JP3052259B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic having an excellent ultraviolet shielding effect, especially in a UV-B wavelength range of 280 to 320 nm and excellent transparency.

[0002]

2. Description of the Related Art Titanium oxide has excellent coloring and hiding power,
It is structurally stable and is a kind of highly safe white pigment. Further, when the particle diameter is 1 μm or less, an unprecedented effect, that is, an ultraviolet shielding effect, etc. is obtained due to the effect of the volume effect and the surface effect. For this reason, this particulate titanium oxide is widely used in cosmetics and the like that require an ultraviolet shielding effect.

[0003]

However, the titanium oxide particles generally used are not sufficiently small in particle size, so that ultraviolet rays in the UV-B wavelength range (280 to 320 nm) which are harmful to the skin are blocked. Since the effect is insufficient or lacks in transparency, when applied to the skin, there are problems such as bluish tinge, unnatural finish and unfavorable cosmetic effect. On the other hand, Japanese Patent Application No. 1-324295 filed by the present inventors (Japanese Unexamined Patent Application Publication No.
JP-A-184905) discloses a method of obtaining a cosmetic having a large ultraviolet shielding effect in a UV-B wavelength region by using fine particle titanium oxide obtained by coexisting a specific silicone or hydrocarbon at the time of production by an alkoxide method. ing. However, since titanium oxide used here is a fine particle, it has a strong surface activity, and has a problem that when it is blended with a product, it causes deterioration of oil and unpleasant odor of fragrance. SUMMARY OF THE INVENTION An object of the present invention is to provide a cosmetic that has a large ultraviolet shielding effect, particularly a large shielding effect in the UV-B wavelength region, is transparent, and has no odor due to deterioration of oils and fragrances.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object. As a result, when the fine particles of titanium hydroxide obtained by a novel production method were added to cosmetics, when applied to the skin, The present invention has been found to provide a transparent feeling with less bluish tinge, to have an excellent ultraviolet shielding effect in a UV-B wavelength region of 280 to 320 nm, which is considered to be harmful to the skin, and to suppress the unpleasant odor due to deterioration of oils and fragrances. completed. That is, in the present invention, when a titanium alkoxide is hydrolyzed to produce titanium hydroxide, a basic compound and a boiling point of 10
A hydrocarbon having a temperature of 0 to 200 ° C. and / or the following general formula:

[(CH ₃ ) ₂ SiO] _n (where n is an integer of 3 to 7) or

Embedded image A silicone represented by CH ₃ — [R ₂ SiO] _n —Si (CH ₃ ) ₃ (where n is an integer of 1 to 4, and R represents a methyl group or a phenyl group). A cosmetic comprising a fine particle titanium hydroxide powder obtained by adding a fine powder.

Hereinafter, the present invention will be described in detail. In order to obtain a novel particulate titanium hydroxide to be blended in the cosmetic of the present invention, a titanium alkoxide generally used for the production of titanium hydroxide can be used. For example, tetramethoxytitanium, tetraethoxytitanium, tetra-i-
Titanium propoxy, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-i-butoxy titanium, tetra-sec-butoxy titanium, tetra-t-butoxy titanium, tetra-octadecyloxy titanium, and the like. Before or during hydrolysis of this
Alternatively, after the hydrolysis, a specific basic compound and a hydrocarbon and / or silicone are added to obtain the titanium hydroxide used in the present invention. A basic compound;
The hydrocarbons and / or silicones may be added simultaneously or separately.

The basic compounds used include, for example, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, calcium hydroxide, calcium carbonate and the like. Of these, potassium hydroxide is particularly preferred.
The hydrocarbon used has a boiling point in the range of 100 to 200C, for example, a hydrocarbon having a boiling point of 116 to 143C (average carbon number: 8.6, molecular weight: 123), and a boiling point of 157 to 177C. (Average carbon number: 10.5, molecular weight:
149), hydrocarbon having a boiling point of 171 to 193 ° C
(Average carbon number: 11.3, molecular weight: 160). The silicone used is represented by the above general formula 1 or general formula 2, and includes, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane,
Examples include decamethyltetrasiloxane, dodecamethylpentasiloxane, hexamethyldiphenyltrisiloxane, hexamethyltetraphenyltetrasiloxane, and hexamethylhexaphenylpentasiloxane.

A titanium alkoxide, a hydrocarbon and / or
Alternatively, the quantitative relationship with silicon is from 5 to 500 parts, preferably from 10 to 300 parts, of hydrocarbon and / or silicone with respect to 100 parts by weight of titanium alkoxide (hereinafter abbreviated as part). . When both a hydrocarbon and a silicone are used, the ratio of the hydrocarbon to the silicone can be arbitrarily selected within the above range of parts by weight. That is, it can be arbitrarily selected depending on the properties of the target powder. Further, the quantitative relationship between the titanium alkoxide and the basic compound is not particularly limited.
0 parts, preferably 20 to 100 parts.

