JPH0674204B2 - Sunscreen cosmetics - Google Patents

Description

TECHNICAL FIELD The present invention relates to an improved sunscreen cosmetic, and more specifically, it is a low molecular weight polyhydric alcohol in which fine particles of metatitanic acid (hereinafter abbreviated as HTO) are specific. By containing a specific aqueous sol that is uniformly and stably dispersed, it transmits visible light and absorbs harmful UV rays that cause sunburn to prevent skin blackening (sunburn), stability over time, skin safety Excellent sunscreen makeup that gives good feel to the skin when applied and spreads well, adheres smoothly and has a smooth finish (no powderiness), and does not show whitening or pale coloration. Regarding fees.

(Prior Art) Sunburn is caused by medium-ultraviolet rays (hereinafter abbreviated as UV-B) having a wavelength of 290 to 320 nm and near-ultraviolet rays (hereinafter, UV-A) having a wavelength of 320 to 400 nm in sun rays. UV-B causes erythema on the skin and causes blackening after inflammation. On the other hand, UV-A
Is much weaker in erythema-inducing force than UV-B, and is said to blacken the skin substantially without causing erythema. Thus, the mid-ultraviolet rays of 290 to 320 nm are said to have the strongest biological effects. Of these, 297.6 nm is the strongest wavelength.

Conventionally, in order to prevent these disorders, cosmetics associated with various ultraviolet absorbers have been developed and are commercially available.
Examples of the UV absorbers used in these include synthetic UV absorbers such as P-aminobenzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, and cinnamic acid derivatives, and inorganic pigments such as titanium oxide, zinc oxide, and iron oxide. .

The former synthetic ultraviolet absorber has a problem of solubility when the amount added to the cosmetic base material is increased, and it is often used as a raw material for cosmetics such as irritation to skin, deterioration due to ultraviolet absorption, deterioration of absorption, coloring, etc. I have a problem.

On the other hand, the latter inorganic pigments have little deterioration due to ultraviolet rays, and since they are not percutaneously absorbed, there is no problem with skin irritation, but those with large particles (for example 350 mμ) have weak ultraviolet absorption and strong hiding power. Too much, whitening or coloring, when applied to the skin, it remains white or becomes thick makeup, giving an unnatural finish and is not desirable for makeup.

Further, JP-B-47-42502 discloses that the average particle size is 30 to 40 m.
A sunscreen cosmetic containing μ titanium oxide has also been proposed, but it has high hiding power, remains white during application, is inconvenient for the cosmetic appearance, and has dispersibility in a cosmetic base material, usability, and stability. Sex is not preferable.

Further, JP-A-61-229809 proposes a cosmetic containing amorphous titanium oxide, which is also white at the time of application and has no effect on blackening prevention, adhesion to the skin, etc. Is enough.

Further, Japanese Patent Application Laid-Open No. 58-62106 proposes a cosmetic containing 10 to 30 μm of ultrafine hydrophobized titanium oxide, which is also whitened during application and has a powdery appearance. ,
It does not spread well or adheres well to the skin, and its blackening prevention effect is not satisfactory.

(Problems to be Solved by the Invention) The inventors of the present invention have conducted diligent research in order to solve the above-mentioned problems in view of such circumstances, and as a result, an aqueous sol of HTO having the structure described below is
Fine particles of HTO are uniformly dispersed by the specific water-soluble polyhydric alcohol coexisting as a stabilizer, without causing secondary particle formation or aggregation even after long-term storage,
The cosmetic that absorbs harmful ultraviolet rays that cause sunburn to prevent blackening of the skin and contains the above-mentioned aqueous sol has good appearance, stability over time, and skin safety. The present invention has been completed by finding that while giving a good feel to the skin, it adheres well with good stretch and is smoothly finished, and does not exhibit whitening (without powder) or pale coloration.

(Means for Solving Problems) That is, according to the present invention, at least one water-soluble polyhydric alcohol having a molecular weight of 400 or less is dissolved as a stabilizer in water, whereby the HTO fine particles are substantially uniformly stable. A sunscreen cosmetic mainly composed of an aqueous sol dispersed in.

The HTO sol of the present invention has a molecular weight of 400 in water.
At least one of the following water-soluble polyhydric alcohols is uniformly dissolved as a stabilizer, and prevents secondary aggregation before it is oriented on the surface of the HTO fine particles,
It is an aqueous sol in which the particles are uniformly dispersed, has a translucent to slightly white appearance, and is excellent in long-term storage stability.
The HTO sol, which contains HTO fine particles, can transmit visible light and absorb harmful ultraviolet rays that cause sunburn, thereby preventing skin blackening (sunburn). (This HT
The O-sol has a pH of usually 4 to 9 and may contain a small amount of particles of anatase-type or rutile-type titanium oxide. ) Further, the water-soluble polyhydric alcohol coexisting with HTO in the aqueous sol preserves (promotes) a stable uniform dispersion of HTO,
It acts as a stabilizer that can prevent secondary particles (giant particles) and aggregation during storage of TO particles.

