JPS6284017A - Cosmetic composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent ultraviolet-shielding property and transparency, by adding a base to an aqueous solution of a metal salt such as Fe<3+>, Ti<4+>, etc., subjecting the resultant ultrafine particles of transparent metal oxide sol to coagulation, filtration, washing and dehydration and compounding a cosmetic base to the product. CONSTITUTION:A cosmetic composition can be produced by compounding 0.05-20wt%, especially 1-10wt% transparent metal oxide having an average particle diameter of <=300Angstrom , preferably <=100Angstrom , such as transparent iron oxide composite, titanium oxide, zinc oxide, etc. Concretely, the composition can be produced by adding a base such as ammonia water to an aqueous solution of a metal salt such as Fe<3+>, Ti<4+>, etc., adding a surfactant to the resultant transparent sol of hydrated metal oxide to effect the coagulation of the sol, filtering, washing and dehydrating the sol and adding or mixing the obtained transparent metal oxide to a cosmetic base. It can be produced in a short step without using organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a cosmetic composition using a transparent metal oxide with excellent visible light transmittance as an ultraviolet shielding agent.

(11) Conventional technology Ultraviolet rays are light rays with a wavelength of 400 nm or less.

Ultraviolet rays cause sunburn on the skin, causing blackening and inflammation of the skin, as well as damage to the fullergen fibers of the skin, which may cause fine wrinkles and abnormal keratosis.

Among ultraviolet rays, wavelength 2 is called the Dorneau ray.
The 90 to 320 row area reaches the papilla of the dermis, causing acute inflammation, producing redness, blisters, and erythema, and at the same time producing melanin, turning the skin black.

On the other hand, ultraviolet rays with a wavelength of 320 to 400 nm only produce black melanin.

In addition, in the presence of certain halogen phenol-based disinfectants and fragrances, the sensitivity of the skin to ultraviolet rays increases, and interactions with these substances can irritate the skin, causing toxicity and photoallergy. Sometimes.

Furthermore, cosmetic compositions contain pigments, oils, fragrances, etc., and ultraviolet rays have the effect of promoting oxidation of these materials.

For example, lotions, emulsions, and the like that contain pigments and are placed in transparent containers may cause the pigments to decompose and fade due to ultraviolet rays. In particular, official pigments that are approved for use in cosmetics are less harmful to the human body, but on the other hand,
Many are also sensitive to UV rays.

In addition, ultraviolet rays may promote the oxidation of oils, fats, and fragrances, causing deterioration and odor.

Conventionally, UV absorbers and UV scattering agents have been added to cosmetics to block UV rays, thereby preventing UV rays from reaching the skin. There is.

In particular, in cosmetics that prevent sunburn, the type and amount of ultraviolet inhibitors are determined and blended with due consideration given to the effects of ultraviolet rays on the skin, that is, the wavelength and action of ultraviolet rays.

(c) Problems to be Solved by the Invention The following two types of ultraviolet screening agents are used in sunscreen cosmetics.

(a) The first ultraviolet #X screening agent is a drug that absorbs the potential energy of ultraviolet rays and converts it into thermal energy, thereby preventing sunburn.

Examples of this type of drug include the following:

■Barami7 benzoic acid compounds Paraamy7an Q@ethyl acid, etc. ■Salicylic acid compounds, phenyl salicylate, etc. ■Cinnamic acid compounds, 4-methoxycinnamic acid-2-ethoxyethyl ester, etc. ■Azole compounds 2 <2 bHaxy 5 -Methylphenylbenzotriazole, etc.■Benzo7ene-based compounds 2-hydroxy-4-methoxybenzo7ene, etc.■Urocanine acid, etc.■Quine salts Quinine hydrochloride, quinine sulfate, quinine oleate, etc. .

The method of use varies depending on which wavelength range of ultraviolet rays the above drug absorbs (maximum absorption wavelength), but this type of drug is one type that covers a wide range of wavelengths, but it is said that it effectively absorbs over the entire wavelength range. things don't exist.

Moreover, these days, there is a fear that these ultraviolet absorbers may be absorbed into the body through the skin and cause three side effects, and for this reason, there is a tendency to avoid the use of these drugs.

(b) The second ultraviolet shielding agent is an inorganic material that effectively disrupts ultraviolet rays, thereby preventing the transmission of ultraviolet rays.

In other words, for the purpose of completely blocking ultraviolet rays from reaching the skin,
A cosmetic composition is formed by mixing titanium oxide, zinc oxide, kaolin, calcium carbonate, talc, etc. with a cosmetic base material,
This is applied to the skin to scatter ultraviolet rays, thereby preventing them from reaching the skin, thereby preventing complete sunburn.

However, the titanium oxide and iron oxide that have been used in the past have large particle sizes and a high refractive index of light, which not only absorbs ultraviolet rays but also strongly disrupts visible light. Because of their strong hiding power, cosmetic compositions containing these particles have fatal flaws, such as being opaque when applied to the skin, making the face slightly visible.

(d) Means for Solving the Problems The present inventors have attempted to solve the above problems (as a result of extensive studies, we have found that when a cosmetic base material contains ultrafine transparent metal oxide particles, ultraviolet rays are The present inventors have discovered that a cosmetic composition that absorbs effectively in a wide wavelength range and has excellent transparency can be obtained, leading to the completion of the present invention.

