JPH0455403B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to cosmetics, and more specifically, by incorporating amorphous and spherical titanium oxide ultrafine particles, it has good dispersibility and stability, and has excellent visible light transmittance and ultraviolet protection effect. , Concerning cosmetics with good usability. [Prior Art and Problems to be Solved by the Invention] Various cosmetics containing titanium oxide are known, and this titanium oxide has an excellent UV protection effect. This conventional titanium oxide is crystalline (anatase or rutile type), and its particle shapes are dice-shaped, diamond-shaped, scale-shaped, needle-shaped, etc., and are not spherical.
Japanese Patent Publication No. 47-42502 discloses a sunscreen cosmetic containing titanium oxide having a particle size of 30 to 40 mμ. In addition, in Japanese Patent Application Laid-open No. 58-49307, 10~
Cosmetics containing 40 mμ surface-treated titanium oxide have been proposed. Furthermore, in JP-A-58-62106, it has been pointed out that the particle size of titanium oxide affects the absorption of ultraviolet rays. Cosmetics containing 40% by weight cause erythema on the skin.
It is said to protect the skin from UV rays by reflecting and scattering the strongest UV rays around 297.6 nm between 290 and 320 nm. The titanium oxide used in the above-mentioned cosmetics etc. is crystalline (anatase or rutile type), and there is no example of amorphous titanium oxide being used, and its shape is also dice-shaped, diamond-shaped, etc. The particles were in the form of scales and needles, and were not spherical. Further, these conventional techniques have disadvantages such as insufficient dispersibility and stability in cosmetic base materials, and poor usability such as spreadability, stickiness, and natural finish. [Means for Solving the Problems] An object of the present invention is to provide a cosmetic composition that is easier to use than the above-mentioned cosmetic compositions. That is, the present invention is a cosmetic composition that contains 0.01 to 50% by weight of amorphous or spherical ultrafine titanium oxide particles. As mentioned above, the titanium oxide used in the present invention has an amorphous crystal form. The amorphous titanium oxide referred to herein is one in which the peak area of the titanium oxide in X-ray diffraction is 5% or less of the peak area of the standard reagents anatase and rutile titanium oxide under the same measurement conditions. Furthermore, the titanium oxide particles used in the present invention are spherical in shape, and the minimum diameter of the particles is 80% or more of the maximum diameter, preferably 90% or more. Each of these spherical particles is independent and moves separately, but some of them combine and move in van der Waalska. Next, FIG. 2 shows the electron beam diffraction pattern of one example of the amorphous spherical titanium oxide fine particles used in the present invention.
FIG. 3 shows an electron micrograph, and FIG. 4 shows an X-ray diffraction pattern. Such titanium oxide can be produced, for example, by the method described in Japanese Patent Application No. 60-41828 (Japanese Unexamined Patent Publication No. 61-201604). An example is shown below. After vaporizing or atomizing volatile titanium compounds such as titanium alkoxides and titanium halides, they are decomposed under heating to form ultrafine titanium oxide particles, and immediately after decomposition, they are cooled to a temperature at which the titanium oxides do not coalesce again. . Here, specific examples of the titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide,
Examples include titanium tetrabutoxide and diethoxytitanium oxide. Further, specific examples of titanium halides include titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide. Furthermore, volatile titanium compounds such as trihalogenated monoalkoxytitanium, monohalogenated trialkoxytitanium, and dihalogenated dialkoxytitanium can also be used. These titanium compounds may be used alone or in combination of two or more. Also,
