JP3495296B2 - Oil-based dispersion of titanium oxide, lipophilic titanium oxide powder, method for producing these, and cosmetics containing these - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oily dispersion of titanium oxide and a lipophilic titanium oxide powder, which are excellent in dispersibility in oily materials and have various properties such as ultraviolet absorption, photocatalytic activity, and photochromic property, and It relates to these manufacturing methods. The oil dispersion of titanium oxide and the lipophilic titanium oxide powder according to the present invention are used for pharmaceuticals, cosmetics, oil paints, resins, adsorbents, ion exchange agents, complex oxide precursors, optical materials, photochromic materials, electronic / electrical materials. It can be applied in a wide range of fields such as materials, recording / memory materials, fibers, photocatalysts, antibacterial and antifungal materials, and environmental pollutant decomposition and removal agents. Further, it is particularly suitable for application to cosmetics having an ultraviolet protection effect.

More specifically, it is obtained by adding an organic compound having an atom having a lone electron pair and / or a polar group in a molecule to a titanium alkoxide or an oily solution or dispersion thereof, and then adding water for hydrolysis. An oily dispersion of titanium oxide obtained, and a lipophilic titanium oxide powder obtained by removing the dispersion medium therefrom and drying, and a method for producing these,
It also relates to cosmetics containing these.

[0003]

2. Description of the Related Art Titanium oxide has a high UV shielding effect and is often used as a pigment in cosmetics and the like for preventing discoloration of paints due to UV rays and for preventing inflammation due to UV rays. To obtain titanium oxide in the form of flakes or fine particles suitable for this purpose, the sol-gel method, whose shape and particle size are easily controlled, is widely used. However, in this method, the addition of water is indispensable for hydrolyzing the titanium alkoxide, and a lower alcohol such as butanol is used as the dispersion medium. Therefore, titanium oxide obtained by the sol-gel method was poor in lipophilicity and poor in dispersibility in oily materials. Further, since it has hydrophilicity, it is poor in water resistance, and it has been necessary to perform a hydrophobic treatment in order to improve dispersibility in compounding into an oily material or to impart water resistance.

[0004]

Therefore, in the present invention, it is possible to obtain an oily dispersion of titanium oxide and a lipophilic titanium oxide powder which are excellent in dispersibility in an oily material and can be applied in a wide variety of fields, and various It is an object of the present invention to provide a method for producing the above-mentioned oily dispersion and lipophilic titanium oxide powder whose shape and properties are suitable for the purpose and which can be easily controlled. Furthermore, it has excellent feeling of use and transparency, and a good finished feeling is obtained,
It was also intended to obtain a cosmetic material having an excellent UV protection effect.

[0005]

[Means for Solving the Problems] As a result of various studies to solve the above problems, when titanium alkoxide or an oily solution or dispersion thereof is allowed to undergo a hydrolysis reaction, particles of titanium oxide are converted from titanium alkoxide. It was found that titanium oxide particles well dispersed in an oil dispersion medium can be obtained by adding an appropriate amount of an organic compound having an atom having a lone electron pair and / or a polar group in the growth process. From the oil dispersion of titanium oxide, by removing the dispersion medium and then drying,
We succeeded in obtaining a lipophilic titanium oxide powder and completed the present invention.

That is, in the present invention, one or more organic compounds having an atom and / or a polar group having a lone electron pair in the molecule and water are added to a titanium alkoxide or an oily solution or dispersion thereof. And hydrolyzed to obtain an oily dispersion of titanium oxide. Further, the dispersion medium is removed from the oily dispersion and then dried to obtain a lipophilic titanium oxide powder. When the titanium alkoxide is hydrolyzed, flakes or needle-like gel particles can be selectively obtained by coexisting one or more of the hydrolysis inhibitors. If necessary, an acid or a base, a salt obtained by neutralizing a weak acid and a weak base, a strong acid and a weak base, or a weak acid and a strong base can be used as a catalyst.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Titanium alkoxides usable in the present invention include titanium tetramethoxide, titanium tetraethoxide, titanium tetranormal propoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetraisobutoxide, and titanium. Examples thereof include tetratertial butoxide, and one or more selected from these are used. Such a titanium alkoxide can be directly dissolved or dispersed in an organic compound having an atom having a lone electron pair and / or a polar group in the molecule in a liquid state. Further, the compound is dissolved or dispersed in an oily solvent, and an organic compound having an atom having a lone electron pair and / or a polar group in the molecule is added to act. The concentration of the titanium alkoxide solution or dispersion is preferably 0.0001 M to 10.0 M, and particularly preferably 0.01 M to 6.0 M.

