JP3516894B2 - Oil-based dispersion of titanium oxide having photochromic properties, lipophilic titanium oxide powder, method for producing the same, film-forming or film composition obtained therefrom, and composition containing these - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oily dispersion of titanium oxide having photochromic properties, a lipophilic titanium oxide powder, a method for producing the same, and a film-forming or film-forming composition obtained therefrom, and further these. Containing skin, paints, resins, container compositions, pharmaceuticals, cosmetics, oil paints, resins, adsorbents, ion exchangers, complex oxide precursors, optical materials, photochromic materials, electronic / electrical materials, recording / memory It can be applied in a wide range of fields such as materials, fibers, photocatalysts, antibacterial and antifungal materials, and environmental pollutant decomposition and removal agents.

[0002]

2. Description of the Related Art Conventionally, for the purpose of color rendering, light control, light shielding, photosensitization, masking and the like, compounds having a photochromic property in which the color tone is reversibly changed by light irradiation have been widely used in various fields. Such compounds include
Tetrachlor-α-ketodihydronaphthalene, quinoline hydrochloride, hydrazones, osazones, azobenzene, thioindigo, triphenylflugide, stilbene, salicylideneaniline, anthracene, triphenylmethane,
In addition to many organic compounds such as spiropyran, silver halide,
Inorganic compounds such as titanium oxide are known.

However, the above organic compounds have a problem that they are inferior in thermal stability and durability. Further, among the above-mentioned inorganic compounds, titanium oxide is excellent in thermal stability, durability and safety, but in order to impart photochromic property, it is necessary to undergo a high temperature firing process in which temperature conditions are highly controlled. Manufacturing is never easy. Furthermore, since titanium oxide, which has photochromic properties, is a solid, in order to impart photochromic properties to liquids and coatings and to control the morphology of photochromic materials, it is necessary to disperse and knead it in an appropriate dispersion medium or resin. Had to do. Furthermore, since titanium oxide has a high refractive index, the transparency of the composition containing it decreases, which makes it unsuitable for application to materials requiring transparency. Recently, studies have been conducted to improve the transparency by controlling the size of titanium oxide crystal particles, but they have not been able to obtain sufficient transparency.

[0004]

Therefore, in the present invention, it can be obtained without a firing process under the control of a high temperature condition, and can be provided in various forms such as a liquid and a film, and is easy to handle. An object of the present invention is to obtain a composition containing a lipophilic photochromic titanium oxide which is excellent, has a high affinity with an oily material, and can impart high transparency.

[0005]

As a result of various investigations for solving the above problems, the present inventors have already found that the Japanese Patent Application No. 11-
As disclosed in 210073, the oiliness of titanium oxide obtained by hydrolyzing a titanium alkoxide with one or more organic compounds having an atom having a lone electron pair and / or a polar group in the molecule We have found that the dispersion has excellent photochromic properties.
Further, it has been found that by adding a metal or a metal compound that acts as a photochromic auxiliary, a better photochromic property can be obtained, and the present invention has been completed.

That is, in the present invention, titanium alkoxide or an oily solution or dispersion thereof is added to one or more kinds of organic compounds having an atom and / or a polar group having a lone electron pair in the molecule, water, and When hydrolyzing by adding a catalyst as needed or after hydrolyzing, by adding one or more of a metal and a metal compound acting as a photochromic auxiliary agent, the oiliness of titanium oxide having photochromic properties A dispersion is obtained, and the dispersion medium is removed from the oily dispersion to obtain a lipophilic titanium oxide powder having photochromic properties, a film-forming composition, a film composition and the like.

[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.

Examples of the oily solvent for dissolving or dispersing the titanium alkoxide include normal alkanes such as normal hexane, normal heptane, and normal octane, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-Undecene and other normal alkenes, benzene,
Benzene such as methylbenzene and ethylbenzene, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol and other alcohols, 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 of 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, isobutyl butyrate, etc. Etc. can be used. Also, avocado oil, almond oil,
Liquid vegetable oils such as olive oil, sesame oil, southern 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, liquid lanolin Liquid animal oils such as 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,
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, and other dihydric alcohol derivatives, cetyl octanoate, isopropyl myristate. , Isopropyl palmitate, hexyl laurate, oleyl oleate, decyl oleate, octyldodecyl 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 cosmetics or paints such as silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and 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, and 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, phosphoric acids such as phosphoric acid, pyrophosphoric acid, metaphosphoric acid, fluorophosphoric acid, glucose-1-phosphate, glucose-6-phosphate, fructose-6-phosphate, glycerol-1-phosphate, phosphoenolpyruvine Phosphates such as acids, acetyl fluoride, amyl fluoride, allyl fluoride, fluorinated compounds such as decyl fluoride, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β- (Methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-amino Propyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysila ,
silane coupling agents such as γ-ureidopropyltriethoxysilane, N-β- (aminoethyl) -β-aminopropylmethyldimethoxysilane, isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) ) Titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis ( Titanium coupling agents such as dioctylpyrophosphate) oxyacetate titanate and tris (dioctylpyrophosphate) ethylene titanate, lactic acid, oxalic acid, tartaric acid, citric acid, malic acid, myristic acid, palmi Phosphate, stearic acid, isooctanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, hydroxy palmitic acid,
Carboxylic acids such as hydroxystearic acid, benzoic acid and hydroxybenzoic acid, higher fatty alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol and behenyl alcohol, diglycerin, glyceryl monopalmityl ether, glyceryl Glyceryl ethers such as monostearyl ether and glyceryl monooleyl ether, glyceryl monopalmitate, glyceryl monostearate, glyceryl monoisostearate, glyceryl diisostearate, and glyceryl tri-2-ethylhexanoate , Phosphatidic acid, phosphatidylinositol, phosphatidylethanolamine, phosphadyl Phosphorus, glycerophospholipids of phosphatidylserine, such as, N- stearoyl sphingosine, N-
Ceramides such as stearoyl phytosphingosine, sphingomyelin, glucosylceramide, sphingolipids such as galactosylceramide, acetylacetone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylenediamine, ethylenediaminetetraacetic acid, dithizone, dimethylglyoxime, 8- Compounds having chelating action such as quinolinol, phthalocyanine, 1,10-phenanthroline, 2,2'-bipyridyl, indigo, decylamine, undecylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, dihexylamine,
Amines such as dioctylamine, didecylamine, N-methyldecylamine, N-methyllaurylamine, N-methylpalmitylamine, N-ethylpalmitylamine, hexylamide, octylamide, decylamide, undecylamide, laurylamide, Amides such as myristylamide, palmitylamide and stearylamide, fatty acid alkanolamides such as myristic acid monoethanolamide, stearic acid monoethanolamide, myristic acid diethanolamide, stearic acid diethanolamide, 2-hydroxy-4-methoxybenzophenone , 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid, dihydroxydimethoxybenzophenone, 2,4-dihydroxybenzophenone, tetrahydroxybenzophenone and other benzophenone derivatives, paraa Paraaminobenzoic acid derivatives such as minobenzoic acid, ethyl paraaminobenzoate, pentyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate, ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, and 2-ethoxy paramethoxycinnamate. Methylcinnamic acid derivatives such as ethyl, octyl salicylate, phenyl salicylate, homomenthyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, myristyl salicylate, salicylic acid derivatives such as methyl salicylate, urocanic acid, ethyl urocanate, 4-tert-butyl-4 UV absorbers such as'-methoxydibenzoylmethane, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, methyl anthranilate, rhodamine B steer Rate (red 215), tetrachlorotetrabromofluorescein (red 218), tetrabromofluorescein (red 223), Sudan III (red 225)
No.), dibromofluorescein (daidai 201
No.), diiodofluorescein (daidai 206
No.), Fluorescein (Yellow No. 201), Quinoline Yellow SS (Yellow No. 204), Quinizarine Green SS
(Green No. 202), Alizurin Purple SS (Purple 20
1), medicinal scarlet (red 501), oil red XO (red 505), orange SS (daidai 403), yellow AB (yellow 404), yellow 405 (yellow 405), Sudan blue B ( Blue 40
No. 3) and other oil-soluble dyes.
One kind or two or more kinds are selected and used. 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.