When using titanium alkoxide, aluminum chloride, zirconium alkoxide, rare earth chloride or rare earth alkoxide may be added in an amount not exceeding 50% of the molar concentration of titanium alkoxide in order to increase the stability of the produced titanium oxide. A volatile metal compound such as the above may also be present. The conditions for vaporizing or atomizing a volatile titanium compound vary depending on the type of compound and cannot be unambiguously determined. For example, when using titanium alkoxide, the temperature at which the titanium alkoxide is evaporated is A temperature at or slightly below the boiling point of the alkoxide is preferred. This is because if the titanium alkoxide is evaporated at a temperature higher than the boiling point, the titanium alkoxide decomposes in a non-uniform state, resulting in particles that are obtained with non-uniform specific surface area, particle diameter, etc. In addition, when performing vaporization or atomization, it is preferable to dilute the titanium compound with a diluent gas to a proportion of 0.1 to 10% by volume. This diluent gas serves as a carrier gas to guide the vaporized titanium compound to the decomposition process. Here, as the diluent gas, an inert gas such as argon, helium, or nitrogen, water vapor, oxygen, or the like is used, and it is particularly preferable to use helium, nitrogen, or oxygen. When selecting a diluent gas,
The decomposition step should be taken into consideration, and in the case of compounds other than titanium alkoxides, it is desirable to select an oxygen-containing gas. Next, the volatile metal compound thus vaporized or atomized is decomposed under heating to form ultrafine metal oxide particles. That is, the volatile metal compound vaporized or atomized as described above is introduced into a decomposition furnace or the like using a carrier gas and decomposed. Here, decomposition includes not only so-called normal thermal decomposition but also oxidation, and decomposition requires the presence of oxygen-containing gas. If oxygen-containing gas is used as the diluent gas as described above, there is no need to use additional oxygen-containing gas. Further, the decomposition temperature is preferably 600°C or lower, particularly preferably 250 to 350°C. At temperatures below this, a sufficient decomposition rate cannot be obtained, and on the other hand, at high temperatures, particles with a large specific surface area cannot be obtained. Further, there are no particular restrictions on the residence time, flow rate, etc. of the volatile titanium compound in a vaporized or atomized state in the decomposition furnace in which the decomposition is performed, and the decomposition can be carried out under various conditions. Preferably the residence time is between 0.1 and
10 sec., and the flow rate is 1 to 100 cm/sec. Further, there are no particular restrictions on the decomposition furnace in which the decomposition is carried out, and any commonly used decomposition furnace can be used, but in consideration of the cooling operation described below, it is preferable to use a decomposition furnace having a cooling means. Further, it is preferable to use a decomposition furnace with metal oxide fine particles adhered to the wall of the decomposition furnace in advance. By using a decomposition furnace in which metal oxide fine particles are attached to the vessel wall in this manner, the reaction temperature can be significantly lowered. In this way, spherical ultrafine titanium oxide particles are produced, but if left as is, there is a risk that the particles will coalesce with each other in the gas phase, so it is necessary to rapidly cool the particles. By rapid cooling, the titanium oxide ultrafine particles can be collected as they are (primary particles). It is preferable to perform the cooling as quickly as possible, and the cooling temperature is a temperature at which the ultrafine titanium oxide particles do not coalesce, but it cannot be determined unambiguously because it varies depending on the cooling rate and the like. Usually, it is preferable to cool to a temperature of 100°C or less in as short a time as possible. Note that there are no particular restrictions on the cooling means, and for example, air, water, etc. may be used. Conversely, the same effect as cooling can be achieved by locally heating the area using an infrared image furnace or the like to create a temperature difference. Furthermore, there are no particular restrictions on the cooling method; for example, cooling may be performed from outside the cracking furnace, but air,
By installing a cooling device using water or the like as a cooling means in the cracking furnace, cooling can be performed more efficiently in a shorter time. It is also possible to cool the generated particles outside the reaction system. Ultrafine titanium oxide particles are obtained as described above, but these can also be separated and collected into a final product by filtration using a membrane filter or the like. Further, when a cooling device is placed in the reaction system, the generated ultrafine particles can be collected on this device by utilizing thermophoresis. In this way, ultrafine titanium oxide particles with a particle size of 0.01 to 0.5 μm are obtained. Here, the particle size refers to the diameter of each sphere. The above amorphous and spherical titanium oxide ultrafine particles are used in cosmetics in an amount of 0.01 to 50% by weight, preferably 0.05 to 20% by weight.
