JP3002171B2 - Surface-coated oxide particles and cosmetics using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to surface-coated oxide particles and cosmetics using the same .

[0002]

2. Description of the Related Art Conventionally, cosmetics are blended with an ultraviolet ray blocking agent such as fine particle titanium oxide, fine particle zinc oxide or fine particle cerium oxide for the purpose of protecting the skin from ultraviolet rays. However, since these fine particle ultraviolet ray blocking agents have a small particle diameter, there is a problem that the ultraviolet ray blocking effect is reduced due to aggregation at the time of prescribing cosmetics. In addition, these fine particle ultraviolet ray blocking agents have strong surface activity, exhibit photocatalytic ability when irradiated with sunlight, and generate active oxygen when exposed to oxygen in the air. At the time of use, it had a problem of causing inflammation on the skin.

[0003] A method of hydrophobizing the surface of fine particles with a hydrophobizing agent composed of a higher fatty acid or a salt thereof for the purpose of suppressing agglomeration during formulation of a cosmetic has been proposed (JP-A-58-62106). No.). However, in this method, since the surface treatment is merely performed, the hydrophobizing agent easily detaches from the surface of the fine particles, and it is difficult to sufficiently suppress the aggregation at the time of formulation. Furthermore, depending on the method,
The surface activity of the fine particles could not be suppressed.

In order to suppress the surface activity of these fine particles, a method has been proposed in which the surface of the fine particles is surface-treated with an N-mono long-chain acyl basic amino acid (Japanese Patent Laid-Open No. 7-2).
No. 77937). However, even with this method, the surface activity could not be sufficiently suppressed.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide titanium oxide, zinc oxide or cerium oxide particles having excellent dispersibility and suppressed catalytic activity. Another object of the present invention is to provide a cosmetic using the particles.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found a method for improving the dispersibility of these particles and suppressing the catalytic activity, and completed the present invention. Was .

According to the present invention, a polymerization catalyst is formed on the surface of an oxide particle selected from titanium oxide, zinc oxide or cerium oxide, and a polymerizable monomer is polymerized on the catalyst to coat the polymer with a polymer. Surface-coated oxide particles
Accordingly, the present invention relates to surface-coated oxide particles having an average particle size of 0.01 to 0.1 μm . The present invention also provides
The present invention relates to a cosmetic containing surface-coated oxide particles.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The core material of the surface-coated oxide particles of the present invention includes one or more oxide particles selected from titanium oxide, zinc oxide and cerium oxide. These may be hydrated. Among them, rutile type, anatase type, monoclinic or amorphous titanium oxide particles are preferable because of their excellent ultraviolet blocking performance,
Among them, rutile-type titanium oxide particles are particularly preferable.

[0009] The average diameter of the particles used is not particularly limited, in the cosmetic applications, 0. 01-0.1
μm is preferably used. Those having a particle size in this range have both smoothness and excellent ultraviolet shielding ability when blended in cosmetics.

[0010] The coating polymer used for the surface-coated oxide particles of the present invention is not particularly limited, and various polymer obtained by polymerizing a polymerizable monomer can be used. . As specific examples of the high molecular polymer,
Examples include olefin-based resins, polyamide resins, polyacrylic resins, polyester resins, polyurethane resins, polytetrafluoroethylene resins, and the like. Among them, olefin resins are particularly preferred in that they can be easily produced and can give a highly dispersible target product. Examples of the olefin used for the olefin resin include ethylene, propylene, butene, and methylpentene, and these can be used alone or in combination of two or more.

In the present invention, the coating amount of the high molecular polymer to the core oxide particles is usually 1 to 500 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of the core.
Parts by weight can be exemplified.

