JPH10291922A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stable cosmetic having excellent ultraviolet ray blocking effect in broad area (UV-A and UV-B area), excellent in dispersibility and having a good spreading property on the skin and natural finish, free from paleness and capable of imparting natural transparency. SOLUTION: This cosmetic comprises fine-particle titanium oxide having spindle like or needle-like particle form and having 0.005-0.1 μm short diameter and 0.01-0.5 μm long diameter, titanium oxide having >0.10 μm and <=0.14 μm average particle diameter and 10-30 m<2> /g specific surface area and/or ion oxide-containing titanium oxide having >0.10 μm and <=0.14 μm average particle diameter and 10-30 m<2> /g specific surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fine particle titanium oxide having a specific particle shape and an average particle diameter, a titanium oxide having a specific average particle diameter and a specific surface area and / or a specific average particle diameter and a specific surface area. More specifically, the present invention relates to a cosmetic containing iron oxide-containing titanium oxide and UV-A.
(320-400 nm), UV-B (290-320 n)
m) Cosmetics that have an excellent ultraviolet blocking effect over a wide area, are excellent in dispersibility, are stable, spread well on the skin, and have a natural finish, that is, a natural clarity without bluish whiteness. About.

[0002]

2. Description of the Related Art Conventionally, in order to impart an ultraviolet ray blocking effect to cosmetics, an organic ultraviolet absorber is blended, or a fine powder of an inorganic compound such as titanium oxide, zinc oxide, cerium oxide or zirconium oxide is used. There was a technique such as blending.

[0003]

When an organic ultraviolet absorber is added to cosmetics, the effect of blocking ultraviolet rays is remarkably improved, but if it is used in a large amount, stickiness or irritation to the skin may occur, which is not preferable. There is. Although the particulate titanium oxide has an ultraviolet blocking ability, when it is added in a large amount to cosmetics, a bluish white peculiar to the particulate titanium oxide appears, and the composition and the coating film have a pale and unnatural finish. In order to solve these drawbacks, fine particle titanium oxide colored with an inorganic pigment such as red iron oxide or tar dye has also been used. In some cases. In addition, generally used fine particle titanium oxide particles are not easily dispersed because of poor dispersibility, and when blended in a large amount in cosmetics or the like, there are disadvantages such as loss of smoothness, poor spread and poor finish. Was. Further, the fine particle titanium oxide has a property that the ultraviolet ray blocking ability in the UV-B region is high, but the ultraviolet ray blocking ability in the UV-A region is not so high. In order to enhance the ultraviolet blocking effect in the UV-A region of the cosmetic, fine powder such as zinc oxide is blended.
In the case where these fine particles were blended in a large amount, they did not have much ultraviolet blocking ability in the region, and when they were blended in a large amount, they had disadvantages such as lack of smoothness and poor elongation and spread, similarly to the case of granular fine particles of titanium oxide. Therefore, it has been desired to develop a cosmetic composition which is excellent in ultraviolet blocking effect in a wide area, has excellent dispersibility, is stable, has good elongation and spread, and has a beautiful finish.

[0004]

