name: Catalysts & Chemicals Co., Ltd. 4, Agent (zip code 141): 2-19-2, Shigotan EIJ, Tokyo Parts Ward No. Arakyu Building
3rd floor [Telephone Tokyo (491) 31B11 hL+c (TL issue,) 7. Contents of amendment (1) In the 5th line of page 16 of the specification, "For transparent film forming" has been replaced with "For transparent film forming." ” he corrected. (2) In the specification, page 17, line 11 to line 12, r p (5 g of ferric chloride as a source of 32Oa, and T
5g as a lO2 source, r p e 2
5 g of ferric chloride as 0 a and 5 g as TlO2
Correct it with "No." (3) 9 g of ferric chloride as a source of r Fe 20 a in the 4th line to the 3rd line from the bottom of No. 18 of the specification;
1 g as a TlO2 source, r F e
9g of ferric chloride as 203 and 1g as T10□
Correct it with "No." (4) From line 7 to line 8 on page 19 of the specification, 1 g of iron sulfate as a source of r p e 20 a and Tl
The statement "9 g as an O2 source" is corrected to "1 g of iron sulfate as Fe2O3 and 9 g of TlO2." (5) In the second line from the bottom of page 19 of the specification, "silica gel" is amended to "silica sol." (6) In lines 6 to 7 of page 20 of the specification, the phrase "cation resin" is amended to read "cation exchange resin." (7) On page 20, line 12 of the specification, “Fe2O
The phrase "as three sources" has been corrected to "as r Fe 20 a." (8) On page 20, line 15 of the specification, “Gel 80
Correct "cake 80g" instead of "g". (9) In the fifth line from the bottom of page 20 of the specification, the phrase "separately as a TlO2 source" is corrected to "separately as a TlO2 source." (10) In the second line from the bottom of page 20 of the specification, "Gel 120gJ" is corrected to "cake 120gJ." (11) In the specification, page 28, line 1, "No pigmentation." The statement was corrected to ``no color change.'' (12) In the third to last line from the bottom of page 29 of the specification, "Curve B similarly shows the light transmission of lotion containing a titanium oxide/iron oxide composite sol of FeO/TiO2-4. "Curve B is a curve showing the light transmittance of a lotion containing titanium oxide sol."

Claims (1)

[Claims] 1) Fe_2O_3/TiO_2 (weight ratio) is 0.05
A titanium oxide/iron oxide composite sol consisting of ~50. 2) Oxidation characterized by adding hydrogen peroxide to a dispersion of hydrated titanium oxide and hydrated iron oxide to dissolve the hydrated titanium oxide and hydrated iron oxide, and then heating the resulting solution. Method for producing titanium/iron oxide composite sol. 3) Hydrogen peroxide is added to a dispersion of hydrated titanium oxide and hydrated iron oxide to dissolve the hydrated titanium oxide and hydrated iron oxide, and then the resulting solution is added to a dispersion of hydrated titanium oxide and hydrated iron oxide. Production of a titanium oxide/iron oxide composite sol characterized by heating in the coexistence of an inorganic compound of one or more elements selected from Group III, Group IV, Group V, and Group VI. Method. 4) A cosmetic characterized by containing titanium oxide/iron oxide composite fine particles. 5) Titanium oxide according to claim 1, 2 or 3.
A method for producing a cosmetic, which comprises blending an iron oxide composite sol into a cosmetic base material.