[0008] The method for producing the particulate titanium hydroxide used in the present invention specifically takes the following aspects. Hydrolysis step → concentration step → drying step This production method will be described for each step. The hydrolysis step is a step of hydrolyzing the titanium alkoxide.
This hydrolysis is performed at room temperature (20 ± 10 ° C.) or at a heating temperature (30-130 ° C.). In a usual method, a suspension of titanium hydroxide is obtained by hydrolyzing a titanium alkoxide and water in a diluted state with a solvent, and then refluxing for 0.5 to 24 hours or without refluxing. If the powder is concentrated and dried as it is, a powder having a particle size of about 1 μm is obtained, and a fine powder having a submicron size or less cannot be obtained. Therefore, if hydrocarbons and / or silicones are added before, during, or after the hydrolysis, aggregation of the particles can be prevented even after the subsequent concentration and drying steps, and submicron or less. Can be obtained. However, since the surface activity is strong in this state, if a basic compound is further added before, during, or after the hydrolysis,
Acid points on the powder surface are blocked, and surface activity can be suppressed during drying.

In the concentration step, excess water, hydrocarbons and / or silicones and basic compounds and the solvent used for dilution are removed from the suspension obtained in the hydrolysis step,
This is a step for increasing the efficiency of the next drying step. As the concentration method, there are methods such as drying under reduced pressure, suction filtration, filtration under pressure, vibration drying, spray drying, freeze drying, etc., which are appropriately selected according to the size of the lot to be manufactured, and the types of hydrocarbons and silicones. . The powder thus obtained has a specific surface area of 100 to 500 m ² / g, and is finely divided into titanium hydroxide by being crushed by a known crushing method. The quantitative relationship between titanium alkoxide and water at the time of hydrolysis can be selected in a very wide range, but is usually 10 to 150 parts, preferably 40 to 80 parts, per 100 parts of titanium alkoxide. The titanium alkoxide and water during the hydrolysis may be used as they are, but are usually used after dilution with a solvent. Diluent solvents used in the present invention include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, and t-butanol. And alcohols such as

The amount of the fine particle titanium hydroxide in the cosmetic of the present invention varies depending on the type of the cosmetic, but is usually required to be 0.1% by weight or more based on the total weight of the cosmetic. If it is less than 0.1% by weight, the effect is not remarkable. The usual compounding amount is 0.1 to 60% by weight, and preferably 0.5 to 20% by weight. The cosmetic of the present invention can be in the form of powder, cake, pencil, stick, ointment, liquid, etc.
Facial cosmetics such as lotions, emulsions and creams, foundations, lipsticks, eye shadows, blushers, makeup cosmetics such as eyeliners, nail enamels, mascaras, hair treatments, hair liquids, set lotions -Includes hair cosmetics, such as cosmetics.

The cosmetic of the present invention may contain, in addition to the above-mentioned essential components, components commonly used in cosmetics as long as the effects of the present invention are not impaired. For example, solid and semi-solid oils such as petrolatum, lanolin, ceresin, carnauba wax, candelilla wax, higher fatty acids and higher alcohols, liquid oils such as squalane, liquid paraffin, ester oil and triglyceride, and oils such as silicone oil. , Moisturizing agents such as sodium hyaluronate and glycerin, surfactants such as cationic surfactants and nonionic surfactants, pigments, preservatives, fragrances, activators and the like can be appropriately compounded.

[0012]

Next, the present invention will be described in more detail with reference to comparative examples and examples, but the present invention is not limited to these examples. The compounding amount is% by weight. First, a production example of the fine particle titanium hydroxide used in the present example will be described below. Production Example 1 A solution obtained by diluting 100 parts of tetra-i-propoxytitanium with 500 parts of i-propanol has a boiling point of 116 to 143 ° C.
100 parts of water and 50 parts of water
-Add a solution diluted with 500 parts of propanol and add at 25 ° C.
For hydrolysis. To this suspension was added potassium hydroxide 20
A solution prepared by dissolving the resulting solution in 20 parts of water and 200 parts of ethanol was added, and the mixture was stirred and concentrated by suction filtration.
Thereafter, drying was performed at 120 ° C. to obtain 35 parts of stable fine particle powder. The specific surface area of this powder was 320 m ² / g.

Production Example 2 35 parts of stable fine powder were obtained in the same manner as in Production Example 1 except that the amount of potassium hydroxide was changed to 5 parts. The specific surface area of this powder was 400 m ² / g. Production Example 3 The addition amount of potassium hydroxide was 200 parts, and the other was Production Example 1.
In the same manner as in the above, 35 parts of stable fine particle powder were obtained. The specific surface area of this powder was 120 m ² / g. Production Example 4 Hydrocarbon 10 having a boiling point of 157 to 177 ° C. was added to a solution obtained by diluting 100 parts of tetramethoxytitanium with 500 parts of methanol.
0 parts were added, and 50 parts of water was added to 500 parts of methanol while stirring.
The solution diluted in part was added to perform hydrolysis. A solution prepared by dissolving 20 parts of sodium hydroxide in 20 parts of water was added to the suspension, and the mixture was stirred and concentrated by suction filtration.
Thereafter, drying was performed at 130 ° C. to obtain 35 parts of stable fine particle powder. The specific surface area of this powder was 150 m ² / g.