That is, the present invention provides a transparent iron oxide-based composite having an average particle diameter of 300 Å or less, transparent titanium oxide, transparent zinc oxide, transparent chromium oxide, transparent Kobal oxide F, and transparent tin oxide selected from the group consisting of at least 1m of transparent metal oxide 0.05-20% by weight and cosmetic base material 99.5-80fi
% of the cosmetic composition.

The present invention will be explained in detail below.

Transparent metal oxides with an average particle size of 300 Å or less used in the present invention include transparent iron oxide composites, transparent titanium oxide, transparent tin oxide, transparent zinc oxide, transparent chromium oxide, transparent Among these, transparent iron oxide complexes and/or transparent titanium oxides are safe and are effective against ultraviolet rays in a wide wavelength range. It is preferable because it absorbs or disturbs, that is, has an excellent ultraviolet light shielding effect.

Furthermore, according to the research results of the present inventors, it is not preferable that the average particle size of the transparent metal oxide exceeds 300 particles because transparency may be impaired and dispersibility in cosmetic base materials may deteriorate. .

In order to effectively exhibit the two characteristics of ultraviolet ray shielding property and visible ray transmittance, it is most preferable to adjust the average particle diameter of the transparent metal oxide to 100 Å or less.

The blending ratio of the transparent metal oxide is 0 to the total weight of the transparent metal oxide and the cosmetic base material described below.
．． It is preferably in the range of 05 to 20% by weight, particularly 1% by weight.
It is desirable that the blending ratio be in the range of ~10% by weight.If this blending ratio is less than 0.05% by weight, the UV shielding effect will be poor, which is undesirable.On the other hand, if it exceeds 20% by weight, the UV shielding effect will reach its limit. This is not preferable because it may result in the occurrence of a chemical reaction and may also deteriorate the properties of the cosmetic composition.

The transparent iron oxide-based composite used in the present invention is produced, for example, by the method described below.

That is, Fe' ten metal salts, Ti'', Zn2+, C''
Add a basic aqueous solution to a mixed salt aqueous solution of at least one of the metal salts mentioned above and p
After adjusting H to 1 to 6 and thereby forming a transparent hydrated iron oxide composite sol with a particle size of 300 Å or less, an anionic surfactant is added to this to form the hydrated iron oxide composite sol. Collect a once. Next, a water-insoluble organic solvent is added to this aggregate and vigorously stirred to transfer and disperse fine hydrated iron oxide-based composite particles into the organic solvent, after which the water is separated and the resulting The resulting organosol is evaporated and refluxed at the boiling point of the organic solvent to remove moisture, and this product is either concentrated to form a paste, or the solvent is completely removed to form a powder.

Further, transparent titanium oxide, transparent zinc oxide, transparent chromium oxide, and transparent cobalt oxide used in the present invention are produced, for example, by the following method.

That is, Ti", Zn", Cr/Co", AI3
Add a basic aqueous solution to a + metal salt aqueous solution to adjust pi to 1 to 6.
311 to! l. This creates a transparent positive hydrated metal oxide hydrosil with an average particle size of 300 Å or less corresponding to these metal ions, and an anionic surfactant is added to this to once aggregate this sol. Next, a water-insoluble organic solvent is added to this aggregate and stirred, thereby transferring and dispersing the fine hydrated metal oxide particles into the R-containing solvent, and then separating the water to form a transparent It can be obtained by preparing an organosol of hydrated metal oxide, removing the organic solvent in this organosol by distillation or other operations, and then drying and dehydrating the solid at a temperature of 300° C. or lower.

Furthermore, the transparent tin oxide used in the present invention can be removed, for example, by the following method.

That is, an aqueous solution of tin salt is hydrolyzed to produce colloidal particles, the colloidal particles are aged and washed with water, then made acidic, an organic solvent is added thereto, and the colloidal particles are transferred and dispersed in the organic solvent. It is obtained by adding a surfactant to the extent that a surfactant is added to form a substantially monomolecular adsorption layer of the surfactant on the surface of the colloidal particles, and separating the layer by standing to collect an oil layer, followed by drying.

The transparent iron oxide-based composite, transparent titanium oxide, transparent zinc oxide, transparent chromium oxide, transparent cobalt oxide, and transparent tin oxide obtained by the above method are all amorphous transparent metal oxides. Yes, visible light <2! On the other hand, it was found that it had the property of absorbing and scattering ultraviolet rays of 40 On+o or less well, and was also well dispersed in the cosmetic base material described below.

These transparent metal oxides are mixed into the cosmetic base material alone or in combination of two or more.

Furthermore, the cosmetic base material used in the present invention is not particularly limited as long as it is used for cosmetic purposes. Cosmetic base materials used to protect the skin by suppressing permeation (for example, sunscreen cosmetics), etc. are included.

Specifically, the above-mentioned cosmetic base materials include, for example, the following.

