Particles of titanium dioxide

 

(57) Abstract:

The invention relates to new particles of titanium dioxide, having a sun-protection properties and is used in cosmetic compositions. Oxide, hydroxide or oxohydroxide metal precipitated on the surface of particles of titanium dioxide of anatase. The particle size of titanium dioxide not more than 100 nm, specific surface area BET of at least 200 m2/g, a density of 2.5. The result is new particles of titanium dioxide with dimensions of not more than 100 nm, covered by a layer of oxide, hydroxide or oxohydroxide metal. These particles have a surface WET at least 70 m2/g and a density of 2.2. These particles are part of the new sunscreen compositions. The content of titanium dioxide in the composition is at least 1% and not more than 25%. 4 C. and 13 C.p. f-crystals, 4 PL.

The present invention relates to new particles of titanium dioxide of anatase with sunscreen properties, used in particular in cosmetic compositions.

Know the use of titanium dioxide as a sunscreen agent in many areas, in particular in cosmetics, paints, plastics,...

In these cases, the titanium dioxide used in the form of particles with dimensions of Maine the dispersion solution of particles of titanium dioxide, reduced to their frequent instability. To control their stability to add dispersing agents, such as organic polymers.

However, the addition of such agents is a solution that is not devoid of drawbacks. So, if the dispersion of titanium dioxide are mixed with other products to obtain the composition for cosmetics, paints or plastics, such an agent may be incompatible with the application (stability, agglomeration, toxicity,...) or with other components of the composition.

Thus, in cases such applications need to have a dispersion solution of particles of titanium dioxide, which would be stable without the addition of dispersing agents.

The aim of the present invention is, therefore, the dispersion solution of particles of titanium dioxide are stable and do not contain dispersing agents.

In this respect, the invention relates to particles of titanium dioxide of anatase with dimensions of not more than 100 nm, and these particles coated at least partially with a layer of at least one oxide, hydroxide or oxohydroxide metal and have a specific surface BET of at least 70 m2/g and a density of about 2.2.

Also the invention the Cam is La precipitated on the surface of particles of titanium dioxide of anatase with dimensions of not more than 100 nm, with a specific surface area BET of at least 200 m2/g and a density of about 2.5.

Finally, the invention also relates to the use of these particles as a sunscreen agent in compositions for cosmetics, paints or varnishes and plastics and, in particular, in cosmetic sunscreen composition containing particles according to the invention in an amount such that the content in the specified composition of titanium dioxide was at least 1%, preferably not more than 25 weight %.

Dispersion of the particles according to the invention have, in addition, stability in a wide pH range without the addition of dispersing agent.

Their dry extract can also be high, thus they remain stable and have low viscosity, in particular below 1000 mPas.

In addition, these dispersion solutions remain the same value of variance even when mixed with components, for example, a cosmetic composition.

Other characteristics, details and advantages of the invention are presented below in the description and in the examples.

The invention concerns, first of all, particles of titanium dioxide of anatase with dimensions not exceeding 100 nm, the particles are covered with, at least, cha is the BET surface of at least 70 m2/g and a density of about 2.2.

Particles according to the invention are particles based on titanium dioxide crystalline, mainly anatase structure. "Mainly" means that the percentage of anatase in the particles of titanium dioxide coating exceeds 50% by weight. Preferably, the proportion of anatase in the coating particles is more than 80%. The degree of crystallization and the nature of the crystalline phases detected by x-ray diffraction.

The average particle diameter is not more than 100 nm, preferably not less than 25 nm, preferably from 50 to 70 nm. This diameter is determined using transmission electron microscope (MET).

Particles according to the invention have a specific surface BET of at least 70 m2/g, preferably not less than 100 m2/,

Under the specific surface VET understand the specific surface determined by nitrogen adsorption in accordance with standard ASTM d 3663-78 established on the basis of method of BRUNAUER-EMETT-TELLER described in "The Journal of the American Society, 60, 309 (1938). To measure the specific surface of the particles according to the invention, if they are presented in the form of a dispersion, it is necessary to follow the measurement procedure, which involves removing the liquid phase of the dispersion and then high the structure also have a density of about 2.2. "Order" means that the density is 2.2 to 0.2. This density value is small in comparison with the normal density of titanium dioxide of anatase, equal to 3.8. This density is determined by pycnometric one.

Particles according to the invention is coated at least partially with a mineral layer at least one oxide, hydroxide or oxohydroxide metal. These oxides, hydroxides or oxohydroxide metals can, in particular, be selected from SiO2, ZrO2, oxides, hydroxides or oxohydroxides aluminum, zinc, titanium or tin in simple or mixed form. Under understand mixed metal compound based on at least two of the listed items (silicates,...). In General, the weight ratio of one or more oxides, hydroxides or oxohydroxides metal to titanium dioxide is not more than 60% of the weight. This ratio depends on the application for which the particles are intended. Preferably, if the particles are intended for use in cosmetics, this ratio does not exceed 25%, better yet not more than 20%.

This amount of oxide, hydroxide or oxohydroxide metal is determined on the particles in the dispersion using fluorescence X.

According predpochtitelno or oxohydroxide aluminum in simple or mixed form.