It is used in proportions of % by weight. [Example] Next, an example of the present invention will be shown. The blending ratio of each component in the examples is weight %. Example 1 A milky lotion was prepared according to the following formulation. Stearic acid 2.4% Cetyl alcohol 1.0% Vaseline 5.5% Liquid paraffin 12.0% Polyoxyethylene monooleate ester
2.0% Polyethylene glycol 1500 3.5% Triethanolamine 1.5% Purified water 72.0% Amorphous, spherical titanium oxide 0.1% (particle size 0.2 to 0.3 μm) Flavor appropriate amount Add polyethylene glycol triethanolamine to purified water, heat and dissolve, and heat to 70℃. (aqueous phase). Meanwhile, mix the remaining ingredients, heat and dissolve and keep at 70°C (oil phase). Next, the oil phase is added to the water phase, pre-emulsified and uniformly emulsified by ultrasonic vibration, and then cooled to room temperature while stirring. Next, apply the above amorphous amorphous and 10% by weight slurry of spherical titanium oxide mixed with castor oil to the black surface of the color matching panel using an applicator to create a thick layer.
It was applied to a thickness of 0.076 mm, and the color tone of visible light was measured using Color Analyzer 607 manufactured by Hitachi. For comparison, titanium oxide fine particles (anatase/rutile type mixed crystal, average particle size of approx.
The color tone of visible light was similarly measured using 0.3 μm (trade name: P-25). The results are also shown in FIG. As shown in FIG. 5, while the conventional titanium oxide fine particles have a bluish color, the amorphous amorphous of the present invention
It can be seen that spherical titanium oxide has better transparency. Example 2 A foundation cream was prepared according to the following formulation. Talc 15.0% Kaolin 4.0% Amorphous, spherical titanium oxide 20.0% (particle size 0.2-0.3 μm) Iron oxide (red) 0.3% Iron oxide (yellow) 0.7% Iron oxide (black) 0.03% Solid paraffin 3.0% Lanolin 10.0% Fluid Paraffin 27.0% Glyceryl monooleate 5.0% Purified water 15.0% Fragrance Appropriate amount Talc, kaolin, amorphous titanium oxide,
Mix iron oxides (red, yellow, black) and process in a ball mill (powder section). Add some liquid paraffin and glyceryl monooleate to the powder part,
Disperse uniformly with a homomixer, heat and dissolve the other ingredients except purified water, add to this, and keep at 70°C (oil phase). After heating purified water to 70℃, add it to the oil phase,
Uniformly emulsify and disperse with a homomixer, while stirring.
Keep at 40℃. This foundation cream was formed into a film with a thickness of 5 μm on a transparent quartz plate, and the absorbance in the wavelength region of 200 to 400 nm was measured using a Hitachi Model 228 double beam spectrophotometer. For comparison, a foundation cream was prepared according to the above formulation using titanium oxides having the same particle size and different crystal forms, and was measured using the same method. Figure 1 shows the measurement results. Curve A shows the one using amorphous titanium oxide according to the present invention,
Curve B uses anatase titanium oxide;
Curve C shows the one using rutile type titanium oxide. As is clear from the figure, those using amorphous titanium oxide have higher absorbance around 290 nm (the ultraviolet wavelength at which biological effects are strongest) than those using rutile and anatase titanium oxides. The reason for this is thought to be that amorphous titanium oxide has excellent dispersibility in cosmetic base oils. Next, 0.1 g of the three types of foundation creams mentioned above were applied to 1 cm ² of skin to examine their UV protection effects during actual use. The investigation was carried out on July 29, 1980 (clear skies) at Futtsu Beach, Futtsu City, Chiba Prefecture.The skin surface on which the sample was applied was exposed to sunlight for 2 hours from 11:00 a.m. to 1:00 p.m., and then the sample was dropped and the skin was exposed to sunburn. The intensity of erythema) was visually determined twice, one hour later and one day later. The results are shown in Table 1.