(b) Water products, such as lotions, colognes, perfumes, etc., (b) Emulsions, such as creams, milky lotions, etc., (c) Mixtures, such as lotions containing powder components, water white powder, etc., (d) Jelly-like substances. Cosmetics such as creams, bags, etc. (e) Paste cosmetics such as foundation, etc. (f) Stick cosmetics such as stink make-up products, lipstick, etc. (g)
Cake-like cosmetics, such as solid white powder, pressed products, blushers, etc. (1) Benzyl-like cosmetics, such as eyebrow ink, eyeliner, etc., (1) Aerosol-type cosmetics, such as cologne, perfume, etc., (1) Soap, for example, for cosmetics. Examples include base soap, cream soap, and the like.

The mixing ratio of the transparent metal oxide is 0.0 with respect to the total weight of the transparent metal oxide and the cosmetic base material.
It is preferable to set it as 1ailIl of 5-20 1% by weight, and it is especially desirable to set it as the range of 1-10% by weight. If the blending ratio is less than 0.05% by weight, it is undesirable because the UV-shielding effect is poor, while if it exceeds 20% by weight, there will be a limit to the UV-shielding effect and the properties as a cosmetic may deteriorate. Undesirable.

Next, the method for producing the cosmetic composition of the present invention will be briefly explained.

That is, the cosmetic composition of the present invention is prepared by putting the transparent metal oxide and the cosmetic base into a stirring device such as a Nigu, a high-speed mixing rock, or a ball mill, and stirring the same uniformly at a desired temperature. , obtained by mixing.

In this case, the desired temperature is an optimum temperature that is appropriately determined depending on the characteristics of these materials, so that the transparent metal oxide and the cosmetic base material are mixed uniformly and the cosmetic base material does not deteriorate due to heat. say.

Cosmetic compositions can be produced economically by the above-mentioned methods, but the most economical method for producing cosmetic compositions suitable for mass production is the novel method described below.

That is, the second gist of the present invention relates to a method for producing the above-mentioned cosmetic composition, in which Fe'', Ti'', Zn'', Co
A basic aqueous solution is added to an aqueous solution containing one or more metal salts of ", Cr", S n44, and A1 co+ to produce transparent positive hydration with an average particle size of 300 Å or less corresponding to these metals. A sol of a metal oxide is prepared, a surfactant is added to it, or a surfactant is added with aluminum ions added to cause the sol to aggregate, and then this aggregate is subjected to After washing, a transparent metal oxide is formed by heat treatment and dehydration under normal pressure or reduced pressure.
The present invention is characterized in that a cosmetic composition is produced by adding the transparent metal oxide to a cosmetic base material and mixing the same.

The second aspect of the present invention will be explained in detail below.

In the present invention, first, Fe'", Ti', 211
A basic aqueous solution is added to an aqueous solution containing one or more metal salts of 2+, Co'', CS÷, and Sn' to produce transparent positive hydration with an average particle diameter of 300 Å or less corresponding to these metals. The process of making 14m of metal oxide sol is carried out.

The metal salt used in the present invention is not particularly limited as long as it is water-soluble and can produce a transparent hydrated metal oxide sol in the basic aqueous solution described below, such as Fc7+, T ;4+, Zn", Co", Cr
Co +, S n4 +, A&”10 sulfate, nitrate rr & salt,
Alternatively, chlorides and the like may be mentioned, and among these, nitrates and chlorides are particularly preferred, and these may be used alone or in combination of two or more as desired.

Examples of the above-mentioned basic aqueous solutions include aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, aqueous solutions of carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and hydrogen carbonate. Examples include hydrogen carbonate such as ammonium, aqueous ammonia, and among these, aqueous ammonia is particularly preferred because it is extremely easy to remove during washing and drying.

The concentrations of each of the metal salt aqueous solution and the basic aqueous solution are appropriately determined so as to obtain a transparent metal oxide having an average particle diameter of 300 Å or less, preferably 200 Å or less, particularly preferably 100 Å or less.

The concentration of the metal salt aqueous solution is 0°1-5.
took/ (preferably in the range of l, 5Io
If it exceeds 1/1, the sol becomes cloudy, or the average particle size exceeds 300, causing precipitation or gelation, making it impossible to obtain a transparent sol; (2) is not preferable because the concentration becomes too thin, the 1 liter productivity is poor, and it is extremely uneconomical.

Further, the concentration of the basic aqueous solution is 0. 5-S
It is preferable to set it as roof/1, and 5IIIo1/
If it exceeds 1, the concentration will be too high and it will be difficult to adjust 1) 11 described below, while if it is less than 0,5 +noffi/ (1), the concentration will be too low (which is undesirable because it will be difficult to handle).

In preparing a transparent positive hydrated metal oxide sol with an average particle size of 300 Å or less corresponding to the metal by reacting this metal salt aqueous solution with a basic aqueous solution, pHl~
It is preferable to carry out the process within the range of p11G, and the particles of the transparent hydrated metal oxide sol obtained in this step A have the same size as the transparent metal oxide particles, therefore, in this step A If the generated sol is heated or left for a long time, the particles may grow and the sol may become cloudy or turn into a delta. It is necessary to avoid leaving the product for a long time before moving from step A to step B, which will be described next.

In the present invention, next, a surfactant is added to the solution obtained in the above step A''C, or a surfactant is added with aluminum ions added to form a transparent hydrated metal oxide. Step B is performed in which the sol is once aggregated.