Examples of the metal and metal compound that can act as the photochromic auxiliary agent used in the present invention include sodium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, aluminum, silicon, zirconium, niobium, molybdenum, silver and the like. , And their sulfates,
Examples thereof include salts such as nitrates, acetates, oxalates, carbonates, ammonium salts, chlorides, oxides, hydroxides, hydrates, alkoxides, etc., and one or more of them can be selected. To use. The blending amount of these is preferably 0.0005 mol to 0.5 mol with respect to 1 mol of titanium alkoxide.

As a method for producing an oily dispersion of titanium oxide having photochromic properties in the present invention, titanium alkoxide or a solution or dispersion thereof of titanium alkoxide or one or more oily solvents acts as a photochromic auxiliary agent. One or more kinds of metals and metal compounds to be obtained,
One or more kinds of organic compounds having an atom having a lone electron pair and / or a polar group in the molecule are added as they are or after being dissolved or dispersed in an oily solvent and added, and then water is added for hydrolysis. One or more metals and metal compounds that can act as a photochromic auxiliary may be added after the hydrolysis. 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 an atom having a lone electron pair and / or a polar group in the molecule, 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.

When the oil dispersion of titanium oxide having photochromic properties according to the present invention is dispersed in a volatile oil solvent or organic compound, it is volatilized by air drying, vacuum distillation or the like and dried. Thus, a titanium oxide powder having a lipophilic photochromic property can be obtained. When a non-volatile oily solvent or organic compound is used, a volatile oily solvent such as cyclohexane is added and azeotropically dried.

Further, a composition capable of forming a photochromic film can be obtained by concentrating the oily dispersion of titanium oxide having photochromic properties according to the present invention or removing the dispersion medium.

Further, the oil dispersion of titanium oxide having photochromic properties according to the present invention is directly or concentrated, or after the dispersion medium is removed as described above, glass plate, film, resin, powder, fiber, etc. It is made into a thin film on various supports, and at temperatures of about 80 ° C to 400 ° C
A strong lipophilic coating composition having photochromic properties can be obtained by heating for about 10 hours to such an extent that one or more of the organic compounds that have acted on the titanium alkoxide remain. In addition to the solution coating method and the dipping method, a thin film can be formed by forming a monomolecular film on the water surface and attaching it to a support by the horizontal attachment method, or by using a cumulative film obtained by the Langmuir-Blodgett method. You can

Further, in the present invention, an oily dispersion of titanium oxide having photochromic properties, or a film-forming composition obtained therefrom is dissolved or dispersed in a solvent, sprayed on a powder serving as a core, and kneaded. , 80 ℃ ~ 100 ℃
The surface coating treatment can be performed by repeating the step of drying for about 10 minutes. As a solvent,
Alcohols such as ethanol and butanol, hydrocarbons such as isoparaffin, xylene and cyclohexane, esters such as ethyl acetate and butyl acetate, ketones such as acetone, ethyl methyl ketone and cyclohexanone, diethylene glycol, ethylene glycol monoethyl ether, ethylene Ethers such as glycol monobutyl ether can be used. The concentration of titanium oxide in the oil dispersion of titanium oxide used for the coating treatment is 5 to 5
It is preferable to set it to about 0% by weight, and it is suitable that the coating amount is finally 10 to 40% by weight with respect to the powder as the core.

In the present invention, a lipophilic titanium oxide powder having photochromic properties obtained by removing the dispersion medium from the above-mentioned titanium oxide oil dispersion and drying, and a photochromic obtained from the titanium oxide oil dispersion. A lipophilic titanium oxide powder or a film-forming composition can be obtained by mixing and grinding in a ball mill one or more kinds selected from a film-forming composition having properties and a powder serving as a core. It is also possible to obtain a coated surface-treated powder. The mixing ratio of the film-forming composition or the like and the powder serving as the core during the surface treatment is appropriately in the range of 1:20 to 1: 1 in terms of weight ratio. The surface coverage of the powder can be controlled by the mixing ratio.

Further, the present invention provides a powder having water resistance and light resistance, the surface of which is coated with a coating composition containing titanium oxide having photochromic properties. The coating treatment of the powder is performed by coating the surface with an oily dispersion of titanium oxide having the above-mentioned photochromic property or a concentrate thereof, or an oily composition containing a photochromic titanium oxide obtained by removing a dispersion medium from the oily dispersion. After that, heat treatment is performed to the extent that one or more of the organic compounds remain. The coating of titanium oxide on the powder surface with an oily dispersion or the like can be performed by a wet treatment by a dipping method, a dry treatment by a mechanochemical method, or a method of spray coating by dispersing in a volatile solvent, if necessary. .