The above-mentioned HTO sol, which can exert such useful and remarkable effects, is applied as it is as a fragrance-free, water-based lotion-type sunscreen cosmetic.

In addition, when a proper amount of fragrance is added to the HTO sol, it becomes a scented water-based lotion-type sunscreen cosmetic, and when a proper amount of ethyl alcohol is further added, it becomes a water-alcohol-based lotion-type sunscreen cosmetic (for example, sunscreen lotion). .

The above HTO sol (unscented water-based lotion-type sunscreen cosmetics), water-based or water-alcohol-based lotion-type sunscreen cosmetics, and the two-layer (oil phase-water phase separation type) sunscreen makeup described below. The total amount (total amount of final composition) of the sunscreen cosmetics of the present invention including a sunscreen cosmetic of an emulsion type (for example, an oil-in-water emulsion)
Based on 1 to 20% by weight of HTO having an average particle size of 0.005 to 0.1 μm (preferably 0.005 to 0.05 μm) as titanium oxide, and at least one of the water-soluble polyhydric alcohols. 0.05 to 80% by weight (preferably 1
˜50% by weight) and water in the range of 20 to 95% by weight. Particles having an average particle diameter of HTO smaller than 0.005 μm are difficult to obtain industrially, and when it is larger than 0.1 μm, the cosmetic tends to be whitened during application and the cosmetic effect tends to deteriorate.

When the content of HTO is less than 1% by weight, the sunburn preventing effect and the adhesion to the skin are likely to decrease, and when it is more than 20% by weight, HTO tends to be secondary particles.

Further, when the water-soluble polyhydric alcohol is less than 0.1% by weight, the feel, storage stability, and adhesiveness are likely to decrease,
If it is more than 80% by weight, the feel tends to be poor.

The water-soluble polyhydric alcohol having a molecular weight of 400 or less, for example, glycerin, dipropylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Diglycerin, triglycerin, tripropylene glycol, 1,4-butylene glycol, pentaerythritol, tetraglycerin, pentaglycerin, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, Examples thereof include sorbitol, maltitol, glucose, sucrose, maltose, fructose and xylitol. With a polyhydric alcohol having a molecular weight of more than 400, it is difficult to orient on the surface of the hydrous titanium oxide particles, so that aggregation or precipitation easily occurs and a sticky feeling is easily imparted to the skin.

The blending amount (content) of ethyl alcohol in the water-alcohol lotion-type sunscreen cosmetic is 0.5
~ 15 wt% is preferred.

The two-layer type (oil phase-water phase separation type) sunscreen cosmetic is obtained by mixing HTO sol and a liquid oily substance and allowing to stand, and the upper layer is a liquid oily substance and the lower layer is HTO. It consists of a sol and is used mixed by shaking. The liquid oily substances are used alone or in combination of two or more, and the compounding amount thereof is 1 to 80% by weight (preferably 10 to 70% by weight) based on the total amount of the final composition (two-layer sunscreen cosmetic). Is.

The liquid oily substance is a known liquid oily substance for cosmetics that is liquid at room temperature, and is, for example, liquid higher aliphatic hydrocarbons, animal and vegetable oils, higher alcohols, higher fatty acids, synthetic ester oils. , Glycol higher fatty acid ester, hydrogenated polybutene, silicone oil and the like.
These liquid oily substances are used alone or in combination of two or more.

Among the emulsified sunscreen cosmetics described above, it can be obtained by uniformly mixing and dispersing the above HTO sol in an oil phase component consisting of an oily substance and a surface-active substance and emulsifying.

The oily substance is a known oily substance for cosmetics,
For example, a liquid, paste-like, solid oily substance,
For example, higher aliphatic hydrocarbons, animal and vegetable oils, higher fatty acids, higher alcohols, synthetic ester oils, waxes,
Examples include polybutene and silicone oil. These oily substances are used alone or in combination of two or more.

The blending amount (content) is in the range of 5 to 80% by weight (preferably 7 to 60% by weight) based on the total amount of the final composition.

The surface-active substance used here is a substance for emulsifying the above-mentioned oily substance, and a normal surface-active agent (for example, a nonionic surface-active agent, an anionic surface-active agent), glycyrrhizic acid salt, pectin, Natural product-based surface-active substances such as xanthan gum and bentonite may also be used.

The content of the surface-active substance is usually 0.05 to 7% by weight (preferably 0.5 to 5) based on the total amount of the final composition.
% By weight).

Sunscreen cosmetics (emulsion type) in which an oily substance, a surface-active substance and a pigment are mixed with the HTO sol described above are, for example, an oily substance after the pigment is uniformly dispersed in an aqueous phase component consisting of HTO sol and additional water. It is obtained by adding an oil phase component comprising a substance and a surface-active substance, mixing and emulsifying.