Means for Solving the Problems In view of such circumstances, the inventors of the present invention have conducted intensive studies and as a result, have found that a fine particle titanium oxide having a specific particle shape and an average particle diameter is compared with a specific average particle diameter and a specific ratio. By containing titanium oxide having a surface area and / or titanium oxide containing iron oxide having a specific average particle diameter and a specific specific surface area, a wide area (UV-
(A and UV-B regions), it was found that a cosmetic having excellent ultraviolet blocking effect, excellent dispersibility, good stability, good spreadability, and a beautiful finish was obtained, and completed the present invention. That is, in the present invention, the particle shape is spindle-shaped or needle-shaped, the minor axis is 0.005 to 0.1 μm, and the major axis is 0.01 to 0.5.
μm fine titanium oxide and an average particle diameter of 0.10
more than 0.14 μm and more than 10 μm
Cosmetics containing 30 m ² / g titanium oxide and / or iron oxide-containing titanium oxide having an average particle size of more than 0.10 μm and 0.14 μm or less and a specific surface area of 10 to 30 m ² / g. To provide.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention has a spindle shape or needle shape and a minor axis of 0.005.
0.1 μm and a long diameter of 0.01 to 0.5 μm (hereinafter referred to as “fine particle titanium oxide of the present invention”). If the minor axis or the major axis of the fine particle titanium oxide of the component (A) is too small, the powder agglomerates, the ultraviolet ray blocking effect is deteriorated, and the usability as a cosmetic is impaired.
If the minor or major axis of the fine particle titanium oxide of the component (A) is too large, the effect of blocking ultraviolet rays is deteriorated, and the transparency of the coating film when used is impaired.

The amount of the fine particle titanium oxide of the present invention is not particularly limited, but it is more preferable that the amount is 1 to 30% by weight (hereinafter simply referred to as "%") in the cosmetic. If the compounding amount is in this range, the effects of the present invention are better exhibited.

The fine particle titanium oxide of the present invention may be, for example, a metal oxide, a metal hydroxide, a fluorine compound,
Surface treatment with a silicone oil, metal soap, wax, oil, hydrocarbon, or the like can be used. As the fine particle titanium oxide of the present invention, one or more kinds thereof can be used.

The component (B) used in the present invention is a titanium oxide having an average particle diameter of more than 0.10 μm and 0.14 μm or less and a specific surface area of 10 to 30 m ² / g (hereinafter referred to as “oxidation of the present invention”). Titanium oxide) and / or iron oxide-containing titanium oxide having an average particle diameter of more than 0.10 μm and 0.14 μm or less and a specific surface area of 10 to 30 m ² / g (hereinafter referred to as “iron-containing oxide of the present invention”). Titanium ").

The titanium oxide of the present invention has an average particle size of 0.1.
If the titanium oxide has a specific surface area of more than 10 μm and not more than 0.14 μm and a specific surface area of 10 to 30 m ² / g, its shape may be any of spherical, plate, flat, needle, spindle, irregular and the like. It does not matter. The method for preparing the titanium oxide of the present invention may be carried out by using an average particle diameter of more than 0.10 μm and 0.14 μm.
If titanium oxide having a specific surface area of 10 to 30 m ² / g or less can be obtained, any method can be used for the preparation. Specifically, the oxidation is adjusted to an average particle diameter of at least smaller than 0.10 μm. By baking the titanium and growing the particles, a titanium oxide having an average primary particle diameter of more than 0.10 μm and not more than 0.14 μm is obtained. The method for producing titanium oxide smaller than 0.10 μm is not particularly limited, and may be any method such as hydrolysis of titanyl sulfate or titanium tetrachloride, direct oxidation of titanium tetrachloride or hydrolysis of titanium alkoxide. No problem. The fired product obtained by such a method,
It can be pulverized by a pulverizer such as an energy fluid mill and subjected to water washing or surface treatment depending on the use.

It is more preferable that the titanium oxide of the present invention contains at least 70% of all the particles within the range of ± 0.03 μm of the average particle diameter. That is, a composition containing titanium oxide in this range, particularly a cosmetic, has improved feeling in use and optical characteristics such as blocking ultraviolet rays.