Subsequently, in the present invention, an oily dispersion of titanium oxide having photochromic properties according to the present invention as an oily component or a film-forming component, or a powder component or a pigment, a lipophilic titanium oxide powder, and a film formation. Sex composition,
1 of the above-mentioned surface-treated powder with an oily dispersion of titanium oxide
By containing one or two or more species, it is possible to obtain a dermatological composition which exhibits photochromic properties and is effective in preventing the adverse effect of ultraviolet rays on the skin. Such dermatological compositions include external preparations for skin such as lotions, emulsions, gels, creams, ointments and pasta, cosmetics for skin such as two- or three-layer lotions, emulsions, creams, gels and packs. , Make-up base lotion, base cosmetics such as make-up base cream, foundations such as milky liquid, cream, oil-based ointment, oil-based stick, powder, make-up cosmetics such as eye colors and cheek colors, It can be provided as lip cosmetics such as lip balms and lipsticks. Regarding the amount of the oily dispersion of titanium oxide having photochromic properties according to the present invention, an amount which can be usually added to the composition for skin as an oily component or the like can be added.

The dermatological composition according to the present invention contains, in addition to the above-mentioned oily dispersion of titanium oxide having photochromic properties, oils and fats, waxes, hydrocarbons, fatty acids, higher alcohols, esters, Lower alcohols, polyhydric alcohols, moisturizers, cell activators, anti-inflammatory agents, whitening agents, bactericides, surfactants, water-soluble polymer compounds, antibacterial and antifungal agents,
Materials such as pigments, fragrances and the like, which are generally blended in external preparations for skin, can be contained. In addition to the surface-treated powder according to the present invention, powders such as extender pigments, color pigments and pearlescent pigments can be contained. In particular, in a sunscreen composition for the purpose of protection against ultraviolet rays, powders having an ultraviolet scattering effect, such as conventionally used fine particle titanium oxide and fine particle zinc oxide, and an ultraviolet absorber can be used in combination.

Further, in the present invention, the above surface-treated powder by the oil dispersion of titanium oxide having photochromic properties, the lipophilic titanium oxide powder, the film-forming composition, the oil dispersion of titanium oxide, etc. according to the present invention. One or more of the above may be contained as an oily component, a film component or a pigment component to provide a coating composition. In these coating compositions, linseed oil, soybean oil, dehydrated castor oil, pentaerythritol, alkyd resin, styrenated oil, maleic oxide oil, synthetic dried oil such as urethane oil, natural resins such as shellac, copal and dammar, Processed resin such as lime rosin and rosin ester, phenol resin, urea resin, melamine resin, phthalic acid resin, synthetic resin such as vinyl resin, cellulose derivatives such as nitrocellulose, acetyl cellulose, benzyl cellulose, chlorinated rubber, cyclized rubber, A coating film forming component such as a rubber derivative such as a synthetic rubber may also be used in combination. Further, a film forming auxiliary component such as a desiccant, a curing agent, a plasticizer, a dispersant, and an emulsifier can be contained. Examples of the solvent or diluent include alcohols such as ethanol and butanol, hydrocarbons such as petroleum spirit, kerosene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, ethyl methyl ketone and cyclohexanone, and diethylene glycol. , Ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, and chloride compounds such as trichloroethylene and methylene chloride can be used. Further, in addition to the oil-based dispersion of titanium oxide having photochromic properties according to the present invention, oil-soluble dyes such as orange 5, red 24, red 25 and black 5 and inorganics such as calcium carbonate, barium sulfate and zinc oxide. Extender pigment, chrome yellow, cadmium yellow, nickel titanium yellow, red iron oxide, cadmium red, molybdenum red,
Inorganic color pigments such as navy blue, ultramarine blue, pigment yellows,
Pigment oranges, pigment reds, pigment violets, pigment blues, pigment greens, pigment browns, pigment blacks and other organic pigments may also be contained.

Further, in the present invention, a styrene resin,
The present invention can be applied to synthetic resins such as olefin resin, methacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, polyester resin, polyurethane resin, polycarbonate resin, polyacetal resin, polyphenylene resin, fluororesin, and silicone resin. To obtain a resin composition having photochromic properties and ultraviolet absorption properties by kneading one or more of the above-mentioned surface-treated powders with an oily dispersion of titanium oxide having photochromic properties, etc. You can The mixing weight ratio of the titanium oxide oil dispersion and the like when kneading with the synthetic resin is 10 to 10 relative to 100 parts by weight of the synthetic resin.
Suitably 0 parts by weight.

The resin composition containing the surface-treated powder of an oily dispersion of titanium oxide or the like is mixed in a Henschel mixer, a tumbler, or the like, and then mixed in a uniaxial or multiaxial extruder, a Banbury mixer, a kneader, a roller, or the like. It is prepared by melt-kneading in a kneading device. The obtained resin composition is molded into various molded bodies by methods such as injection molding, extrusion molding, blow molding, inflation molding and vacuum molding. Also, films and biaxially stretched films, sheets,
After being molded into foam beads or the like, it may be molded into a desired molded body.

For the above-mentioned synthetic resins, after molding these, an oily dispersion of titanium oxide having photochromic properties according to the present invention, or a film-forming composition according to the present invention or the surface of the oily dispersion or the like. It is also possible to impart photochromic properties and ultraviolet absorptivity by spraying a treated powder, which is appropriately dissolved or dispersed in a solvent, by spraying or the like for coating.

Also, after the resin composition is molded, it contains an oily dispersion of titanium oxide having photochromic properties or a concentrate thereof, or a photochromic titanium oxide obtained by removing a dispersion medium from the oily dispersion. By coating the surface with an oily composition and performing heat treatment to such an extent that one or more of the organic compounds remain,
A resin composition whose surface is coated with the coating composition having photochromic properties according to the present invention is obtained. Coating of the surface of the resin composition with an oily dispersion of titanium oxide or the like includes wet treatment by a dipping method and dry treatment by a mechanochemical method,
If necessary, it may be dispersed in a volatile solvent and spray-coated.

Then, a container having photochromic properties and ultraviolet absorptivity can be obtained by molding one or more kinds of the above resin compositions having photochromic properties. Further, the surface of the container molded with a resin is sprayed with one or more of an oily dispersion of titanium oxide having photochromic properties according to the present invention and a surface-treated powder with the oily dispersion or the like. You may coat with.

Alternatively, a photochromic titanium oxide obtained by removing a dispersion medium from the oily dispersion of titanium oxide having photochromic properties or a concentrate thereof according to the present invention in a container molded from a resin is used. After coating the surface with the oily composition containing the composition, the composition is heat-treated to such an extent that one or more of the organic compounds remain, and thus the container composition is surface-coated with the coating composition having photochromic properties according to the present invention. You can get things.

[0034]

EXAMPLES The features of the present invention will be described in detail with reference to Examples.