[0008] as an oily solvent for dissolving or dispersing the titanium alkoxide, A Bokado oil, almond oil, olive oil, sesame oil, sasanqua oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor Liquid vegetable oils such as oil, cottonseed oil, peanut oil, jojoba oil, mink oil, egg yolk oil, liquid animal oils such as liquid lanolin, liquid paraffin, isoparaffin, squalane,
Hydrocarbon oils such as pristane, oleyl alcohol, 2-
Hexyldecanol, isostearyl alcohol, 2-octyldodecanol liquid higher alcohols such as, OH Kuta <br/> phosphate cetyl, isopropyl myristate, isopropyl palmitate, hexyl laurate, oleyl oleate, decyl oleate, myristate Octyldodecyl, hexyldecyl dimethyloctanoate, diethyl phthalate, dibutyl phthalate, propylene glycol dioleate, glyceryl tri-2-ethylhexanoate, tri 2-
Liquid ester oils such as trimethylolpropane ethylhexanoate, dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane,
An oily substance generally used for cosmetics or paints such as silicone oil such as decamethylcyclopentasiloxane can be used. In the present invention, one kind or two or more kinds are selected from these and used.

In the present invention, an organic compound is allowed to act on the titanium alkoxide to control the hydrolysis of the titanium alkoxide, but as the organic compound usable in the present invention, an atom having a lone electron pair in the molecule or The organic compound having a polar group is not particularly limited as long as it is liquid or can be dissolved or dispersed in an oily solvent. For example, Mi Risuchin acid, palmitic acid, stearic acid, isooctanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, hydroxypalmitic acid, hydroxystearic acid, benzoic acid, carboxylic acids such as hydroxy benzoic acid, A cetyl acetone, ethylene Compounds with chelating action such as glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylenediamine, ethylenediaminetetraacetic acid, dithizone, dimethylglyoxime, 8-quinolinol, phthalocyanine, 1,10-phenanthroline, 2,2'-bipyridyl, indigo etc. things include, selected and used one or more from these. The addition amount to the titanium alkoxide is preferably about 0.001 to 4 mol per 1 mol of the titanium alkoxide.

In the present invention, it is also possible to add a hydrolysis inhibitor for controlling the hydrolysis during the polycondensation of titanium alkoxide to titanium oxide. By adding a hydrolysis inhibitor, it is possible to control the progress of hydrolysis of the titanium alkoxide and selectively obtain flaky or acicular gel particles.

The above-mentioned hydrolysis inhibitor is selected from chelating agents and electron-donating reagents, and includes alkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol. Alkyl ethers of alkylene glycols such as monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether, Ethylene glycol mono Aryl ethers of alkylene glycols such Nji ether, beta-diketones such as acetylacetone, ethylene diamine, include such amines such as triethanolamine, it is used to select one or more from these. Among the above, alkylene glycols are particularly preferably used.

The above hydrolysis inhibitor is preferably added in a ratio of 1 mol to 20 mol per 1 mol of titanium alkoxide, more preferably 2 mol to 10 mol. When the addition amount of the hydrolysis inhibitor is less than 1 mol, the effect of controlling the hydrolysis of titanium alkoxide cannot be sufficiently obtained, and when it exceeds 20 mol, the hydrolysis of titanium alkoxide does not proceed sufficiently, which is not preferable. .

Further, in the present invention, if necessary, an acid or a base, a weak acid and a weak base, a strong acid and a weak base, or a salt obtained by neutralizing a weak acid and a strong base can be added as a catalyst. Examples of the acid or base include strong acids such as hydrochloric acid and sulfuric acid, weak acids such as carbonic acid, formic acid, acetic acid, myristic acid, palmitic acid and stearic acid, strong bases such as sodium hydroxide and potassium hydroxide, hydroxyammonium, acetamidine, Weak bases such as hydrazine are used. The addition amount of these acids or bases is 10 with respect to 1 mol of titanium.
^It is suitable to be in the range of ^-3 to 10 ^-4 mol.

The salt obtained by neutralizing a weak acid and a weak base, a strong acid and a weak base, and a weak acid and a strong base is one selected from the group consisting of carbonic acid, carboxylic acid and its derivatives, and phenoxide and its derivatives. 1 selected from the group consisting of the above, an alkali metal, an alkaline earth metal, an amine, an ammonium compound, a hydrazinium compound, a pyridinium compound and a hydroxyaluminum compound.
Salts with one or more species are preferably used and include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, ammonium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate,
Cesium hydrogen carbonate, ammonium hydrogen carbonate, lithium formate, sodium formate, potassium formate, rubidium formate,
Cesium formate, calcium formate, ammonium formate, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, calcium acetate, ammonium acetate, sodium myristate, sodium palmitate, sodium stearate, hydroxyammonium hydrochloride, acetamidine hydrochloride Examples thereof include salts and hydrazine hydrochloride. Of these, sodium carbonate, ammonium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, sodium acetate, ammonium acetate, and sodium stearate are particularly preferable. Although one or more selected from the above are used, the state of the titanium alkoxide gel produced can be controlled by the salt used. Incidentally, these salts may be added after the salt is formed by performing a neutralization reaction, but an acid and a base capable of forming a salt are separately added to an oily solution or dispersion of titanium alkoxide, Salts may be formed in the solution or dispersion.
The amount of these salts added is preferably 0.001 to 2 mol per 1 mol of titanium alkoxide.