The polymerization catalyst formed on the surface of the core material particles includes benzoyl peroxide, azobisisobutyronitrile,
Radical polymerization catalysts such as tertiary butyl hydroperoxide, cationic polymerization catalysts such as boron trifluoride and titanium chloride, anion polymerization catalysts such as n-butyl lithium, and coordination anion polymerization catalysts represented by Ziegler catalysts, etc. In the case of polyolefin coating on fine particles, a coordination anion polymerization catalyst is preferable, and a transition metal compound (first catalyst component) and a group II or group II of the periodic table are preferred.
An organometallic complex catalyst comprising an organometallic compound of a Group I metal (second catalyst component) is particularly preferred. Examples of the transition metal compound include vanadium tetrachloride, vanadium oxytrichloride, titanium trichloride, titanium tetrachloride, tungsten hexachloride, and iron trichloride. Examples of organometallic compounds of Group II or Group III metals of the periodic table include diethylaluminum trichloride, triethylaluminum, triisobutylaluminum, diethylzinc and diethylmagnesium.

The method for forming a polymerization catalyst on the surface of the core material particles is as follows.
Although it can be appropriately selected depending on the type of the catalyst and the size of the core material particles, examples thereof include a spray coating method, an impregnation method, a tumbling method, a coprecipitation method, a vapor deposition method, and a sputtering method.

Hereinafter, a method for forming an organometallic complex catalyst on the surface of a core material and polymerizing an olefin on the catalyst will be described in more detail. In the case of forming an organometallic complex catalyst, it is preferable to dry the core particles in advance at a temperature of 100 ° C to 200 ° C for 1 to 3 hours because the organic metal easily reacts with water.

In the first method, the first catalyst component is attached to the core material particles, and then reduced by heating to precipitate the first catalyst component, and the second catalyst component is reacted with the first catalyst component. This is a method in which after an organometallic complex catalyst is used, an olefin is introduced and polymerized on the surface of the core material.

The core material particles are charged into a reactor that has been evacuated or filled with an inert gas such as nitrogen gas or argon gas. The amount of the first catalyst component and the amount of the second catalyst component to be used are usually 0.1 to 100 parts by weight of the core material.
The ratio is preferably 001 to 0.1 parts by weight.

To adhere the first catalyst component to the core material surface, the vaporized first catalyst component may be introduced into the reactor and brought into contact with the core material particles. The first catalyst component precipitates on the surface of the core material due to a functional group such as an OH group or a defect in the crystal structure. When introducing the vaporized first catalyst component into the reactor, it can be introduced together with the inert gas.

Heat reduction is carried out in a non-oxidizing atmosphere at 80 ° C. to 3
It can be performed at a temperature of 00 ° C. The reaction between the second catalyst component and the first catalyst component attached to the core material can be performed in a gas phase or a liquid phase.

When the reaction is carried out in the gas phase, the vaporized second catalyst component is introduced together with an inert gas into a reactor containing a core material to which the first catalyst component has adhered, and is brought into contact therewith. Can be. The reaction can be usually performed at normal temperature to about 300 ° C. under normal pressure or under pressure, and is completed in about 5 minutes to 2 hours.

When the reaction is carried out in a liquid phase, the core material having the first catalyst component attached thereto is dispersed in an organic solvent such as n-heptane or benzene, and the second catalyst component is added to the dispersion. , Can be performed by bringing it into contact therewith. The reaction in the liquid phase is a preferable method when a liquid second catalyst component such as diethylaluminum chloride, triethylaluminum, triisobutylaluminum, diethylzinc or dimethylmagnesium is used. The reaction is usually carried out at normal pressure or under pressure within a range from normal temperature to the boiling point of the solvent to be used, and the reaction can be carried out for 5 minutes to
It is completed in about 3 hours.

The olefin can be polymerized in the gas or liquid phase. When the polymerization is carried out in the gas phase, the olefin may be introduced directly or together with an inert gas into the reactor. The polymerization conditions are the same as those of ordinary polymerization conditions.
A condition of 0 ° C. and a pressure of 1 to 60 atm can be exemplified, and the reaction is completed in about 1 minute to 8 hours.

When the reaction is carried out in a liquid phase, the reaction can be carried out with stirring by blowing gaseous olefin into an organic solvent such as n-heptane or benzene or by circulating the reaction mixture. As the polymerization conditions in this case, a temperature of 50 ° C to 100 ° C and a pressure of 1 to 1
A condition of 60 atm can be exemplified, and the reaction is completed in about 1 minute to 8 hours.

