JP2001206718A - Coloring preventing method of system containing oily dispersion of titanium oxide and lipophilic titanium oxide powder, and composition for skin prevented from coloring - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of effectively preventing the coloring generated due to the other compound component such as a phenolic compound in a system containing an oily dispersion of titanium oxide and one or more kinds of lipophilic titanium oxide powder and to provide a composition for skin, which is prevented from coloring and has high aging stability. SOLUTION: One or more kinds selected from the group consisting of polyamino carboxylic acid and the salt, hydroxycarboxylic acid and the salt, phosphoric acid and the salt, polyphosphoric acid and the salt, metaphosphoric acid and the salt, polymeta phosphoric acid and the salt and a compound having phosphne group are contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a system containing one or more of an oily dispersion of titanium oxide and a lipophilic titanium oxide powder, which is effective for coloring caused by other compounding components such as phenolic compounds. The present invention relates to a method for preventing skin discoloration and a composition for skin which is highly stable with time and in which such coloring is prevented.

[0002]

BACKGROUND OF THE INVENTION The present applicant has disclosed an oil-based dispersion of titanium oxide and lipophilic titanium oxide powder having various properties such as ultraviolet absorption, photocatalytic activity and photochromic properties, which are excellent in dispersibility in oily materials. (Japanese Patent Application No. 11-2)
10073). However, when a phenolic compound such as butylhydroxytoluene, tocopherol, or paraoxybenzoate is added to a system containing these, yellow coloration occurs, and the formulation of the formulation is required to provide a skin composition and the like. It has been clarified that there may be a problem that the appearance is unfavorably affected.

[0003]

Accordingly, in the present invention, in a system containing one or more of an oil-based dispersion of titanium oxide and a lipophilic titanium oxide powder, the system may contain other components as described above. An object of the present invention is to provide a method for effectively preventing coloring, and to obtain a skin composition which is excellent in stability over time without coloring even when the above components are used in combination.

[0004]

As a result of various studies to solve the above problems, the present inventors have found that polyaminocarboxylic acids and their salts, hydroxycarboxylic acids and their salts,
It is effective to contain one or more selected from the group consisting of phosphoric acid and salts thereof, polyphosphoric acid and salts thereof, metaphosphoric acid and salts thereof, polymetaphosphoric acid and salts thereof, and compounds having a phosphonic group. The inventors have found that a coloring prevention effect can be obtained, and have completed the present invention.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The oily dispersion of titanium oxide and the lipophilic titanium oxide powder used in the present invention are disclosed in
Prepared by the method disclosed in US Pat. That is, the oily dispersion of titanium oxide is obtained by adding one or more kinds of organic compounds having an atom having a lone electron pair and / or a polar group to a titanium alkoxide or an oily solution or dispersion thereof and water. To obtain a lipophilic titanium oxide powder. When titanium alkoxide is hydrolyzed, flaky or acicular gel particles can be selectively obtained by coexisting one or more hydrolysis inhibitors. If necessary, an acid or a base, or 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.

[0006] Titanium alkoxides which can be used in the preparation of an oil-based dispersion of titanium oxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetranormal propoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetraisobutoxide. , Titanium tetra tert-butoxide and the like, and one or more kinds are selected from these and used. In the case where an atom having a lone electron pair and / or an organic compound having a polar group is in a liquid state, such a titanium alkoxide can be directly dissolved or dispersed therein.
Further, the compound is dissolved or dispersed in an oily solvent, and an atom having a lone electron pair and / or an organic compound having a polar group is added to the molecule to act. The concentration of the titanium alkoxide solution or dispersion is preferably from 0.0001 M to 10.0 M, particularly preferably from 0.01 M to 6.0 M.