[Table] △: Weak erythema is observed ×: Slightly strong erythema is observed
As is clear from the table, the foundation using the amorphous titanium oxide of the present invention has an excellent ultraviolet protection effect even in actual use. Example 3 Lipsticks were prepared according to the following recipe. Red No. 204 1.0% Orange No. 203 1.0% Red No. 223 1.0% Candelilla wax 10.0% Solid paraffin 8.0% Beeswax 6.0% Carnauba wax 5.0% Lanolin 12.0% Castor oil 43.0% Isopropyl oleate 5.0% Amorphous Spherical titanium oxide 8.0% ( particle size 0.2 to 0.3 μm, specific surface area 200 m ² /g) Amorphous, spherical titanium oxide, red No. 204 and orange No. 203 are added to a portion of castor oil and treated with a roller (pigment part). Also, dissolve Red No. 223 in part of the castor oil (dye part). After mixing the remaining ingredients and heating and melting, add the pigment part and dye part,
Disperse evenly with a homomixer. After dispersion, it is poured into a mold and rapidly cooled, and the stick-shaped mixture is inserted into a container for framing. Example 4 A cream was prepared according to the following formulation. Microcrystalline wax 10.0% Beeswax 3.0% Vaseline 4.0% Hydrogenated lanolin 8.0% Squalane 30.0% Glyceryl monooleate 3.0% Hexadecyl adipate 7.0% Polyoxyethylene sorbitan monooleate 0.5% Propylene glycol 3.5% Purified water 20.0% Amorphous, spherical titanium oxide (particle size 0.2-0.3μm) 11.0% Fragrance Appropriate amount Add propylene glycol to purified water and heat.
Keep at 70°C (aqueous phase). Mix other ingredients, heat and dissolve and keep at 70℃ (oil phase). Add water phase to oil phase,
Pre-emulsify and uniformly emulsify using a homomixer, then stir while cooling. This cream was evaluated in terms of ``spreadability,''``stickiness,''``freshness,'' and ``overall evaluation.'' For comparison, a cream was prepared according to the above formulation using titanium oxide having the same particle size and different crystal form as in Example 2, and was evaluated using the same method. The evaluation is based on 10 female panelists who used three types of creams, and the number of people who answered that each item was the best is shown. The results are shown in Table 2.

[Table] Use of titanium chloride
Rutile-type titanium oxide 2 2 2 1
Use of tongue
As is clear from the table, the cream using amorphous and spherical titanium oxide of the present invention is excellent in actual use. Example 5 A solid white powder was prepared according to the following recipe. Talc 45.0% Amorphous, spherical titanium oxide 43.0% (particle size 0.2-0.3μm) Iron oxide (red) 1.0% Iron oxide (yellow) 2.5% Iron oxide (black) 0.5% Stearic acid 2.0% Squalane 2.5% Lanolin 1.0% Hexa Decyloleate 0.5% Triethanolamine 1.0% Fragrance Appropriate amount Talc, amorphous, spherical titanium oxide, and iron oxide are thoroughly mixed and kneaded in a blender. Mix. Next, it is processed in a pulverizer and compression molded in a press. Example 6 A rod-shaped eyelid dough was prepared according to the following recipe. Ceresin 27% Castor oil 42% Hydrogenated oil 5% Carnauba wax 3% Liquid paraffin 6% Amorphous, spherical titanium oxide 9% (particle size 0.2-0.3μm) Iron oxide (ocher color) 4% Iron oxide (Sheena color) 4% Fragrance Add appropriate amounts of amorphous, spherical titanium oxide, and iron oxide (ocher color, sheener color) to a portion of castor oil,
Process with a roller (pigment part). After mixing the other components and melting them by heating, the pigment part is added thereto and uniformly dispersed using a homomixer. Next, pour it into a mold,
Cool rapidly and form into a bar. Example 7 A compact blusher was prepared according to the following formulation. Talc 48% Kaolin 16% Chiyolk 3% Magnesium carbonate 4% Zinc stearate 5% Amorphous, spherical titanium oxide 13% (particle size 0.2-0.3 μm, specific surface area 200 m ² /g) Pigment 11% Fragrance Appropriate amount Talc, amorphous, spherical While titanium oxide and the pigment are sufficiently mixed in a blender, a mixture of other components is uniformly added thereto and further mixed well. Next, it is crushed and compression molded using a press. The fragrance retention properties of the above blusher were evaluated by actual use. For comparison, rutile-type titanium oxide (manufactured by sulfuric acid method, particle size 1-2 μm, specific surface area 10 m ² /g)
A blush prepared in the same manner using was also evaluated in the same manner. The evaluation was conducted by having 10 female panelists use the two types of compact blushers and judge the fragrance retention after 8 hours.Table 3 shows the number of people who answered that the fragrance retention was good. Table 3 Sample Fragrance Retention Amorphous Titanium Oxide 8 Rutile Titanium Oxide 2 As is clear from the table, the compact blusher using amorphous and spherical titanium oxide of the present invention has very excellent fragrance retention. Since amorphous titanium oxide has a large specific surface area and extremely well-developed pores (porous), it is thought that the fragrance is retained within the pores. Reference Example 1 In order to examine the dispersibility of titanium oxide in oils commonly used as cosmetic base materials, as shown in Example 2, three types of titanium oxide with different crystal forms (all with particle sizes of 0.2 to 0.3 μm). For the test, 1 g of titanium oxide was weighed into a 50 ml graduated sedimentation tube (Ukena tube), 50 ml was added, stirred and dispersed using a disperser, and left to stand for 1 minute, 5 minutes, 30 minutes, and 60 minutes.
