JPH09315939A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an odorless cosmetic formulated with highly water-repellent metal oxide fine particles. SOLUTION: This cosmetic is such one as to be formulated with metal oxide fine particles prepared by surface treatment of silica-treated metal oxide fine particles each 5-100nm in average primary particle size with an alkylalkoxysilane of the general formula R<1> x Si(OR<2> )4-x (R<1> is a 4-15C alkyl chain; R<2> is a 1-3C straight-chain or side chain-bearing alkyl chain; (x) is 1-3) in such an amount as to be (1:99) to (15:85) in the weight ratio of the alkylalkoxysilane to the silica-treated metal oxide fine particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetics containing no particulate odor and having excellent water repellency and containing fine particle metal oxides.

[0002]

2. Description of the Related Art Fine particles of titanium oxide treated with alkylalkoxysilane are excellent in water resistance, feel, and hardly show bluish whiteness (Japanese Patent Application No. 6-270475).

[0003]

However, when a fine particle metal oxide such as titanium oxide is surface-treated with an alkylalkoxysilane having a long chain, since the reactivity of the silane is insufficient, a unique odor is obtained after the surface treatment. There was a problem that occurs.

[0004]

[Means for Solving the Problems] As a result of intensive studies to solve this problem, as a result, in order to improve the reactivity of the long-chain alkylalkoxysilane, the surface of the fine particle metal oxide was previously coated with silica rich in surface hydroxyl groups. Then, it was found that when the surface treatment of this with a long-chain alkylalkoxysilane, the reactivity of the silane was improved and the specific odor disappeared.

That is, according to the present invention, R ¹ _X Si (OR ² )
_4-x (wherein R ¹ is an alkyl chain having 4 to 15 carbon atoms,
R ² is a linear or branched alkyl chain having 1 to 3 carbon atoms, and X is 1 to 3. 5-10 as an average primary particle diameter of the alkylalkoxysilane represented by the general formula
The present invention relates to a cosmetic composition in which a fine particle metal oxide surface-treated with a surface treatment amount within a range of 1:99 to 15:85 is added to a silica-treated fine particle metal oxide within a range of 0 nm.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.
The alkylalkoxysilane referred to in the present invention includes R ¹ _X
Si (OR ² ) _4-x (wherein R ¹ is an alkyl chain having 4 to 15 carbon atoms, R ² is an alkyl chain having 1 to 3 carbon atoms in a straight chain or a side chain, and X is 1 to 3) can be used. Of these, R ¹
Preferably has 8 to 10 carbon atoms, and R ² is preferably methyl or ethyl.

Examples of the fine particle metal oxide used in the present invention include titanium oxide, zinc oxide, aluminum oxide, cerium oxide, low-order titanium oxide, zirconium oxide, and cobalt oxide. Zinc oxide and cerium oxide are preferred. Examples of the shape of the particulate metal oxide include spherical shapes, rod shapes, needle shapes, and irregular shapes, but are not particularly limited. Also, the crystal form is not particularly limited.

The fine particle metal oxide used in the present invention must be surface-treated with silica. As a method of surface treatment, a conventionally known method can be used, and examples thereof include a method of performing treatment by a wet method using a silicate such as sodium silicate, chlorosilane, or alkoxysilane. The amount of surface treatment is preferably 0.3 to 12% by weight in terms of silicon dioxide with respect to the particulate metal oxide. It is also possible to perform treatment with alumina, zirconia, ceria, etc. simultaneously with silica.

As the silica-treated fine particle metal oxide used in the present invention, those having an average primary particle diameter in the range of 5 to 100 nm can be used. A scanning or transmission electron microscope can be used for the method of measuring the average primary particle diameter.

The treatment amount of the alkylalkoxysilane used in the present invention with respect to the silica-treated fine particle metal oxide is such that the weight ratio thereof is within the range of 1:99 to 15:85. Within this range, the specific odor is small and the effects such as water repellency can be obtained at the same time.