The iron-containing titanium oxide of the present invention has an average particle diameter of more than 0.10 μm and not more than 0.14 μm and a specific surface area of 10 to 30 m ² / g. May be spherical, plate-like, flat-like, needle-like, spindle-like, irregular, etc. The method for preparing the iron-containing titanium oxide of the present invention has an average particle diameter of 0.10.
more than 0.14 μm and a specific surface area of
If an iron oxide-containing titanium oxide of up to 30 m ² / g can be obtained, it can be prepared by any method. Specifically, first, it was prepared to have an average particle diameter smaller than at least 0.10 μm by a conventionally known method such as hydrolysis of titanyl sulfate or titanium tetrachloride, direct oxidation of titanium tetrachloride or hydrolysis of titanium alkoxide. Obtain titanium oxide. This is fired to grow the particles, so that the average particle size of the primary particles is approximately 0.10 μm to 0.14 μm.
A titanium oxide having an average particle diameter within a range of μm is obtained. Next, the method of containing iron oxide in the titanium oxide can be a conventionally known method, and is not particularly limited. However, iron sulfate or chloride is added to the surface of the titanium oxide adjusted to the desired average particle diameter. After the precipitation of iron hydroxide by hydrolysis of iron or the like, a method of firing and the like can be used. Alternatively, at least 0.
A method in which iron hydroxide is precipitated on the surface of titanium oxide prepared to have an average particle diameter smaller than 10 μm by hydrolysis of iron sulfate or iron chloride, and then calcined at 830 to 880 ° C. it can. The fired product obtained by such a method can be subjected to pulverization by a pulverizer such as an energy fluid mill, classification by elutriation or the like, or water washing or surface treatment depending on the use.

The iron-containing titanium oxide of the present invention has a content of 7
It is more preferable that 0% or more be contained within the range of ± 0.03 μm of the average particle diameter. Cosmetics containing the iron-containing titanium oxide in this range have further improved optical properties such as feeling in use and blocking of ultraviolet rays.

When the amount of iron oxide contained in the iron-containing titanium oxide of the present invention is in the range of 0.5 to 3.0% by weight, the finish of the composition, the cosmetic itself and its coating film is natural,
It is particularly preferable in that it also has an excellent ultraviolet blocking effect.

When the average particle diameter of the titanium oxide of the present invention and the iron-containing titanium oxide of the present invention is 0.10 μm or less,
The tendency to become pale and unnatural finish which is characteristic of fine-grained titanium oxide is remarkable. If it exceeds 0.14 μm, whitening or white floating characteristic of pigment-grade titanium oxide occurs and thick and unnatural. The tendency to become finished cosmetics appears remarkably.

The amount of the titanium oxide of the present invention and / or the amount of the iron-containing titanium oxide of the present invention is not particularly limited, but is preferably 1 to 30% in the cosmetic. If the compounding amount is in this range, the effects of the present invention are better exhibited.

The titanium oxide of the present invention or the iron-containing titanium oxide of the present invention may be, for example, a metal oxide, a metal hydroxide, a fluorine compound, a silicone oil, a metal soap,
It is also possible to use the material after surface treatment with wax, oil, hydrocarbon or the like. As the titanium oxide of the present invention or the iron-containing titanium oxide of the present invention, one or more kinds can be used.

The dosage form of the cosmetic of the present invention may be any of powder, powder solid, cream, emulsion, lotion, oily solid, oily liquid, paste and the like.
It is preferable to use skin care cosmetics, makeup cosmetics, hair cosmetics and the like. In particular, cosmetics that easily exert the effects of the present invention include foundations, white powders, blushers,
Lipsticks, nail polish, eye products, sunscreen cosmetics, concealers, and the like.

In the cosmetic of the present invention, components usually used in cosmetics can be appropriately compounded as needed within a range not to impair the effects of the present invention. Examples of the powder include inorganic pigments such as talc, kaolin, sericite, mica, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, and silicic anhydride, and zinc oxide. Such as inorganic white pigments, red iron oxide, yellow iron oxide, black iron oxide, ultramarine,
Inorganic color pigments such as navy blue and carbon black, pearlescent agents such as titanium mica, iron oxide mica titanium, bismuth oxychloride, organic pigments such as tar pigments, natural pigments, nylon powder, silicone resin powder, silk powder, polystyrene, Organic powders such as polyethylene powder, crystalline cellulose, N-acyl lysine and the like can be mentioned. These powders may be surface-treated using a fluorine compound, a silicone compound, a metal soap, a wax, a fat, a hydrocarbon, or the like. Further, as long as the effects of the present invention are not particularly impaired, pigment-grade titanium oxide or granular fine particle titanium oxide having various average particle diameters and particle size distributions and shapes, and a composite of these and iron oxide or the like may be used in combination. Is also possible.