That is, a surfactant may be directly added to the solution obtained in the above step A to once aggregate the transparent hydrated metal oxide sol, or alternatively, the solution obtained in the above step A may be added directly to the solution obtained in the above step A. To,
The transparent hydrated metal oxide sol may be aggregated by first adding aluminum ions and then adding a surfactant.

The reason why aluminum ions are added is that the surface of transparent metal oxides such as titanium oxide is coated with aluminum oxide, which improves the affinity and dispersibility with cosmetic base materials. The amount of addition is determined appropriately depending on the type of transparent metal oxide used.

Therefore, transparent metal oxides that have good affinity with cosmetic base materials and are stable in cosmetic base materials are needed as described above (
, there is no need to add aluminum ions.

Examples of the surfactant used in the present invention include sodium totyl sulfate, sodium dodecylbenzenesulfonate, sodium caproate, sodium caprylate, sodium laurate, sodium oleate, sodium alkylnaphthalene sulfonate, or phosphate ester. Salt-type anionic surfactants, such as higher alcohol phosphate hepta/ester nonatrihum salts, higher alcohol phosphate diester sodium salts, oleic acid, linoleic acid, lyluic acid, lauric acid, Fatty acids such as palmitic acid, myristic acid, and stearic acid, salts of low polymerization degree polycarboxylic acids, such as low polymerization degree polyacrylic acid sorg, low polymerization degree polybutyl acrylate, low polymerization degree polymethacrylic acid sorg, and conventional Ether surfactants such as polyoxyethylene octylphenyl ether, glycerin esters, sorbitan esters, sorbitol ether ester surfactants such as Sonoike castor oil, polyethylene glycol, glycerin, etc., which are added to cosmetics. Surfactants such as sucrose-based surfactants, nitrogen-containing surfactants such as alkylolamide, fatty acid amide-based surfactants such as polyoxyethylene stearamide, and the following general formula (however, molecular weight 5,000 to 6,000,000, In addition, surfactants such as sulfonated borisnarene represented by (or alkali metal, tetraalkylammonium hydroxide), etc. are mentioned, and among these, surfactants that are conventionally added to cosmetics, lafric acid, Preference is given to using valmitic acid, myristic acid and stearic acid.

In this step B, the amount of surfactant added varies depending on the type and amount of the transparent metal oxide and the type of surfactant used, and is appropriately determined.

In the present invention, Step C is performed in which the aggregate obtained in Step B is filtered and washed.

The most significant feature of the present invention lies in the introduction of this step C.

By filtering and washing the aggregates, the advantages described below are achieved compared to the conventional method of transferring and dispersing the aggregates into a growth solvent.

(a) First, productivity is greatly improved, mass production is realized, and fine transparent metal oxides can be obtained economically.

That is, as in the past, 1) a step of transferring and dispersing the two pseudoproducts of a hydrated metal oxide sol prepared in an aqueous solution into an organic solvent, 2) a step of further separating water to create an organosol, and 2) this step. The process of removing and recovering the organic solvent in the organosol by distillation etc. is no longer necessary, and
Since fine hydrated metal oxides are washed by repeating filtration and washing, the cleaning effect is extremely good, and PL+ can be easily neutralized, and the product has high purity and transparency.
Therefore, oxides of group 2 can be obtained.

The aggregate obtained in step B above is spongy and has a very good flow of water during filtration, so that the aggregate can be washed and filtered extremely well.

(B)? The amount of IT surfactant used can be reduced.

In the present invention, the amount of surfactant required is sufficient to coagulate the hydrated metal oxide sol obtained in an aqueous solution (1/2 to 2/3 of the amount used in conventional methods is sufficient). be.

(c) Since the excess surfactant adsorbed in the orientation can be easily removed, the content of the transparent metal oxide can be increased.

(d) Since the orientated adsorbed surfactant has a parent group on the surface of the transparent metal oxide particles, it reduces the lipophilicity of the transparent metal oxide particles.

However, surfactants that are oriented and adsorbed are physically adsorbed, and can be easily removed by repeated filtration and washing, increasing their lipophilicity, which greatly increases their dispersibility in solvents. .

(E) Since the present invention does not use an organic solvent, water-soluble low polymerization degree polyacrylic acid sodium chloride, sulfonated polystyrene, and other surfactants can be used as surfactants.
When this type of surfactant is used, its affinity with water increases, resulting in excellent dispersibility in water.For this reason, this type of transparent metal oxide is used as an aqueous (alcohol)-based cosmetic base. It can be used for materials (fragrances, etc.).

The filtration method is not particularly limited, and conventionally known methods such as suction filtration, natural filtration,
Various methods can be employed, such as pressure filtration.

In the present invention, the transparent metal oxide obtained in step C is dehydrated by heat treatment at normal pressure or in vacuum to obtain a transparent metal oxide with an average particle size of 300 Å or less. do.

This drying method is not particularly limited,
It may be heated and dried in a flame (vacuum drying, or heated and dried in an inert gas); The temperature is such that the adsorbed surfactant does not separate.Therefore, this drying temperature varies depending on the drying method, the type of hydrated metal oxide and the surfactant, but is usually 3.
The temperature is below 00°C.