As a method for producing an oily dispersion of titanium oxide in the present invention, first, a titanium alkoxide is dissolved or dispersed in one or more oily solvents, and the oily solution or dispersion is stirred to form an intramolecular compound. One or two of the organic compounds having an atom having a lone pair of electrons and / or having a polar group
After dissolving or dispersing one or more species in an oily solvent and adding them, water is added to hydrolyze them. It is appropriate that the amount of water added is about 0.001 to 4 mol per 1 mol of titanium alkoxide. When the organic compound having an atom having a lone electron pair and / or a polar group in the molecule is liquid, the organic compound may be added directly to the titanium alkoxide. The shape of titanium oxide produced can be controlled by adjusting the type of organic compound having an atom having a lone electron pair and / or a polar group in the molecule and the amount added to the titanium alkoxide. Moreover, as the addition ratio of water is increased, the obtained titanium oxide oil dispersion changes from transparent to slightly cloudy to cloudy, and the transparency can be controlled.

Further, in the present invention, a flaky or acicular gel can be selectively obtained by dissolving or dispersing the hydrolysis inhibitor in one or more oily solvents and adding it. When a salt obtained by neutralizing an acid or a base, a weak acid and a weak base, a strong acid and a weak base, or a weak acid and a strong base is added as a catalyst, these oily solutions or dispersions should be added simultaneously with water. However, it may be added after the hydrolysis has proceeded to some extent, and the shape of the gel particles can be controlled by the time of addition. Further, as the oily solvent or the organic compound having a coordinating ability, one having a hydrolysis suppressing action may be used.

With respect to the above reaction system, the stirring was stopped and 2
Let stand for about 120 hours to continue the reaction. If necessary, 5 to 7 times the molar amount of acid is added to the titanium to stop the reaction, and excess water is added to confirm that unreacted titanium alkoxide does not remain. Wash and remove with excess water. The acid added to stop the reaction is not particularly limited.

The oily dispersion of titanium oxide according to the present invention comprises
When dispersed in a volatile oily solvent or organic compound, a lipophilic titanium oxide powder can be obtained by evaporating these by air-drying, vacuum distillation or the like and drying. When a non-volatile oily solvent or organic compound is used, a volatile oily solvent such as cyclohexane is added and azeotropically dried.

The oil dispersion of titanium oxide and the lipophilic titanium oxide powder according to the present invention are excellent in dispersibility in oily materials and water resistance, and have various properties such as ultraviolet absorption, photocatalytic activity, photochromic activity and antibacterial activity. It is easy to control the shape, and can be in the shape of flakes, needles, fibers or the like. Further, it is possible to obtain a material having high transparency. Therefore, the oily dispersion of titanium oxide according to the present invention can be used for pharmaceuticals, cosmetics, oil paints, resins, adsorbents, ion exchange agents,
Complex oxide precursor, optical material, photochromic material,
It can be applied in a wide range of fields such as electronic / electrical materials, recording / memory materials, fibers, photocatalysts, antibacterial / antifungal materials, agents for decomposing and removing environmental pollutants. Among them, it is particularly suitable for application to cosmetics having an ultraviolet protection effect.

That is, in the present invention, as the oily raw material for cosmetics, one or two of the above-mentioned oily dispersions of titanium oxide are used.
One or more of the above lipophilic titanium oxide powders as a powder for cosmetics, and / or two or more of the above lipophilic titanium oxide powders, thereby making it effective to prevent the harmful effects of ultraviolet rays on the skin. You can get a fee. Such cosmetics include skin cosmetics such as two- or three-layered lotions, emulsions, creams, gels and packs, base cosmetics such as makeup base lotions and makeup base creams,
Emulsion, cream, oily ointment, oily stick,
It can be provided as makeup cosmetics such as powdery foundations, eye colors and cheek colors, and lip cosmetics such as lip balms and lipsticks.