The oily solvent for dissolving or dispersing the above titanium alkoxide includes normal alkanes such as normal hexane, normal heptane, normal octane, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, Normal alkenes such as 1-undecene, benzene,
Benzenes such as methylbenzene and ethylbenzene, alcohols such as hexyl alcohol, heptyl alcohol, octyl alcohol, caprylic alcohol, nonyl alcohol, decyl alcohol, propyl ether, isopropyl ether, butyl ether, isobutyl ether, normal pentyl ether, isopentyl ether; Methyl butyl ether, methyl isobutyl ether, methyl normal pentyl ether, methyl isopentyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl normal pentyl ether, ethyl isopentyl ether, allyl ether, ethyl allyl ether, anisole , Phenetole, phenyl ether, benzyl ether Ethers etc., ethyl acetate,
Esters such as isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, and isobutyl butyrate Etc. can be used. Avocado oil, almond oil,
Liquid vegetable oils such as olive oil, sesame oil, sasanqua oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor oil, cottonseed oil, peanut oil, jojoba oil, mink oil, egg yolk oil, and liquid lanolin Such as liquid animal oils, liquid paraffin, isoparaffin, squalane,
Hydrocarbon oils such as pristane, oleyl alcohol, 2-
Liquid higher alcohols such as hexyldecanol, isostearyl alcohol, 2-octyldodecanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol Dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Dihydric alcohol derivatives such as diethylene glycol dibutyl ether, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, ethylene glycol phenyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, cetyl octoate, and isopropyl myristate Isopropyl palmitate, hexyl laurate, oleyl oleate, decyl oleate, octyl dodecyl myristate, hexyldecyl dimethyloctanoate, diethyl phthalate, dibutyl phthalate, propylene glycol dioleate,
Liquid ester oils such as glyceryl tri-2-ethylhexanoate and trimethylolpropane tri-2-ethylhexanoate;
Oily substances generally used for skin external preparations, such as silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane, can be used. In the present invention, one or more of these are selected and used.

The organic compound that acts on the titanium alkoxide in the preparation of the oil-based dispersion of titanium oxide is an organic compound having an atom having a lone electron pair or a polar group in the molecule, and is either liquid or dissolved in an oily solvent. There is no particular limitation as long as it can be dispersed. For example, phosphoric acids such as phosphoric acid, pyrophosphoric acid, metaphosphoric acid, and fluorophosphoric acid, glucose-1-phosphate, glucose-6-phosphate, fructose-6-phosphate, glycerol-1-phosphate, phosphoenolpyruvine Phosphoric acid esters such as acid, fluorine compounds such as acetyl fluoride, amyl fluoride, allyl fluoride, decyl fluoride, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β- Methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N silane coupling agents such as -β- (aminoethyl) -β-aminopropylmethyldimethoxysilane, isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate,
Isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) Titanium coupling agents such as phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene titanate, lactic acid, oxalic acid, tartaric acid, citric acid, malic acid, myristic acid, palmitic acid, stearic acid , Isooctanoic acid,
Carboxylic acids such as isomyristic acid, isopalmitic acid, isostearic acid, hydroxypalmitic acid, hydroxystearic acid, benzoic acid, and hydroxybenzoic acid;
Higher aliphatic alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, glyceryl ethers such as diglycerin, glyceryl monopalmityl ether, glyceryl monostearyl ether, glyceryl monooleyl ether, and glyceryl Glyceryl esters such as monopalmitate, glyceryl monostearate, glyceryl monoisostearate, glutseryl diisostearate, glyceryl tri-2-ethylhexanoate, phosphatidic acid, phosphatidylinositol, phosphatidylethanolamine, phosphatidylcholine , Glycerophospholipids such as phosphatidylserine, N-stearoyl spheres Ceramides such as ngosine, N-stearoyl phytosphingosine, sphingolipids such as sphingomyelin, glucosylceramide, galactosylceramide, acetylacetone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylenediamine, ethylenediaminetetraacetic acid, dithizone, dimethylglycol Compounds having a chelating action such as oxime, 8-quinolinol, phthalocyanine, 1,10-phenanthroline, 2,2'-bipyridyl, indigo, decylamine, undecylamine, dodecylamine, tetradecylamine, hexadecylamine,
Amines such as octadecylamine, dihexylamine, dioctylamine, didecylamine, N-methyldecylamine, N-methyllaurylamine, N-methylpalmitylamine, and N-ethylpalmitylamine; hexylamide, octylamide, decylamide, unamine Amides such as decylamide, laurylamide, myristylamide, palmitylamide and stearylamide; fatty acid alkanolamides such as myristic acid monoethanolamide, stearic acid monoethanolamide, myristic acid diethanolamide and stearic acid diethanolamide; Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, dihydroxydimethoxybenzophenone, 2,4-dihydroxybenzophenone, tetrahydroxybenzoph Benzophenone derivatives such as enone, paraaminobenzoic acid, ethyl paraaminobenzoate, pentyl paradimethylaminobenzoate, paraaminobenzoic acid derivatives such as octyl paradimethylaminobenzoate, ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, Methoxycinnamic acid derivatives such as 2-ethoxyethyl paramethoxycinnamate, salicylic acid derivatives such as octyl salicylate, phenyl salicylate, homomenthyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, myristyl salicylate, methyl salicylate, urocanic acid, ethyl urocanate, 4 -Tertial butyl-4'-
UV absorbers such as methoxydibenzoylmethane, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and methyl anthranilate, rhodamine B stearate (Red No. 215), tetrachlorotetrabromofluorescein (Red No. 218) , Tetrabromofluorescein (Red No. 223), sudan III (Red No. 225), dibromofluorescein (Dai No. 201), diiodofluorescein (Dai No. 206), fluorescein (Yellow No. 201), quinoline yellow SS (Yellow 20)
No. 4), quinizarin green SS (green 202), alizulin purple SS (purple 201), medicinal scarlet (red 501), oil red XO (red 505)
No.), Orange SS (Daily No. 403), Yellow AB (Yellow 404), Yellow 405 (Yellow 405)
No.) and oil-soluble dyes such as Sudan Blue B (Blue No. 403), and one or more of these are selected and used. The amount added to the titanium alkoxide is preferably about 0.001 mol to 4 mol per 1 mol of the titanium alkoxide.