Examples of the oils include oils and fats such as olive oil, castor oil, jojoba oil and mink oil, waxes such as beeswax, lanolin and candelilla wax, liquid paraffin,
Hydrocarbons such as squalane, petrolatum, paraffin wax and microcrystalline wax, fatty acids such as stearic acid and oleic acid, higher alcohols such as cetanol, stearyl alcohol and behenyl alcohol, isopropyl myristate, glyceryl trioctanoate and diglyceryl triisostearate Esters, lanolin derivatives such as isopropyl lanolin fatty acid and lanolin alcohol, silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane, silicone oils modified with polyoxyalkylene and alkyl, fluorine-based oils such as perfluorodecane and perfluorooctane And the like. Others include organic solvents, resins,
Examples include plasticizers, ultraviolet absorbers, antioxidants, preservatives, surfactants, humectants, fragrances, water, alcohol, thickeners, and the like.

[0020]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

Production Example 1 The titanium oxide of the present invention (0.
(12 μm titanium oxide) The titanyl sulfate solution was thermally decomposed by a conventional method, and the caustic soda solution was added to the filtered and washed hydrous titanium oxide slurry while stirring, and heated at 95 ° C. for 2 hours. Next, hydrochloric acid was added to the slurry obtained by sufficiently washing the treated product while stirring, and heated at 95 ° C. for 2 hours to prepare a titania sol. The titania sol thus obtained is heated at 80 ° C.
The H value was adjusted to 7.0, filtered, washed with water, and dried at 105 ° C. This is fired at 850 ° C. for 2 hours in an electric furnace, and then pulverized by an air jet mill to obtain an average particle diameter of 0.1.
2 μm of titanium oxide was obtained. When the particle diameter and distribution of the titanium oxide prepared by the above method were measured using a transmission electron microscope, the average particle diameter was 0.12 μm, and 70% or more of all the particles had a mean particle diameter of ± 0.2%. It was confirmed that it was in the range of 03 μm. Further, when the specific surface area was measured by the BET method, it was confirmed that the specific surface area was in the range of 10 to 30 m ² / g.

Production Example 2 Iron-containing titanium oxide of the present invention (0.12 μm iron oxide-containing titanium oxide) The titanyl sulfate solution was thermally decomposed by a conventional method, and the caustic soda solution was stirred into the filtered and washed hydrous titanium oxide slurry. It was charged and heated at 95 ° C. for 2 hours. Next, hydrochloric acid was added to the slurry obtained by sufficiently washing the treated product while stirring, and heated at 95 ° C. for 2 hours to prepare a titania sol. An aqueous ferrous chloride solution was further added to the titania sol thus obtained to adjust the pH to 7.0. After aging, filtration and washing were performed, and then drying was performed at 105 ° C. This is fired at 850 ° C. for 2 hours in an electric furnace, and then pulverized by an air jet mill to obtain an average particle diameter of 0.12 μm.
Was obtained. Next, classification was performed by elutriation, and 70% or more of all particles were ± 0.0 of the average particle diameter.
It was adjusted to be in the range of 3 μm, dried again and pulverized. When the particle size and the distribution of the iron-containing titanium oxide prepared by the above method were measured using a transmission electron microscope, the average particle size was 0.12 μm, and 70% or more of all the particles were ±± of the average particle size. It was confirmed that the value was in the range of 0.03 μm. Further, when the specific surface area was measured by the BET method, it was confirmed that the specific surface area was in the range of 10 to 30 m ² / g.