As the pigment, an inorganic pigment or an organic pigment for cosmetics is used. The pigment content (content) is preferably 5 to 20% by weight based on the total amount of the final composition.

The oily substance, the surface-active substance, and their compounding amounts (contents) are the same as in the case of the emulsified sunscreen cosmetic.

The emulsified sunscreen cosmetic in which the oily substance and the surface-active substance or pigment are mixed with the HTO sol preferably forms an oil-in-water (O / W) emulsion.

The HTO sol used in the present invention is a commercially available HTO sol.
The required amount of the water-soluble polyhydric alcohol was added to the hydrochloric acid-acidic aqueous solution and dissolved under stirring, and then the mixed aqueous solution was dialyzed under running water, or titanium tetrachloride was added to cold water for hydrolysis. After that, a required amount of the water-soluble polyhydric alcohol is dissolved, and then the mixed aqueous solution is neutralized with a caustic soda aqueous solution under water cooling, and then dialyzed in running water.

In the sunscreen cosmetic of the present invention, in addition to the above-mentioned essential components, a fragrance, a coloring agent, a moisturizing agent, an antiseptic, a sequestering agent for metal,
A water-soluble polymer, a pH adjusting agent and the like can be appropriately blended within the range where the object of the present invention can be achieved.

The sunscreen cosmetics of the present invention include sun oil, suntan lotion, sunscreen, stick-shaped sunscreen, sunscreen lip balm, sancalamine, sun gely, sunscreen cream, sunscreen lotion,
Widely used as sunscreen water white powder, foundation lotion, makeup base, hairnic, hair liquid, etc.

(Example) In the examples,% means% by weight, and part means part by weight. The methods of the blackening prevention test, storage stability test and practical property test are as follows.

(1) Blackening prevention test (sunburn prevention test) Animal test A test is carried out using the shaved back of 10 black guinea pigs per group. The test sites are 3 on each side, 4 cm ² each.

The test method is as follows: 0.1% of 8-
Orally administer 1 ml of methoxypsoralen, and after 30 minutes, apply 8 mg of each sample to the right test site only, 320-420 nm
UV-A light of 15 Joules is irradiated. The test-applied portion was judged one week later and evaluated according to the following criteria.

Human body test (practical test) The test is performed using the backs of 10 subjects. The test method is to cover the left side of the back with a thick cloth and apply 2 mg / cm of each sample to the right side,
I lie face down for 90 minutes in the hot summer sun. The judgment of the sample application part was carried out after 1 week, and the judgment was made according to the following criteria.

(2) Storage stability test Samples (sunscreen cosmetics) were stored in a constant temperature bath at 45 ° C for 3 months, and then evaluated for separation and precipitation.

(3) Practical characteristic test (sensory test) Twenty female subjects tried the sample (sunscreen cosmetics) for one week, and in the questionnaire, A1: "Smooth finish, no powderiness", A2: "Skin" Adheres well to each other ", A3:" There is no whitening or pale coloration on the applied part, it does not change to a natural skin color ", A4:" No skin irritation ", A5:" Good spread during application ", A6: The number of respondents answered that "there was no sticky feeling and gave the skin a moist feel."

Example 1 (1) Production of HTO sol Commercially available HTO (H ₂ TiO ₃ ) hydrochloric acid acidic water-soluble (titanium oxide) TiO
₍₂ ) 30%) and 3 parts of dipropylene glycol are added and dissolved uniformly, and this mixture (aqueous solution) is put into a cellophane tube and kept at 5 to 15 ° C. and dialyzed in running water for 48 hours. After that, transfer the contents of cellophane tube to a container, add purified water to make 200 parts of HTO as titanium oxide.
HTO sol containing 15% (average particle size of HTO is 0.03-0.05μ
m, dipropylene glycol content 1.5%, water content 8
3.5%) was obtained.

(2) Absorption spectrum in the visible and ultraviolet regions of HTO sol (a) Sample: Sample A: HTO sol obtained in (1) above B: Ultrafine particle titanium oxide (average particle size 0.03 to 0.05μ)
m) 15% water dispersion 〃 C: Titanium oxide (average particle size 0.35 μm) (anatase type) 15% water dispersion (b) Measurement method: Spectrophotograph using a quartz cell measuring 0.1 mm Absorbance in a wavelength range of 200 to 700 nm was measured with a meter. The results are shown in FIG.

(C) Measurement method As is clear from FIG. 1, in the curve C of ordinary titanium oxide having a relatively large particle size, the absorption effect in the ultraviolet region is small and the absorbance in the visible region is high (transparency is poor). In the curve B of the ultrafine titanium oxide, the absorption effect in the ultraviolet region can be seen and the absorbance of visible light is good (the transmittance is good). In contrast to these curves, the curve A of the HTO sol of the present invention has the highest ultraviolet absorption effect in all the samples, and the specificity is recognized in that the visible light absorbance is low (the transmittance is very high).