In the present invention, finally, a step E is carried out in which the transparent metal oxide obtained in the above step is added to a cosmetic base material and mixed to obtain a cosmetic composition.

In this case, the mixing of the transparent metal oxide and the cosmetic base material does not require special techniques, equipment, or conditions, and can be carried out using conventionally known mixing methods such as mixing using a niegu, mixing using a high-speed mixer, etc. The cosmetic composition is mixed by a ball mill or the like.

Furthermore, the third key point of the present invention is that T H4+, Zn'', C
r", Co", S n"+, A1" A transparent positive hydrated metal with an average particle size of 300 Å or less corresponding to the metal is obtained by adding a basic aqueous solution to an aqueous solution of any one of the ten metal salts. 3' oxide sol! 51. To this, add an aqueous solution of another metal salt among the above metal salts, and add a basic aqueous solution to this mixture to prepare a transparent positive hydrated metal oxide corresponding to the other metal. to form a composite sol of transparent metal oxide, and add a surfactant to this, or
Alternatively, a surfactant is added with aluminum ions added to aggregate the composite sol, and then the aggregate is filtered, washed, and then dehydrated by heat treatment under normal pressure or reduced pressure. By making transparent metal oxides! ! ! The present invention also features a method for producing a resin composition containing the transparent metal oxide in a base material by dry mixing or melt mixing.

This third point will be explained in detail below.

In the present invention, first, Ti′, Zn”, Cr1+
, Co'', Sn4+, 80''4, for example, by adding a basic aqueous solution to an aqueous solution of 7;4+, the average particle diameter corresponding to the metal is 300.
A transparent positive hydrated metal oxide sol, in this case a transparent titanium oxide sol, of less than Å is prepared, and this is added with m! of the metal salts mentioned above. , an aqueous solution of a metal salt of Mi, i.e., Ti4“
A transparent positive hydrated metal oxide corresponding to the other metal is prepared by adding an aqueous basic solution to the mixture. A transparent metal oxide composite sol is formed by adjusting the sol.

Other conditions are the same as in the above steps.

Hereinafter, the cosmetic composition of the present invention is obtained in the same manner as steps B to E above.

The cosmetic composition thus obtained can be used in exactly the same way as conventional cosmetics.

(e) Effect The cosmetic fF1 composition of the present invention contains a transparent metal oxide with an average particle size of 300 Å or less, and the transparent metal oxide is a transparent particle with extremely excellent transparency and a visible circle. While it transmits ultraviolet rays, the amorphous metal oxide has the effect of absorbing ultraviolet rays in a wide wavelength range, or 6L.

Moreover, according to the +A method of applying the cosmetic composition of the present invention, the number of manufacturing steps of the cosmetic composition can be significantly reduced, and since no solvent is used, safety is extremely high. It has an effect.

(r) Examples Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

(1) Production of transparent metal oxide■ Production of transparent iron oxide-based composite 1+ool/1 ferric chloride aqueous solution 100J and 1 mo
B/1 water-soluble titanium chloride ifflroomN is mixed, and 200 ai' of 1.5 mol/i7 ammonia water is added to this mixed aqueous solution to prepare a transparent hydrated iron oxide-hydrated titanium oxide composite sol. The pH at that time was 3.5
), 250 wN of 0.2 mol/N sodium dodecylbenzenesulfonate aqueous solution is added to this composite sol to completely aggregate the hydrated iron oxide-hydrated titanium oxide composite particles. Next, add 300 JjlJD of xylene to the mixture and shake vigorously to transfer and disperse the composite particles into the xylene phase, and then remove water. After the second repeat, the composite sol is completely dispersed in xylene and becomes a transparent olga/sol. This orgafsol is refluxed at a temperature of about 140°C to form an iron oxide-titanium oxide olga/sol, and then distilled under reduced pressure using a water bath until all xylene is removed, leaving transparent iron oxide-titanium oxide. take this out,
Transparent iron oxide - yield as transparent titanium oxide is 91%
The average particle size was 908.

■Production of transparent titanium oxide Add 4°8 g of titanium tetrachloride to 100 nf of 0.3N hydrochloric acid.
Dissolve and add 1.5 mol/l of ammonia water to this solution for 100 mj! In addition, a transparent hydrated titanium oxide sol was prepared, and the pif at this time was 1.8).
Add 250 m/l of sodium dodecylbenzenesulfonate solution (I 250 m/l) to completely agglomerate the hydrated titanium oxide image particles.

Next, xylene 300+off was added thereto, and the same procedure as described in "2.2" below was carried out to obtain powdery transparent titanium oxide. The yield of this transparent titanium oxide was 92.0%, and the average particle size was 65.

■Production of transparent tin oxide 5nC1,・5 ■Dissolve 420130[+ in 4R of a mixed solution of water and ethanol/- (1:1 by volume), and in this solution,
5N NH,OH to pH 7, O! The colloidal particles of tin oxide are generated by adding the tin oxide at a constant rate until the amount of tin oxide is reached. This reaction is preferably carried out with good stirring. After the reaction, the above colloidal particles were
After aging at 0° C. for 3 hours, ammonia (2) cosmetic compositions (Examples ① to [Co., Ltd.]) In the examples, parts or % refer to parts by weight or % by weight.