Even more preferred variant, when the particles are coated with a layer of silica and hydroxide or oxohydroxide aluminum when the weight content of 30% SiO2and 15% Al2O3with respect to the titanium dioxide.

Finally, an even more preferred variant, when the particles are coated with a layer of silica and hydroxide or oxohydroxide aluminum when the weight content of 15% SiO2and 5% Al2O3with respect to the titanium dioxide.

It is desirable that the particles were in the form of a dispersion.

In General, this dispersion has a specific conductivity not more than 3 msiemens. Such variance may be the proportion of solids in suspension (dry extract) from 10 to 60 wt.%, preferably at least 35%, better still at least 40%.

Dispersion of the particles according to the invention, containing at least 35% of dry extract, have this advantage, that are not highly viscous, the viscosity not greater than 1000 mPas.

The measure of dispersion of the particles in the liquid phase is for such dispersion is not more than 0,5... the Measure of dispersion is determined by the formula:

< / BR>
where:

-84is a particle diameter at which 84% of the particles have a diameter less84,;
-50represents the average particle diameter.

The diameters used to determine the magnitude of dispersion, determined by centrifugal sedimentation particle dispersion controlled X-rays using the apparatus of Brookhaven type XDC.

Such indicator means good dispersibility of the particles. In the case of aqueous dispersions, this indicator receives in a wide range of pH from 5.5 to 10. The dispersions are stable and retain the specified index value over time, despite the absence of a dispersing agent.

Particles according to the invention can also aglomerirovanie and take the form of a powder. The size of the agglomerates can be from 1 to 40 μm (measurement MET).

Due to the organic processing this powder can have a good dispersibility in water or in an organic environment. This organic treatment may be performed, for example, by atomization in the presence of fatty acids such as stearic acid, metal salts of fatty acids or graft polymerization of dialkoxybenzene,....

The invention also concerns a method for obtaining such particles, which is that at least one oxide, hydroxide or oxohydroxide the BET surface of at least 200 m2/g and a density of about 2.5.

Such deposition can be done by:

- the introduction of a dispersion of particles of titanium dioxide having the above characteristics, the precursors of the oxides, hydroxides or oxohydroxides metals in the form of aqueous solutions of salts and then,

- changing the pH to effect the deposition of these oxides, hydroxides or oxohydroxides particles of titanium dioxide.

This deposition is carried out at a temperature of not less than 50oC.

In the case of deposition of silica and hydroxide or oxohydroxide aluminum deposition can be performed at acidic or native pH. the pH is controlled by adding acid, such as sulfuric acid or simultaneous and/or sequential introduction of alkaline silicon compound and an acidic aluminum compounds. In this case, the pH is preferably from 8 to 10.

Silica can precipitate of the salt of silicon, such as alkaline silicate.

Hydroxide or oxohydroxide aluminum can precipitate of aluminum salts such as aluminum sulfate, sodium aluminate, basic aluminum chloride, aluminum hydroxide diacetate.

After deposition can be collected and washed particles, obtained in result the Finance and washing or preferably, washing ultrafiltration. the pH of the wash water is preferably about 5.5. Then particles dispersed in another liquid medium thereby to obtain a dispersion of particles of titanium dioxide. This liquid medium may be acidic or basic, preferably, the basic solution with a pH of 8-9.

To get the powder particles according to the invention, the resulting dispersion is dried at a temperature below 110oC.

Primary particles of titanium dioxide of anatase must be no larger than 100 nm, BET specific surface not less than 200 m2/g and a density of about 2.5.

Primary particles are particles based on titanium dioxide crystalline, mainly anatase structure, as defined above. The average diameter of such particles is not more than 100 nm, preferably not less than 25 nm, better still from 50 to 70 nm. This diameter is measured using transmission electron microscopy (WET).

Primary particles have a specific surface BET of at least 200 m2/g, preferably not less than 250 m2/,

This specific BET surface measured in such a way, as defined above.

Elementary particles also etousa formula:

density

where:

- is the density of anatase, i.e., 3,8,

Vi represents the volume of the interparticle pores, as measured by the bjh's method. Under volume, measured by the bjh's method, see volume measured by the method of BARRETT - JOYNER - HELENDA described in the article of work equipment engineer under the heading "porous Texture or dispersed solids", p. 3645-1 - 3645-13.

To measure the amount of interparticle pores of the particles according to the invention, if they are presented in the form of a dispersion, it is necessary to follow the measurement Protocol, which is to remove the liquid phase dispersion and then dried particles under vacuum at a temperature of 150oC for at least 4 hours.

Such particles can be obtained by hydrolysis of at least one compound of titanium And in the presence of at least one connection selected from:

(1) acids containing:

or one carboxyl group and at least two hydroxyl and/or amino groups,

or, at least, two

carboxyl group and at least one hydroxyl and/or amino group,

(II) organophosphorus acids of the following formula:

< / BR>
< / BR>
< / BR>
in which n and m represent the whole is predstavlyaet a hydroxyl, amino, aralkyl, aryl, alkyl or hydrogen,

(III) compounds capable of releasing sulfate ions in an acidic environment,

(IV) salts of the above acids

and in the presence of sources of titanium dioxide of anatase with dimensions of not more than 5 nm and the weight ratio, expressed in TiO2listed in the sources/titanium present to make sources hydrolysis in the environment, expressed in TiO2from 0.01% to 3%.