(3) Lotion-type sunscreen cosmetic comprising the HTO sol diluted solution of (1) The HTO sol obtained in (1) above was diluted with purified water so that the concentration of HTO was 5% as titanium oxide. The sunscreen cosmetic (lotion type) of the present invention was obtained. This was subjected to various tests as described above.

As a result, the blackening prevention effect (sunburn prevention effect) in both animal and human tests was good (good), storage stability was good, and no change was observed. In the practical characteristic test (sensory test), the panelists (female subjects) 20
According to the results by people, the number of people who answered that they were finished smoothly and were not powdery (hereinafter referred to as the number of people in A1) was 20 out of 20, and the number of people who answered that they were in good contact with the skin (hereinafter referred to as the number of people in A2).
18 out of 20 respondents said that the applied part was not whitened or bluish and did not change to a natural skin color (hereinafter referred to as A3), 20 out of 20 responded that there was no skin irritation 20 people
20 out of 20 (hereinafter referred to as A4) number of people who answered that the growth during application was good (hereinafter referred to as A5), 19 out of 20 people, who said that they did not feel sticky and had a moist feel. It was confirmed that the number (hereinafter referred to as the number of A6) was 19 out of 20, which was extremely good.

Example 2 An HTO sol (HTO sol containing 15% of HTO as titanium oxide) was prepared in the same manner as in (1) of Example 1 except that polyethylene glycol (average molecular weight 300) was used instead of dipropylene glycol. (Average particle size 0.03-0.05μm, polyethylene glycol content 1.8%, water content 83.2%)
After obtaining the above, it was diluted with purified water in the same manner as in (3) of Example 1 to obtain the lotion type sunscreen cosmetic of the present invention.
As a result of various tests as described above, the effect of preventing blackening in the animal and human tests was good (good), and the storage stability was good, and no change was observed. The result of 20 panelists in the sensory test is that the number of A1 is 20 out of 20.
20 people, the number of A2 is 19 out of 20, the number of A3 is 19 out of 20,
The number of A4 was 20 out of 20, the number of A5 was 18 out of 20, and the number of A6 was 18 out of 20.

Example 3 The procedure of (1) of Example 1 was repeated except that glycerin was used in place of dipropylene glycol, and HTO sol (H
TO average particle size is 0.03-0.05μm, glycerin content 3.
After obtaining 0% and a water content of 82%), it was diluted with purified water in the same manner as in (3) of Example 1 to obtain the lotion type sunscreen cosmetic of the present invention. As a result of various tests as described above, the effect of preventing blackening in the animal and human tests was good (good), storage stability was good, and no change was observed. In the sensory test, the results of 20 panelists were that the number of people in A1 was 18 out of 20, the number of people in A2 was 17 out of 20,
The number of A3 was 17 out of 20, the number of A4 was 20 out of 20, the number of A5 was 17 out of 20, and the number of A6 was 19 out of 20.

Example 4 An HTO sol containing 15% of HTO as titanium oxide (average particle size of HTO was 0.03) was performed in the same manner as in (1) of Example 1 except that maltitol was used instead of dipropylene glycol. ˜0.05 μm, maltitol content 2.0%, water content 83.0%), and then diluted with purified water in the same manner as in Example 1 (3) to obtain the lotion-type sunscreen cosmetic of the present invention. It was As a result of various tests as described above, the effect of preventing blackening in the animal and human tests was good (good), storage stability was good, and no change was observed. The result of 20 panelists in the sensory test was A1.
The number of people in 20 is 20 out of 20, the number of A2 is 19 out of 20, the number of A3 is 18 out of 20, the number of A4 is 20 out of 20, the number of A5 is 18 out of 20, A6 The number of students was 19 out of 20, which was extremely good.

Example 5 (1) Production of HTO sol 20 parts of titanium tetrachloride was added to 80 parts of purified water while cooling with ice, and the uniformly dissolved aqueous solution was heated under reflux at 100 ° C. for 5 hours. After cooling this, 10 parts of propylene glycol was added to and dissolved in this solution, and then a caustic soda aqueous solution was added to the solution while stirring under ice cooling to neutralize the pH to 7.0. The obtained mixture is transferred to a cellophane tube and dialyzed in running water for 48 hours while maintaining at 5 to 15 ° C. After dialysis, transfer the contents of the cellophane tube to a glass container, add purified water to make the total amount 200 parts, and HTO sol containing 10% of HTO as titanium oxide (average particle size of HTO is 0.03 to 0.05 μm, propylene glycol Content 5
%, Water content 85%).

(2) Lotion-type sunscreen cosmetic comprising the diluted solution of the HTO sol obtained in (1) Purified water containing the HTO sol obtained in (1) above so that the HTO concentration is 5% as titanium oxide. And the sunscreen cosmetic (lotion type) of the present invention was obtained. This was subjected to various tests as described above.