In the second method, the first catalyst component is deposited on the core material particles, and then the first catalyst component is reduced by the second catalyst component to form an organometallic complex catalyst on the surface of the core material particles. Olefin is introduced and polymerized on the surface of the core material.

In the third method, after the first catalyst component is deposited on the core particles, the olefin and the second catalyst component are simultaneously introduced, and the first catalyst component is reduced by the olefin or the second catalyst component. In this method, the second catalyst component is reacted with the reduced first catalyst component on the core material particles to form an organometallic complex catalyst, and the olefin is polymerized by the catalyst.

The use ratio of the catalyst, the reaction method, the polymerization method and the like in the second and third methods can all be carried out according to the first method. In addition, any of the first, second and third steps may be performed while stirring the powder by mechanical means such as fluidized bed stirring or atmospheric pressure means, or by boiling vibration stirring or weight stirring. desirable.

The surface-coated oxide particles of the present invention are excellent in safety and stability, have high ultraviolet blocking performance, and are also excellent in lubricity. Therefore, they can be used as cosmetic compounding materials, resin fillers, paint compounding materials and the like. High usefulness.

When the surface-coated oxide particles of the present invention are used as cosmetics, the cosmetics include white powder, foundation, pressed powder, lipstick, blusher, eye shadow,
Examples include eyebrows, eyeliners, mascaras, nail colors, sunscreens, and the like. When the surface-coated oxide particles of the present invention are used as cosmetics, higher fatty acids usually used in cosmetics, as long as the effects of the present invention are not impaired,
Higher alcohols, synthetic esters, waxes, vegetable fats and oils, animal fats and oils, hydrocarbons, fluorocarbons, perfluoropolyethers, fluoroalkoxyphosphazenes and other oils, dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, fluorine Oils such as silicone oils such as modified silicone, methylcetyl-modified silicone, amino-modified silicone, and cyclic dimethylpolysiloxane; solvents such as water, alcohol, and propylene glycol; anionic, cationic, amphoteric or nonionic surfactants; Agents, preservatives, bactericides, preservatives, antioxidants, hormonal agents, vitamins, humectants, fragrances, dyes, pigments and the like can be simultaneously incorporated. Regarding the surface-coated oxide particles of the present invention and the powders in each of the above components, a coupling agent treatment, a silicone treatment, a fluorine treatment, a metal soap treatment, a silica treatment, an alumina treatment, an amino acid treatment, a metal coating treatment during compounding, Surface treatment such as plasma treatment may be performed.

[0028]

The present invention will be described in more detail with reference to Reference Examples, Examples, Comparative Examples and Test Examples.

Reference Example (Synthesis of Titanium Oxide Particles) Titanium tetraisopropoxide was introduced into the heater simultaneously at a flow rate of 2.4 g / hour and nitrogen gas at a flow rate of 0.17 Nm ³ / hour. Upon heating, titanium tetraisopropoxide was vaporized.

On the other hand, water was simultaneously introduced into the heater at a flow rate of 8.5 g / hour and nitrogen gas at a flow rate of 0.16 Nm ³ / hour, and heated to 500 °. The heated steam and the vaporized titanium tetraisopropoxide were mixed in a reactor, and titanium tetraisopropoxide was hydrolyzed at a temperature of 260 ° C. to obtain titanium oxide particles having an average particle diameter of 0.02 μm.

[0031] sufficiently drying the resulting titanium oxide particles 30g in Example Reference Example was charged degassed rotating metal reactor drum dryer type. While stirring the titanium oxide particles in the reactor, a mixed gas of 0.014 g of titanium tetrachloride vapor and nitrogen gas was introduced into the reactor, and stirring was continued for 15 minutes, followed by 0.08 g of diethyl aluminum chloride vapor. A gas mixture of nitrogen and nitrogen gas was introduced into the reactor, and the mixture was further stirred for 15 minutes. Then, while stirring was continued, ethylene gas was introduced into the reactor to raise the pressure in the reactor to 3 atm. Then, the introduction of ethylene gas was continued and the reactor was maintained at 80 ° C. and 3 atm.
The reaction was performed for 0 minutes.