The initial solution used for hydrolysis is preferably fully aqueous solution; you can add another solvent, such as alcohol, provided that the compound of titanium and connection are soluble in this mixture.

As compounds of titanium And is used as a compound selected from halides, oxyhalogenation, alkoxides of titanium, sulfates, and in particular, synthetic sulfates.

Under a synthetic sulfates understand the solutions of sulfates of titanium obtained by ion exchange with a very pure solution of titanium chloride or by reaction of sulfuric acid with a titanium alkoxide.

Preferably used compounds of titanium halide type or oxychloride titanium. The halides or oxychloride titanium, the person is responsible, oxychoride, oxychloride, oxybromide and oxyiodides) titanium.

According to a particularly preferred method, the compound of titanium is titanium oxychloride TiOCl2.

The amount of titanium compounds And hydrolyzable solution is not critical.

In addition, the initial solution contains at least one compound B, such as defined above. As examples of compounds included within the present invention can, in particular, include:

- hydroxypolycarboxylic acid and, in particular, hydroxide and hydroxycarbonate acid, such as citric acid, maleic acid and grape acid,

(polyhydroxy)monocarboxylic acids, for example, glucoheptonate acid and gluconic acid,

- poly(hydroxycarbonate) acid, for example, grape acid,

- dicarboxylic monocellate and their corresponding amides, for example, aspartic acid, asparagine and glutamic acid,

- monocarboxylic acids, gidroksilirovanii or not, for example, lysine, serine and threonine,

- aminocrotonate of methylene ethylendiaminetetraacetic of methylene Triethylenetetramine methylene, tetraethylene the Lena; 1,2-ethylene; 1,1'-propylene; 1,3-propylene; 1,6-hexamethylene; 2,4-dihydroxyindoline-2,4-diphosphonate; 2,5-dihydroxy-hexamethylen-2,5-diphosphonate; 2,3-dihydroxybutyl-2,3-diphosphonate; 1-hydroxybenzyl-1,1'-diphosphonate; 1-aminoethyl-1,1'-diphosphonate; hydroxymethylphosphonate; 1-hydroxyethylene-1,1'-diphosphonate; 1-hydroxypropane-1,1'-diphosphonate; 1-hydroxybutane-1,1'-diphosphonate; 1-hydroxyhexanoate-1,1'-diphosphonate.

As noted, can also be used as a connection In all of salts of the above acids. In particular, these salts are, or alkaline salts, especially sodium salts, or ammonium salts.

These compounds can be selected from sulphuric acid and sulphate of ammonium, potassium,...

Preferably, compound B, as defined above, are aliphatic hydrocarbon series. In this case, the length of the main hydrocarbon chain does not exceed, preferably 15 carbon atoms, better still 10 carbon atoms. Prefer as connections In citric acid.

The amount of compound B is not critical. In General, the molar concentration of compound B with respect to the molar concentration of the compound of titanium And ranges from 0.2 to 10%, pritani, used in a special way.

Thus, the centers of crystallization of titanium dioxide used in the present invention, should primarily be smaller than 8 nm (measurement by x-ray diffraction X). Preferably, use the centers of crystallization of titanium dioxide with sizes ranging from 3 to 5 nm.

Further, the weight ratio of embryos of titanium dioxide to titanium hydrolytic environment prior to the introduction of centers of crystallization, i.e., made by the connection of titanium, expressed as TiO2is from 0.01 to 3%. Preferably, this ratio is from 0.05 to 1.5%. The execution of these two related to the centers of crystallization conditions (size and weight) when using the above method allows you to precisely control the final particle size of titanium dioxide, correlating particle size content of crystallization centers. Thus it is possible to obtain particles with a size of 25 to 100 nm.

The germ of titanium dioxide in the form of anatase is used so as to cause the deposition of titanium dioxide in the form of anatase. In General, due to the small size, these embryos have the form of poorly crystallized anatase. Embryos are usually in the form of aqueous suspensions consisting of titanium dioxide. I'm in the implementation of the hydrolysis of this initial solution by any known method, usually by heating. In this latter case, the hydrolysis can be carried out, preferably at a temperature higher than or equal to 70oC. it is Also possible, for the first time, to work at a temperature below the boiling temperature of the environment, then support hydrolytic environment at the level of the boiling point.

On the implementation of the hydrolysis, the obtained particles of titanium dioxide are selected separation of solids precipitated from the mother liquor, prior to their re-dispersion in a liquid medium to obtain a dispersion solution of titanium dioxide. This liquid medium may be acidic or basic. Preferably, use a basic solution, for example, an aqueous solution of soda. Based on this dispersion solution is performed then the stage of deposition of oxides, hydroxides or oxohydroxides metals.