Observe the dispersion state 7 times for 1 minute, 1 day, 3 days, and 7 days, and score 5 points if no settled particles are observed, and 1 point if all particles are settled or aggregated. This was done by assigning an evaluation score for each observation, summing the scores, and making an evaluation using a 10-point scale, with 10 points for very good dispersibility and 1 point for poor dispersion. The results are shown in Table 4.

[Table] Rutile type 1 1 2
Amorphous 9 9 8
As is clear from the table, amorphous titanium oxide showed very good dispersibility in commonly used cosmetic base oils. Since most cosmetic base oils have a specific gravity of around 1, it is advantageous to use titanium oxide with a low specific gravity to prevent sedimentation. Therefore, when the true specific gravity of each of the above samples was measured using a pentapycnometer manufactured by Quantachrome (USA) using the He substitution method (pretreatment conditions: 115°C, dehydration for 4 hours), the true specific gravity of the anatase type was 3.9, the rutile type was 4.2, Amorphous was 2.9. As described above, amorphous titanium oxide has a small true specific gravity, which is considered to be the reason for the above results. Reference Example 2 In order to evaluate the stability of titanium oxide against light, as shown in Example 2, a foundation was made using three types of titanium oxide with different crystal forms and evaluated. Three types of samples were irradiated with a xenon lamp at 50°C for 90 hours, and the degree of blackening was examined. The results are shown in Table 5.

[Table]
As is clear from the table, those using amorphous and spherical titanium oxide have excellent stability against light. Examples 8 to 12 and Comparative Example 1 Five types of amorphous and spherical titanium oxide with different particle sizes shown in Table 6 (Examples 8 to 12) and titanium oxide fine particles manufactured by Degussa AG (anatase/rutile type mixed crystal) The following tests were conducted using Comparative Example 1, particle size 0.02 to 0.04 μm, trade name P-25). (1) Ultraviolet (UV) shielding properties Each foundation cream was prepared with the same formulation as described in Example 2, and the absorbance of the foundation cream was measured in the same manner as described in Example 2, The UV shielding effect was investigated. For the evaluation of UV shielding property, absorbance at 300 nm (abbreviated as UV-B) is 2.8 or more with ◎ mark, absorbance between 2.7 and 2.5 with ○ mark,
Absorbance of 2.4 to 2.0 is marked △, absorbance of 1.9 or less is marked ×
We each went with a mark. Also, 360nm (abbreviated as UV-A)
The absorbance of 1.8 or more was evaluated as ◎, the absorbance of 1.7 to 1.5 was evaluated as ○, the absorbance of 1.4 to 1.0 was evaluated as △, and the absorbance of 0.9 or less was evaluated as ×. The evaluation results are shown in Table 6. As is clear from Table 6, the amorphous and spherical titanium oxide of the present invention is superior to the conventional titanium oxide commonly used by selecting the particle size.