Example 1 Liquid Paraffin Dispersion of Photochromic Titanium Oxide First, titanium tetraethoxide was dissolved in liquid paraffin to prepare a 0.2 M solution. While stirring 1 liter of this solution, 0.1 mol of isostearic acid was added as a liquid paraffin solution, followed by 0.2 mol of water and 0.00
6 mol ferric chloride was added. After stirring was stopped and the mixture was allowed to stand at room temperature for 24 hours, 1.4 mol of stearic acid was added to stop the reaction, and then water was added to wash, and then the mixture was allowed to stand in a warm bath for 20 hours to flow. Paraffin was evaporated and concentrated to obtain. The liquid paraffin dispersion of titanium oxide according to this example showed good transparency.

Example 2 Liquid Paraffin Dispersion of Photochromic Titanium Oxide First, titanium tetraethoxide was dissolved in liquid paraffin to prepare a 0.2 M solution. While stirring 1 liter of this solution, 0.1 mol of isostearic acid was added as a liquid paraffin solution, followed by 0.2 mol of water and 0.00
6 moles of aluminum triethoxide were added. After stirring was stopped and the mixture was allowed to stand at room temperature for 24 hours, 1.4 mol of stearic acid was added to stop the reaction, and then water was added to wash, and then the mixture was allowed to stand in a warm bath for 20 hours to flow. Paraffin was evaporated and concentrated to obtain. The liquid paraffin dispersion of titanium oxide according to this example showed good transparency.

Photochromic properties of Examples 1 and 2 of the present invention were evaluated. For the liquid paraffin dispersion of the photochromic titanium oxide of Example 1 and Example 2, a xenon lamp equipped with a WG320 filter manufactured by SCHOTT was used as a light source and 40 mJ /
Irradiation with ultraviolet rays of cm ^{2 to} 300 mJ / cm ² and change in color tone (ΔE) at that time were calculated based on the transmittance of 380 to 720 nm measured by SHIMADZU 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 clear from FIG. 1, in both the liquid paraffin dispersions of titanium oxide according to Example 1 and Example 2 of the present invention, the color tone change (ΔE) was large with the increase of the ultraviolet irradiation amount. Further, as shown in FIG. 2, it was confirmed that the color tone was quickly restored to the original color when the irradiation of ultraviolet rays was stopped, and good photochromic properties were observed.

Next, other examples of the oil dispersion of photochromic titanium oxide according to the present invention will be shown.

Example 3 Squalane Dispersion of Titanium Dioxide Having Photochromic Property Titanium tetraethoxide was dissolved in squalane to 0.2.
M solution. While stirring 1 liter of this solution,
0.05 mol of isostearic acid 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 of the compound, water was added to wash the product, and then 0.005 mol of sodium chloride was added, followed by mixing and stirring. The squalane dispersion of titanium oxide according to the present example showed good transparency.

[Example 4] Dimethylpolysiloxane dispersion of titanium oxide having photochromic property Titanium tetraethoxide was dispersed in dimethylpolysiloxane (10cs) so as to have a concentration of 0.5M, and 1 liter of this dispersion was stirred. While isostearic acid 0.25
0.25 mol of water, then 2.5 mol of diethylene glycol and 0.004 mol of silicon, respectively. After stirring was stopped and the mixture was allowed to stand at room temperature for 5 days, 3.5 mol of stearic acid was added to stop the reaction, and water was added to wash it. The dimethylpolysiloxane dispersion of titanium oxide according to this example showed good transparency.

Example 5 Isochromic Dispersion of Titanium Oxide Having Photochromic Property Titanium tetraethoxide was dissolved in isoparaffin so as to have a concentration of 0.5 M, and 1 liter of this solution was stirred to obtain 0.25 isostearic acid. Mol, followed by 0.25 mol of water and 2.5 mol of diethylene glycol, respectively. After stirring was stopped and the mixture was allowed to stand at room temperature for 5 days, 3.5 mol of stearic acid was added to stop the reaction,
It was obtained by adding water and washing, then adding 0.01 mol of zirconium chloride, mixing and stirring. The titanium oxide isoparaffin dispersion according to this example showed good transparency.

Example 6 Lipophilic Titanium Oxide Powder Having Photochromic Property The liquid paraffin dispersion of titanium oxide having photochromic property according to Example 1 was further allowed to stand in a warm bath to remove liquid paraffin, Then, it was obtained by drying at 90 ° C. for 1 hour.

Example 7 Lipophilic Titanium Oxide Powder Having Photochromic Property Cyclohexane was added to the squalane dispersion of titanium oxide having photochromic property according to Example 3, cyclohexane was added thereto, and the mixture was dried.

[Example 8] Photochromic film-forming composition A liquid paraffin dispersion of titanium oxide having photochromic properties according to Example 2 was obtained by further standing in a warm bath to remove liquid paraffin. It was

Example 9 Photochromic coating composition 2 moles of titanium tetraethoxide and 1 mole of isostearic acid were mixed and dissolved in a dry box, and 2 moles of purified water and 0.2 mole of ferric chloride were added thereto. Add 06 moles and add 24 at room temperature.
After allowing the mixture to stand for a reaction for 1.4 hours, 1.4 mol of stearic acid was added to stop the reaction, and water was added to wash. The obtained titanium oxide dispersion was heat-treated at 110 ° C. for 1 hour to be concentrated, applied on a glass plate to form a coating film, and further heat-treated at 200 ° C. for 1 hour to be applied on the glass plate. A transparent yellow film composition was obtained.

Example 10 Photochromic coating composition 1.5M dimethylpolysiloxane solution of titanium tetraethoxide was prepared, and 0.75 mol of isostearic acid was added to dimethylpolysiloxane while stirring 1 liter of the solution. Dissolved in and added, and then 0.75 mol of water and 7.5 mol of diethylene glycol, 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, water was added to wash, and then 0.04 mol of aluminum triethoxide was added and mixed. After that, it was concentrated under reduced pressure at 50 ° C. After silica beads were dipped in this concentrate to form a thin film on the beads, heat treatment was performed at 130 ° C. for 1.5 hours to obtain a yellow film composition on the silica beads.

[Example 11] Talc surface-coated with a titanium oxide dispersion having photochromic properties A liquid paraffin dispersion of titanium oxide having photochromic properties according to Example 1 was prepared at a titanium oxide concentration of 20.
The mixture was adjusted to 100% by weight, sprayed little by little on 100 g of talc, mixed, kneaded, and dried at 100 ° C. for 10 minutes. This operation was repeated until the coating amount of the titanium oxide liquid paraffin dispersion reached 30% by weight.

Example 12 Kaolin surface-coated with a lipophilic titanium oxide powder having photochromic properties 30 g of the lipophilic titanium oxide powder having photochromic properties according to Example 6 and 150 g of kaolin were placed in a ball mill at 4 g. It was obtained by time-mixing and grinding treatment.