According to a particular variant, after selection resulting from hydrolysis of the particles and before returning them to the dispersion, the particles are neutralized and subjected to at least one washing. Particles can be, for example, selected by centrifugation of the solution formed by hydrolysis, then neutralized by a base, for example, a solution of ammonia or soda, then rinsed and radish is gcih leaching of the same type, the particles are again dispersed in an acidic or basic solution.

These particles usually have a high degree of purity, that can be used in cosmetics.

Finally, the invention relates to the use of the above particles as a sunscreen agent. In particular, they can be used as a sunscreen agent in cosmetic compositions, varnishes, paints and plastics.

When introduced into the cosmetic compositions of these dispersions or powders of titanium dioxide can achieve index SPF (sun protection factor) of at least 20.

On the other hand, the resulting compositions are photostability, i.e. not blue under UV, according to the test described in the examples.

They are particularly stable in storage, and we can conclude that the particles of titanium dioxide retain the amount of dispersion in the composition.

The invention concerns a cosmetic sunscreen compositions comprising the above-described particles in such an amount that the content of titanium dioxide in these compositions is at least 1%, preferably not more than 25 wt.%, better still from 2 to 10%.

In cosmetic compositions can be entered particles of different sizes, the products, such as sunscreen products like gels, lotions, oils, creams, and, more generally, in the means of makeup, tools for tanning, hygienic means, capillaries, full screens, lip gloss and many other songs of this type.

The term "cosmetic composition or a composition see any cosmetic products, such as those described in Annex I (the"Illustrative list by category of cosmetic products") of the European Directive N 76/768/ EEC of 27 July 1976, the so-called cosmetic Directive.

Cosmetic compositions forming the subject of the invention may require the use of a carrier or a mixture of several media playing the role of a diluent, dispersant or carrier for the other components of the composition and allowing their distribution in the case of applying the composition to the skin or hair.

Media other than water can be liquid or solid softening agents, solvents, wetting agents, thickeners or powders.

For example, can be used singly or in mixtures, the following media types:

- softening agents such as stearyl alcohol, glycerylmonostearate, alerby alcohol, cetyl alcohol, isoprop the oleate, octadecan-2-ol, societally alcohol, eicosanol alcohol, beganovic alcohol, cetylpalmitate, silicone oils, such as dimethylpolysiloxane, di-n-BUTYLCARBAMATE, isopropylmyristate, isopropyl, isopropylene, butilstearat, polyethylene glycol, lanolin, coconut oil, oil seeds, cotton, olive oil, palm oil, rapeseed oil, soybean oil, sunflower oil, avocado oil, almond oil, Kungaeva oil, peanut oil, castor oil, mineral oil, myristate butyl, ezoterikova acid, palmitic acid, isopropylidene, laurinlactam, decillia, Priscillianists;< / BR>
- propulsory, such as propane, butane, isobutane, dimethylether, carbon dioxide, nitrogen dioxide;

- solvents such as ethanol, methylene chloride, isopropanol, acetone, etilenglikolevye ether, diethylethylenediamine ether, diethylethylenediamine ether, oxide, dimethyl sulfide, dimethyl formamide, tetrahydrofuran;

powders such as chalk, talc, kaolin, starch, gum, colloidal silica, sodium polyacrylate, the smectite tetraalkyl and/or trialkylamine, chemically modified magnetofluorescent, organically modified monticellos, ethylenglykolether.

The composition of the invention include typically from 10 to 99 wt.%, at least one of the above carriers.

Preferably, the composition according to the invention have the form of emulsions in which the oil component with an emulsifier to form an emulsion oil in water or water in oil, in accordance with the value of the hydrophilic-lipophilic balance (products HLB).

The composition of the invention may contain one or more oil components with the properties of oil. This can be of vegetable or mineral oils suggested above in the list of softening substances. You can also use silicone oils, volatile or not, such as polydimethylsiloxane.

These oil components can be up to 90%, preferably from 10 to 80% of the total composition.

The composition of the invention may also include one or more emulsifiers. Depending on the nature of these emulsifiers, the songs have a kind of emulsion, oil in water or water in oil.

To obtain emulsions of the type water-in-oil selected(s) emulsifier(s) must have secondary products HLB of 1 to 6. To obtain emulsions of the type oil-in-water selected(s) is Yu can vary from 1 to 50 wt.%, preferably from 2 to 20%.

These cosmetic compositions can also contain surface-active agents, which are used for dispersion, emulsification, solubilization, stabilization of the various components used for their softening or wetting properties. These surface-active agents used in the compositions in concentrations of from 0.05 to 50% by weight of the composition. Use of anionic, nonionic, cationic, zwitterionic or amphoteric surfactants or mixtures thereof, such as:

- anionic surfactants:

*the sulfonates complex alkylation formula R-CH(SO3M)-COOR', where R represents alkyl, C8-C20preferably C10-C16, R' is alkyl (C1-C6preferably C1-C3and M is the cation of an alkali metal (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, Tetramethylammonium, dimethylpiperidinium. . . or derived alkanolamine (monoethanolamine, diethanolamine, triethanolamine. . . ). In particular, we can mention the sulfonates complex methylation, in which R is the radical C14-C16;