Further, the hydrolysis inhibitor is selected from a chelating reagent and an electron donating reagent.
Alkylene glycols such as triethylene glycol, polyethylene glycol and polypropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol 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, etc. Alkyl ethers of alkylene glycols; aryl ethers of alkylene glycols such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; β-diketones such as acetylacetone; and amines such as ethylene diamine and triethanolamine. Select one or more than one There. Among the above, alkylene glycols can be particularly preferably used.

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

Acids or bases that can be added in the preparation of the oily dispersion of titanium oxide 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, sodium hydroxide, and the like. Strong bases such as potassium hydroxide, hydroxyammonium, acetamidine,
A weak base such as hydrazine is used. The addition amount of these acids or bases is 10 ^-3 to 10 ^{-4 with respect} to 1 mol of titanium.
Suitably, it is in the molar range. The salts obtained by neutralizing weak acids and weak bases, strong acids and weak bases, and weak acids and strong bases are selected from the group consisting of carbonic acid, carboxylic acids and derivatives thereof, and phenoxides and derivatives thereof.
Salts of at least one species selected from the group consisting of alkali metals, alkaline earth metals, amines, ammonium compounds, hydrazinium compounds, pyridinium compounds and hydroxyaluminum compounds are preferably used, and lithium carbonate, sodium carbonate, Potassium carbonate, rubidium carbonate, cesium carbonate, ammonium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, ammonium bicarbonate, 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 Beam, sodium stearate, hydroxylammonium hydrochloride, acetamidine hydrochloride, hydrazine hydrochloride and the like. Of these, sodium carbonate, ammonium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate, sodium acetate, ammonium acetate, and sodium stearate are particularly preferred. One or two or more types are selected from the above, and the state of the generated titanium alkoxide gel can be controlled by the salt used. In addition, these salts may be added after performing a neutralization reaction to form a salt, but an acid and a base capable of forming a salt are separately added to an oily solution or dispersion of titanium alkoxide, A salt may be formed in the solution or dispersion. The addition amount of these salts is preferably 0.001 mol to 2 mol per 1 mol of titanium alkoxide.