[Example 13] Nylon powder surface-coated with a film-forming composition having photochromic properties The film-forming composition having photochromic properties according to Example 8 was 40% by weight in terms of titanium oxide concentration. Thus, it was dispersed in octamethylcyclotetrasiloxane, sprayed little by little on 100 g of nylon powder, mixed, kneaded and then dried at 80 ° C. for 10 minutes. This operation was repeated until the coating amount of the titanium oxide-containing film-forming composition reached 40% by weight.

Example 14 2 mol of mica titanium tetraethoxide surface-treated with a photochromic film composition and 1 mol of isostearic acid were mixed and dissolved in a dry box, and 2 mol of purified water and Add 0.06 mol of ferric chloride and add 24 at room temperature.
After allowing the mixture to stand for a reaction for 1.4 hours, 1.4 mol of stearic acid was added to stop the reaction, and water was added to wash. 100 g of mica was immersed in 200 g of the obtained titanium oxide dispersion, and allowed to stand at room temperature for 24 hours with occasional stirring. Mica having the titanium oxide dispersion adsorbed on its surface was recovered by decantation, and then heated at 200 ° C. for 1 hour to obtain the mica.

[Example 15] A 1.5M isoparaffin solution of sericite titanium tetraethoxide surface-coated with a coating composition having a photochromic property was prepared. While stirring 1 liter of the solution, 0.75 of isostearic acid was prepared. Mol was dissolved in isoparaffin and added, and then 0.75 mol of water and 7.5 mol of diethylene glycol were added. After the 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, water was added to wash, and 0.04 mol of aluminum triethoxide was added and mixed. , 2 in hot bath
After standing for 0 hour, the isoparaffin was evaporated and removed. 100 g of the titanium oxide-containing oily composition on which isostearic acid was allowed to react and 100 g of sericite were mixed in a ball mill for 4 hours, and then the mixture was heated at 180 ° C. for 2 hours to obtain a mixture.

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

[Example 16] Two-layered lotion (1) 8.00 (wt%) of titanium oxide having photochromic property Dimethylpolysiloxane dispersion (Example 4) (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 further (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 17 Oil-in-Water Emulsion (1) Squalane 6.0 (wt%) (2) Cetanol 1.0 (3) Beeswax 0.5 (4) Vaseline 2.0 (5) Dimethylpolysiloxane 2.0 (6) 1.0 liquid paraffin dispersion of titanium oxide having photochromic properties (Example 1) (7) polyoxyethylene (10 E.O.) monooleic acid 1.0 ester (8) glyceryl monostearin Acid ester 1.0 (9) Tocopherol acetate 0.5 (10) Glycerin 4.0 (11) 1,3-Butylene glycol 4.0 (12) Methyl paraoxybenzoate 0.1 (13) Purified water 71.9 (14) Ethanol 5.0 Manufacturing method: Mix the oil phase components of (1) to (9), heat and dissolve, and heat to 70 ° C.
And On the other hand, add (10) to (12) to (13) and dissolve,
Heat to 0 ° C. The oil phase is added to this aqueous phase and the mixture is uniformly emulsified with a homomixer. Then cool down at 40 ° C
Add (14) and mix.

[Example 18] Water-in-oil type emollient emulsion (1) Microcrystalline wax 1.0 (wt%) (2) Beeswax 2.0 (3) Lanolin 2.0 (4) Liquid paraffin 15.0 ( 5) squalane 10.0 (6) 5.0 liquid paraffin dispersion of titanium oxide having photochromic properties (Example 2) (7) sorbitan sesquioleate 4.0 (8) polyoxyethylene (20E.O. ) Monooleic acid 1.0 ester (9) Fragrance 0.1 (10) Propylene glycol 7.0 (11) Methyl paraoxybenzoate 0.1 (12) Purified water 52.8 Production method: (1) to (8) The oily ingredients in (3) are mixed, dissolved by heating, and (9) is added to 70 ° C. On the other hand, the water phase components (10) to (12) are mixed, heated and dissolved to 70 ° C. This aqueous phase component is added to the above oil phase component to be pre-emulsified and homogenized with a homomixer.

Example 19 Oil-in-water cream (1) Vaseline 5.0 (% by weight) (2) Stearyl alcohol 3.0 (3) Stearic acid 3.0 (4) Glyceryl monostearate 3.0 (5) Squalane 8.0 (6) Tocopherol acetate 0.2 (7) 2.0 Squalane dispersion of titanium oxide having photochromic properties (Example 3) (8) 1,3-butylene glycol 7.0 (9) ) Potassium hydroxide 0.2 (10) Methyl paraoxybenzoate 0.1 (11) Purified water 68.4 (12) Perfume 0.1 Process: Mix the oil phase components (1) to (7) and heat. 7 after melting
Set to 0 ° C. On the other hand, (8) to (10) are added to (11), dissolved and heated to 70 ° C. The oil phase was added to this aqueous phase while stirring, and the mixture was emulsified with a homogenizer and then cooled,
Add (12) and mix at 40 ° C.

[Example 20] Sunscreen water-in-oil cream (1) Squalane 42.0 (% by weight) (2) Glyceryl diisostearate 3.0 (3) Organically modified montmorillonite 1.5 (4) Oxybenzone 2.0 (5) Film-forming composition having photochromic properties 5.0 (Example 8) (6) Lipophilic titanium oxide having photochromic properties 3.0 Powder (Example 6) (7) 1,3 -Butylene glycol 5.0 (8) Methyl paraoxybenzoate 0.1 (9) Purified water 38.3 (10) Perfume 0.1 Production method: Mix and heat-dissolve the oil phase components (1) to (5). , (6) are dispersed, and the temperature is raised to 70 ° C. On the other hand, (7) to (9) are mixed, dissolved and heated to 70 ° C. This aqueous phase is added to the oil phase while stirring, emulsified by a homogenizer, then cooled, and (10) is added and mixed at 40 ° C.

Example 21 Makeup Base Cream (1) Stearic Acid 10.00 (wt%) (2) Squalane 5.85 (3) Cetanol 1.50 (4) Cetyl Octanoate 2.00 (5) Self-emulsifying glyceryl monostearate 2.00 (6) Lipophilic titanium oxide 1.00 powder having photochromic properties (Example 7) (7) Film-forming composition 1.00 having photochromic properties (Example) 8) (8) Propylene glycol 8.00 (9) Potassium hydroxide 0.20 (10) Methyl paraoxybenzoate 0.10 (11) Purified water 67.00 (12) Titanium oxide 1.00 (13) Red iron oxide 0 .05 (14) Yellow iron oxide 0.20 (15) Perfume 0.10 Manufacturing method: The oil phase components (1) to (7) were mixed, dissolved by heating, and heated to 75 ° C.
And On the other hand, the water phase components (8) to (11) are mixed and dissolved,
Add the pigments (12) to (14) to the one heated to 75 ° C,
Disperse with a homomixer. The oil phase component is added to the aqueous phase component, the mixture is uniformly emulsified with a homomixer, then cooled, and (15) is added and mixed at 40 ° C.