Production Example 5 Hydrocarbon 10 having a boiling point of 171 to 193 ° C. was added to a solution obtained by diluting 100 parts of tetramethoxytitanium with 500 parts of methanol.
0 parts were added, and 50 parts of water was added to 500 parts of methanol while stirring.
The solution diluted in part was added to perform hydrolysis. A solution prepared by dissolving 20 parts of potassium hydroxide in 20 parts of water and 100 parts of ethanol was added to the suspension, stirred, and then concentrated by suction filtration. After that, it is dried at 140 ° C.
35 parts of stable fine particle powder were obtained. The specific surface area of this powder was 220 m ² / g. Production Example 6 100 parts of octamethylcyclotetrasiloxane was added to a solution obtained by diluting 100 parts of tetra-i-propoxytitanium with 500 parts of i-propanol, and 50 parts of water was diluted with 500 parts of i-propanol while stirring. The resulting solution was added for hydrolysis. A solution prepared by dissolving 20 parts of potassium hydroxide in 20 parts of water and 200 parts of ethanol was added to the suspension, and the mixture was stirred and concentrated by suction filtration. Thereafter, drying was performed at 130 ° C. to obtain 40 parts of stable fine particle powder. The specific surface area of this powder was 450 m ² / g. Production Example 7 100 parts of decamethylcyclopentasiloxane was added to a solution obtained by diluting 100 parts of tetra-i-propoxytitanium with 500 parts of i-propanol, and 50 parts of water was added with stirring.
Hydrolysis was carried out by adding a solution diluted with 500 parts of propanol. To this suspension was added 20 parts of potassium hydroxide to water 2
A solution dissolved in 0 parts and 200 parts of ethanol was added, and the mixture was stirred and concentrated by suction filtration. After this,
It was dried at 130 ° C. to obtain 40 parts of stable fine particle powder. The specific surface area of this powder was 300 m ² / g.

Production Example 8 100 parts of hexamethyldisiloxane was added to a solution obtained by diluting 100 parts of tetra-i-propoxytitanium with 500 parts of i-propanol, and 50 parts of water was added to 500 parts of i-propanol while stirring. The solution diluted with was added to perform hydrolysis. A solution prepared by dissolving 20 parts of potassium carbonate in 30 parts of water and 300 parts of ethanol was added to the suspension, and the mixture was stirred.
The mixture was concentrated using suction filtration. Thereafter, drying was performed at 130 ° C. to obtain 35 parts of stable fine particle powder. The specific surface area of this powder was 110 m ² / g. Production Example 9 100 parts of octamethyltrisiloxane was added to a solution obtained by diluting 100 parts of tetra-n-propoxytitanium with 500 parts of i-propanol, and 50 parts of water was diluted with 500 parts of i-propanol while stirring. The solution was added for hydrolysis. A solution prepared by dissolving 20 parts of calcium hydroxide in 50 parts of water and 500 parts of ethanol was added to the suspension, stirred, and then concentrated by suction filtration. After this, 13
It was dried at 0 ° C. to obtain 37 parts of stable fine particle powder. The specific surface area of this powder was 100 m ² / g. Production Example 10 100 parts of tetra-n-butoxytitanium was added to i-propano-
100 parts of octamethyltrisiloxane was added to the solution diluted with 500 parts of toluene, and a solution obtained by diluting 50 parts of water with 500 parts of i-propanol was added thereto with stirring to carry out hydrolysis. A solution prepared by dissolving 20 parts of potassium hydroxide in 20 parts of water and 200 parts of ethanol was added to the suspension, and the mixture was stirred and concentrated by suction filtration. After this, 130
Drying at 40 ° C. yielded 40 parts of stable fine powder. The specific surface area of this powder was 100 m ² / g.

Production Example 11 100 parts of tetra-n-butoxytitanium was added to i-propano-
50 parts of octamethylcyclotetrasiloxane and 5 parts of octamethyltrisiloxane 5
0 parts were added, and a solution obtained by diluting 50 parts of water with 500 parts of i-propanol was added thereto with stirring, and hydrolysis was carried out. A solution prepared by dissolving 10 parts of calcium carbonate in 20 parts of water and 500 parts of ethanol was added to the suspension, and the mixture was stirred and concentrated by suction filtration. Thereafter, drying was performed at 130 ° C. to obtain 40 parts of stable fine particle powder. The specific surface area of this powder was 110 m ² / g. Production Example 12 50 parts of hexamethyldisiloxane and 50 parts of octamethyltrisiloxane were added to a solution obtained by diluting 100 parts of tetra-i-propoxytitanium with 500 parts of i-propanol. Then, a solution diluted with 500 parts of toluene was added to carry out hydrolysis. To this suspension was added 10 parts of potassium hydroxide, 20 parts of water and 5 parts of ethanol.
After the solution dissolved in 0 parts was added and stirred, the mixture was concentrated using suction filtration. After that, it is dried at 130 ° C.
Part of stable fine powder was obtained. The specific surface area of this powder is 2
It was 30 m ² / g. Production Example 13 A solution obtained by diluting 100 parts of tetra-n-propoxytitanium with 500 parts of i-propanol has a boiling point of 116 to 143 ° C.
50 parts of hydrocarbon and 50 parts of octamethylcyclotetrasiloxane were added, and a solution obtained by dissolving 20 parts of potassium carbonate in 50 parts of water and diluting with 500 parts of i-propanol was added thereto with stirring to carry out hydrolysis. . The suspension was concentrated by means of suction filtration, dried at 130 ° C.
Part of stable fine powder was obtained. The specific surface area of this powder is 1
It was 80 m ² / g.