In the cosmetics according to the present invention, in addition to the above-mentioned oily dispersion of titanium oxide and / or lipophilic titanium oxide powder,
Fats, waxes, hydrocarbons, fatty acids, higher alcohols, esters, lower alcohols, polyhydric alcohols, humectants, cell activating agents, anti-inflammatory agents, surfactants, water-soluble polymer compounds, Ingredients generally contained in cosmetics such as antibacterial and antifungal agents, pigments, and fragrances can be contained.
In addition to the lipophilic titanium oxide powder according to the present invention, powders such as extender pigments, coloring pigments and pearlescent pigments can be contained. Particularly in sunscreen cosmetics for the purpose of protecting against ultraviolet rays, powders having an ultraviolet scattering effect such as fine particle titanium oxide and zinc oxide which have been conventionally used, and an ultraviolet absorber can be used in combination.

[0022]

The present invention will be described in more detail with reference to examples.

Examples 1 to 3 Squalane dispersion of titanium oxide treated with isostearic acid Titanium tetraethoxide was dissolved in squalane to 0.2.
M solution. While stirring 1 liter of this solution,
The amount of isostearic acid shown in Table 1 was added as a squalane solution, followed by the amount of water shown in Table 1. After stirring was stopped and the mixture was allowed to stand at room temperature for 24 hours, stearic acid 1.
The reaction was stopped by adding 4 mol, and water was added for washing.

[0024]

[Table 1]

[Examples 4 to 6] Lipophilic titanium oxide powder prepared by the action of isostearic acid Cyclohexane was added to the squalane dispersion of titanium oxide of Examples 1 to 3, and the mixture was azeotropically dried. Then, titanium oxide powder was obtained, which were referred to as Example 4 to Example 6, respectively.

[Example 7] Squalane dispersion of titanium oxide treated with 8-quinolinol Titanium tetraethoxide was dissolved in squalane to 0.2.
M solution. While stirring 1 liter of this solution,
0.001 mol of 8-quinolinol was added as a squalane solution, followed by 0.1 mol of water. After stirring was stopped and the mixture was allowed to stand at room temperature for 24 hours, stearic acid 1.4 was added.
The reaction was stopped by adding mol and water was added for washing.

[Example 8] Lipophilic titanium oxide powder formed by reacting with 8-quinolinol [0027] Cyclohexane was added to the squalane dispersion of titanium oxide treated with 8-quinolinol of Example 7 and azeotroped to dry. Then, it is referred to as Example 8.

Examples 1 to 3 and 7 of the present invention
As a result of observing the shape of the particles, it was confirmed that flaky particles were generated. Next, the particle size, X-ray diffraction and ultraviolet absorption spectrum of these particles were measured. The particle size is Shimadzu Shimadzu laser diffraction particle size distribution analyzer SALD-2.
The average value of the major axis and the minor axis of the flaky titanium oxide particles was determined and calculated at 000 J. Ultraviolet absorption spectrum and X-ray diffraction are Hitachi spectrophotometer U-
It was measured with a 3000 and RINT2000 vertical type goniometer manufactured by Rigaku Corporation. Moreover, the SPF value was also obtained by the SPF analyzer. The above results are summarized in Table 2. In addition, titanium ethoxide and isostearic acid or 8-
The action with quinolinol was confirmed by infrared absorption spectrum.

[0029]

[Table 2]

As is clear from Table 2, in Examples 1 to 3 and 7 of the present invention, the particle size is 3 to 116 μm.
Although it was a fairly large dispersion of flaky titanium oxide, it had very excellent transparency. From the results of X-ray diffraction, it was shown that each exhibited an amorphous crystalline state. Further, Examples 1 to 3 have absorption maximums at 264 to 271 nm, and in Example 7, absorption due to 8-quinolinol was observed on the longer wavelength side. The viscosity of all the dispersions was low, and the SPF value was around 7 as measured by the SPF analyzer.

Subsequently, in the titanium oxide oil dispersion according to Example 3, liquid paraffin was used as a solvent instead of the solvent, and the same procedure was followed except that the liquid paraffin was evaporated by leaving it in a warm bath for 20 hours. The concentrated product was used as Example 9 and its photochromic property was evaluated. Example 9
To the oil dispersion of titanium oxide of W, manufactured by SCHOTT Co.
Using a xenon lamp equipped with a G320 filter as a light source and irradiating ultraviolet rays of 40 mJ / cm ^{2 to} 300 mJ / cm ² , the change in color tone (ΔE) at that time is calculated by SHIMADZ.
It was calculated based on the transmittance of 380 to 720 nm measured by U UV-1600. The result is shown in FIG. Further, the change in color tone after stopping the irradiation of ultraviolet rays was calculated in the same manner and is shown in FIG.