*the alkyl sulphates of the formula ROSO3M, where R submitted the>C18M represents a hydrogen atom or a cation of higher number, as well as their ethoxyline (OE) and/or propoxylate (OP) derivatives, having on average from 0.5 to 6 units, preferably from 0.5 to 3 units of OE and/or OP;

*alkylarylsulfonate formula RCONHR'OSO3M, where R represents a C2-C22-alkyl, preferably C6-C20, R'-C2-C3-alkyl, M represents a hydrogen atom or a cation of higher-level definitions, and their ethoxyline (OE) and/or propoxylate (OP) derivatives, having on average from 0.5 to 60 structural units of OE and/or OP;

*salts of saturated or unsaturated fatty acids (C8-C24preferably, C14-C20C9-C20-alkylbenzenesulfonates, primary or secondary C8-C22the alkyl sulphonates, alkylglycerols, sulfonic polycarboxylic acid described in the patent application GB-A-1082179, paraffin sulfonates, N-acyl-N - alliterate, alkylphosphate, alkalization, alkylacrylate, alkylsulfonate, complex mono - and diesters of sulfosuccinates, N-acylcarnitine, sulfates Alkylglucoside, polyethoxysiloxane, while the cation is a cation of an alkaline metilammonia, dimethylpiperidine. . .) or a derivative of alkanolamine (monoethanolamine, diethanolamine, triethanolamine...);

- non-ionic surfactants:

*polyoxyalkylene (polyethoxyethanol, polyoxypropylene, polyoxyethylene) alkyl phenols, substituted C6-C12-alkyl, containing from 5 to 25 oxyalkylene structural units, as examples, TRITON X-45, X-114, X-100 or X-102, manufactured by Rohm & Haas Cy;

*glucosamine, glutamine;

*glycerolipids derivatives of N-alkylamines followed (US-A-5223179 and FR-A-1585966);

*WITH8-C22- polyoxyalkylene aliphatic alcohols containing from 1 to 25 oxyalkylene (oxyethylene, oxypropylene) structural units; examples are TERGITOL 15-S-9, TERGITOL 24-L-6 NMW, manufactured by Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4, manufactured by Shell Chemical Cy, KYRO EOB, manufactured by The Procter & Gamble Cy,

*condensation products of ethylene oxide with a hydrophobic compound which is the condensation product of propylene oxide with propylene glycol, such as PLURONIC, manufactured by BASF;

*oxide amines, such as oxide C10-C18-alkyldiphenylamine, oxide C8-C22-the alkoxy ethyldihydro
*amides of C8-C20fatty acids;

*ethoxylated fatty acids;

*ethoxylated amides, amines, amidoamines;

- amphoteric and zwitterionic surfactants;

*allyltrimethylsilane, condensation products of fatty acids and of protein hydrolysates, alkylamidoamines or dipropionate, alkylsulfonyl, amphoteric derivatives of acylpolyamines, such as AMPHIONIC manufactured by RHONEPOULENC, AMPHOLAC 7 and AMPHOLAC 7 manufactured by BEROL NOBEL, are used to reduce irritation caused by other surface-active agents, mainly anionic surface-active agents.

You can also use the emulsifier, selected from the following list (see tab. 1).

The composition of the invention may also contain water, which can reach up to 80% of the volume, preferably from 5 to 80%.

The composition of the invention may also contain silicone surface-active agent with a high molecular weight, which may be an emulsifier used instead of the above-mentioned emulsifiers.

This agent can be dimethylpolysiloxane with high molecular weight with Poliak the>/BR>in which

groups R' and R" is selected from H, C1-C18-Akilov and [CH2CH2O]a[CH2CH(CH(CH3)O] bH, one of the groups R' and R" may be Laurila, while the other has a molecular weight of from 1000 to 5000,

and is from 9 to 115, preferably from 10 to 114,

- b is from 0 to 50, preferably from 0 to 49,

- x is from 133 to 673, preferably from 388 to 402,

- y is from 25 to 0.25, preferably from 15 to 0.75.

Dimethylpolysiloxane can be used in the form of a dispersion in the volatile siloxane, such dispersion contains from 1 to 20% of the volume of dimethylpolysiloxane.

Dimethylpolysiloxane can be selected from cyclomethicone and dimethiconol, such as: DC S (Dow Corning) or laurylamidopropyl, such as DC Q2-5200 (Dow Corning).

It can also be Mirasil DMCO (Rhone-Poulenc), camilleritaconchita Abil AM 90 (TH. Goldschmidt AG).

The composition according to the invention may contain up to 25 wt.% such a surface-active agent.

The composition of the invention may also include organic solar filter, such as (see tab. 2)

As a solar filter you can use any connection that was allowed Europalaces Sunny agents, such as zinc oxide in the form of particles with an average size of from 1 to 300 nm, the iron oxide in the form of particles with an average size of from 1 to 300 nm, the silica in the form of particles with an average size of from 1 to 100 nm.