As a result, the effect of preventing blackening (sunscreen cosmetics) in both animal and human tests was good (good), storage stability was good, and no change was observed. Also, in the practical characteristic test (sensory test), the results of 20 panelists (female examinees) were as follows: A1 was 19 out of 20, A2 was 18 out of 20, and A3 was 20 out of 20. 19 people, 20 out of 20 people in A4
The number of people in A5 was 18 out of 20, and the number of people in A6 was 19 out of 20, which was extremely good.

Example 6 An HTO sol containing 10% of HTO as titanium oxide (HT) was prepared in the same manner as in (5) of Example 5 except that 1,3-butylene glycol was used instead of propylene glycol.
The average particle size of O was 0.03 to 0.05 μm, the content of 1,3-butylene glycol was 5%, and the content of water was 85%. Then this HT
The O sol was diluted with purified water in the same manner as in (2) of Example 5 so that the concentration of HTO was 5%, and titanium oxide was obtained to obtain the lotion-type sunscreen cosmetic of the present invention. As a result of various tests as described above, the effect of preventing blackening in the animal and human tests was good (good), storage stability was good, and no change was observed. In the sensory test, the results of 20 panelists were 19 out of 20 people in A1,
The number of A2 is 19 out of 20, the number of A3 is 19 out of 20, the number of A4 is 20 out of 20, the number of A5 is 18 out of 20, the number of A6 is 20.
Of the 19 people, it was extremely good.

Example 7 The procedure of Example 5 (1) was repeated except that sorbitol was used instead of propylene glycol, and the HTO sol of the present invention (HTO having an average particle size of 0.03 to 0.05 μm,
Sorbitol content was 5% and water content was 85%). Next, this HTO sol was diluted with purified water so as to have a titanium oxide content of 5% to obtain a sunscreen cosmetic of the present invention.
As a result of various tests as described above, the effect of preventing blackening of the animal and human body was good (good), the storage stability was good, and no change was observed.

In a practical property test (sensory test), the panel-20
The results by people are 19 out of 20 in A1, 18 out of 20 in A2, 19 out of 20 in A3, 20 out of 20 in A4.
The number of people in A5 was 18 out of 20, and the number of people in A6 was 19 out of 20, which was extremely good.

Example 8 The procedure of Example 5 was repeated, except that fructose was used instead of propylene glycol, to give a compound of the present invention.
An HTO sol (average particle size of HTO: 0.03 to 0.05 μm, fructose content: 5%, water content: 85%) was obtained. Then this
The HTO sol was diluted with purified water to a titanium oxide content of 5% to obtain the sunscreen cosmetic of the present invention. As a result of various tests as described above, the effect of preventing blackening in the animal and human body tests was good (good), the storage stability was good, and no change was observed. Also, in the practical characteristic test (sensory test), the results by 20 panelists are
The number of A1 is 20 out of 20, the number of A2 is 18 out of 20, the number of A3 is 19 out of 20, the number of A4 is 20 out of 20, and the number of A5 is 20.
18 out of 20 and 19 out of 20 were very good.

Example 9 Liquid paraffin (10 parts), white petrolatum (1 part), polyoxyethylene (20EO) sorbitan monooleate (3 parts), and sorbitan sesquioleate (2 parts) were mixed and heated to 70 ° C.
Dissolves uniformly (oil phase component).

HTO sol obtained in (1) of Example 1 (average particle size of HTO
0.03-0.05μm, HTO content is 15 as titanium oxide
%, Dipropylene glycol content is 1.5%, water content is 83.5%) 20 parts, paraben 0.1 parts and water 63.9 parts are mixed,
It is heated to 0 ° C and uniformly dissolved (aqueous phase component). Next, the aqueous phase component was added to the above oil phase component with stirring, mixed and emulsified, and then cooled to room temperature to obtain an emulsion type (oil-in-water type) sunscreen cream of the present invention.

Various tests were carried out on this sunscreen cosmetic.

As a result, the effects of preventing the blackening of the animal and human body were good (∘), the storage stability was also good (∘), and no change was observed. Also, in the practical characteristics test, the results by 20 panelists (female examinees) were as follows: the number of A1 was 20 out of 20, the number of A2 was 19 out of 20, and the number of A3 was 19 out of 20.
The number of people in A4 was 20 out of 20, and the number in A20 was 19 out of 20 people who gave a moist and good feeling without giving a greasy and unpleasant feeling. .

Comparative Example 1 Instead of the HTO sol, 3 parts of ordinary titanium oxide having an average particle size of 0.3 to 0.5 μm was used, and 80.9 parts of purified water was used. I got a sunscreen cosmetic.

As a result of performing the above-mentioned tests on this sunscreen cosmetic, the effect of preventing blackening of the animal and human body was slightly bad (△), the storage stability was slightly poor, and a small amount of titanium oxide aggregates precipitated. . A1
The number of people is 4 out of 20, the number of A2 is 4 out of 20, the number of A3 is 3 out of 20, the number of A4 is 20 out of 20, and the number of A6 is 5. It was bad.