As is apparent from FIG. 1, in the titanium oxide oil dispersion according to Example 9 of the present invention, the change in color tone (ΔE) increased with the increase of the ultraviolet ray irradiation amount, and further in FIG. As shown, it is confirmed that the color tone is quickly restored to the original color when the irradiation of ultraviolet rays is stopped, which suggests that it is also useful as a photochromic material.

Further, other examples of the transparent titanium oxide oil dispersion according to the present invention will be shown. Using the oily solvent shown in Table 3, a 1.5M solution of titanium tetraethoxide was prepared, and 0.75 mol of isostearic acid was dissolved in each oily solvent and added while stirring 1 liter of each solution, Then 0.75 mol of water and 7.5 mol of diethylene glycol were added respectively. After stirring was stopped and the mixture was allowed to stand at room temperature for 5 days, 9.0 mol of stearic acid was added to stop the reaction, and water was added to wash the mixture to obtain Examples 10 to 14.

[0034]

[Table 3]

Example 15 A needle-shaped titanium oxide oil dispersion of titanium tetraethoxide (40 mmol) was dissolved in isoparaffin (5 ml), and isodecanoic acid (40 mmol) and purified water (2) were added.
0 mmol and sodium stearate 0.025 mm
was added with stirring. After the stirring was stopped, the mixture was allowed to stand at room temperature for 24 hours to obtain a titanium oxide dispersion having a needle shape.

[Example 16] Needle-shaped lipophilic titanium oxide powder A needle-shaped lipophilic titanium oxide powder was dried from the needle-shaped titanium oxide oil dispersion according to Example 15 by evaporating the solvent in a warm bath and dried. Recovered.

Next, the formulations of the examples of the cosmetics according to the present invention will be shown.

[Example 17] Two-layered lotion (1) 8.00 (wt%) of titanium oxide treated with isostearic acid Squalane dispersion (Example 1) (2) β-carotene 0.02 (3) ) Ethanol 10.00 (4) Polyoxyethylene (20E.O.) sorbitan 0.20 Tetraoleic acid ester (5) Methyl paraoxybenzoate 0.10 (6) Perfume 0.10 (7) Sorbitol 1.00 ( 8) Glycerin 1.00 (9) Purified water 79.58 Manufacturing method: (2) was added to (1) and dissolved, and then (4) to (6)
Add the dissolved alcohol part to (3) to make an oil layer. (9)
An aqueous layer is prepared by dissolving (7) and (8) in (1), and an oil layer is added to this aqueous layer at room temperature, followed by stirring and mixing.

[Example 18] Oil-in-water emulsion (1) Cetanol 1.0 (wt%) (2) Beeswax 0.5 (3) Vaseline 2.0 (4) Titanium oxide treated with isostearic acid 6 0.0 Squalane dispersion (Example 2) (5) Titanium oxide treated with isostearic acid 2.0 Glyceryl tri-2-ethylhexanoate dispersion (Example 11) (6) Polyoxyethylene (10E.O. ) Monooleic acid 1.0 ester (7) Glyceryl monostearate 1.0 (8) Glycerin 4.0 (9) 1,3-butylene glycol 4.0 (10) Methyl paraoxybenzoate 0.1 (11 ) Purified water 58.2 (12) Carboxyvinyl polymer (1.0 wt% 15.0 aqueous solution) (13) Potassium hydroxide 0.1 (14) Perfume 0.1 (15) Ethanol 5.0 Manufacturing method: (1 ) ~ (7) oil phase components are mixed, heated and dissolved, 70 ℃
And Meanwhile, add (8) to (10) to (11) and dissolve,
Heat to 0 ° C. The above oil phase is added to this aqueous phase for preliminary emulsification, then (12) is added and stirred, and then (13) is added to increase the viscosity and uniformly emulsified with a homomixer. Then, the mixture is cooled, and (14) is dissolved in (15) at 40 ° C., and the mixture is added and mixed.

[Example 19] Oil-in-water cream (1) 10.0 (wt%) of titanium oxide treated with isostearic acid Squalane dispersion (Example 3) (2) Vaseline 5.0 (3) Stearyl Alcohol 3.0 (4) Stearic acid 3.0 (5) Glyceryl monostearate 3.0 (6) Polyethyl acrylate 1.0 (7) Tocopherol acetate 0.2 (8) Apply isostearic acid Lipophilic 6.0 titanium oxide powder (Example 4) (9) 1,3-butylene glycol 7.0 (10) potassium hydroxide 0.2 (11) methyl paraoxybenzoate 0.1 (12) purified Water 61.4 (13) Perfume 0.1 Manufacturing method: The oil phase components of (1) to (7) are mixed and heated to dissolve (8), and then the mixture is heated to 70 ° C. On the other hand, (9) to (11) are changed to (1
In addition to 2), dissolve and heat to 70 ° C. The oil phase is added to this aqueous phase with stirring, emulsified by a homogenizer and then cooled, and (13) is added and mixed at 40 ° C.