Example■ A cosmetic base material (perfume) consisting of the following formulation is obtained.

Bergamotu oil 8 Bisweet orenno oil 5g Lemon oil 68 Orris oil
1g lavender oil
IF1 alcohol (75v/v%) 540+n
(!Preparation method: Mix the above formulation thoroughly at room temperature to form a homogeneous solution.

This solution was allowed to stand for 24 hours and then distilled to obtain a distillate (A) of 500I111.

The following formulation was added to this distillate (A), and neroli oil was added.
2.5 theory e rosemary oil
0.5+nN Petitgrain Oil 0.5iN Ansono Coraleno 7 Gu 3.0+oN Alcohol (7
5v/v%) 500. After uniformly mixing OII+N, it is aged for 2 months.

(1) per 100 parts of the cosmetic base material obtained by
) 3 parts of the transparent iron oxide-titanium oxide composite fine particles obtained in step (2) were added and blended to prepare the cosmetic JTI composition of the present invention.

Example ■ A cosmetic base material (pancake) consisting of the following formulation was obtained by the method described below.

Zinc white 3 parts Kaolin 5 parts Tal 2 3 parts Colorant 0.5 part Hydrophilic emulsifier
2 parts dehydrated uric acid/phosphorus 1 part internally colored petrolatum 5 parts propylene glyfur 3 parts fragrance 1 part Manufacturing method: Mix kaolin, talc and colorant, grind,
The powder is spread, mixed uniformly with an emulsifier and oil, and treated to make it hydrophobic, and the powder thus obtained is dried, pulverized, and pressed to obtain a cosmetic base having the above-mentioned compounding ratio.

A cosmetic composition of the present invention was obtained by adding 7 parts of the transparent titanium oxide obtained in (1) above to 100 parts of the obtained cosmetic base material.

Example ■ A cosmetic base material (water white powder) consisting of the following formulation was obtained by the method described below.

Under zinc 5 B titanium dioxide
2 parts Tal 2 5 parts Kaolin 4 parts Coloring agent 0.5 part Glycerin 5 parts Pure water 69 parts A/L/:L (75v/v%) 10
Part magnesium sulfate 0.2 part Water glass 0.1 part Boric acid 0.3 part Fragrance
0.5 part Manufacturing method: Mix titanium dioxide, talc, kaolin and coloring agent under zinc, crush and spread, first add fragrance, then add glycerin and a part of water and knead well. Make it into a paste, then gradually add water to make it into a liquid.

Finally, dissolve magnesium sulfate, boric acid, and water in a small amount of water, add alcohol, stir well, and pass through a sieve to obtain the product.

To 100 parts of this cosmetic base material, 5 parts of the transparent titanium oxide obtained in (1) (2) above were added and mixed until uniform, thereby obtaining a cosmetic composition of the present invention.

Example ■ A cosmetic base material (77th edition) consisting of the following formulation was obtained by the method described below.

Isopropyl myrite) 54.0 parts by weight Karnavaparov 5.0 parts by weight ￥L part Sarashimitsurof
1.0 part titanium dioxide 5
Part inorganic pigment 5 parts Talc
5 parts fragrance
Appropriate manufacturing method: Melt the two types at about 72℃, add isopropyl myristate, add titanium dioxide, zinc white, and talc that have been thoroughly ground in advance to this, pass through a colloid mill, and gradually stir (rotation speed 50 to 80 r, p
When the mixture has cooled to 45°C, add flavoring and pack into containers.

5 parts of the transparent iron oxide-titanium oxide composite fine particles obtained in (1) (1) above were added to 100 ffIN of the thus obtained cosmetic base material and mixed thoroughly, thereby forming the cosmetic composition of the present invention. Obtained.

Example ■ A cosmetic base material (liquid form is omitted) consisting of the following formulation was obtained by the method described below.

Liquid paraffin 39.4% oleic acid
7.3% titanium dioxide
O, 6% zinc stearate 0.4%ln
S-↓ 0.42% aluminum hydroxide 0.36% water
47.7% triethanolamine 3.7% paraoxybenzoic acid methyl ester 0.1% Fragrance Optional preparation method: Warm liquid paraffin and oleic acid to 60'C, and separately add water and triethanolamine to 60°C. After adding the warmed ingredients, zinc stearate, which has been ground in advance, pigment, and aluminum hydroxide are sequentially added, and the mixture is stirred until cooled, and when the temperature reaches 45°C, the fragrance is added.

The above (1
) 5 parts of the transparent iron oxide-titanium oxide composite image particles obtained in step (2) were added and thoroughly mixed to obtain the cosmetic composition of the present invention.

Example (2) A cosmetic base material (pencil-shaped eye shadow) consisting of the following formulation was obtained by a known method.

Ceresin 26% Hydrogenated oil 5% Castor oil ・13% Carnauba wax 4ri51 paraffin
6% titanium dioxide 8% iron oxide (ocher color) 4% iron oxide (seener color) 4% Cosmetic base material 1 thus obtained
00 parts, and 5 parts of the transparent iron oxide-titanium oxide composite particles obtained in (1) (1) above and 5 parts of the transparent titanium oxide obtained in (1) (1) above were added to prepare the cosmetic product of the present invention. A composition was obtained.