It can be seen that the shielding effect is excellent for both UV-A and UV-B. (2) Dispersibility in cosmetic base oil In order to investigate the dispersibility in cosmetic base oil, a test was conducted using the same method and evaluation method as described in Reference Example 1. The results are shown in Table 6. As is clear from Table 6, the amorphous and spherical titanium oxide of the present invention is well dispersed in cosmetic base oil. (3) Visible light transmittance As mentioned above, conventional fine particle titanium oxide has a bluish color due to interference light and has little effect on brightening the skin. Therefore, visible light transmittance was investigated using two types of amorphous and spherical titanium oxide of Examples 8 and 9 with different particle sizes and titanium oxide of Comparative Example 1. In the method, 4 g of each titanium oxide was suspended in 6 g of castor oil, and then thoroughly kneaded using three rollers. 0.25 g of the kneaded slurry was weighed into 0.75 g of castor oil and thoroughly dispersed with an ointment spatula. The dispersion was applied to a thickness of 0.076 mm on the black surface of a color matching panel using an applicator, and the reflectance of the coated film was measured using a Color Analyzer Model 607 manufactured by Hitachi. The measurement results are shown in FIG. As is clear from the figure, the amorphous amorphous and spherical titanium oxide of the present invention have good visible light transmittance, and
It can be seen that the blue-tinged reflectance at 500 nm is also low. This also shows that while conventional titanium oxide looks pale, amorphous spherical titanium oxide is not pale. (4) Fragrance Retention Compact blushes were prepared using the same formulation as described in Example 7, and the perfume retention of the compact blushers was evaluated in the same manner as in Example 7. The evaluation results are shown in Table 6. As is clear from Table 6, the compact blusher using amorphous and spherical titanium oxide of the present invention had very excellent fragrance retention. Furthermore, the larger the specific surface area of amorphous and spherical titanium oxide, the better the fragrance retention. This is considered to be because the amorphous spherical titanium oxide is porous and the fragrance is retained within the pores. (5) Practical usability Creams were prepared using the same formulation as described in Example 4, and the practical usability of the creams was tested and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 6. As is clear from Table 6, the cream using amorphous and spherical titanium oxide of the present invention does not "spread" or "stick" in actual use.
Both the "freshness" and the "overall evaluation" were excellent. Incidentally, electron micrographs, high-magnification electron micrographs, electron diffraction diagrams, and x-ray diffraction diagrams of titanium oxide of Examples 8 to 12 and Comparative Example 1 are shown in Figs. 7 to 20.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a curve showing the absorbance of various titanium oxides in the wavelength range of 200 to 400 nm. Figure 2 is an electron diffraction diagram (photograph) of amorphous amorphous and spherical titanium oxide ultrafine particles of the present invention, and Figure 3 is a micrograph of amorphous amorphous and spherical titanium oxide ultrafine particles of the present invention.
FIG. 4 is an x-ray diffraction diagram of amorphous amorphous and spherical titanium oxide ultrafine particles of the present invention, FIG. 5 is a graph showing the color tone of visible light in Example 1, and FIG. Graph showing visible light transmittance, FIG. 7 is an electron micrograph of ultrafine titanium oxide particles of Example 8, FIG. 8 is an electron micrograph of ultrafine titanium oxide particles of Example 9, and FIG. 9 is an example.
Electron micrograph of 10 ultrafine titanium oxide particles, 1st
Fig. 0 is an electron micrograph of ultrafine titanium oxide particles of Example 11, Fig. 11 is an electron micrograph of ultrafine titanium oxide particles of Example 12, and Fig. 12 is an electron micrograph of titanium oxide particles of Comparative Example 1. Figure 13 is a high-magnification electron micrograph of titanium oxide particles of Comparative Example 1, Figure 14 is an electron diffraction diagram (photograph) of titanium oxide particles of Comparative Example 1, and Figure 15 is a high-magnification electron micrograph of titanium oxide particles of Example 8. X-ray diffraction diagram, Figure 16 is the X-ray diffraction diagram of ultrafine titanium oxide particles of Example 9, Figure 17 is the example
FIG. 18 is an X-ray diffraction diagram of ultrafine titanium oxide particles of Example 11,
FIG. 19 shows an X-ray diffraction diagram of ultrafine titanium oxide particles of Example 12, and FIG. 20 shows an X-ray diffraction diagram of titanium oxide particles of Comparative Example 1.

Claims (1)

[Claims] 1 Amorphous, spherical titanium oxide ultrafine particles
A cosmetic characterized by containing 0.01 to 50% by weight.