As a method for preparing an oily dispersion of titanium oxide, first, a titanium alkoxide is dissolved or dispersed in one or more oily solvents, and while the oily solution or dispersion is stirred, lone electrons are dispersed in the molecule. After dissolving or dispersing one or more kinds of organic compounds having an atom having a pair and / or a polar group in an oily solvent, water is added to hydrolyze. It is appropriate that the amount of water to be added is about 0.001 mol 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 a molecule is in a liquid state, the organic compound may be directly added to the titanium alkoxide.

When an acid or base, or a salt obtained by neutralization of 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 are added simultaneously with water. Alternatively, it may be added after the hydrolysis has progressed to some extent, and the shape of the gel particles can be controlled by the timing of addition. As an oily solvent or an organic compound having an atom having a lone electron pair in a molecule and / or a polar group, a compound having a hydrolysis inhibiting action may be used.

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

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

In the present invention, in order to prevent coloring in a coexistence system of one or more of the above-mentioned oil-based dispersion of titanium oxide and lipophilic titanium oxide powder with another additive component such as a phenolic compound. Substances to be added include polyaminocarboxylic acids such as ethylenediaminetetraacetic acid and their salts, hydroxycarboxylic acids such as hydroxyacetic acid, lactic acid, citric acid, tartaric acid, and gluconic acid and their salts, phosphoric acid and its salts, pyrophosphoric acid, Polyphosphoric acid such as triphosphoric acid and salts thereof, metaphosphoric acid and salts thereof, polymetaphosphoric acid such as trimetaphosphoric acid and tetrametaphosphoric acid and salts thereof, and phosphonic groups such as phenylphosphonic acid, hydroxyethanediphosphonic acid, and methylenediphosphonic acid And one or more of these are selected and used. Of these, phenylphosphonic acid,
Compounds having a phosphon group, such as hydroxyethanediphosphonic acid and methylenediphosphonic acid, are preferably used.
The compounding amount of such a substance may be one or two or more selected from the group consisting of an oily dispersion of titanium oxide and a lipophilic titanium oxide powder, and a mole of an additive component such as a phenolic compound which causes coloring. Preferably, the ratios are 0.1 to 5 times and 0.01 to 0.2 times, respectively.

The method for preventing coloring according to the present invention is characterized in that one or more kinds selected from the group consisting of an oily dispersion of titanium oxide and a lipophilic titanium oxide powder are used in combination with an additive component which causes coloring. It can be applied to systems comprising.
Examples of such additional components include antibacterial agents such as phenol, salicylic acid and salts thereof, paraoxybenzoic acid esters and resorcinol, antioxidants such as tocopherol, butylhydroxytoluene and butylhydroxyanisole, gallic acid and derivatives thereof, tannins and flavonoids Phenolic compounds and extracts of plants and the like containing these as a main component. Therefore, it can be particularly effectively applied to a skin composition comprising the above-mentioned oil-based dispersion of titanium oxide and a phenolic compound in combination.

Further, features of the present invention will be described in detail with reference to examples.

[0019]

[Examples 1 to 8] 2 mol of titanium tetraethoxide and 1 mol of isostearic acid were mixed and dissolved in a dry box, 2 mol of purified water was added thereto, and the mixture was allowed to stand at room temperature for 24 hours. After the reaction, stearic acid 1.
The reaction was stopped by adding 4 moles, washed by adding water,
Then, the mixture was concentrated by heating at 110 ° C. for 1 hour to obtain an oily dispersion of titanium oxide. 0.0025 of this oily dispersion
M, phenol 0.5M, and the substances shown in Table 1 at 0.
The mixture was mixed with normal butanol so as to obtain 01M, thereby obtaining Examples 1 to 8 and Comparative Examples 1 to 13, respectively.

[Table 1]

Examples 1 to 8 and Comparative Examples 1 to 13 and a control containing only an oily dispersion of titanium oxide and phenol were subjected to 405 after 2 hours from the preparation.
Absorbance A _s and A ₀ in nm was measured, percent inhibition of coloration I a (%) I = determined by _{(A 0 -A s) / A} 0 × 100, shown in Table 2.