Comparative Example 2 The same procedure as in Example 9 was carried out except that ultrafine titanium oxide (average particle size: 0.03 to 0.05 μm) was used in place of the HTO sol, and 80.9 parts of purified water was used, and a sunburn for comparison was obtained. I got a stop cosmetic. As a result of conducting the above-mentioned tests on this sunscreen cream, the effect of preventing darkening of the animal and human body was rather poor (Δ) and the storage stability was poor, and titanium oxide aggregates were considerably precipitated. A1
The number of people is 10 out of 20, the number of A2 is 6 out of 20, the number of A3 is 9 out of 20, the number of A4 is 20 out of 20, and the number of A6 is 13 out of 20. The overall evaluation was poor.

Comparative Example 3 Instead of the HTO sol, amorphous spherical titanium oxide described in JP-A-61-229809 (average particle size 0.05 to 0.08) was used.
μm) and 80.9 parts of purified water were used, and the same procedure as in Example 9 was carried out to obtain a sunscreen cream for comparison. As a result of carrying out the above-mentioned tests on this sunscreen cream, the effect of preventing darkening of the animal and human body was slightly (Δ), and the storage stability was poor, and agglomerates of titanium oxide were considerably precipitated. Also, in the practical characteristic test, the number of A1
12 out of 20 people, A2 is 9 out of 20, A3 is 20 out of 20
12 people, 20 people in A4, 20 people in A6, 12 people in 20 people, the overall evaluation was poor.

Comparative Example 4 Comparative Example 4 was carried out in the same manner as in Example 9 except that ethyl paradimethylaminobenzoate (ultraviolet absorber) was used as the oil phase component instead of the HTO sol and 80.9 parts of purified water was used. Got sunscreen cream. As a result of conducting the above-mentioned various tests on this sunscreen cream, the effect of preventing darkening of animals and humans was good (◯) and the storage stability was also good. Also, in the practical characteristics test, the number of A1 is 20 out of 20.
People, A2: 15 out of 20, A3: 20 out of 20, A4
2 out of 20 people, A6 is 18 out of 20 people,
The overall evaluation was rather poor.

Example 10 60 parts of liquid paraffin and the HT obtained in (5) of Example 5
Diluted solution of O sol (average particle size of HTO sol is 0.03 ~ 0.05μ
m, HTO content was 10% as titanium oxide, and 40 parts of propylene glycol content was 5%) to prepare a two-layer sun oil (for preventing sunburn) of the present invention. Next, various tests of this two-layer type sun oil were conducted as described above. As a result, the effect of preventing blackening in the animal and human body tests was good (good), the storage stability was good, and no change was observed. In the sensory test, the results by 20 panelists showed that the number of people in A1 was 19 out of 20 and the number of people in A2 was 18 out of 20.
Number of people A20 is 20 out of 20, A4 is 20 out of 20, A5
The number of people in was 18 out of 20, and the number of people in A6 was 19 out of 20, and the overall evaluation was extremely good.

Comparative Example 5 Instead of the HTO sol, the same procedure as in Example 10 was carried out except that 4 parts of ultrafine titanium oxide (average particle size 0.03 to 0.05 μm) and 36 parts of purified water were used, and a two-layer type for comparison. Got sun oil. As a result of various tests of this two-layer type sun oil, the effect of preventing blackening of the animal or human body was ◯ (good), the storage stability was poor, and titanium oxide coagulated and precipitated. Also, in the sensory test, the results by 20 panelists showed that the number of people in A1 was 20.
3 out of 10, 7 out of 20 in A2, 1 out of 20 in A3
20 people out of 20 people in A4, 12 people out of 20 people in A5, A6
The number of people was 10 out of 20, and the overall evaluation was rather poor.

Example 11 An aqueous solution in which 0.3 part of xanthan gum was dissolved in 52.5 parts of purified water, an ethyl alcohol part, 10 parts of glycerin and HTO sol (average particle size of HTO was 0.03 to 0.05 μm, HTO was titanium oxide 10%, dioxane). 30 parts of HTO sol diluted solution (1) of Example 1 consisting of propylene glycol content of 1.0% and water content of 89.0% and 0.2 parts of methylparaben were uniformly mixed to obtain the sunscreen lotion of the present invention. It was

The various tests of this sunscreen lotion were carried out. As a result, the effect of preventing blackening in the animal and human body tests was good (good) and the storage stability was good, and no change was observed.

Comparative Example 6 Instead of HTO sol, ultrafine titanium oxide (average particle size 0.0
A sunscreen lotion for comparison was prepared in the same manner as in Example 10 except that 3 parts of 3 to 0.05 μm) and 79.5 parts of purified water were used. The sunscreen lotion had an effect of preventing blackening in animal and human body tests which was Δ (slightly poor) and showed poor storage stability, and titanium oxide particles were aggregated and precipitated. In the sensory test, 20 panelists showed that the number of A1 was 10 out of 20, the number of A2 was 10 out of 20, the number of A3 was 7 out of 20, and the number of A4 was 20 out of 20. Therefore, the comprehensive evaluation was poor.