Example 22 Oil-based ointment type foundation (1) Solid paraffin 3.00 (wt%) (2) Microcrystalline wax 6.00 (3) Beeswax 2.00 (4) Vaseline 12.00 (5) Lanolin acetate 1.00 (6) Squalane 6.00 (7) Isopropyl palmitate 18.00 (8) Tocopherol acetate 0.20 (9) Butyl paraoxybenzoate 0.02 (10) Lipophilic titanium oxide having photochromic properties 15.50 Powder (Example 6) (11) Titanium oxide having photochromic properties 17.48 Talc surface-coated with a dispersion (Example 11) (12) Lipophilic titanium oxide having photochromic properties 15.00 Powder Kaolin surface-coated with the body (Example 12) (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 dissolve, and firstly (10) to (12) is added and dispersed, and then (13)-(1
After thoroughly mixing and crushing 5), add it with stirring, and grind and disperse with a colloid mill. After adding (16) and degassing, pour into a container at 70 ° C. and cool.

[Example 23] Oily stick-like foundation (1) 18.08 (wt%) of titanium oxide having photochromic properties Liquid paraffin dispersion (Example 1) (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 titanium oxide having photochromic properties 10.00 powder (Example 6) (11) Lipophilic titanium oxide having photochromic properties 10.00 powder (Example 7) (Example 7) ( 12) Titanium oxide having photochromic property 2.80 Dispersed surface Treated talc (Example 11) (13) Lipophilic titanium oxide having photochromic property 14.60 Kaolin surface-coated with powder (Example 12) (14) 3.00 surface by photochromic coating composition Coated Mica (Example 14) (15) Red iron oxide 1.00 (16) Yellow iron oxide 3.00 (17) Black iron oxide 0.20 (18) Perfume 0.10 Production method: (1) to (9) The base components of (1) are mixed, heated and melted at 70 ° C to 80 ° C, and (10) to (14) are added and dispersed. On the other hand, (1
The pigment components of 5) to (17) are mixed, added to the above base, and kneaded with 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) Liquid paraffin 5.0 (wt%) (2) Octyldodecyl myristate 2.5 (3) Vaseline 2.5 (4) Methyl paraoxybenzoate 0.1 ( 5) Fragrance 0.1 (6) Lipophilic titanium oxide having photochromic properties 12.0 Powder (Example 6) (7) Titanium oxide having photochromic properties 42.3 Talc surface-coated with dispersion (Example) 11) (8) Nylon powder surface-coated with photochromic film-forming composition 10.0 (Example 13) (9) Mica surface-coated with photochromic film composition 20.0 Example 14) (10) Red iron oxide (3.0) (11) Yellow iron oxide (2.0) (12) Black iron oxide (0.5) Production method: (6) to (12) pigment composition The minutes are mixed and milled through a mill. 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) 4.0 dimethyl polysiloxane dispersion of titanium oxide having photochromic properties (Example) 4) (4) Methyl paraoxybenzoate 0.1 (5) Perfume 0.1 (6) Lipophilic titanium oxide having photochromic properties 10.0 Powder (Example 6) (7) Lipophilic oxidation having photochromic properties Titanium 5.0 Powder (Example 7) (8) Titanium oxide having photochromic properties 30.2 Talc surface-coated with a dispersion (Example 11) (9) Lipophilic titanium oxide having photochromic properties 5.0 Kaolin surface-treated with powder (Example 12) (10) 25.0 with a coating composition having photochromic properties Surface-coated sericite (Example 15) (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 mixed and crushed through a crusher. 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.

[0064]   [Example 26] Nail enamel (1) 10.0 (wt%) of titanium oxide having photochromic properties       Isoparaffin dispersion (Example 5) (2) Film-forming composition having photochromic properties 10.0       (Example 8) (3) Alkyd resin 10.0 (4) Acetyltributyl citrate 5.0 (5) Ethyl acetate 20.0 (6) Butyl acetate 15.0 (7) Ethanol 5.0 (8) Toluene 24.3 (9) Organically modified bentonite 0.2 (10) Red iron oxide 0.5 Manufacturing method: Mix (1) to (9) and dissolve uniformly.

Usage tests were carried out on Examples 16 to 26 of the present invention. At that time, the liquid paraffin dispersion of titanium oxide having photochromic properties according to Examples 1 and 2 of the present invention blended in each of the above-described examples was used as liquid paraffin, and the titanium oxide having photochromic property according to Example 3 was used. The squalane dispersion was used for squalane, the dimethylpolysiloxane dispersion of titanium oxide having photochromic properties according to Example 4 was used for dimethylpolysiloxane, and the isoparaffin dispersion of titanium oxide for photochromic properties according to Example 5 was used for isoparaffin. The lipophilic titanium oxide powder having photochromic properties according to Example 6 and Example 7 was used as silicone-treated titanium oxide, the film-forming composition having photochromic properties according to Example 8 was used as hydroxyethyl cellulose, and Examples 11 to 11 were used. Photochromic property of 15 The surface treated talc due titanium oxide dispersion or the like having, as Comparative Examples 1 to 11 obtained by alternate to each siliconized talc, was evaluated at the same time. In the preparation of Comparative Example, hydroxyethyl cellulose, which is an alternative component of the film-forming composition having photochromic properties according to Example 8, was added to the aqueous phase. Use test is 2
Twenty female panelists in their 0s to 50s 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 use test is completed, the composition for skin is attached, elongation, color change of appearance, UV protection effect,
A sensory evaluation of the finished feel and makeup lasting was performed, and the evaluation results were scored according to the evaluation criteria shown in Table 1 to calculate the average value of 20 persons, and shown in Table 2.