[0021]

[Table 2]

As is clear from Table 2, in Examples of the present invention, a high color inhibition rate of 60% or more was recognized. In particular, in Examples 7 and 8 containing methylenediphosphonic acid and hydroxyethanediphosphonic acid having two phosphon groups, almost complete suppression of coloring was observed at 94% or more. In contrast, Comparative Examples 1 to 1
In No. 3, even the one showing the maximum suppression rate was about 40%, and no effective suppression of coloring was observed.

Next, examples of the skin composition according to the present invention will be described.

Example 9 Double-Layered Lotion (1) 8.00 (wt%) squalane dispersion of titanium oxide treated with isostearic acid (2) Ethanol 10.00 (3) Polyoxyethylene (20E. O.) Sorbitan 0.20 Tetraoleate (4) Methyl paraoxybenzoate 0.10 (5) Fragrance 0.10 (6) Sorbitol 1.00 (7) Glycerin 1.00 (8) Sodium lactate 0.05 (9) Purified water 79.55 Production method: Add an alcoholic part obtained by dissolving (3) to (5) in (2) to (1) to form an oil layer. A solution obtained by dissolving (6) to (8) in (9) is used as an aqueous layer. An oil layer is added to the aqueous layer at room temperature, and the mixture is stirred and mixed. Incidentally, the squalane dispersion of titanium oxide of (1),
Dissolve titanium tetraethoxide in squalane and add 0.2
M solution, and while stirring 1 liter of this solution,
0.1 mol of isostearic acid was added as a squalane solution, then 0.1 mol of water was added, stirring was stopped, and the mixture was allowed to stand at room temperature for 24 hours. Then, 1.4 mol of stearic acid was added. Was stopped and washed by adding water.

Example 10 Oil-in-Water Emulsion (1) Cetanol 1.00 (% by weight) (2) Beeswax 0.50 (3) Vaseline 2.00 (4) 6 of titanium oxide treated with isostearic acid 5.00 Liquid paraffin dispersion (5) Polyoxyethylene (10E.O.) monooleic acid 1.00 ester (6) Glyceryl monostearate 1.00 (7) Glycerin 4.00 (8) 1,3- Butylene glycol 4.00 (9) Methyl paraoxybenzoate 0.10 (10) Purified water 64.24 (11) Carboxyvinyl polymer (1.0 wt% 15.00 aqueous solution) (12) Potassium hydroxide 0.10 ( 13) Extract of Hamamelis with 50% by volume aqueous ethanol solution 1.00 (14) Citric acid 0.05 (15) Hydroxyethanediphosphonic acid 0.01 Production method: (1) to (6) The oil phase components are mixed and dissolved by heating.
And On the other hand, (7) to (10) are mixed and dissolved, and heated to 70 ° C. Preliminary emulsification by adding the oil phase to the aqueous phase,
Next, (11) is added and stirred, and then (12) is added to increase the viscosity, and the mixture is uniformly emulsified by a homomixer. Then cool down,
At 40 ° C., add (13) to (15) and mix. In the liquid paraffin dispersion of titanium oxide (4), titanium tetraethoxide is dissolved in liquid paraffin to form a 0.2 M solution. Added as a paraffin solution,
Next, 0.2 mol of water was added to stop stirring, and the mixture was allowed to stand at room temperature for 24 hours. Then, 1.4 mol of stearic acid was added to stop the reaction, and water was added for washing. 2 in
It was left standing for 0 hours and concentrated.

Example 11 Water-in-oil emulsion (1) Microcrystalline wax 1.00 (% by weight) (2) Beeswax 2.00 (3) Lanolin 2.00 (4) Liquid paraffin 20.00 (5) ) Squalane 10.00 (6) Sorbitan sesquioleate 4.00 (7) Polyoxyethylene (20E.O.) Sorbitan 1.00 Monooleate (8) Tocopherol acetate 0.02 (9) Lipophilic oxidation Titanium powder 0.25 (10) 1,2-pentanediol 7.50 (11) Disodium ethylenediaminetetraacetate 0.10 (12) Purified water 52.13 Production method: Oil phase components of (1) to (8) Are mixed and dissolved by heating, and (9) is added and dispersed to 75 ° C. On the other hand, the aqueous phase components (10) to (12) are mixed and dissolved to 75 ° C. After adding this to the oil phase and pre-emulsifying, it is uniformly emulsified by a homomixer,
Cooling. The lipophilic titanium oxide powder of (9) is obtained by mixing 40 mmol of titanium tetraethoxide with 5 ml of isoparaffin.
And 40 mmol of isodecanoic acid, 20 mmol of purified water and 0.025 mmol of sodium stearate were added thereto with stirring. After stopping the stirring, the mixture was allowed to stand at room temperature for 24 hours, and then the isoparaffin was evaporated in a warm bath. ,
Obtained by drying.