The composition may also contain additives such as:

- preservatives, for example, esters of parahydroxybenzoate;

- antioxidants, such as equivalent;

- moisturizers such as glycerol, sorbitol, dibutyl phthalate, gelatin, PEG, for example, PEG 200-600;

- buffer solutions, such as a mixture of lactic acid and sodium or triethanolamine;

- wax, such as beeswax, paraffin;

- plant extracts;

- preservatives, such as methyl, ethyl, propyl and butyl, esters of p-hydroxybenzoic acid, sodium benzoate, GERMABEN (brand name) or any chemical agent that protects against the proliferation of bacteria and mold, and commonly used in cosmetic compositions, which may be included in amounts of from 0.01 to 3 wt.%. A number of these products verify in order to avoid proliferation of bacteria, mold or yeast in cosmetic compositions. As an alternative to these chemical agents can sometimes use the modifiers of the water activity, greatly increasing the work the subject of the invention, may also contain fixing resin. These fixing resin is typically present in concentrations of from 0.01 to 10%, preferably from 0.5 to 5%. Fixing resin for cosmetic compositions that are the subject of the invention, chosen mainly from the following resins: acrylate/acrylamide copolymer, polyvinylacetate/ maleicanhydride, vinyl acetate/crotonic acid copolymer, octylacrylamide/acrylate butylmethacrylate copolymer, polyvinylpyrrolidone (V), copolymers of polyvinylpyrrolidone and methyl methacrylate, copolymer of polyvinylpyrrolidone and vinyl acetate (VA), polyvinyl alcohol, copolymer of polyvinyl alcohol and crotonic acid, a copolymer of polyvinyl alcohol and maleic anhydride, hydroxypropylcellulose, hydroxypropanoyl, polystyrenesulfonate sodium, polyvinylpyrrolidone/ethyl methacrylate/methacrylic acid terpolymer, monomethylether (methylphenylcarbinol acid), the copolymers of polyterephthalate the glycol/polyethylene glycol, copolymers of polyterephthalate/glycol/polyethylene glycol/ political sulfonate sodium, and mixtures thereof. Fixing resin may also contain grafted functional organopolysiloxane unit, the pyrrolidone (PVP), copolymers of polyvinylpyrrolidone and methyl methacrylate, copolymer of polyvinylpyrrolidone and vinyl acetate (VA), copolymers of polytetrafluorethylene /polyethylene glycol, copolymers of polyterephthalate the glycol/ glycol/political sulfonate sodium and mixtures thereof.

These fixing resin is preferably dispersed or solubilization in the selected media.

Cosmetic compositions forming the subject of the invention may also contain polymeric derivatives that perform safety functions.

These polymer derivative may be present in amounts of from 0.01 to 10%, preferably from 0.1 to 5% (approximately), preferably about 0.2 to 3 wt.%, this is such agents as:

*derivatives of cellulose, such as simple hydroxyether cellulose, methylcellulose, ethylcellulose, hypromellose, hydroxyethylmethylcellulose;

*complex of polyvinyl esters grafted to polyalkylene links, such as polyvinyl acetate grafted to polyoxyethylenated links (EP-A-219048);

*polyvinyl alcohols;

*polyclonality copolymers on the basis of the motives of ethyleneterephthalate and/or propietaria the Talat/(number of motifs) polyoxyethylenated order from 1/10 to 10/1, preferably, of the order of 1/1 to 9/1, and polyoxyethylenated contain polyoxyethylene units with a molecular weight of from 300 to 5000, preferably from 600 to 5000 (US-A-3959230, US-A-3893929, US-A-4116896, US-A-4702857, US-A-4770666);

*sulfonic polyclonality oligomers obtained by the sulfonation of oligomer - derived ethoxylated allyl alcohol, dimethyl terephthalate and 1,2-PROPANEDIOL containing from 1 to 4 sulfonic groups (US-A-4968451);

*polyclonality copolymers on the basis of the motives of propellantregulator and polyoxyethylenated and ending with ethyl, methyl motifs (US-A-4711730) or polyclonality the oligomers terminated groups alkylphenate- (US-A-4702857) or anionic sulfamonomethoxine (US-A-4721580), anionic solitarily groups (US-A-4877896);

*polyester-polyurethanes obtained by reaction of a complex of the polyester with a molecular mass of 300-4000, obtained from adipic acid and/or terephthalic acid and/or sulfoisophthalic acid and diol weight less than 300, with prepolymers with isocyanate terminal groups derived from polyoxyethyleneglycol with a molecular mass of 600-4000 and a diisocyanate (FR-A-2334698);

ethoxyresorufin oligomers, obtained by condensation of isophthalic acid, sulfosuccinate of dimethyl and diethylene glycol (FR-A-2236926).

The quality of the cosmetic compositions forming the subject of the invention may also be enhanced by the use of plasticizers. Plasticizers can be from 0.1 to 20% of the composition, preferably from 1 to 15%. Among the most suitable plasticizers can be called adipate, phthalates, isophthalate, azelate, stearates, silicone copolyol, glycols, castor oil or mixtures thereof.

You can also with advantage be added to these compositions sequester metals, especially sequester calcium, such as citrate ions, or softening agents, such as silicones or oils, or fatty body used for these purposes in the cosmetic industry (mineral oils, esters of fatty acids, triglycerides, silicones,...).