Production Example 14 100 parts of tetra-n-butoxytitanium was added to i-propano-
20 parts of potassium hydroxide, 50 parts of a hydrocarbon having a boiling point of 157 to 177 ° C. and 50 parts of decamethylcyclopentasiloxane are added to the solution diluted with 500 parts of toluene, and 50 parts of water are added with stirring to 50 parts of i-propanol 500. The solution diluted in part was added to perform hydrolysis. The suspension was concentrated by means of suction filtration and dried at 130 ° C. to obtain 35 parts of stable fine powder. The specific surface area of this powder is 110 m ²
/ G. Production Example 15 100 parts of tetra-i-butoxytitanium was added to i-propano-
To a solution diluted with 500 parts of toluene, 50 parts of a hydrocarbon having a boiling point of 171 to 193 ° C. and 50 parts of hexamethyldisiloxane are added, and while stirring, a solution obtained by diluting 50 parts of water with 500 parts of i-propanol is added. Hydrolysis was performed. To this suspension was added 20 parts of potassium hydroxide and 20 parts of water and 2 parts of ethanol.
After adding the solution dissolved in 00 parts and stirring, the mixture was concentrated by means of suction filtration. After that, it is dried at 130 ° C.
5 parts of stable fine powder were obtained. The specific surface area of this powder was 100 m ² / g. Production Example 16 A solution obtained by diluting 100 parts of tetra-sec-butoxytitanium with 500 parts of i-propanol had a boiling point of 116 to 143.
50 ° C. hydrocarbons and 157-177 ° C. hydrocarbons 50
And 50 parts of water were added to i-propanol 5 while stirring.
Hydrolysis was performed by adding a solution diluted in 00 parts. A solution prepared by dissolving 20 parts of potassium hydroxide in 20 parts of water and 200 parts of ethanol was added to the suspension, and the mixture was stirred and concentrated by suction filtration. Thereafter, drying was performed at 130 ° C. to obtain 35 parts of stable fine particle powder. The specific surface area of this powder was 100 m ² / g.

Production Example 17 100 parts of tetra-i-butoxytitanium was added to i-propano-
50 parts of a hydrocarbon having a boiling point of 116 to 143 ° C. and 50 parts of a hydrocarbon having a boiling point of 171 to 193 ° C. are added to the solution diluted with 500 parts of toluene, and 50 parts of water are stirred and mixed with i-propanol 500.
The solution diluted in part was added to perform hydrolysis. A solution prepared by dissolving 20 parts of potassium hydroxide in 20 parts of water and 200 parts of ethanol was added to the suspension, and the mixture was stirred and concentrated by suction filtration. After that, it is dried at 130 ° C.,
35 parts of stable fine particle powder were obtained. The specific surface area of this powder was 120 m ² / g. Production Example 18 100 parts of octamethylcyclotetrasiloxane was added to a solution obtained by diluting 50 parts of water with 500 parts of i-propanol, and the mixture was stirred.
00 parts were added to a solution diluted with 500 parts of i-propanol, and hydrolysis was carried out at 25 ° C. A solution prepared by dissolving 20 parts of potassium hydroxide in 20 parts of water and 200 parts of ethanol was added to the suspension, and the mixture was stirred and concentrated by suction filtration. Thereafter, drying was performed at 130 ° C. to obtain 35 parts of stable fine particle powder. The specific surface area of this powder is 350 m
² / g. Production Example 19 A solution prepared by diluting 50 parts of water with 500 parts of i-propanol was added to a solution obtained by diluting 100 parts of tetra-i-propoxytitanium with 500 parts of i-propanol while stirring.
Hydrolysis was performed at ° C. This suspension has a boiling point of 116-1.
100 parts of 43 ° C. hydrocarbon was added and stirred. To this suspension was added 20 parts of potassium hydroxide and 20 parts of water and 2 parts of ethanol.
After adding the solution dissolved in 00 parts and stirring, the mixture was concentrated by means of suction filtration. After that, it is dried at 130 ° C.
5 parts of stable fine powder were obtained. The specific surface area of this powder was 230 m ² / g.