[Example 11] Oil-in-water cream (1) 10.00 (wt%) squalane dispersion of titanium oxide treated with isostearic acid (2) Vaseline 5.00 (3) Stearyl alcohol 3.00 ( 4) Stearic acid 3.00 (5) Glyceryl monostearate 3.00 (6) Ethyl polyacrylate 1.00 (7) 1,3-butylene glycol 7.00 (8) Potassium hydroxide 0.20 ( 9) Gallic acid 0.10 (10) Methylene diphosphonic acid 0.04 (11) Purified water 67.56 (12) Fragrance 0.10 Production method: Mix oil phase components (1) to (6) and heat 7 after melting
0 ° C. On the other hand, (7) to (11) are mixed, dissolved and heated to 70 ° C. The oil phase was added to the aqueous phase with stirring, emulsified by a homogenizer, and then cooled.
Add (12) at ℃ and mix. In addition, the squalane dispersion of titanium oxide of (1) is obtained by dissolving titanium tetraethoxide in squalane to form a 0.2 M solution, and stirring 1 liter of this solution to form a squalane solution of 0.1 mol of isostearic acid. Then, 0.1 mol of water and 1.0 mol of diethylene glycol were added, stirring was stopped, and the mixture was allowed to stand at room temperature for 24 hours. Then, 1.4 mol of stearic acid was added to stop the reaction. Was added and washed.

[Example 13] Water-in-oil cream (1) Liquid paraffin 20.00 (% by weight) (2) Squalane 20.00 (3) Glyceryl diisostearate 3.00 (4) Organically modified montmorillonite 50 (5) Talc coated with lipophilic titanium oxide 5.00 (6) 1,3-butylene glycol 5.00 (7) Methyl parahydroxybenzoate 0.10 (8) Ethylenediaminetetraacetic acid 0.15 (9) L-tartaric acid 0.10 (10) Purified water 45.05 (11) Ethanol extract of tea 0.05 (12) Fragrance 0.05 Production method: Mix and heat dissolve the oil phase components of (1) to (4), After dispersion of 5), the temperature is raised to 70 ° C. On the other hand, (6) to (10) are mixed, dissolved and heated to 70 ° C. This aqueous phase is added to the oil phase with stirring, emulsified by a homogenizer, cooled, and (11) and (12) are added and mixed at 40 ° C. Note that
The lipophilic titanium oxide-coated talc (5) is obtained by mixing and dissolving 2 mol of titanium tetraethoxide and 1 mol of isostearic acid in a dry box, adding 2 mol of purified water thereto, and allowing to stand at room temperature for 24 hours. After the reaction, 1.4 mol of stearic acid was added to stop the reaction, water was added and the mixture was washed to obtain an oily dispersion of titanium oxide.
After 100 g of talc was immersed in 00 g and allowed to stand at room temperature for 24 hours with occasional stirring, the talc having the titanium oxide dispersion adsorbed on its surface was recovered and subjected to a heat treatment at 200 ° C. for 1 hour.

In Examples 9 to 13, the presence or absence of coloration over time was observed. At that time, purified water was used instead of sodium lactate, citric acid, L-tartaric acid, hydroxyethanediphosphonic acid, methylenediphosphonic acid, ethylenediaminetetraacetic acid, or disodium salt thereof, which were blended in each example, in Comparative Example 14. Comparative Example 18 was evaluated at the same time. The presence or absence of coloring was determined in Examples and Comparative Examples by 2
After storage at 5 ° C. for one month, the coloring was visually evaluated,
The results are shown in Table 3 as “○: no problematic coloring is observed”, “△: slight coloring is observed”, and “×: significant coloring is observed”.