You can also add a water-soluble or water-dispersed polymers, such as collagen or certain non-allergenic derivatives of animal or vegetable proteins (e.g. protein hydrolysates of wheat), natural hydrocolloids (guar, Karuna, Tarawa gum) or obtained by fermentation, such as xanthan gum, and derivatives of these polikar, wroye or karunya derivatives, such as their cationic or non-ionic derivatives (for example, hydroxypropanoyl), anionic derivatives (carboxymethylthio and carboxyphenoxypropane). These compounds can be added in Association with mineral powders or particles such as calcium carbonate, mineral oxides in powder form or in colloidal form (particles with sizes of the order of one micrometer or less, sometimes several tens of nanometers), for example, silica, aluminum salts, is commonly used as antitranspirant, kaolin, talc, clays and their derivatives. These ingredients usually added to increase the attractiveness of the compositions when used by the consumer, one or more flavoring agents, dyes, among which are the products described in Annex IV (list of colouring agents allowed for use in cosmetic products) of the European Directive no76/768/EEC of 27 July 1976, the so-called cosmetic Directive, and/or fogging agents such as pigments.

Finally, the composition may also contain binders or gelling polymers, such as cross-linked polyacrylates-CARBOPOL, manufactured by GOODRICH-derived cellulose as hydroxypropylcellulose, carboxymethylcellulose, guar, and their PR is on, such as chitosan, used separately or together, or the same compounds, usually in the form of water-soluble polymers modified with hydrophobic groups, linked by covalent bonds to the polymer skeleton, as described in patent WO 92/16187, and/or water to add up to 100% of the total number of components.

Cosmetic compositions forming the subject of the invention may also contain a polymeric dispersant agents in quantities of from 0.1 to 7% by weight to control the stiffness for calcium and magnesium; such agents can be:

*water-soluble salts of polycarboxylic acids with a molecular mass of from 2000 to 100,000, obtained by polymerization or copolymerization Ethylenediamine carboxylic acids such as acrylic acid, maleic acid or maleic anhydride, fumaric acid, taconova acid, konitova acid, musicanova acid, Tarakanova acid, metromanila acid and, in particular, polyacrylates with a molecular mass of from 2000 to 10000 (US-A-3308067), copolymers of acrylic acid and maleic anhydride with a molecular weight of from 5000 to 75000 (EP-A-66915);

*the glycols with a molecular weight of from /BR> Example 1 to Obtain a dispersion of particles according to the invention with the processing based on the silica

Getting the elementary particles

To 1300 g of a solution of titanium oxychloride is 1.73 mol/kg consistently add:

- 121 g of 36% - hydrochloric acid,

- 15,14 g of citric acid,

- 1562 g of purified water,

- 10.30 g (3.6% of TiO2) anatase nuclei with sizes from 5 to 6 nm.

The mixture is brought to a boil and so maintained for 3 hours. Then the solution is filtered, and the obtained particles are washed with water to remove chloride, after which they dispersed at pH 9 (controlled by the addition of soda) with a dry extract 20 wt.%.

The particle size determined MET, is 60 nm. X-ray diffraction analysis (PDA) shows that the particles are particles based on titanium dioxide exclusively anatase form. Their density is 2,52 (Vi = of 0.14 CC/g).

Specific surface area, determined by the method of WET on dry particle dispersion at a temperature of degassing 150oC, equal to 300 m2/,

Processing of silica particles

When shaken, make a 750 g of the above dispersion in 750 g of deionized water.

The resulting mixture was placed in a reactor and increase tempvar of sodium silicate (solution 335 g/l SiO2), containing the equivalent of 30 g of SiO2and a solution of sulfuric acid 80 g/l, the Flow rate of the solution of alkali silicate is 2 ml/min, pH 9 regulate the addition of sulfuric acid.

After making reagents temperature 90oC is maintained for 2 hours. After cooling, the dispersion is centrifuged. The precipitate was washed with water three times, and then dispersed at a pH of 8.5 with a dry extract 40 wt.%.

Properties of the obtained particles

Particle size, as defined by the MET, is 60 nm.

Specific surface area measured by the BET method to dried under vacuum at a temperature of 150oC for 4 hours the particle dispersion equal to 140 m2/,

The content of SiO2defined by X-fluorescence, is 19 wt.% with respect to the titanium dioxide.

Density equal to 2.2.

A viscosity of 750 mPas.

The measure of dispersion equal to 0.45. This dispersion is particularly stable: after one month the measure of dispersion remains at the level of 0.45.

Example 2 to Obtain a dispersion of particles according to the invention with the processing of silica and aluminum hydroxide

Elementary particles are the same as in example 1.

Treatment of the particles Thor, equipped with vesbaltawati. Then add 750 g of purified water and raise the temperature to 90oC. the pH is brought to 9 by adding soda.

First of all make, continuously and simultaneously, a solution of sodium silicate (solution 335 g/l SiO2), containing the equivalent of 22.5 g of SiO2and a solution of sulfuric acid 80 g/l in an amount such that the pH was 9. The flow of sodium silicate solution is 2 ml/min Withstand time of ripening for 1 hour at 90oC. Then contribute, at pH 9 and 90oC, continuous, aqueous sodium aluminate solution (a solution of 240 g/l Al2O3), containing the equivalent of 7.5 g of Al2O3. The flow rate of the solution of aluminate is 2 ml/min, pH 9 regulate the simultaneous administration of an aqueous solution of sulfuric acid 6 n

After making reagents withstand the maturing time of 2 hours at 90oC, then the dispersion is cooled.