[0066]

[Table 1]

[0067]

[Table 2]

As is clear from Table 2, in the groups used in the examples according to the present invention, good evaluations were obtained for all items such as stickiness, elongation, UV protection effect, finish feeling and makeup lasting, The change in appearance color tone was also clearly perceived, and it was confirmed to exhibit photochromic properties. In particular, as for attachment, Example 22 to Example 2
Regarding the 6-use group and the elongation, the evaluation was higher in the use groups of Examples 20 to 26 than in the corresponding use groups of Comparative Examples. Regarding the ultraviolet protection effect, Example 16 to
In the use group of Example 19, although no significant ultraviolet protection effect was observed in each of the corresponding use groups of Comparative Examples,
A considerably high protective effect is recognized, and especially Example 20
-A remarkable improvement in the protective effect was observed in the group used in Example 25. In addition, in the use groups of Examples 20 to 26, the unnaturalness of the feeling of finish was improved, and the makeup retention was significantly higher than that of the corresponding use group of each Comparative Example. Was getting In the group used in Comparative Example, a notable change in color tone of appearance was not observed.

Regarding Examples 16 to 26 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.

Next, Table 3 shows examples of coating compositions according to the present invention. These are oily dispersions of titanium oxide having photochromic properties in the table and orange 5
Is mixed with butyl acetate and cyclohexanone and dissolved uniformly to produce.

[0071]

[Table 3]

Photochromic properties and light resistance of the above examples were evaluated. The photochromic property was evaluated in the same manner as the above-mentioned method performed for Example 1 and Example 2. On the other hand, for light resistance, JIS standard K
Evaluation was made in accordance with 5400 "Paint General Test Method". That is, the coating materials of Examples 27 to 31 were applied to one surface of a copper plate of 150 × 70 × 0.8 mm, and dried to obtain test pieces. This test piece was irradiated with an ultraviolet carbon arc lamp type light resistance tester for 100 hours and then measured with a photoelectric colorimeter. The results are as follows: "○; clearly recognized", "△; slightly recognized", "x; not recognized" for photochromic property, "○;good","△; slightly bad" for light resistance, The results are shown in Table 4 as "x;bad".

[0073]

[Table 4]

As is clear from Table 4, all of Examples 27 to 31 of the present invention showed photochromic property and good light resistance.

Next, examples of the resin composition according to the present invention will be shown.

Examples 32 to 36 Light-Resistant Resin Composition Having Photochromic Properties (1) Polystyrene 87.5 (wt%) (2) Photochromic Compositions 12.5 shown in Table 5 Manufacturing Method: Mixing (1) and (2), twin screw extruder (ZSK-25,
Melt and knead using a WERNER & PFLEIDER company.

[0077]

[Table 5]

Example 37 A photochromic light-resistant resin film polypropylene was spread and molded into a film, and then 25% by weight of a photochromic film-forming composition (Example 8) was used as a butyl acetate solution. It was obtained by spraying and coating.

Example 38 Polypropylene resin titanium tetraethoxide 2 mol surface-treated with a photochromic film composition and isostearic acid 1 mol were mixed and dissolved in a dry box, and purified water 2 mol was added thereto. Was added and allowed to react at room temperature for 24 hours, then 1.4 mol of stearic acid was added to stop the reaction,
Water was added to wash. The obtained titanium oxide dispersion 25
100 g of polypropylene resin molded in a flat shape in 0 g
g was immersed and then heat-treated at 110 ° C. for 1 hour to obtain a polypropylene resin surface-coated with a film containing titanium oxide reacted with isostearic acid.

Photochromic properties of Examples 32 to 38 of the present invention were evaluated in the same manner as described above, and after irradiation with an ultraviolet carbon arc lamp type light resistance tester defined in JIS B7551 for 100 hours. The tensile strength, bending strength and chemical resistance of each resin composition were measured and compared with the values before ultraviolet irradiation. The results show that the photochromic property is "○; clearly recognized", "△; slightly recognized", "x; not recognized", and the tensile strength, bending strength and chemical resistance after ultraviolet irradiation are "○". "No change", "△; Slightly decreased",
The results are shown in Table 6 as "x; markedly decreased".

[0081]

[Table 6]

As is clear from Table 6, Examples 32 to 38 of the present invention show clear photochromic properties,
Further, even if the ultraviolet irradiation was carried out, no significant decrease in tensile strength, bending strength and chemical resistance was observed, indicating that it was excellent in light resistance.

Further, examples of the container according to the present invention will be shown.

[Examples 39 to 43] Light-proof containers having photochromic properties The light-resistant resin compositions of Examples 32 to 36 were blow molded to obtain containers.

[Example 44] Light-proof container having photochromic property A container made of polyvinyl chloride resin was sprayed with 30 wt% of a film-forming composition having photochromic property (Example 8) as an isoparaffin solution to coat it. Obtained after processing.

[Example 45] Light-proof container having photochromic property A container made of polypropylene resin was spray-injected with a 30 wt% butyl acetate dispersion of liquid paraffin dispersion of titanium oxide having photochromic property according to Example 2. Then, after coating treatment, it was obtained by heat treatment at 120 ° C. for 1.2 hours.

With respect to Examples 39 to 45 of the present invention, the photochromic property and the light resistance were evaluated in the same manner as the resin composition. The results are shown in Table 7 as in the case of the above resin composition.

[0088]

[Table 7]

As is clear from Table 7, Examples 39 to 45 of the present invention show clear photochromic properties,
Further, even if the ultraviolet irradiation was carried out, no significant decrease in tensile strength, bending strength and chemical resistance was observed, indicating that it was excellent in light resistance.

[0090]

As described in detail above, according to the present invention, it is possible to provide various forms such as a liquid and a film without undergoing a firing process under the control of high temperature conditions, and it is easy to handle. It is possible to obtain a composition containing a lipophilic photochromic titanium oxide, which has a high affinity with an oily material and can also impart high transparency, and by containing these, the photochromic property and the UV resistance can be obtained. It was possible to obtain a dermatological composition, a coating composition, a resin composition and a container composition having properties.

[Brief description of drawings]

FIG. 1 is a diagram showing a change in color tone upon irradiation with ultraviolet rays in Example 1 and Example 2 of the present invention.

FIG. 2 is a diagram showing a change in color tone after stopping the irradiation of ultraviolet rays in Example 1 and Example 2 of the present invention.