[0030]

[Table 3]

As is apparent from Table 3, no problematic coloring was observed in Examples 9 to 13 of the present invention. On the other hand, in the comparative example in which the hydroxycarboxylic acid such as sodium lactate added to prevent coloring in the present invention was all replaced with purified water, slight coloring was observed in Comparative Example 16, and in other Comparative Examples, Remarkable coloring was observed.

[0032]

As described in detail above, according to the present invention, in a system containing one or more of an oily dispersion of titanium oxide and a lipophilic titanium oxide powder, other components such as a phenolic compound are contained. Thus, a method for effectively preventing the coloring caused by the above can be provided, and a skin composition which is prevented from coloring and has high temporal stability can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/00 A61K 7/00 Q 7/021 7/021 B01J 13/00 B01J 13/00 B // C09K 15/02 C09K 15/02 15/06 15/06 15/20 15/20 15/32 15/32 CF term (reference) 4C083 AA082 AA112 AB032 AB241 AB281 AB432 AB442 AC012 AC022 AC072 AC102 AC112 AC122 AC132 AC242 AC301 AC302 AC402 AC422 AC442 AC472 AC482 AC531 AC532 AC891 AC892 AD092 AD512 AD662 BB45 CC02 CC04 DD05 DD23 DD27 DD31 DD32 DD33 EE01 EE03 EE07 FF01 FF05 4G047 CA02 CA10 CB06 CC01 CD03 4G065 AA05 AA05 AA05 AA06 AB01X AB03A01 A13A01 AB13 A01A12 AB13 AC07

Claims (6)

[Claims] 1. Hydrolysis of a titanium alkoxide or an oily solution or dispersion thereof by adding one or more kinds of organic compounds having an atom having a lone electron pair and / or a polar group in a molecule and water. A system comprising one or more selected from the group consisting of an oil-based dispersion of titanium oxide obtained by drying and a lipophilic titanium oxide powder obtained by removing a dispersion medium and drying the dispersion. Acids and their salts, hydroxycarboxylic acids and their salts, phosphoric acids and their salts, polyphosphoric acids and their salts, metaphosphoric acids and their salts, polymetaphosphoric acids and their salts,
A method for preventing coloring of a system, comprising one or more kinds selected from the group consisting of compounds having a phosphon group. 2. The method for preventing coloration according to claim 1, wherein the oil-based dispersion of titanium oxide is obtained by further adding one or more kinds of hydrolysis inhibitors and hydrolyzing the dispersion. 3. The oil-based dispersion of titanium oxide further comprises one or more selected from an acid or a base, or a 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. 3. The method for preventing coloration according to claim 1, wherein the method is obtained by adding and hydrolyzing. 4. Hydrolysis of titanium alkoxide or an oily solution or dispersion thereof by adding one or more kinds of organic compounds having an atom having a lone electron pair and / or a polar group in a molecule and water. And one or more selected from the group consisting of an oil-based dispersion of titanium oxide obtained by drying, and a lipophilic titanium oxide powder obtained by drying after removing a dispersion medium, and a polyaminocarboxylic acid and salt,
One or two selected from the group consisting of hydroxycarboxylic acids and their salts, phosphoric acid and its salts, polyphosphoric acids and their salts, metaphosphoric acids and their salts, polymetaphosphoric acids and their salts, and compounds having a phosphonic group A composition for skin which is prevented from coloring, comprising the above. 5. The skin composition according to claim 4, wherein the oily dispersion of titanium oxide is obtained by further adding one or more kinds of hydrolysis inhibitors and hydrolyzing the dispersion. 6. The oily dispersion of titanium oxide may further comprise one or more selected from an acid or a base, or a salt obtained by neutralization of a weak acid and a weak base, a strong acid and a weak base, and a weak acid and a strong base. The skin composition according to claim 4 or 5, which is obtained by adding and hydrolyzing.