Production Example 20 100 parts of octamethylcyclotetrasiloxane was added to a solution obtained by diluting 100 parts of tetra-i-propoxytitanium with 500 parts of i-propanol, and 50 parts of water was added with stirring to 50 parts of i-propanol 500. 25 parts of the diluted solution
The hydrolysis was carried out at 90 ° C., followed by reflux at 90 ° C. for 10 hours. A solution prepared by dissolving 20 parts of potassium hydroxide in 20 parts of water and 200 parts of ethanol was added to the suspension, and the mixture was stirred and concentrated by suction filtration. After this, 130
Drying at ℃ yielded 35 parts of stable fine powder. The specific surface area of this powder was 320 m ² / g. Production Example 21 A solution obtained by diluting 100 parts of tetraoctadecyloxytitanium with 500 parts of i-propanol had a boiling point of 171 to 193.
100 parts hydrocarbon at ℃, octamethyltrisiloxane 1
00 parts and 100 parts of hexamethyltetraphenyltetrasiloxane were added, and the mixture was heated to 50 ° C. This solution was added with stirring to a solution obtained by diluting 50 parts of water with 500 parts of i-propanol, and hydrolysis was carried out at 50 ° C. A solution prepared by dissolving 20 parts of potassium hydroxide in 20 parts of water and 200 parts of ethanol was added to the suspension, and the mixture was stirred and concentrated by suction filtration. After that, it is dried at 130 ° C.,
35 parts of stable fine particle powder were obtained. The specific surface area of this powder was 130 m ² / g.

For the powders obtained in Production Examples 1 to 14 and commercial products, the absorbance at ultraviolet (300, 350 nm)
Table 1 shows the reflectance of the visible region (550 nm) and the decomposition ratio of t-BuOH. The absorbance of ultraviolet rays was measured by dispersing 1% by weight of powder in castor oil, applying 5 μm thick on a quartz plate, and measuring with a spectrophotometer. The reflectance of the visible part was measured by dispersing 10% by weight of powder in castor oil, applying the powder to a black opacity test paper at a thickness of 0.1 mm, and measuring with a colorimeter. Further, the decomposition rate of t-BuOH was determined by injecting 10 μl of t-BuOH into a glass tube having an inner diameter of 2 mm in which 10 mg of powder was sealed, holding the mixture at 200 ° C. for 10 minutes, and analyzing the remaining amount by gas chromatography. Then, the decomposition rate was calculated.

[0021]

[Table 1] 吸 光 Absorbance Reflectivity (%) Decomposition rate (% ) {T-BuOH 300 nm 350 nm 550 nm} ────────── Commercial product 0.30 0.28 43.4 100.0 Production Example 1 0.55 0.31 34.2 0.0 Production Example 2 0.57 0.39 36. 3 5.2 Production Example 3 0.41 0.26 41.0 0.0 Production Example 4 0.46 0.32 38.5 1.2 Production Example 5 0.39 0.25 42.3 0.0 Production Example 6 0.57 0.22 31.6 0.0 Preparation 7 0.55 0.23 34.5 0.0 Preparation 8 0.51 0.25 38.8 0.0 Preparation 9 0.42 0.26 4.8 0.0 Production Example 10 0.45 0.29 36.8 0.0 Production Example 11 0.42 0.27 36.1 1.4 Production Example 12 0.58 0.25 33.8 1. 1 Production Example 13 0.45 0.27 38.5 0.0 Production Example 14 0.44 0.28 39.7 0.0 ───────────────── (Results) As shown in the table, the powder of this Production Example showed good results in the ultraviolet shielding effect, transparency and suppression of surface activity.

Example 1 Emulsion foundation 1) Deionized water 60.9 2) Distearyl dimethyl ammonium chloride 0.1 3) Sodium L-glutamate 2.0 4) Polyoxyalkylene-modified organopolysiloxane (MW 3000) 4 5.0 (18% polyoxyalkylene group) 5) Decamethylcyclopentasiloxane 12.06 6) Liquid paraffin (120 cSt) 5.0 7) Fine particle titanium hydroxide obtained in Production Example 1 5.0 8) Sericite 5.36 9) Kaolin 4.0 10) Titanium oxide 0.32 11) Iron oxide yellow 0.80 12) Iron oxide red 0.36 13) Iron oxide black 0.16 (Production method) Components 1) to 3) After heating and stirring at 70 ° C., the fine particle titanium hydroxide powder obtained in Production Example 1 and components 8) to
13) was added and dispersed. 70 ° C beforehand
And added to the components 4) to 6), which had been heated in advance, and emulsified and dispersed. Thereafter, the mixture was stirred and cooled to room temperature to obtain a desired emulsified foundation.

Example 2 Powder foundation 1) Fine particle titanium hydroxide obtained in Production Example 7.0 2) Talc 40.0 3) Mica 26.3 4) Nylon powder 12.05) Oxidation Iron red 1.0 6) Iron oxide yellow 2.0 7) Iron oxide black 0.2 8) Dimethyl polysiloxane 1.0 9) 2-Ethylhexyl palmitate 9.0 10) Sorbitan sesquioleate 1.0 11 ) Preservative 0.3 12) Antioxidant 0.1 13) Fragrance 0.1 (Preparation method) Components 1) to 7) were mixed with a Henschel mixer, and components 8) to 13) were heated and dissolved in this mixture. Were added and mixed. Thereafter, the mixture was pulverized with a 5HP pulperizer (Hosokawa Micron) and formed into a middle plate to obtain a desired powdery foundation.