The resulting dispersion is centrifuged. The precipitate was washed with water three times, and then dispersed.

the pH of the dispersion was adjusted to 7.5 by addition of H2SO4its dry extract is 30 wt.%.

Properties of the obtained particles

The particle size determined MET, is 60 nm.

The specific surface IG.

The content of SiO2defined by X-fluorescence, is 14.9 wt.%, the content of Al2O3- 5%.

A viscosity of 750 mPas.

Density equal to 2.25.

The measure of dispersion equal to 0.45. This dispersion is particularly stable: at the end of the month the measure of dispersion remains at the level of 0.45.

Example 3 Stability of the dispersion of example 2, depending on pH

the pH of the dispersion from example 2 change by adding sulfuric acid or soda. Estimates of variance in accordance with pH is shown in table. 3.

It is seen that for pH from 5.5 to 10 measure of dispersion remains below 0,45.

Example 4 - Sunscreen cosmetic composition

Preparing a sunscreen composition according to the invention of the dispersion of titanium dioxide of example 3 according to the following procedure (see tab. 4).

Measurement of photostability songs

Cosmetic composition is injected through a quartz chamber in the apparatus of Sun-Test (Heraeus) and exposed to energy E 500 W/m2when the temperature T 30oC for 1 hour.

Control of photostability is carried out by visual observation of the dyeing composition. Not visually see any blue in the face.

The dimension in which the method described in "Cosmetics & Toiletries", T. 107, No. 10, page 119.

SPF index is 202 for the application of 2 mg/see

Measurement of the index of dispersion of particles of titanium in the composition of

The index of dispersion is 0.45, i.e. identical to the measure of dispersion of particles of titanium dioxide to prepare a composition.

1. Particles of titanium dioxide of anatase with dimensions of not more than 100 nm, characterized in that they are covered, at least partially, a layer of at least one oxide, hydroxide or oxohydroxide metal, and the fact that these particles have a specific surface BET of at least 70 m2/g and a density of about 2.2.

2. Particles under item 1, characterized in that the weight ratio of one or more oxides, hydroxides or oxohydroxides metal to titanium dioxide is not more than 60 wt.%.

3. Particles under item 1 or 2, characterized in that they are covered at least partially with a layer of silica, or hydroxide, or oxohydroxide aluminum in simple or mixed form.

4. Particles under item 2, characterized in that they are covered with a layer of silica and hydroxide or oxohydroxide aluminium containing 15 wt.% SiO2and 5 wt.% Al2O3with respect to the titanium dioxide.

5. Caste under item 5, characterized in that the rate of dispersion of the particles in the liquid phase is not more than 0.5.

7. Particles under item 5 or 6, characterized in that the liquid phase of the dispersion is an aqueous phase.

8. Particles under item 7, characterized in that the dispersion has a specific conductivity not more than 3 MSM.

9. Particles in one of the paragraphs.5 to 7, characterized in that the dry extract of the dispersion is at least 35 wt.%, and the fact that the viscosity of the specified dispersion is not more than 1000 MPa with.

10. Particles in one of the paragraphs.1 to 4, characterized in that they are agglomerated and are in powder form.

11. A method of producing particles according to one of paragraphs.1 - 10 providing for the deposition of at least one oxide, hydroxide or oxohydroxide metal on the surface of particles of titanium dioxide of anatase with dimensions of not more than 100 nm, with a specific surface area BET of at least 200 m2/g and a density of about 2.5.

12. The method of obtaining on p. 11, characterized in that the precipitated, at least one oxide, hydroxide or oxohydroxide metal on the surface of particles of titanium dioxide obtained by hydrolysis of at least one compound of A titanium in the presence of at least one compound B, defined the dust, or at least two carboxyl groups and at least one hydroxyl and/or amino group, (II) organophosphorus acids of the following formula:

< / BR>
< / BR>
< / BR>
in which n and m are integers from 1 to 6, p is an integer from 0 to 5, R1, R2, R3identical or different, represent a hydroxyl, amino, Uralkaliy, aryl, alkyl group or hydrogen, (III) compounds capable of releasing sulfate ions in an acidic environment, (IV) salts of the above acids, and in the presence of sources of titanium dioxide of anatase with dimensions of not more than 5 nm and the weight ratio, expressed in TiO2sources/titanium hydrolytic environment before making sources, expressed as TiO2from 0.01 to 3%.

13. The method according to p. 12, characterized in that the compound of titanium is a titanium oxychloride.

14. The method according to p. 12 or 13, characterized in that the compound B is citric acid.

15. Sunscreen agent, characterized in that it is a particle of titanium dioxide on one of the PP.1 to 9.

16. Sunscreen agent p. 15, characterized in that it is used in formulations for cosmetics, varnishes, paints and plastics.

17. Cosmetic Sol number, the content of titanium dioxide in the specified composition is at least 1%, preferably not more than 25 wt.%.

 

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