Examples 1 to 8 and Comparative Examples 1 to 6 Powder foundation A powder foundation having the composition shown in Table 1 was prepared.
The following methods were used to perform sensory evaluations on (a) usability (good elongation and spread), (b) dullness (no bluish whiteness), and (c) finished feeling (natural transparency).
The ultraviolet ray blocking effect was determined by measuring the transmittance. Table 2 shows the results.

[0024]

[Table 1]

Note 1: Minor axis 0.015 μm, major axis 0.07
5 μm spindle-shaped fine particle titanium oxide Note 2: Titanium oxide obtained in Production Example 1 (average particle diameter 0.12 μm) Note 3: Iron-containing titanium oxide obtained in Production Example 2 (average particle diameter 0.12 μm) Note 4: Average particle diameter 0.03 μm Note 5: Average particle diameter 0.3 μm

(Production method) A. Mix components (1)-(9). B. The components (10) to (16) are dissolved by heating and mixed. C. A and B were mixed and dispersed, and filled in a gold plate to obtain a powder foundation.

(Evaluation items) (a) Usability (good stretch and spread) (b) Dullness (no bluish whiteness) (c) Finish (natural transparency) (d) Ultraviolet ray blocking effect

(Evaluation Method and Evaluation / Judgment Criteria) Evaluation items (a) to (c): A use test was conducted by 16 specialized panels, and judgment was made based on the average score of the five-grade evaluation based on the sensory evaluation criterion (a). The judgment was made based on the standard (b). Evaluation criteria (a) Very good: 5 points Good: 4 points Normal: 3 points Slightly poor: 2 points Bad: 1 point Judgment criteria (b) 4.0 points or more: ◎ 3.0 to less than 4.0 points: ○ 2.0 to less than 3.0 points: △ Less than 2.0 points: ×

Evaluation item (d): An alcohol solution of polyvinylpyrrolidone was applied on a quartz plate using a 25 μm doctor blade. After alcohol evaporation, each sample was uniformly applied to the adhesive surface using a soft brush to obtain a sample for measurement. Shimadzu self-recording spectrophotometer UV-2
The transmittance was measured with 65FW and the unit integrator ISR-260. The measurement wavelength is in the ultraviolet region (290 to 400
nm), the transmittance was determined from the transmission area, and the ultraviolet blocking effect was determined by the criterion (c). Judgment Criteria (c) Ultraviolet transmittance (%) Less than 10 (UV blocking effect is high): ◎ Less than 10 to 25 (UV blocking effect is somewhat high): ○ 25 to less than 50 (UV blocking effect is slightly low) : 以上 50 or more (poor UV blocking effect): ×

[0030]

[Table 2]

As is evident from the results in Table 2, the powder foundations of Examples 1 to 8 of the present invention have an excellent ultraviolet ray blocking effect, and have better usability and dullness than those of Comparative Examples 1 to 6. It was also excellent in terms of naturalness and natural finish.

Example 9 W / O Type Sunscreen Cream (Ingredients) (%) 1. Dimethyl polysiloxane 2.0 2. Decamethylcyclopentasiloxane 30.0 3. Polyether-modified silicone 3.0 4. 2-ethylhexyl paramethoxycinnamate 7.0 Organically modified bentonite 1.0 6. 6. Fine particle titanium oxide of the present invention (Note 1) 15.0 7. Iron-containing titanium oxide of the present invention (Note 3) 15.0 Purified water balance 9. Preservative appropriate amount 10. Appropriate amount of fragrance

(Production method) A. Components (1) to (7) are mixed and dispersed. B. Add components (8) to (10) to A and emulsify, and
A sunscreen cream was obtained. The W / O type sunscreen according to the present invention has a high ultraviolet blocking effect and is excellent in usability, dullness and natural finish.