Example (2) 5 parts of the transparent tin oxide obtained in (1) (2) above was added to 100 parts of the cosmetic base material in Example (2) above to obtain a cosmetic composition of the present invention.

Example ■ 2111 ol in 2 moi'/1 ferric chloride aqueous solution 21
/1(r) Add sodium carbonate aqueous solution until pl+ becomes 4 to prepare a transparent positive water-use iron oxide sol, and add 0.2...ol/l sodium lafurinate aqueous solution 16 to this.
Add 30+aN to flocculate the water-containing iron oxide sol. Filter this and remove the precipitate from 0.01 to 0.02+eoN/I
! Washing with aqueous ammonia and filtration were repeated to bring the pH to 6.
5 to 7.0, then further 60' (: -70°C
Washing and filtration are performed twice with hot water 242. Next, this precipitate was heat treated at 2.tOoC for 1 hour and then ground to obtain transparent iron oxide powder with a V average particle diameter of 75 mm. The yield was 95%.

5 parts of the transparent iron oxide obtained in the above example ■
The cosmetic composition of the present invention was obtained by adding 7IL to 100 parts of the cosmetic base material (perfume) in the same manner as in Example (2).

Example ■ 21noi/(!2 +
no+! / i' of ammonia water is added until 1) 11 becomes 2 to prepare a transparent positive hydrated titanium oxide sol, and 6001 nl of 0°051 nol/I' of aluminum nitrate is added to this.

Then 0, 2 moI to this! / 1 sodium dodecylbenzenesulfonate aqueous solution 1 (I2170 mN
is added to coagulate the composite sol of hydrated titanium oxide and hydrated aluminum oxide.

Thereafter, filtration, washing and heat treatment were carried out in the same manner as in Example 2 to obtain transparent titanium oxide powder coated with aluminum oxide having an average particle size of 95.

The present invention was prepared by adding and mixing 5 parts of powdered transparent titanium oxide coated with aluminum oxide thus obtained to 100 parts of the cosmetic base material (pancake) in Example 2 above in the same manner as in Example 2. A cosmetic composition was obtained.

Example [Stock] 1 ωol/e ferric chloride aqueous solution and 1111Ol/e
2...ol/l for mixed dissolution of titanium tetrachloride aqueous solution II
A transparent positive composite sol of hydrated iron oxide sol and hydrated titanium oxide sol was prepared by adding an aqueous solution of sodium carbonate until the pH reached 2, followed by filtration, washing, and heat treatment for 22 hours in the same manner as in Example ①. Transparent iron oxide-titanium oxide composite fine particles having an average particle diameter of 95 mm were obtained. The yield was 93%.

The present invention was prepared by adding and mixing 5 parts of the thus obtained transparent iron oxide-titanium oxide composite fine particles to 100 parts of the cosmetic base material (foundation tan) in Example 2 above in the same manner as in Example 2. Eleven cosmetic products were obtained.

Example 0 1 moZ/N titanium tetrachloride aqueous solution 11 to 2 Tao1
/ (1) of an aqueous solution of sodium carbonate is added until pl+ becomes 2 to prepare a transparent positive hydrated titanium oxide sol, and to this is added 1 +aoN/ (l of zinc chloride aqueous solution Qlρ, and to this solution 0 , 1 + ao (1/1 aqueous sodium hydrogen carbonate solution was added until pl+ reached 2.5 to prepare a transparent composite sol of titanium oxide coated with transparent zinc oxide, and then filtered in the same manner as in Example ①. After washing and heat treatment, transparent titanium oxide-zinc oxide composite particles having an average particle diameter of 85 were obtained.The yield was 90%.

5 parts of the thus obtained transparent titanium oxide-zinc oxide composite fine particles were added to 10 parts of the cosmetic base material (water white powder) in Example ①.
A cosmetic composition of the present invention was obtained by adding and mixing to 0 parts in the same manner as in Example (2).

Example @ 1vno1/1 chromium chloride aqueous solution ll & 1Uao1/
Add an aqueous solution of sodium carbonate until 911 becomes 3 to prepare a transparent positive chromium oxide sol.
38SO+aN was added to this 0.2+aoN/1 aqueous solution of sodium dodecylbenzenesulfonate, followed by filtration, washing, and heat treatment in the same manner as in Example ①, until the average particle size was 6.
Five powdered transparent chromium oxides were obtained. The yield is 9
It was 4%.

5 parts of the thus obtained transparent chromium oxide was added to the above Example ■
A cosmetic composition of the present invention was obtained by adding and mixing 100 parts of a cosmetic base material (7 andesion).

Example ■ 0.5+++o1/1' ferric chloride aqueous solution Q250to
Add O1Smol/(l of sodium carbonate aqueous solution to 1.
Add 3 transparent positive water iron oxide sol until + is 2.5! ! sulfonated polystyrene (
The hydrated iron oxide sol is aggregated by adding 87 mN of a 1% by weight solution (molecular weight: 6,000,000).