[Example 20] Sunscreen water-in-oil cream (1) 20.0% by weight of titanium oxide treated with isostearic acid Liquid paraffin dispersion (Example 9) (2) Squalane 20. 0 (3) Glyceryl diisostearate 3.0 (4) Organically modified montmorillonite 1.5 (5) 2-Ethylhexyl paramethoxycinnamate 5.0 (6) Oxybenzone 3.0 (7) 4-tert-Butyl-4 ' -Methoxydibenzoyl 1.0 Methane (8) Lipophilicity obtained by the action of isostearic acid 3.0 Titanium oxide powder (Example 5) (9) 1,3-butylene glycol 5.0 (10) paraoxybenzoic acid Methyl 0.1 (11) Purified water 38.3 (12) Perfume 0.1 Manufacturing method: The oil phase components of (1) to (7) are mixed and dissolved by heating, and (8) is dispersed and then at 70 ° C. To do. On the other hand, mix (9)-(11),
Melt and heat to 70 ° C. This aqueous phase is added to the oil phase while stirring, emulsified by a homogenizer, then cooled, and (12) is added and mixed at 40 ° C.

Example 21 Makeup Base Cream (1) Stearic Acid 10.00 (wt%) (2) 8.85 Squalane Dispersion of Titanium Dioxide Treated with 8-Quinolinol (Example 7) (3) ) Cetanol 1.50 (4) 2.00 Cetyl octoate dispersion of titanium oxide treated with isostearic acid (Example 10) (5) Self-emulsifying glyceryl monostearate 2.00 (6) Propylene glycol 8 0.000 (7) Potassium hydroxide 0.20 (8) Methyl paraoxybenzoate 0.10 (9) Purified water 69.00 (10) Titanium oxide 1.00 (11) Red iron oxide 0.05 (12) Yellow iron oxide 0.20 (13) Perfume 0.10 Manufacturing method: The oil phase components (1) to (5) are mixed, dissolved by heating, and heated to 75 ° C.
And On the other hand, the water phase components (6) to (9) are mixed and dissolved, and
The pigments (10) to (12) are added to the mixture heated to 5 ° C. and dispersed by a homomixer. The oil phase component was added to this aqueous phase component, and the mixture was uniformly emulsified with a homomixer and then cooled,
Add (13) at 40 ° C. and mix.

[Example 22] Oil-based ointment type foundation (1) Solid paraffin 3.00 (% by weight) (2) Microcrystalline wax 6.00 (3) Beeswax 2.00 (4) Vaseline 12.00 (5) Lanolin acetate 1.00 (6) 6.00 squalane dispersion of titanium oxide treated with isostearic acid (Example 1) (7) Isopropyl palmitate 18.00 (8) Tocopherol acetate 0.20 (9) Paraoxybenzoic acid Butyl acid 0.02 (10) 8-Quinolinol lipophilic 15.50 titanium oxide powder (Example 8) (11) Talc 17.48 (12) Kaolin 15.00 (13) Red iron oxide 1. 00 (14) Yellow iron oxide 2.50 (15) Black iron oxide 0.20 (16) Perfume 0.10 Manufacturing method: (1) to (9) are mixed and heated to 85 ° C. to be dissolved. First, add (10) and disperse, then mix (11) to (15) thoroughly. After crushed, it was added with stirring and grinding the dispersion in a colloid mill. After adding (16) and degassing, pour into a container at 70 ° C. and cool.

[Example 23] Oily stick-shaped foundation (1) 18.08 (wt%) of titanium oxide treated with isostearic acid Liquid paraffin dispersion (Example 12) (2) Isopropyl myristate 15.00 ( 3) Liquid lanolin 4.50 (4) Microcrystalline wax 4.50 (5) Ceresin 10.00 (6) Carnauba wax 2.00 (7) Sorbitan sesquioleate 1.00 (8) Tocopherol acetate 0.20 ( 9) Butyl paraoxybenzoate 0.02 (10) Lipophilic 10.00 titanium oxide powder formed by acting isostearic acid (Example 4) (11) Lipophilic 10.00 formed by acting isostearic acid 10.00 Titanium oxide Powder (Example 5) (12) Kaolin 14.60 (13) Talc 2.80 (14) Mica 3.00 (15) Red iron oxide 1.00 (16) Yellow iron oxide 3.0 0 (17) Black iron oxide 0.20 (18) Perfume 0.10 Production method: Mix the base components of (1) to (9), heat and melt at 70 ° C to 80 ° C, and then (10), (11 ) Is added and dispersed. On the other hand, (1
The pigment components of 2) to (17) are mixed, added to the above base, and kneaded by a roll mill. The kneaded product is heated and melted, toned and then defoamed,
(18) is added and the mixture is filled in a mold and cooled and solidified.