The method for treating the silica-treated fine particle metal oxide of the alkylalkoxysilane used in the present invention is, for example, an alkylalkoxysilane in the atmosphere of nitrogen, an inert gas, a kind of dry air or the like, and the silica-treated fine particle metal oxide. The vapor phase method in which the surface hydroxyl groups and the surface water are used to carry out a heat reaction on the particle surface, or the alkylalkoxysilane and the silica-treated fine particle metal oxide are put into a solvent such as alcohol and reacted in the presence of a small amount of water. And a wet method.

In either method, after reacting the silane, 6
It is preferable to perform the heat treatment at a temperature of 0 to 200 ° C.

The modified fine particle metal oxide used in the present invention is
It can be used after being dispersed in advance in cyclic silicone, alcohol, oil, etc. As a method of dispersion, for example, as disclosed in Japanese Patent Application No. 6-279931, a method using a wet pulverizer such as a bead mill is preferable. In addition to the modified fine particle metal oxide and the dispersion medium, a surfactant, a resin, other powders, and the like may be simultaneously mixed during the pulverization. The concentration of the modified fine particle metal oxide in the dispersion is 1 with respect to 100 parts by weight of the dispersion.
-60 parts by weight is preferred.

In the cosmetic of the present invention, it is preferable to use the above-mentioned modified fine particle metal oxide in an amount of 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, per 100 parts by weight of the cosmetic. It is preferably used within the range of parts. Within this range, the feel and bluishness of the fine particles are less noticeable.

In the cosmetics of the present invention, in addition to the above-mentioned components, oils, powders (pigments, dyes, resins), fluorine compounds, resins, surfactants, viscous agents, preservatives, fragrances, which are usually used in cosmetics, UV absorbers (including organic and inorganic types. UV
-It may correspond to either A or B), a humectant, a physiologically active ingredient, salts, a solvent, an antioxidant, a chelating agent, a neutralizing agent, a pH adjusting agent and the like components may be blended at the same time. it can.

The cosmetics of the present invention include makeup cosmetics such as foundation, white powder, lipstick, eye shadow, cheek, nail color, and basic cosmetics such as emulsions, lotions, creams, cleansing, packs and sunscreens. Is mentioned.

[0017]

The present invention will be described in detail below with reference to examples and comparative examples. The evaluation method used in the present invention is as follows.

Evaluation of odor The smell of the sample was smelled by three panelists to determine the presence or absence of odor. When all three persons evaluated that they were odorless, they were evaluated as "odorless".

Evaluation of water repellency of powder sample 0.03 g of the powder was put into a test tube containing an ethanol aqueous solution having a different concentration, and the sedimentation state of the sample when the sample was irradiated with ultrasonic waves for 30 seconds was observed. Then, the sample was evaluated according to the criteria in Table 1 based on the ethanol volume concentration of the aqueous ethanol solution in which precipitation started.

[0020]

[Table 1]

Example 1 Silica-alumina-treated fine particle titanium oxide (MT-100SA manufactured by Teika Co., Ltd., average primary particle size is 20 nm) 1
00 parts by weight of R ¹ _X Si (OR ² ) _4-x (where R ¹ = C ₈ H
₁₇ , R ² ═CH ₃ , X = 1) 10 parts by weight of the alkoxysilane represented by the formula 1 is sprayed, and then the mixture is sprayed at 120 ° C. in a nitrogen atmosphere at
The mixture was heated for a while under mild stirring to obtain modified fine particles of titanium oxide. Then, deodorization was carried out by heating under air circulation at 100 ° C. for 5 hours with gentle stirring.

Comparative Example 1 Untreated fine particle titanium oxide (P-2 manufactured by Degussa Co., Ltd.
5, the average primary particle size is 30 nm) R ¹ _X S in 100 parts by weight
i (OR ² ) _4-x (provided that R ¹ = C ₈ H ₁₇ , R ² = CH ₃ , X
After spraying 10 parts by weight of the alkoxysilane represented by the formula (1), it was heated in a nitrogen atmosphere at 120 ° C. for 8 hours with gentle stirring to obtain modified fine particle titanium oxide. Then, deodorization was carried out by heating under air circulation at 100 ° C. for 5 hours with gentle stirring.