Hereafter, filtration, washing, and heat treatment were carried out in the same manner as in Example ①.
Powdered transparent iron oxide with an average particle size of 75 was obtained. The yield was 94%.

1.5 parts of the thus obtained transparent iron oxide was added to the above Example ■
Example ■ 100 parts of makeup m base material (liquid is red)
A cosmetic composition of the present invention was obtained by adding and mixing in the same manner as above.

'X Example phase] 1 mol/(l of zinc chloride 500+n(0.2
A clear positive hydrated zinc oxide sol was prepared by adding mo1/1 ammonia water until pl+ was 2.5, and to this was added 0°5 mo(1/(l) of sodium dodecylbenzenesulfonate aqueous solution 3250+of. In addition, filtration, washing, and heat treatment were performed in the same manner as in Example ①, and the average particle size was 4.
Five powdered transparent metal oxides were obtained. The yield is 8
It was 7%.

A cosmetic composition of the present invention was obtained by adding and mixing 5 parts of the transparent zinc oxide thus obtained to 100 parts of the cosmetic base material (water white powder) in Example 2 above in the same manner as in Example 2. .

Comparative Examples (2) to [Phases] The cosmetic compositions of (2) (2) to [Phases] above, in which no transparent metal oxide was added, were used as comparative examples.

Comparative Example ■ Pancakes consisting of the following formulation were obtained in the same manner as in Example ■.

Zinc white 3 parts by weight Kaolin
Sol quantity part talc
20 parts by weight Colorant 1 part by weight Hydrophilic emulsifier 5 parts by weight Dehydrated lanolin 1 part by weight White petrolatum
5 parts by weight propylene glycol
5-m Rn fragrance 1 part by weight Comparative Example [Phase] A foundation gin consisting of the following formulation or C) was obtained in the same manner as in Example (2).

Isopropyl myristate 54.0% by weight Carnauba wax 5.0% by weight White beeswax
1.0% by weight titanium dioxide
1511% mineral-free pigment 15% melon talc 10% melon fragrance
Appropriately, each Example product and each Comparative Example product described in 1 above were uniformly coated on a 25 μm thick polyethylene film using a roll coater, and then the actual transmittance was measured using a Hitachi self-recording spectrophotometer. The results are shown in Table 1.

(Leaving space below) Part 1 & (Part 1) F51 table (Part 2) When each example product and each comparative example product were applied to 10 women aged 20 to 35, each large example product showed no visible light rays. Although the transmittance was good and the so-called make-up effect was excellent, the rays of Comparative Examples 15 and 16 had poor visible light transmittance and the face looked dull.

(8) Effects of the Invention The cosmetic composition of the present invention is formed by containing a transparent metal oxide with an average particle size of 300 Å or less in a cosmetic base material, and as a result, ultraviolet rays, especially the spread of 32
It is possible to almost certainly block the Dorneau line of 0 omega and prevent it from reaching the skin as much as possible, and as a result, the effect of reliably protecting the skin can be achieved.

In addition, this cosmetic A11 composition has excellent transparency due to its excellent visible light transmittance, and as a result, problems such as dull appearance of the face do not occur due to its use.

Claims (4)

[Claims] (1) at least one selected from the group consisting of a transparent iron oxide composite with an average particle size of 300 Å or less, transparent titanium oxide, transparent zinc oxide, transparent chromium oxide, transparent cobalt oxide, and transparent tin oxide; 1 type of transparent metal oxide 0.05
A cosmetic composition comprising ~20% by weight and 99.5-80% by weight of a cosmetic base. (2) The cosmetic composition according to claim 1, wherein the average particle diameter of the transparent metal oxide is 100 Å or less. (3) Fe^3^+, Ti^4^+, Zn^2^+, C
r^3^+, Co^2^+, Sn^4^+, Al^3^
A basic aqueous solution is added to an aqueous solution containing one or more metal salts of +, and the average particle size corresponding to these metals is 30.
Prepare a transparent positive hydrated metal oxide sol with a size of 0 Å or less, add a surfactant to it, or add a surfactant with aluminum ions added to cause the sol to aggregate, and then After filtering and washing this aggregate, a transparent metal oxide is formed by dehydrating it by heat treatment under normal pressure or reduced pressure, and the transparent metal oxide is added to a cosmetic base material. 1. A method for producing a cosmetic composition, the method comprising: (4) Fe^3^+, Ti^4^+, Zn^2^+, C
r^3^+, Co^2^+, Sn^4^+, Al^3^
A basic aqueous solution is added to an aqueous solution of any one of the + metal salts to prepare a transparent positive hydrated metal oxide sol with an average particle size of 300 Å or less corresponding to the metal, and to this, the above-mentioned hydrated metal oxide sol is prepared. A transparent metal oxide is prepared by adding an aqueous solution of another type of metal salt among the metal salts and adding a basic aqueous solution to this mixture to prepare a transparent positive hydrated metal oxide corresponding to the other type of metal. Form a composite sol, add a surfactant to this, or add a surfactant with aluminum ions added to aggregate the composite sol, then filter this aggregate and wash it. After that, a transparent metal oxide is formed by heat treatment and dehydration under normal pressure or reduced pressure, and the transparent metal oxide is added to a cosmetic base material and mixed. A method for producing a cosmetic composition.