Example 12 10 parts of octyldodecyl myristate, 2 parts of cetyl palmitate, 2 parts of glyceryl monostearate, 2 parts of polyoxyethylene cetyl ether (5E.O) and polyoxyerene sorbitan monooleyl ether (6E.O) are mixed. Then, it is heated to 80 ℃ and dissolved (oil phase).

HTO sol (average particle size of HTO 0.03 ~ 0.05μm, HTO content is 10% as titanium oxide, maltitol content 6.0
%, Water content 84.0%), 40 parts of methylparaben, 0.2 parts of methylparaben, 5 parts of propylene glycol and 36.8 parts of purified water are uniformly mixed and heated to 80 ° C. (aqueous phase).

To the above oil phase, with stirring, an aqueous phase was added, mixed and emulsified,
After cooling, an emulsion type (oil-in-water type) sunscreen lip balm of the present invention was obtained. As a result of conducting various tests as described above,
The storage stability was good and no change was observed. The results of the sensory test showed that the number of people in A1 was 20 out of 20, the number of people in A2 was 19 out of 20, the number of A3 was 20 out of 20, and the number of A4 was 20.
20 out of 20, 19 out of 20 in A5, 20 out of A6
19 people were very good.

Example 13 An HTO sol containing 15% of HTO as titanium oxide (average particle of HTO) was performed in the same manner as in Example 2 except that polyethylene glycol having an average molecular weight of 400 was used instead of polyethylene glycol having an average molecular weight of 300. After obtaining a diameter of 0.04 to 0.06 μm and a polyethylene glycol content of 1.8% and a water content of 83.2%), the lotion-type sunscreen makeup of the present invention is diluted with purified water in the same manner as in (1) of Example 1. Got paid. As a result of conducting various tests as described above, the results of the blackening test in the animal and human body tests were both good (good), the storage stability was good, and there was no change. Sensory test results by 20 panelists showed that A1 was 18 out of 20 and A2 was 20 out of 20.
The overall evaluation was extremely good, with 17 people, the number of A3 people was 18 out of 20, and the number of A5 people was 5 out of 20.

Comparative Example 7 An HTO sol containing 15% of HTO as titanium oxide (average particle size of HTO) was carried out in the same manner as in Example 2 except that polyethylene glycol having an average molecular weight of 600 was used instead of polyethylene glycol having an average molecular weight of 300. Of 0.2 to 0.5 μm and a polyethylene glycol content of 1.8% and a water content of 83.2%), and then diluted with purified water in the same manner as in Example 1 (1) to obtain a lotion-type sunscreen cosmetic for comparison. Got As a result of conducting various tests as described above, the results of the blackening test in the animal and human tests were both Δ (somewhat poor), the storage stability was poor, and some precipitation of aggregates was observed. Panelist 20
The result of the sensory test by a person is that the number of A1 is 10 out of 20, A2
The overall evaluation was poor, with 9 out of 20 people, 18 out of 18 people in A3 and 5 out of 20 people in A5. Thus, with a water-soluble polyhydric alcohol (polyethylene glycol) having a molecular weight of more than 400, the action and effect of the HTO sol as a stabilizer cannot be exerted, and the above-mentioned object of the present invention cannot be achieved.

Example 14 To the lotion-type sunscreen cosmetic obtained in Example 2, 0.6 part of polyethylene glycol having a molecular weight of 600 was further added and stirred to uniformly dissolve it.

The above-mentioned various tests were also performed on this lotion-type sunscreen cosmetic. As a result, the effect of preventing blackening in the animal and human body tests was good (◯), the storage stability was good, and no change was observed.

Furthermore, in the sensory test, the results by 20 panelists showed that the number of people in A1 was 20 out of 20, the number of people in A2 was 19 out of 20, and A3.
The number of people in was 20 out of 20, the number in A4 was 20 out of 20, the number in A5 was 20 out of 20, and the number in A6 was 19 out of 20. As is clear from the comparison between this result and Comparative Example 7 and Example 2, the HTO sol in which polyethylene glycol having a molecular weight of 300 was added to stabilize the fine particles of HTO at the time of preparing the HTO sol was the lotion-type sunscreen of the present invention. Addition of polyethylene glycol having a molecular weight of 600 at the time of preparation does not have any adverse effect on the sunscreen effect and sensory characteristics.

Example 15 HTO sol (HTO sol produced according to (1) of Example 1, having an average particle size of HTO of 0.03 to 0.05 μm, a maltitol content of 10%, and HTO of 20% as titanium oxide, Water content 70%) 50 parts, titanium oxide 2 parts, talc 5 parts, red iron oxide 0.2 parts, black iron oxide 0.1 part, yellow iron oxide 0.5 part and glycerin 5 parts are uniformly mixed. This mixture was uniformly mixed and dispersed in a mixed solution containing 7 parts of ethyl alcohol and 32.2 parts of water to prepare a white powder for sunscreen. The above-mentioned various tests were conducted on this white powder.