Example 10 O / W Type Sunscreen Cream (Ingredients) (%) Stearic acid 1.5 2. Cetanol 1.0 3. Monoalkyl glyceride 1.0 4. Polyoxyethylene lauryl ether 1.05. 5. 2-ethylhexyl paramethoxycinnamate 7.0 Cetyl octoate 10.0 7. Liquid paraffin 7.0 8. 8. Fine particle titanium oxide of the present invention (Note 1) 10.0 10. Titanium oxide of the present invention (Note 2) 10.0 Butylene glycol 10.0 11. Glycerin 5.0 12. 12. Purified water balance Triethanolamine appropriate amount 14. Preservative appropriate amount 15. Water-soluble thickener appropriate amount 16. Appropriate amount of fragrance

(Production method) The components (1) to (7) are dissolved by heating and mixed. B. Components (8), (9), and (10) and (11)
(12) to (14) are added and mixed by heating. C. A was added to B and emulsified. After cooling, components (15) and (16) were added to obtain an O / W type sunscreen. The O / W type sunscreen according to the present invention has a high ultraviolet ray blocking effect and is excellent in usability, dullness and natural finish.

Example 11 Concealer (Component) (%) 1. Candelilla wax 4.0 Paraffin wax 6.0 3. Vaseline 5.0 4. Methylpolysiloxane 10.0 5. Squalane 10.0 6. 6. Diglyceryl triisostearate Remaining amount 7. Fine particle titanium oxide of the present invention (Note 1) 15.0 8. Iron-containing titanium oxide of the present invention (Note 3) 25.0 Nylon powder 5.0 10. Color pigment appropriate amount 11. Antioxidant appropriate amount 12. Appropriate amount of fragrance

(Production method) A. The components (1) to (6) are heated and dissolved. B. The components (7) to (12) were added to A, mixed and dispersed uniformly, and cooled and solidified to obtain a concealer. The concealer of the present invention has a high ultraviolet protection effect and is excellent in usability, dullness and natural finish.

Example 12 Lipstick (Component) (%) Microcrystalline wax 9.0 2. 2. Candelilla wax 6.0 Paraffin wax 5.0 4. 4. Diglyceryl triisostearate Remaining amount Glyceryl trioctanoate 20.0 6. Squalane 3.0 7. Red No. 202 3.0 8. Yellow No. 4 1.09. 10. Fine particle titanium oxide of the present invention (Note 1) 10.0 10. Titanium oxide of the present invention (Note 2) 5.0 Antioxidant appropriate amount 12. Appropriate amount of fragrance

(Production method) The components (1) to (6) are heated and dissolved. B. The components (7) to (12) were added to A, mixed and dispersed uniformly, poured into a mold, cooled and solidified to obtain a lipstick. The lipstick of the present invention has a high ultraviolet blocking effect, and is easy to use,
It was excellent in terms of dullness and natural finish.

[0040]

The cosmetic of the present invention comprises a fine particle titanium oxide having a specific particle shape and an average particle diameter, a titanium oxide having a specific average particle diameter and a specific specific surface area and / or a specific average particle diameter and By containing iron oxide containing titanium oxide having a specific specific surface area, a wide area (UV
-A and UV-B regions), has an excellent ultraviolet blocking effect, is excellent in dispersibility, is stable, and has good spread on the skin,
It is very good in terms of dullness and natural finish.

Claims (2)

[Claims] 1. The following components (A) and (B): (A) a particle shape of a spindle or needle, and a minor axis of 0.005.
Fine particle titanium oxide having a major axis of 0.01 to 0.5 μm and a major axis of 0.01 to 0.5 μm. (B) Average particle diameter of 0.14 μm exceeding 0.10 μm.
Hereinafter, and surface area below 0.14μm beyond titanium oxide and / or an average particle diameter of 0.10μm is 10 to 30 m ² / g ratio, and a specific surface area of 10 to 30 m ² /
g. Iron oxide-containing titanium oxide which is g. 2. The cosmetic according to claim 1, comprising 1 to 30% by weight of the component (A) and 1 to 30% by weight of the component (B).