As a result of chemical analysis and TEM observation, the product was coated with polyethylene on the surface of titanium oxide particles.
The surface-coated oxide particles consisted of 79% by weight of titanium oxide and 21% by weight of polyethylene, and substantially no free polyethylene was present.

Comparative Example 24 g of titanium oxide obtained in Reference Example was sufficiently dispersed in 50 ml of a 0.5% aqueous solution of potassium N-cocoylglutamate. Next, 6 g of Nε-lauroyl-L-lysine was dissolved in 25 ml of sodium hydroxide at pH13. This aqueous solution of Nε-lauroyl-L-lysine was mixed with a fine titanium dioxide dispersion, and 1N hydrochloric acid was added dropwise with stirring to neutralize. The solid was separated and washed with water to obtain 30 g of a powder.

Dispersibility test To 50 g of dimethylpolysiloxane (30000 cs), 150 mg of the untreated titanium oxide fine particles, the powder obtained in the example, and the powder obtained in the comparative example were added and stirred well. Thereafter, the mixture was dispersed using a roller.
The obtained sample was formed into a film having a thickness of 40 μm, and a spectrophotometer (MP
S-2000 type, manufactured by Shimadzu Corporation), a dispersion composition of untreated titanium oxide fine particles (A), a dispersion composition of powder obtained in Examples (B), and a dispersion composition of Comparative Examples. When the light transmittance (%) at a wavelength of 300 nm of the dispersion compound (C) of the powder was measured, BA = 10.6.
%, CA = 3.8%. From these results, it can be seen that the dispersibility of the powder of the example is superior to that of the untreated titanium oxide fine particles and the powder of the comparative example.

Evaluation of catalytic activity Untreated titanium oxide fine particles, the powder obtained in the examples, and the powder obtained in the comparative example were each filled with 0.2 g of an inner diameter of 5 g.
While heating a 280 ° C. glass tube at 280 ° C. and injecting 3 μl of isopropyl alcohol while flowing helium gas at a flow rate of 80 ml / min, the remaining amount of isopropyl alcohol was analyzed by a gas chromatograph connected downstream to calculate the decomposition rate. . As a result, the decomposition rate of the powder obtained in the example was 0.7%, the decomposition rate of the powder obtained in the comparative example was 1.9%, and the decomposition rate of the untreated titanium oxide fine particles was Was 87.1%. From these results,
It can be seen that in the powders obtained in the examples according to the present invention, the catalytic activity was suppressed.

[0036]

According to the present invention, titanium oxide, zinc oxide, or cerium oxide particles having excellent dispersibility and suppressed catalytic activity can be obtained. Therefore, oxide particles suitable for blending cosmetics and the like can be obtained.

Further, according to this onset bright, to form a polymerization catalyst on the surface of the oxide particles, by polymerizing a polymerizable monomer on the catalyst, because is covered with high molecular weight polymer,
The surface of the oxide particles can be uniformly coated with the high-molecular polymer. Accordingly, oxide particles having excellent dispersibility and suppressed catalytic activity can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C09C 1/04 C09C 1/04 1/36 1/36 // C01F 17/00 C01F 17/00 A (58) Field surveyed ( Int.Cl. ⁷ , DB name) C09C 3/10 A61K 7/00 C09C 1/04 C09C 1/36 C08F 2/44

Claims (3)

(57) [Claims] 1. A polymerization catalyst is formed on the surface of an oxide particle selected from titanium oxide, zinc oxide or cerium oxide, and a polymerizable monomer is polymerized on the catalyst to coat the polymer with a polymer . a front surface coated oxide particles,
Characterized in that the average particle size is 0.01 to 0.1 μm
Surface-coated oxide particles . 2. The high molecular weight polymer is a polyolefin,
Polymerization catalyst is transition metal compound (first catalyst component) and periodic table
Organometallic compounds of Group II or III metals (second catalyst
The surface-coated oxide particles according to claim 1, which is an organometallic complex compound catalyst comprising the component (1). 3. A cosmetic comprising the surface-coated oxide particles according to claim 1 .