Example 3 Oily stick foundation 1) Fine titanium oxide hydroxide 13.0 obtained in Production Example 7 2) Kaolin 8.0 3) Talc 2.0 4) Iron oxide red 3.0 5) Oxidation Iron yellow 2.0 6) Iron oxide black 1.0 7) Squalane 27.0 8) Cetyl 2-ethylhexanoate 11.0 9) Sorbitan sesquioleate 1.0 10) Aristo wax 3.4 11) Carnauba wax 1 0.0 12) Preservative 0.3 13) Antioxidant 0.1 14) Fragrance 0.2 (Preparation method) Components 7) to 9) are mixed at 80 ° C, and components 1) to 6) are added thereto. After mixing with a disper, a roller treatment was performed. Components 10) to 13) were dissolved by heating, degassed after addition and mixing. 80 after gently mixing component 14)
The desired stick foundation was obtained by filling the mixture in a container at ℃ and cooling.

Example 4 Emulsion lipstick 1) Polyethylene 7.0 2) Celesin 4.0 3) Candelilla wax 7.0 4) Carnauba wax 1.0 5) Castor oil 20.0 6) Liquid paraffin 18.3 7) Glycerol tristearate 20.0 8) Titanium coated mica 5.0 9) Fine titanium oxide hydroxide obtained in Production Example 9 5.0 10) Yellow No. 4 A1 lake 1.0 11) Carmine A1 lake 0.3 12) Red No. 201 0.2 13) Dibutylhydroxytoluene 0.1 14) Fragrance 0.1 15) Sorbitan sesquioleate 2.0 16) Ion-exchanged water 5.0 17) Propylene glyco 18) SORBIT 2.0 (Preparation method) Components 1) to 7) are heated and dissolved at 90 ° C., and components 8) to 14) are added and dispersed.
5) and 18) were gradually added and mixed by stirring. Next, the components 16) and 17) were gradually added at 80 ° C., mixed by stirring, and filled in a predetermined container to obtain a target emulsified lipstick.

Example 5 Sun tank dream 1) Ion exchange water 57.25 2) Sodium L-glutamate 3.0 3) 1,3 Butylene glycol 5.0 4) Silicon wax 0.5 5) Dimethyl poly Siloxane (100 cSt) 5.0 6) Decamethylcyclopentasiloxane 15.0 7) Dioctadecyldimethylammonium chloride 0.1 8) Polyoxyalkylene-modified organopolysiloxane 5.0 (MW 6000, 20% polyoxyalkylene group) 9 ) Palmitic acid 0.2 10) 4-tert-butyl-4'-methoxydibenzoylmethane 0.3 11) Glyceryl mono-2-ethylhexanoyl diparamethoxycinnamate 1.0 12) Antioxidant 0 0.05 13) Preservative 0.3 14) Fragrance 0.3 15) Production Example 27 The obtained fine particle titanium hydroxide 5.0 16) kaolin 0.37 17) iron oxide yellow 0.3 18) iron oxide red 0.18 19) iron oxide black 0.15 20) titanium oxide coated mica 1.0 ( Production method) After heating and stirring components 1) to 3) at 70 ° C.,
5) to 20) are added and dispersion treatment is performed.
The mixture was added to components 4) to 14) heated to 0 ° C and emulsified and dispersed. Thereafter, the mixture was stirred and cooled to room temperature to obtain a desired sun tank stream.

Comparative Examples 1 to 5 In the cosmetics of Examples 1 to 5, fine titanium oxide powder (D-25, P-25) obtained by subjecting titanium chloride to gas phase oxidation instead of fine titanium hydroxide was used. The blended cosmetics were set as Comparative Examples 1 to 5, respectively. This powder is a mixed type powder of anatase and rutile. Comparative Examples 6 to 10 In the cosmetics of Examples 1 to 5 described above, instead of the fine particle titanium hydroxide, a cosmetic compounded with the fine particle titanium hydroxide produced without adding the basic compound solution in each production example was used. Comparative Examples 6 to 10 were made.

With respect to the cosmetics obtained in Examples 1 to 5 and Comparative Examples 1 to 10, the absorbance at ultraviolet (300 nm)
Table 2 shows the reflectance of the visible region (420 nm, 550 nm). The absorbance of Example 5 and Comparative Examples 5 and 10 was applied on a transparent quartz plate with a thickness of 5 μm, and Examples 1-4 and Comparative Examples 1-4 and 6-9 were 0.02 g of a sample on a transparent quartz plate.
Was applied almost uniformly over an area of 4 × 5 cm, and measured with a spectrophotometer. In Example 5, and Comparative Examples 5 and 10, the reflectivity was kept as it was, and Example 4 and Comparative Examples 4 and 9 were heated and dissolved to obtain a black opacity test paper having a reflectance of 0.3.
It was applied to a thickness of 5 nm, and Examples 1 to 3 and Comparative Examples 1 to
For samples 3, 6 to 8, 0.7 g of a sample was applied to a black opacity test paper so as to be almost uniform over an area of 4 × 5 cm, and measured with a colorimeter. (Results) As shown in Table 2, the cosmetics of this example exhibited good results in both the ultraviolet scattering effect and the transparency, and did not show any odor due to oils or fragrances.