[Example 24] Powder foundation (1) 5.0 (wt%) of titanium oxide treated with isostearic acid Liquid paraffin dispersion (Example 12) (2) Octyldodecyl myristate 2.5 (3) ) Vaseline 2.5 (4) Methyl paraoxybenzoate 0.1 (5) Perfume 0.1 (6) Needle-like lipophilic titanium oxide (Example 16) 6.0 (7) 8-quinolinol Lipophilic titanium oxide 6.0 powder (Example 8) (8) Nylon powder 10.0 (9) Mica 20.0 (10) Talc 42.3 (11) Red iron oxide 3.0 (12) Yellow iron oxide 2 0.0 (13) Black iron oxide 0.5 Manufacturing method: The pigment components of (6) to (13) are mixed and pulverized through a pulverizer. This is moved to a high speed blender, (1) to (5) are mixed and added, and they are mixed uniformly. This is processed with a crusher,
After adjusting the particle size through a sieve, it is filled in a gold plate and compression molded.

[Example 25] Two-way foundation (1) Liquid paraffin 4.0 (wt%) (2) Squalane 2.0 (3) Titanium oxide 4.0 methylphenylpolysiloxane dispersion treated with isostearic acid (Example 14) (4) Methyl paraoxybenzoate 0.1 (5) Perfume 0.1 (6) Lipophilicity obtained by the action of isostearic acid 10.0 Titanium oxide powder (Example 4) (7) Isostearin Lipophilic 5.0 titanium dioxide powder (Example 6) formed by the action of acid (8) Silicone-treated sericite 25.0 (9) Silicone-treated talc 30.2 (10) Silicone-treated kaolin 5.0 (11) ) Silicone-treated red iron oxide 2.5 (12) Silicone-treated yellow iron oxide 2.0 (13) Silicone-treated black iron oxide 0.1 (14) Polyethylene powder 10.0 Manufacturing method: The pigment components of (6) to (14) are added. Mix and pass through a crusher Grinding. This is moved to a high speed blender, (1) to (5) are mixed and added, and they are mixed uniformly. This is processed with a crusher,
After adjusting the particle size through a sieve, it is filled in a gold plate and compression molded.

Usage tests were carried out on Examples 17 to 25 of the present invention described above. At this time, the squalane of the titanium oxide squalane according to Examples 1 to 3 and 7 of the present invention blended in each of the above Examples was allowed to act on squalane and the isostearic acid according to Examples 4 to 6 was allowed to act on the squalane. And a lipophilic titanium oxide powder obtained by reacting 8-quinolinol according to Example 8 with silicone-treated titanium oxide, and an oily solvent for titanium oxide according to Examples 9 to 14 Comparative examples 1 to 9 were obtained by replacing the needle-shaped lipophilic titanium oxide powder according to Example 16 with a silicone-treated needle-shaped titanium oxide powder in the oil solvent used for each preparation of the dispersion. did. The usage test is
Twenty female panelists in their twenties to fifties were used as one group, and each group was allowed to use each of the examples and comparative examples for 2 weeks in the blind. After the end of the use test, sensory evaluation was performed on the amount of cosmetics, elongation, transparency, UV protection effect, finish feeling and makeup retention, and the evaluation results were scored according to the following evaluation criteria to calculate the average value of 20 persons. , Shown in Table 4.

[With cosmetics] Good 5 points Good 4 points Normally 3 points Two bad points 1 bad point

[Growth of cosmetics] Good 5 points Good 4 points Normally 3 points Two bad points 1 bad point

[Transparency] There are 5 points There are 4 points 3 points that can not be said 2 points Not 1 point

[UV protection effect] 5 points high 4 points which are slightly high Normally 3 points 2 points that are a little low 1 point low

[Finishing feeling] 5 points that are natural 4 points that are a little natural 3 points that can not be said 2 points that are a little unnatural One point that is unnatural

[Makeup lasting] Good 5 points Good 4 points Normally 3 points Two bad points 1 bad point

[0054]

[Table 4]

As is clear from Table 4, in the groups used in the examples of the present invention, generally good evaluation was obtained regarding the sticking and elongation of the cosmetics. In addition, in all cases, almost good transparency was obtained, and a UV protection effect higher than normal was recognized. Especially Example 2
In the 0 use group, a synergistic improvement in the ultraviolet protection effect was observed. Further, in each case, a natural finish feeling is obtained, and also for water-based and oil-in-water emulsion cosmetics,
Almost good makeup lasting was obtained.