As a result, the effect of preventing blackening in animal and human tests was good (◯), the storage stability was good, and no change was observed. 20 panelists in a sensory test
As for the results by people, the number of people in A1 is 20 out of 20, and the number of people in A2 is 20.
19 out of 20, 20 out of 20 in A3, 20 out of 20 in A4
The number of people in A5 was 19 out of 20, and the number in A6 was 19 out of 20. The color development (color appearance) was also very natural and good.

Comparative Example 8 Instead of HTO sol, ultrafine titanium oxide (average particle size
The same procedure as in Example 15 was carried out except that (0.03 to 0.05 μm) was used to obtain a comparative sunscreen white powder. The above-mentioned various tests were conducted on this white powder. As a result, the effect of preventing blackening of animals and humans was rather poor (Δ) and the storage stability was poor, and titanium oxide aggregates were considerably precipitated. In the practical characteristics test, the number of A1 was 7 out of 20 and the number of A2 was
6 out of 20; A3: 9 out of 20; A6: 10 out of 20
In the person, the comprehensive evaluation was bad. In addition, the color was reddish black, which was not good.

Example 16 Stearic acid 2.8 parts, propylene glycol monostearate 2.8 minutes, self-emulsifying glyceryl monostearate
2.8 minutes, 15.0 parts of liquid paraffin is heated to 70 ° C. and uniformly dissolved. (A) 7 parts of titanium oxide, 0.5 part of red iron oxide, 1.0 part of yellow iron oxide, 0.2 part of black iron oxide and 1.3 parts of talc are uniformly mixed. (B) Triethanolamine 1.4 parts, propylene glycol 5
Parts, 1.4 parts of sodium laurin sulfate, a proper amount of preservative, 92.2 parts of purified water and HTO sol (HTO sol produced according to (1) of Example 5 and containing 20% of HTO as titanium oxide, HTO has an average particle size of 0.03 to 0.05 μm, a fructose content of 7%, and a water content of 75%) 50 parts are heated to 70 ° C. and uniformly dissolved and dispersed. (C) Next, (B) was uniformly dispersed in (C), and then added to (A) to emulsify and cool to prepare a sunscreen foundation.

As a result of the test, the effect of preventing blackening in the animal and human body tests was good (good), the storage stability was good, and no change was observed. In the sensory test, the results by 20 panelists were that the number of people in A1 was 20 out of 20 and the number of people in A2 was
19 out of 20, 19 in A3, 20 out of 20 in A4
The numbers of 20 and A5 were 19 out of 20, and the number of A6 was 19 out of 20, which was very good. Further, the color development (color appearance) was extremely natural and preferable.

(Effects of the Invention) The present invention contains fine particles of metatitanic acid having a specific aqueous sol in which the molecular weight is uniformly and stably dispersed by a water-soluble polyhydric alcohol having a molecular weight of 400 or less, thereby transmitting visible light to prevent sunburn. It protects the skin from darkening (sunburn) by absorbing the harmful ultraviolet rays it causes, and has good stability over time and skin safety. When applied, it gives good feel to the skin, spreads well, and adheres well. It is possible to provide an excellent sunscreen cosmetic that has a smooth finish (no powderiness) and does not exhibit whitening or pale coloration.

[Brief description of drawings]

Figure 1 shows the absorbance and wavelength (n
The relationship with m) is shown. A of the curve is an aqueous sol of metatitanic acid of the present invention (the above-mentioned HT
O sol). B is an aqueous dispersion of ultrafine titanium oxide. C is an ordinary aqueous dispersion of titanium oxide.

Claims (7)

[Claims] 1. An aqueous sol in which at least one of water-soluble polyhydric alcohols having a molecular weight of 400 or less is dissolved as a stabilizer in water, whereby fine particles of metatitanic acid are uniformly and stably dispersed as a main component. As a sunscreen cosmetic. 2. The fine particles of metatitanic acid have an average particle size of 0.00
The sunscreen cosmetic according to claim (1), which has a thickness of 5 to 0.1 μm. 3. The sunscreen makeup according to claim 1, wherein at least one of the water-soluble polyhydric alcohols is contained in the range of 0.1 to 80% by weight based on the total amount of the final composition. Fee. 4. The sunscreen cosmetic according to any one of claims (1) to (3), which further contains ethyl alcohol. 5. A liquid oily substance is further compounded,
The sunscreen cosmetic according to any one of claims (1) to (3). 6. The sunscreen cosmetic according to any one of claims (1) to (3), which further comprises an oily substance and a surface-active substance. 7. The sunscreen cosmetic according to any one of claims (1) to (3), further comprising an oily substance, a surface-active substance and a pigment.