[0029]

[Table 2] 吸 光 Absorbance Reflectance (%) Oil smell官能 (Sensory evaluation) 300 nm 420 nm 550 nm ────────────────────────── ────────── Example 1 0.82 31.9 21.2 ○ Comparative Example 1 0.54 61.2 45.7 × Comparative Example 6 0.79 30.1 20.5 △ Implementation Example 2 0.86 48.7 34.1 ○ Comparative example 2 0.67 69.3 50.1 × Comparative example 7 0.85 42.8 29.2 △ Example 3 0.98 28.5 18.9 ○ Comparative Example 3 0.70 65.7 46.1 × Comparative Example 8 0.95 25.0 14.1 △ Example 4 0.67 33.4 24.1 ○ Comparative Example 4 0.49 67.2 4 0.3 × Comparative Example 9 0.68 32.1 23.3 Δ Example 5 0.90 40.2 26.2 ○ Comparative Example 5 0.64 60.5 38.7 × Comparative Example 10 0.93 36. 8 24.2 △ ────────────────────────────────────

Example 6 Emulsion foundation 1) Deionized water 46.65 2) Dipropylene glycol 3.0 3) Sodium L-aspartate 2.0 4) Sodium L-glutamate 2.0 5) Deca Methylpolysiloxane 15.0 6) Dimethylpolysiloxane 5.0 7) Dioctadecyldimethylammonium chloride 0.2 8) Polyoxyalkylene-modified organopolysiloxane 5.0 (MW 6000, 20% polyoxyalkylene group) 9) Palmitic acid 0.5 10) Fine particle titanium hydroxide obtained in Production Example 13 5.0 11) Antioxidant 0.05 12) Preservative 0.3 13) Fragrance 0.3 14) Sericite 8.03 15) Oxidation Titanium 6.0 16) Iron oxide yellow 0.6 17) Iron oxide red 0.25 18) Iron oxide black 0.12

Example 7 Emulsion foundation 1) Ion-exchanged water 25.0 2) 1,3-butylene glycol 5.0 3) Caustic potassium 0.1 4) Dihexadecyldimethylammonium chloride 1.0 5) L -Sodium glutamate 2.0 6) Sodium hyaluronate 0.1 7) Liquid paraffin (120 cSt) 5.0 8) Octamethylcyclotetrasiloxane 10.0 9) Decamethylcyclopentasiloxane 10.0 10) Dimethylpolysiloxane 5 0.0 11) Sorbitan sesquiisostearate 2.0 12) Polyoxyalkylene-modified organopolysiloxane 4.0 (MW 6000, 20% polyoxyalkylene group) 13) Antioxidant 0.1 14) Preservative 3 15) Fragrance 0.3 16) Fine particle hydroxylation obtained in Production Example 14 Tan 0.1 17) Kaolin 5.0 18) Sericite 7.4 19) Talc 3.0 20) Zinc oxide 3.0 21) Titanium oxide 10.0 22) Iron oxide yellow 1.0 23) Iron oxide red 0.4 24) Iron oxide black 0.2

Example 8 Emulsion 1) Octamethylcyclotetrasiloxane 10.0 2) Dimethylpolysiloxane (6 cSt) 10.0 3) Cetyl isooctanoate 2.0 4) Liquid paraffin (120 cSt) 2.05 ) Sorbitan diisostearate 3.0 6) Polyoxyalkylene-modified organopolysiloxane 3.0 (MW 6000, 20% polyoxyalkylene group) 7) Antioxidant 0.05 8) Fragrance 0.3 9) Ion exchange Water 53.25 10) Sodium dextran sulfate 1.0 11) Sodium chondroitin sulfate 2.0 12) Glycerin 3.0 13) Sodium hyaluronate 0.1 14) Sodium glycyrrhizinate 0.1 15) Preservative 0.216 ) Fine particle titanium hydroxide obtained in Production Example 18 10.0

Example 9 Sunscreen 1) Deionized water 46.15 2) Monohexadecyltrimethylammonium chloride 1.5 3) Sodium pyrrolidone carboxylate 1.0 4) Propylene glycol 5.0 5) Lysine 1 0.0 6) Sodium L-glutamate 3.5 7) Cetanol 0.5 8) Stearic acid 0.5 9) Sorbitan diisostearate 8.0 10) Silicon wax 1.0 11) Decamethyloctasiloxane 15.0 12) Liquid paraffin (70 cSt) 3.0 13) Olive oil 2.0 14) Lanolin 1.0 15) Vitamin E acetate 0.1 16) Antioxidant 0.05 17) Preservative 0.3 18) Fragrance 0.3 19) Fine particle titanium hydroxide obtained in Production Example 21 35.0