[Explanation of symbols]

1 Example 1 2 Example 2

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI A61K 7/00 A61K 7/00 QV 7/02 7/02 P 7/021 7/021 7/043 7/043 7/42 7/42 B65D 1/09 C08K 3/22 C08K 3/22 9/04 9/04 C08L 101/00 C08L 101/00 C09C 1/36 C09C 1/36 C09D 7/12 C09D 7/12 201/00 201 / 00 C09K 9/00 D C09K 9/00 B65D 1/00 A B (72) Inventor Hiroshi Castle 112-1 Nogami, Okada-cho, Yokaichi-shi, Shiga Prefecture Noevir Co., Ltd. (72) Inventor Yasushi Murakami Ueda, Nagano Prefecture 3-15-1 Tsuneta City, Shinshu University (72) Inventor Yoshio Takasu 3-15-1, Tsuneda, Ueda City, Nagano Prefecture (56) Reference, Shinshu University (56) Reference JP-A-7-25617 (JP, A) JP, 2000-26849 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 17/00 A61K 7/00 B65D 1/09 C08K 3/22 C08K 9/04 C08L 101/00 C09C 1/36 C09D 7/12 C09D 201/00 C09K 9/00

Claims (20)

(57) [Claims] 1. A titanium alkoxide or an oily solution or dispersion thereof containing one or more metals and metal compounds acting as a photochromic auxiliary, and an atom and / or a polar group having a lone electron pair in the molecule. and one or more organic compounds, water, and be an oily dispersion of titanium oxide obtained by hydrolysis by adding a catalyst if necessary, is the organic compound painters carboxylic acid compound having An oily dispersion of titanium oxide having photochromic properties, which is characterized in that 2. A titanium alkoxide or an oil-based solution or dispersion thereof, wherein at least one organic compound having an atom having a lone electron pair and / or a polar group in the molecule, water, and if necessary, after hydrolysis by the addition of catalyst, it is an oily dispersion of titanium oxide obtained by adding one or more metals and metal compounds which act as photochromic aids, the organic compound painters carboxylic < br /> oil dispersion of titanium oxide having photochromic properties, characterized in that an acid compound. 3. The method according to claim 1, further comprising adding one or two or more hydrolysis inhibitors for hydrolysis.
Alternatively, the oily dispersion of titanium oxide according to claim 2. 4. A titanium alkoxide or an oily solution or dispersion thereof containing one or more metals and metal compounds acting as a photochromic auxiliary, and an atom and / or a polar group having a lone electron pair in the molecule. and one or more organic compounds having, water, and optionally with addition of a catalyst, a process for the preparation of an oily dispersion of hydrolyzing titanium oxide, Oh in the organic compound painters carboxylic acid compound <br /> A method for producing an oily dispersion of titanium oxide having photochromic properties, which comprises: 5. A titanium alkoxide or an oily solution or dispersion thereof, wherein at least one organic compound having an atom having a lone electron pair and / or a polar group in the molecule, water, and if necessary, after hydrolysis by the addition of catalyst, a process for the preparation of an oily dispersion of the titanium oxide to add one or more metals and metal compounds which act as photochromic aids, the organic compound painters Rubo < br /> characterized in that it is a phosphate compound, a manufacturing method of the oil dispersion of titanium oxide having photochromic property. 6. The method according to claim 4, further comprising adding one or two or more hydrolysis inhibitors for hydrolysis.
Alternatively, the method for producing an oily dispersion of titanium oxide according to claim 5. 7. A lipophilic oxidation having photochromic properties, which is obtained by removing the dispersion medium from one or more selected from the oily dispersions of titanium oxide according to claim 1 and then drying. Titanium powder. 8. A photochromic property, characterized in that the dispersion medium is removed from one or more selected from the oily dispersions of titanium oxide according to any one of claims 1 to 3 and then dried. Method for producing lipophilic titanium oxide powder. 9. A film-forming composition having photochromic properties, which is obtained by concentrating the oil dispersion of titanium oxide according to claim 1 or removing a dispersion medium from the oil dispersion. 10. An oily dispersion of titanium oxide or a concentrate thereof according to any one of claims 1 to 3, or an oily composition containing titanium oxide formed by removing a dispersion medium from the oily dispersion to form a thin film, A coating composition having photochromic properties, which is formed by heat treatment to such an extent that one or more organic compounds having an atom having a lone electron pair and / or a polar group in the molecule remain. 11. An oil-based dispersion of titanium oxide according to claim 1, a lipophilic titanium oxide powder according to claim 7, and a film-forming composition according to claim 9. A surface-treated powder having photochromic properties, which is formed by coating the surface with one kind or two or more kinds. 12. The surface is coated with an oily dispersion of titanium oxide or a concentrate thereof according to any one of claims 1 to 3, or an oily composition containing titanium oxide obtained by removing a dispersion medium from the oily dispersion. Then, one or two of the organic compounds having an atom having a lone electron pair and / or a polar group in the molecule.
A surface-treated powder having photochromic properties, which is formed by heat treatment to such an extent that at least one species remains. 13. An oily dispersion of titanium oxide according to any one of claims 1 to 3, a lipophilic titanium oxide powder according to claim 7, a film-forming composition according to claim 9, and an eleventh aspect. And a skin composition containing one or more selected from the group consisting of the surface-treated powder according to claim 12. 14. An oily dispersion of titanium oxide according to any one of claims 1 to 3, a lipophilic titanium oxide powder according to claim 7, a film-forming composition according to claim 9, and an eleventh aspect. And a coating composition containing one or more selected from the group consisting of the surface-treated powder according to claim 12. 15. A lipophilic titanium oxide powder according to claim 7, and one or more selected from the group consisting of the surface-treated powder according to claims 11 and 12, Resin composition. 16. An oily dispersion of titanium oxide according to any one of claims 1 to 3, a lipophilic titanium oxide powder according to claim 7, a film-forming composition according to claim 9, and an eleventh aspect. And a resin composition having photochromic properties, the surface of which is coated with one or more selected from the group consisting of the surface-treated powder according to claim 12. 17. The surface is coated with an oily dispersion of titanium oxide or a concentrate thereof according to any one of claims 1 to 3, or an oily composition containing titanium oxide obtained by removing a dispersion medium from the oily dispersion. Then, one or two of the organic compounds having an atom having a lone electron pair and / or a polar group in the molecule.
A resin composition having photochromic properties, which is formed by heat treatment to such an extent that at least one species remains. 18. A claim 15, a claim 16, and a claim 1.
A container composition formed by molding one kind or two or more kinds selected from the resin composition described in 7. 19. An oily dispersion of titanium oxide according to any one of claims 1 to 3, a lipophilic titanium oxide powder according to claim 7, a film-forming composition according to claim 9, and an eleventh aspect. And a container composition having a photochromic property, the surface of which is coated with one or more selected from the group consisting of the surface-treated powder according to claim 12. 20. The surface is coated with the oil dispersion of titanium oxide according to any one of claims 1 to 3, or a concentrate thereof, or an oil composition containing titanium oxide obtained by removing a dispersion medium from the oil dispersion. Then, one or two of the organic compounds having an atom having a lone electron pair and / or a polar group in the molecule.
A container composition having photochromic properties, which is formed by heat treatment to such an extent that at least one species remains.