Comparative Example 2 100 parts by weight of alumina-treated fine particle titanium oxide (TTO-55A manufactured by Ishihara Sangyo Co., Ltd., average primary particle size is 35 nm) was dispersed in 1000 parts by weight of isopropyl alcohol, and R ¹ _X Si ( OR ² ) _4-x (However, R ¹ = C ₈ H
₁₇ , 10 parts by weight of alkoxysilane represented by R ² = CH ₃ , X = 1) was added. After 50 parts by weight of purified water was slowly added under strong stirring, the whole system was heated under reduced pressure to remove the solvent. Then, after pulverizing with a mixer, it was heated at 100 ° C. for 5 hours under air circulation under gentle stirring to obtain modified fine particle titanium oxide.

Comparative Example 3 Untreated fine particle titanium oxide (P-25) was used as a comparative product.

Example 2 A sunscreen agent was prepared according to the following formulation.

Component A Modified particulate titanium oxide of Example 1 12 parts Dimethicone copolyol (KF-6017 manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Parasol MCX (organic UV absorber) 8 parts Squalane 1 part Octamethylcyclotetrasiloxane 20 Part Silicone beads (average primary particle size 4.5 μm) 2 parts Component B ethanol 4 parts Purified water 50 parts

After the mixture of the component A was dispersed using a paint conditioner, the component B was added and further dispersed using a disper, and then the product was filled in a container. The resulting product has excellent UV protection and transparency.
There was no paleness.

Example 3 A sunscreen agent was prepared according to the following formulation.

Component A Modified particulate titanium oxide of Example 1 6 parts Fine particle zinc oxide 8 parts Polyoxyethylene / trifluoropropyl co-modified silicone (HLB value = 4) 3 parts Dimethylpolysiloxane 1 part Octamethylcyclotetrasiloxane 25 Part fluorinated silicone resin 5 parts spherical urethane beads (average primary particle size 8 μm) 2 parts component B purified water 50 parts

The mixture of the component A was dispersed using a paint conditioner, the component B was added and further dispersed using a disper, and then the product was filled in a container. The resulting product has excellent UV protection and transparency.
There was no paleness.

Comparative Example 4 A sunscreen agent was obtained in the same manner as in Example 2 except that the modified fine particle titanium oxide of Comparative Example 1 was used instead of the modified fine particle titanium oxide of Example 1.

Comparative Example 5 A sunscreen agent was obtained in the same manner as in Example 2, except that the modified fine particle titanium oxide of Comparative Example 2 was used in place of the modified fine particle titanium oxide of Example 1.

Comparative Example 6 A sunscreen agent was obtained in the same manner as in Example 2, except that the particulate titanium oxide of Comparative Example 3 was used instead of the modified particulate titanium oxide of Example 1.

The modified fine particle metal oxides obtained in the above examples and their mixed cosmetics were compared with the corresponding metal oxides obtained in Comparative Examples and their mixed cosmetics. The results are shown in Tables 2 and 3. Similar results were obtained when the particulate metal oxide was zinc oxide or cerium oxide.

[0035]

[Table 2]

[0036]

[Table 3]

No peculiar odor was observed in any of the modified fine particle metal oxides obtained in the examples. It was also confirmed that the cosmetics containing the modified fine particle metal oxide of the present invention had no odor and had water repellency.

[0038]

From the above, it is clear that the present invention provides a cosmetic composition containing no particulate odor and excellent particulate water-repellent metal oxide.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09C 1/36 PAV C09C 1/36 PAV PAW PAW 3/06 3/06 PBT PBT 3/12 PCH 3 / 12 PCH

Claims (2)

[Claims] 1. R ¹ _X Si (OR ² ) _4-x (wherein R ¹ is an alkyl chain having 4 to 15 carbon atoms, and R ² is 1 to 3 carbon atoms).
Is a straight chain or an alkyl chain having a side chain, and X is 1 to 3.
It is. The surface which is in the range of 1:99 to 15:85 in each weight ratio with respect to the silica-treated fine particle metal oxide in which the alkylalkoxysilane represented by the general formula (1) is in the range of 5 to 100 nm as the average primary particle diameter. Cosmetics containing finely divided metal oxides surface-treated with a treatment amount. 2. The cosmetic material according to claim 1, wherein the particulate metal oxide is selected from titanium oxide, zinc oxide and cerium oxide.