Example 10 Suntan lotion 1) Dimethylpolysiloxane 5.0 2) Decamethylcyclopentasiloxane 3.0 3) Olive oil 5.0 4) Liquid paraffin (70 cSt) 5.0 5) 4- tert-butyl-4'-methoxydibenzoylmethane 0.3 6) glycerylmono-2-ethylhexanoyl diparamethoxycinnamate 1.0 7) polyoxyalkylene-modified organopolysiloxane 6.0 (MW 6000, poly 8) Fine-particle titanium hydroxide 2.5 obtained in Production Example 22 9) Fine-particle titanium hydroxide 2.5 obtained in Production Example 8 10) Antioxidant 0.05 11) Fragrance 0 3.3 12) Ion-exchanged water 57.05 13) Dipropylene glycol 5.0 14) Sodium L-glutamate 5.0 15) Sodium pyrrolidonecarboxylate 2.0 16) Preservative 0.3

Example 11 Makeup Base 1) Ion-exchanged water 54.05 2) Sodium L-aspartate 2.0 3) L-serine 1.0 4) Sodium citrate 0.5 5) 1,3-butylene glyco- 5.0 6) Preservative 0.3 7) Organically modified montmorillonite 0.5 8) Cetine isooctanoate 2.0 9) Octamethylcyclotetrasiloxane 2.0 10) Decamethylcyclopentasiloxane 5.0 11) Dimethyl polysiloxane (6 cSt) 5.0 12) Liquid paraffin (120 cSt) 3.0 13) Dioctadecyl dimethyl ammonium chloride 0.2 14) Polyoxyalkylene-modified organopolysiloxane 5.0 (MW 6000, polyoxyalkylene group) 15) 4-tert-butyl-4'-methoxydibenzoy Methane 0.3 16) glyceryl mono-2-ethylhexanoyl diparamethoxycinnamate 1.0 17) fine particle titanium hydroxide obtained in Production Example 24 5.0 18) oleyl alcohol 0.519 ) Stearic acid 0.5 20) Sorbitan diisostearate 4.0 21) Antioxidant 0.05 22) Fragrance 0.3 23) Cobalt titanate 0.3 24) Talc 1.5 25) Nylon powder (Particle size 5 μm) 1.0

Example 12 Blush 1) Ion-exchanged water 49.25 2) Monohexadecylmonophenyl dimethylammonium chloride 0.5 3) Sodium L-glutamate 2.0 4) Glycerin 5.0 5) Sodium pyrrolidone carboxylate 2 0.0 6) Decamethylcyclopentasiloxane 20.07) Glyceryldiolate 2.0 8) Stearic acid 1.0 9) Silicon wax 0.5 10) Polyoxyalkylene-modified organopolysiloxane 5.0 (MW 6000) , Polyoxyalkylene group 20%) 11) 4-tert-butyl-4'-methoxydibenzoy 0.3 methane 12) Fine-particle titanium hydroxide obtained in Production Example 5.0 5.0 13) Antioxidant 0.05 14) Preservative 0.2 15) Fragrance 0.2 16) Titanium oxide 4.0 17) Katetsuaka 1.0 18) sericite 2.0

Example 13 Oily stick foundation 1) Fine particle titanium hydroxide obtained in Production Example 4 45.0 2) Kaolin 8.0 3) Talc 2.0 4) Iron oxide red 3.0 5) Oxidation Iron yellow 2.0 6) Iron oxide black 1.0 7) Squalane 27.0 8) Cetyl 2-ethylhexanoate 11.0 9) Sorbitan sesquioleate 1.0 10) Aristo wax 3.4 11) Carnauba wax 1 0.0 12) Preservative 0.3 13) Antioxidant 0.1 14) Fragrance 0.2 (Preparation method) Components 7) to 9) are mixed at 80 ° C, and components 1) to 6) are added thereto. After mixing with a disper, a roller treatment was performed. Components 10) to 13) were dissolved by heating, degassed after addition and mixing. 80 after gently mixing component 14)
The desired stick foundation was obtained by filling in a container at a temperature of ° C. and cooling.

[0038]

The cosmetic composition of the present invention has an ultraviolet shielding effect, in particular, 280 to 320 n, which cannot be sufficiently achieved only by blending conventional fine particles of titanium oxide or titanium hydroxide powder.
It has excellent shielding effect and transparency in the UV-B wavelength region of m, and suppresses unpleasant odor accompanying deterioration of oil and fragrance.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI A61K 7/025 A61K 7/025 7/031 7/031 (56) References JP-A-3-184905 (JP, A) JP Hei 2-279519 (JP, A) JP-A-63-275516 (JP, A) JP-A-63-270618 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 7 / 42 A61K 7/00 A61K 7/02 A61K 7/025 A61K 7/031

Claims (1)

(57) [Claims] 1. When a titanium alkoxide is hydrolyzed to produce titanium hydroxide, a basic compound and a boiling point of 100
A hydrocarbon having a temperature of up to 200 ° C. and / or the following general formula: [(CH ₃ ) ₂ SiO] _n (where n is an integer of 3 to 7) or CH _{3 - [R 2 SiO] n -Si} (CH 3) 3 ( wherein, n an integer of 1 to 4, R represents a methyl group, a phenyl group.) silicone represented by - is obtained by adding the emissions A cosmetic comprising a finely divided titanium hydroxide powder.