On the other hand, in the group using the comparative example, the evaluation of the stickiness and elongation of the cosmetics was lower in the group using the silicone-treated titanium oxide powder. In addition, the evaluations of transparency and finish were also poor.
No significant ultraviolet protection effect was observed in the groups using Comparative Examples 1 to 3 and Comparative Example 5. Furthermore, in each of the groups used in Comparative Examples, the evaluation of makeup retention was decreased.

That is, Example 17 to Example 2 of the present invention
Regarding No. 5, the adhesion to the skin and the elongation were good, an excellent transparency and a natural finish were obtained, and the makeup lasting was also good. Furthermore, even if it does not contain an inorganic UV blocking agent such as an organic UV absorber or particulate titanium oxide, it has some UV protection effects and is effective in protecting UV exposure to daily life. Was shown. It was also shown that the UV protection effect was synergistically improved by using it together with the UV absorber.

Regarding Examples 17 to 25 of the present invention, no change in state was observed when the sample was stored at room temperature for 6 months. In the use test, no panelists showed skin irritation reaction or skin sensitization reaction.

[0059]

As described above in detail, according to the present invention, excellent dispersibility in oily materials, ultraviolet absorption, photocatalytic activity,
Having various properties such as photochromic properties, pharmaceuticals, cosmetics, oil paints, resins, adsorbents, ion exchangers, complex oxide precursors, optical materials, photochromic materials, electronic / electric materials, recording / memory materials, fibers, Photocatalysts, antibacterial / antifungal materials, agents for decomposing / removing environmental pollutants, etc., which can be applied in a wide range of fields, to obtain oil dispersions of titanium oxide and lipophilic titanium oxide powders, and especially to have an ultraviolet protection effect. I was able to provide cosmetics.

[Brief description of drawings]

FIG. 1 is a diagram showing a change in color tone of an oil dispersion of titanium oxide according to Example 9 of the present invention when irradiated with ultraviolet rays.

FIG. 2 is a diagram showing disappearance of change in color tone when the irradiation of ultraviolet rays is stopped in the oil dispersion of titanium oxide according to Example 9 of the present invention.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-7-25617 (JP, A) JP-A-3-103324 (JP, A) JP-A-3-184905 (JP, A) JP-A-1- 230407 (JP, A) JP 9-100124 (JP, A) JP 6-157648 (JP, A) JP 11-171543 (JP, A) JP 9-239269 (JP, A) JP-A-11-199230 (JP, A) JP-A-10-265223 (JP, A) JP-A-63-30706 (JP, A) JP-A-2000-44242 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) A61K ^7/ 00-7/50 C01G 23/053 C09C 1/36

Claims (7)

(57) [Claims] 1. An oily solution or dispersion of titanium alkoxide is hydrolyzed by adding one or more organic compounds having an atom having a lone electron pair and / or a polar group in the molecule and water. An oily dispersion of titanium oxide obtained by satisfying the following requirements A to C: A: The oily solvent used in the oily solution or dispersion is one selected from the group consisting of liquid vegetable oils, liquid animal oils, hydrocarbon oils, liquid higher alcohols, liquid ester oils and silicone oils, or It is an oily solvent containing two or more kinds. B: The organic compound is a carboxylic acid or a compound having a chelating action. C:
The titanium oxide is flaky or acicular titanium oxide on which the organic compound acts. 2. The organic compound is isostearic acid,
An oily dispersion of titanium oxide according to claim 1. 3. The organic compound is 8-quinolinol,
An oily dispersion of titanium oxide according to claim 1. 4. Oxidation by hydrolyzing an oily solution or dispersion of titanium alkoxide with one or more organic compounds having an atom having a lone electron pair and / or a polar group in the molecule and water. A method for producing an oily dispersion of titanium, wherein the following A to C are satisfied, the method for producing an oily dispersion of titanium oxide. A: The oily solvent used in the oily solution or dispersion is selected from the group consisting of liquid vegetable oils, liquid animal oils, hydrocarbon oils, liquid higher alcohols, liquid ester oils and silicone oils 1
It is an oily solvent containing two or more species. B: The organic compound is a carboxylic acid or a compound having a chelating action. C: The titanium oxide is flaky or acicular titanium oxide on which the organic compound acts. 5. The organic compound is isostearic acid,
The method for producing the oil dispersion of titanium oxide according to claim 4. 6. The organic compound is 8-quinolinol,
The method for producing the oil dispersion of titanium oxide according to claim 4. 7. A cosmetic comprising one or more selected from the oil dispersions of titanium oxide according to claim 1.